JPS58113266A - Aqueous composition containing blocked isocyanate bridging agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to aqueous coating compositions containing blocked incyanate crosslinkers. In more detail,
The present invention relates to aqueous coating compositions suitable for being applied to a support by cathodic magnetization.

Blocked incyanates are used very extensively as crosslinking agents in aqueous coating compositions, especially in cationic electrodeposition systems. Among the many patent documents teaching the use of such blocked isocyanate crosslinkers, e.g.
U.S. Patent Nos. 5,799,854, 6,965,087, and 4,031
No. 050, No. 4036795 and No. 41548.65
No. 3 specification can be mentioned. Typically, according to the prior art, a di- or tri-functional zolized isocyanate or incyanate prepolymer is mixed with a hydroxyl or amine functional polymer and then dispersed together in a water/acid solution. However, because these blocked isocyanate or incyanate prepolymers do not contain ionizable groups, there are certain limitations that affect paint bath formulation. In particular, there are limitations on the amount of crosslinking agent that can be co-dispersed in the composition in practical terms, and there are limitations on the type of blocking agent that can be used to block free incyanate groups in the preparation of blocked incyanate groups. be. Both of these factors are related to the properties of the composition.

The amount of crosslinker that can be introduced into these types of systems is important since the hydrophilicity of the resin depends on the number of ionizable groups present in the total mixture containing the crosslinker (
It is limited depending on the eIl of the resin synthesized and used as the main film forming agent (resin forming the solution, emulsion or dispersion). For this reason, mixtures containing multiple crosslinkers that do not contain ionizable groups are
This may constitute a system that is substantially less stable. The type of blocking agent can also affect the stability of the entire system. For example, commonly used blocking agents, cyclic compounds such as lactams and triazoles, result in crosslinking agents with bulky and rigid structures that are difficult to disperse with the other components of the composition.

As a result of the above, stable solution or bath formulations according to these prior art techniques require the use of less violet blocked isocyanate crosslinker than is desirable when attempting to optimize the overall system, and/or Alternatively, restrictions on the types of blocking agents that can be used are required. In fact, systems of the type shown in U.S. Pat. Yes, this dispersion would obviously require a lot of expense for axis purposes. As a result, in order to feminize it, it is necessary to add significant amounts of water to the system, converting such a dispersion into an oil-in-water type.

As will be appreciated, the need for such additional water to be added results in a relatively low solids content system and, in order to be stable, a large amount of water transport. This fact is economically unattractive.

Other methods of using blocked isocyanates in electrodeposition systems are described in U.S. Pat.
It is taught by a number of US patent specifications, such as No. 4. According to these patents, semi-blocked incyanates are reacted with the hydroxy functional backbone resulting in the formation of self-crosslinked systems. However, this kind of system is ]! ! Subsequent reactions, such as chain extension or the introduction of ionizable groups, may result in unblocking of the isocyanate groups at the temperatures at which these reactions occur.
) has the serious drawback of being limited.

The compositions of the present invention are not subject to the above limitations due to the use of special blocked isocyanate crosslinkers containing ionizable groups. By using blocked isocyanate crosslinkers containing such ionizable groups, it is possible to produce aqueous coating compositions, in particular cationic electrodeposition resin systems, in which the system is partially crosslinked. As a result of being able to retain the agent and remain stable, high solids contents can be present in the form of an unconverted dispersion. By preparing compositions containing blocked isocyanate crosslinkers containing ionizable groups, we have achieved improved crosslinking efficiency and produced cathodically electrodeposited yarns that allow curing at reduced temperatures. made it possible to obtain.

The composition of the present invention is an aqueous-based composition comprising a film-forming resin having reactive functional groups and a blocked isocyanate crosslinker that is stable at room temperature due to the presence of the reactive functional groups and reacts with the reactive functional groups at elevated temperatures. It is a paint composition. Particularly preferred according to the improvements of the invention, this apple composition is suitable for application by electrodeposition to a cathode support and is capable of being ionized at least in part as a result of norotonization of the amine nitrogen atoms by an organic acid. It is a water-based coating composition that has been solubilized. Such compositions generally include an epoxy/amine adduct film-forming resin with hydroxyl functionality and a blocked incyanate crosslinker that is stable at room temperature in the presence of the hydroxyl functionality and reacts with the hydroxyl functionality at elevated temperatures. It consists of In particular, such compositions can be used in the form of aqueous bath compositions suitable for electrodepositing corrosion-resistant, curable coatings on cathode supports. Generally such baths contain water, at least 10-5
an amine-functional film-forming resin that has been at least partially solubilized by norotonation with the organic acid as described above, and a blocked polyisocyanate crosslinker.

In all of the coating compositions or baths described above, the improvement of the present invention involves the use of an acid-soluble blocked polyisocyanate crosslinking agent as a crosslinking agent in the system or composition, comprising a compound formulated as follows: (A) (1) one isocyanate more reactive than the other, an organic diisocyanate having a group;
0) a sufficient amount of an active water-based blocking agent to react with substantially all of the highly reactive isocyanate groups; and 0) at least two hydroxyl groups and at least one tertiary isocyanate group. reaction of the droxy-functional amine with an amine nitrogen atom sufficient to cause substantially all of the free or unblocked isocyanate groups of reaction product (4) to react with the barbed oxyl groups of said amine; The blocked isocyanate bridge Im@ containing the compound obtained by reacting with the product cA) can be at least partially solubilized or dispersed by introducing an organic acid into said aqueous composition. , at least some of the tertiary nitrogen atoms of the divisor crosslinker are norotonized to ionize the crosslinker molecule. The structure of the blocked isocyanate crosslinkers useful in the compositions of the present invention and other components in the compositions in which the improved crosslinkers may be used will be more fully understood from the following detailed description of the invention. Dew.

As noted above, the first step in the preparation of blocked isocyanate crosslinkers useful in the compositions of the present invention is to prepare (1) an organic diisocyanate having one incyanate that is more reactive than the other; Reaction with a sufficient amount of blocking agent containing active hydrogen atoms to react with substantially all of the more reactive isocyanate groups, thus providing a semi-monoblocked diisocyanate reactant. The organic diisocyanates used in the production of the crosslinking agent include aliphatic, BFiJR group and aromatic diisocyanates as well as hybrids of these diisocyanates.
), provided that any of the diisocyanates selected as described above must have one isocyanate group that is more reactive than the other. Many such diisocyanates will be apparent to those skilled in the art; representative examples of these organic diisocyanates suitable for use in preparing the crosslinking agents of the present invention include the following compounds: 1-incyanato-1 (p-phenylisocyanate)methane; 1-incyanato-2(p-phenylisocyanato)ethane; isophorone diisocyanate; 4,4-diisocyanato-
2-nitro-biphenyl; and the following formula: (wherein R is a methyl group, an ethyl group, a tertiary ethyl group, a chlorine atom, a bromomethyl group, an ethoxy group, an isobutoxy group, an isonorobyl group,
Represents trichloromethyl group and methoxy group. ) diisocyanate.

The active hydrogen-containing blocking agent to be reacted with the organic diisocyanate can be selected from a number of blocking agents, which will also be apparent to those skilled in the art. Representative examples of preferred blocking agents include (
(1) aliphatic, cycloaliphatic and aromatic alkyl monoalcohols; (11) oximes; Aromatic alkyl monoalcohols can also be used as blocking agents according to the invention, for example methyl, ethyl, chloroethyl, propyl, ethyl, amyl, hexyl, hegetyl, octyl, nonyl, 5,5.5-)9 Aliphatic alcohols such as methylhexanol, decyl, lauryl alcohol, and the like can be used. Suitable alicyclic alcohols include, for example, cyclopentanol, cyclohexanol, etc., and aromatic-alkyl alcohols include phenylcarbinol, methylphenylcarbinol, and the like. Suitable oxime blocking agents include, for example, methyl ethyl ketone oxime, acetone oxime and cyclohexanone oxime. Lactams that can be used as blocking agents include, for example, -monocaprolactam, γ-butyrolactam and pyrrolidone; suitable triazoles include 1,2.4-)lyazole, 1.2.3-benketriazole, 1.2-benketriazole; .3-
Tolyltriazole and 4,5-diphenyl-1°2.
5-) Compounds such as lyazole are released.

The organic polyisocyanate-blocking agent adduct intermediate is formed by reacting the organic diisocyanate with enough of the blocking agent to ensure that one of the two -NOO groups of the diisocyanate reacts. be done.

The reaction of the organic diisocyanate and the blocking agent is an exothermic reaction; therefore, the diisocyanate and the blocking agent' are mixed at a temperature not higher than about 80° C., preferably at a temperature below about 50° C., to reduce exothermic effects. is preferable.

As mentioned above, the reaction product of an organic diisocyanate and an active hydrogen-containing blocking agent is
Substantially all of the isolated or unblocked incyanate groups of the zolocking agent intermediate and the amine group
Then at least 21
The amines may be selected from aromatic amines having one hydroxyl group and at least one tertiary amine nitrogen atom. Many such amines containing one or more tertiary amine nitrogen atoms will be apparent to those skilled in the art.

A preferred class of hydroxy-functional amines includes compounds selected from the group consisting of diols and triols containing a single tertiary nitrogen atom.

Preferred tertiary amine-functional diols and triols include those of the following formula:
-1~5; or +0H20H20+n011011g
-OHSn -1~12 t or +an2aH2an
, an2am116-o+aH2aH2-on, n
-1 to 12; f' is OH3 +0H-OH2-0-)nOH20H2-OH, It
= 1 to 12; the kyl group preferably represents a methyl group, or R1 or R2 represents any one of a suitable group. ) may be mentioned.

Particularly preferable compounds included in this type of compounds include:
Mention may be made of tertiary amine functional diols and triols such as methylgetanolamine, ditylgetanolamine, triethanolamine and phenyldiethanolamine, to name a few. Hydroxy-functional amines containing one or more tertiary nitrogen atoms and at least two hydroxyl groups as well as other suitable groups will be apparent to those skilled in the art.

As stated above, in all compositions to which the improvements of the present invention are applied, the blocked isocyanate crosslinking agent prepared as described above is at least partially modified by introducing an organic acid into the aqueous composition. It is dissolved or dispersed in a bath, where at least a portion of the tertiary nitrogen atoms of the crosslinker are norotonized to ionize the crosslinker molecule, which makes it more easily separated or dissolved. Allowing the crosslinker to be more easily dispersed and resulting in a more stable coating composition that may contain higher amounts of blocked isocyanate crosslinker.
It is the tertiary azine nitrogen atom in the crosslinking agent of the composition of the present invention that undergoes acid norotonation.

The acid used to solubilize the blocked isocyanate crosslinking agent of the present invention is preferably an organic acid having a decomposition constant of at least 10@-6. Representative examples of the many alcohols that fall within this category include icic acid, acetic acid, lactic acid, and phosphoric acid.

More specifically, according to the method for producing a blocked isocyanate crosslinking agent of the present invention, the ionizable crosslinking agent comprises 1 mol of a profking agent and 1 mol of a diisocyanate whose two isocyanate groups have different reactivities. can be produced by reacting, in this way 1
Only the incyanate groups block. This reaction occurs by slowly adding the blocking agent into the isocyanate at 90° to 150'kF.

After the addition is complete, the reaction is continued at the same temperature until half of the isocyanate groups are consumed. This is the isocyanate group of Yukan to 111! You can be persuaded by determining f. The semi-blocked incyanate is then reacted with a polyol containing tertiary amine groups. Slowly add one equivalent of polyol to one equivalent of isocyanate. Since the reaction is exothermic, it is maintained at a temperature of at least 60'F below the unblocking temperature of the particular blocking agent used. In some cases, a small amount of solvent can be added to control temperature and viscosity increases. Solvents such as butyl carpitol acetate, methyl isodityl ketone and generally those that do not have autofunctional groups reactive with incyanate can be used. The end point of the reaction is indicated by the absence of incyanate groups in the external spectrum.

Many waterborne coating compositions employing the improved blocked isocyanate-1 crosslinking agents of the present invention include cationic electrolytes based on epoxy/amine adducts and epoxy ester/amine adducts as well as acrylic wheels themselves. The layer composition is wrapped.

Non-electrodepositable aqueous compositions in which blocked isocyanate crosslinkers can be used include, for example, water-based coating compositions including Totsunocoat and Baked Zolaimer.

Several preferred electrodeposition coatings (elec
trocoat) composition was described in more detail.

As mentioned above, one type of composition in which the solated isocyanate crosslinkers of the present invention may be used consists of epoxy/amine adducts. The epoxy material used to form the adduct can be any monomeric or polymeric compound or mixture of these compounds having one or more epoxy groups per molecule. Although monoepoxides can be used, it is preferred that the epoxy compound is resinous and that the polyepoxide contains two or more epoxy groups per molecule.

Preferred polyepoxides are of relatively high molecular weight with a molecular weight of at least 350 DO and preferably 650 to 20 DO. The polyepoxide can be essentially any of the well-known persimmons, such as polyglycidyl ethers of polyhydric phenols (eg, bisphenols such as bisphenol A). These, in the presence of alkalino,
It can be produced by etherifying polyhydric phenol with epichlorohydrin. Phenolic compounds c, e.g. evabis(4-hygeroxyphenol)-2,
2-propane, 4,4'-dihydroyampenzophenone, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenol) -i + i
-isobutane, bis(4-hydroxy-tert-zotylphenyl)-2,2-710pan, bis(2-hydroxy-naphthyl)methane, 1.5=dihydroxynaphthalene, etc. In many cases, it is preferable to use polyepoxides containing aromatic groups in the violet molecule. This is the above diglycidyl ether and bisphenol A (1
) and then further reacting this product with shrimp chlorohydrin to give a polyglycidyl ether.

The polyglycidyl ethers of polyhydric phenols preferably contain hydroxyl groups in addition to epoxide groups.

The polyglycidyl ethers of polyhydric phenols can be used on their own, but the reactive sites (hydroxyl or epoxy when present) can be reacted with modifiers to change the film properties of the resin. In such compositions it is often desirable. The esterification reaction between epoxy resin and carboxylic acid, especially fatty acid, is
It is well known in the art and does not need to be explained in detail. Particularly preferred are saturated fatty acids, especially pelargonic acid. Epoxy resins can likewise be modified with organic substances containing isocyanate groups or other reactive organic substances.

Another very useful class of polyepoxides are the polyglycidyl ethers of phenolic novolac resins.

Ethylene glycol, diethylene glycol, triethylene glycol, 1.2-7"ropylene glycol, 1
．． 4-norodalene glycol, 1,5-bentanediol, 1,2. Also suitable are polyglycidyl ethers of similar polyhydric alcohols, which may be derived from polyhydric alcohols such as (S-hexanetriol, glycerol, bis(4-hydroxycyclohexyl)-2,2-propane, etc.).

Polyglycidyl ethers of polyhydric phenols are preferred polyepoxides. Preferred polyglycidyl ethers of polyhydric phenols have a molecular thickness of at least 650, preferably in the range of 350 to 2000, and an epoxy equivalent weight in the range of 180 to 1000.

As described above, the epoxy-containing material is reacted with an amine to form an adduct. The amine used is
The secondary amine may preferably be a secondary amine. Preferably the amine is a water-soluble amino compound. Such amines include, for example, mono- and dialkylamines such as methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, diethylamine, diptylamine, methylbutylamine, methylethanolamine, jetanolamine, diglobanolamine, etc. can be mentioned.

Although in most cases it is legitimate to use low molecular weight amines, it is also possible to use high molecular weight monoamines, especially if the molecule is softened or further modified by the structure imparted by the amine. Additionally, mixtures of low and high molecular weight amines can be used to modify the properties of the resin.

Additionally, such amines can contain other components so long as they are of such a nature that they do not interfere with the reaction of the amine with the epoxy or are used under conditions that do not gel the reaction mixture.

The reaction with the amine epoxy group-containing substance occurs by mixing the amine and the epoxy group-containing substance. It is in fact an exothermic reaction. If desired, the reaction mixture may be stored at a medium temperature.
It can be heated to 0°C to 150°C. However, higher or lower temperatures can be used depending on the desired reaction. In any case, it is often desirable to raise the temperature at least slightly for a sufficient period of time to ensure completion of the reaction.

The amine cap that is reacted with the epoxy group-containing material is at least sufficiently violet to render the resin cationic, ie, capable of migrating to the cathode when acid is solubilized. If the
Substantially all of the epoxy groups in the resin are reacted with the amine. However, it is also possible to leave an excess of epoxy groups, which hydrolyze on contact with water to form hydroxyl groups.

The blocked isocyanate crosslinking agents of this invention are preferably mixed with an amine epoxy adduct within a range providing from about 0.5 to about 2.0 urethane groups for each hydroxyl group.

In order to ensure a rapid and complete reaction of the two components, it is usually necessary to have a catalyst for urethane formation in the coating mixture. However, if the gorge temperature after deposition is high enough, a catalyst may not be necessary. In addition, if a suitable blocking agent for isocyanate groups is used,
A catalyst may not be necessary. Externally added catalysts include, for example, dibutyltin-dilaurate and tin acetate, although other urethane-forming catalysts known in the art may also be used. The catalyst is used in an amount that effectively promotes the reaction in the deposited film, such as within the range of about 0.5 to about 4.4 percent by weight of the amine-epoxy adduct. Typically about 2% by weight is preferred. The capped isocyanate/amine epoxy adduct catalyst mixture is electrodeposited onto a suitable support and cured at an elevated temperature, such as from about 25[ly] to about 600'F. Curing of the film involves at least some crosslinking in the urethane. The liberated alcohol may evaporate or remain in the mixture as a plasticizer, depending essentially on the boiling point.

The polymeric polyepoxide can be reacted with a dimer acid to chain extend, thereby increasing the molecular welfare of the polymeric polyepoxide.

The reaction occurs between the carboxylic acid group and the epoxide ring, forming an ester bond and a secondary hydroxyl group. These epoxy ester resins are about 0.0.0% per equivalent of epoxy group.
It is prepared by reacting 1 to about 0.6 g of the violet dimer acid. Essentially pasty polymer products are preferred; however, branched condensation polymers can also be used and dimer acids containing up to 60% by weight of one trimer unit can also be used. Chain extension is carried out by mixing the dimer acid and polyepoxide, optionally in the presence of an inert solvent, and in the presence of a catalyst such as a tertiary amine catalyst.
It is produced by carrying out the reaction at a temperature of ~170°C. Chain extenders include organic dimers and dimer acids, as is well known to those skilled in the art. Relatively high molecular weight dimer and ternate acids are polymerization products of 04-018 fatty acids.

Although several mixtures of dibasic, tribasic and -basic acids are present, the most useful in this composition are primarily dibasic acids and minor tribasic and −
It is a product containing basic acid. Also useful are low molecular weight dibasic and tribasic acids such as adipic acid and azelaic acid.

Ionizable groups are introduced into these chain-extended epoxy resins in the same manner as described above for unextended resins. The remainder of the composition, including delt-forming crosslinker, catalyst, etc., is also similar to the unextended epoxy resin-containing composition.

Acrylic polymers with ionizable groups and sufficient hydroxy functionality can be synthesized by two methods. In the first method, amine-functional monoethylenically unsaturated monomers are copolymerized with hydroxy monomers and various other non-functional acrylic and vinyl heptamers. Monoethylenically unsaturated amines are well known and commercially available. Compounds useful in these compositions are dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, monoethylaminoethyl methacrylate, aminoethyl methacrylate and corresponding acrylates.

Aminoethyl methacrylate and tert-butylaminoethyl methacrylate can also be used.

%/! f L/N-based unsaturated tertiary aminoamides are also useful in this bale composition. Amine functional group unsaturation
, hydroxy-functional monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxynolopyl-methacrylate and various non-reactive monoethylenically unsaturated monomers such as styrene, vinyltoluene, methyl methacrylate, ethyl acrylate, acrylonitrile, etc. Copolymerize with.

A second method for producing acrylic polymers of this type consists of using monoethylenically unsaturated epoxy-functional monomers and copolymerizing them with hydroxy-functional monomers and various non-functional monomers.

The copolymers contain up to 50% epoxy functional copolymers such as glycidyl methacrylate and up to 60% hydroxy functional monomers such as hydroxyacrylate, hydroxyethyl acrylate, etc. The epoxy groups of the acrylic resin are then reacted with a secondary amine of the type described above, and a sufficient amount of ionizable crosslinking agent is mixed into the system and water/l! Codisperse in solution.

The use of these resins in electrocoating compositions and the properties of the compositions will be apparent to those skilled in the art, especially in view of the initially described compositions.

Aqueous compositions containing the above components are very useful as coating compositions and are particularly suitable for application by electrodeposition, although they can also be applied by conventional painting techniques. Generally, to obtain a suitable aqueous composition it is necessary to add a neutralizing acid to the composition. It is desirable to electrodeposit the coating from a solution with a pH of 5 to about 9.

Neutralization of these products is achieved by reacting all or part of the amino groups with a water-soluble acid such as formic acid, acetic acid or phosphoric acid. The degree of neutralization will depend on the particular resin and it will be necessary to add sufficient acid to dissolve or disperse the resin. In the compositions of this invention, it is the addition of this same acid that serves to dissolve or disperse the blocked isocyanate crosslinking agents of this invention.

All electrodepositable compositions referred to as being "solubilized" or "dispersed" may actually be complex solutions, dispersions or suspensions, or combinations of one or more of these in water; It acts as an electrolyte under the action of an electric current. When the resin is present, the resin is undoubtedly in solution, but when it is, and perhaps in most cases, the resin is a dispersion, which is a molecular intermediate between a colloidal suspension and a true solution. It is clear that it can be called a molecular dispersion with a size of .

In many cases, pigment compositions and optionally additives well known in the electrodeposition art, such as antioxidants, surfactants, cutting solvents, etc., are included in the compositions.

As noted above, when using the blocked isocyanate crosslinkers of the present invention in which the crosslinkers contain ionizable tertiary amine groups, compositions having higher resin concentrations than previously possible are obtained. becomes possible. As mentioned above, this allows the composition to exist as an unconverted dispersion, thereby avoiding the transport of large amounts of water;
It also allows the incorporation of a sufficient amount of crosslinking agent to more completely cure the composition at lower temperatures.

In cathodic electrodeposition methods using aqueous coating compositions of the type described above and the blocked incyanate crosslinkers of the present invention, the aqueous composition is placed in contact with a conductive anode and a conductive cathode, and the coating is The surface to be used is on the cathode. When an electric current is passed between an anode and a cathode that are in contact with a bath containing the coating composition, a layerable film of the coating composition adheres to the cathode. This is in contrast to methods that use polycarboxylic acid resins that are deposited on the anode.

The conditions under which electrodeposition is carried out are generally similar to those used for electrodeposition of other types of paints. The applied voltage can vary widely and is typically 50 to 500 volts, but for example 1 volt F.
It can be as low as a few thousand ports or as high as a few thousand ports. The current density is typically about 1.0 amps to 1.0 amps.
5 amps/(ft,)" and tends to decrease during electrodeposition.

After electrodeposition, the coating can be cured at elevated temperatures by any conventional means such as baking in an infrared heat lamp, open or storage. Curing temperatures are preferably from about 550° to about 425°F, although temperatures from about 250° to about 500° or even 600° can be used if desired.

Next, the present invention will be further explained with reference to Examples. Unless otherwise specified, "part" in the examples means "heavy part".

Example I 2.4-) Luene diisocyanate (H71ene from Dubond) T ml 1392
% was placed in a suitable reaction vessel under a nitrogen gas blanket.

904 parts of C-caprolactam were charged in one hour while maintaining the temperature below 110°F (43°C).

After the addition was complete, the batch was held at 120'F for 60 minutes and -NCO conversion was determined to be 50%.

At this point, 476 parts of N-methyljetanolamine was charged over 1 hour. The temperature of the exothermic reaction was kept below 240°F by external cooling. After the addition was complete, the batch was held at 240°F for 15 minutes, at which point the infrared spectrum of the product showed that all isocyanate groups were showed that it had responded. This batch was then diluted with 1190 parts of ethyl cellosolve. The final product had a viscosity of z3.

Example (2) 582 parts of toluene diisocyanate were placed in a suitable reaction vessel under a nitrogen gas blanket. With external cooling to maintain the temperature below 110'F, 287 parts of methyl ethyl ketoxime was added dropwise over 2 hours; after the addition was complete, the batch was held at 170 parts for 1 hour. 164 parts of triethanolamine were added over 1 hour. The temperature of the exothermic reaction was kept below 220°C by external cooling.

After addition was complete, hold the batch at 2201” for 15 minutes;
Diluted with 442 parts of ethyl cellosolve.

EXAMPLE ■ Epon 1001 (775% N in xylene), a polyglycidyl ether of bisphenol A with an epoxy weight of 471 m, commercially available from Shell Chemical Company, 63
4 parts, POP-02 commercially available from Union Carbide Co.
00 polycanololactone, t-ol, and >1.1 parts of dimethylbenzylamine were charged into a reaction vessel. The charge was heated at 125° C. for 6 hours for chain extension. The batch was then cooled to 90°C and N-
60 parts of methylethanolamine and 36.7 parts of methyl isobutyl diketoimine (70% solution in methyl isobutyl ketone) of diethylene triamine were added.

The container was kept at 115 DEG C. for 1 hour, and 83 parts of hexyl cellosolve, 8.3 parts of dibutyltin dilaurate, and 410 parts of the ionizable crosslinking agent of Example 2 were added. This batch was then dispersed in a bath containing 1000 parts of water, 22 parts of acetic acid, 10416 parts of sulfynol and 6 parts of Geigyamine A2. An electrodeposition bath was prepared by diluting 560 parts of the above resin with 186 parts of water. Phosphate-treated steel panels were coated at 250 delt for 2 minutes and cured at 180°C for 20 minutes to a
．． A smooth, hard-flexible film of 7 mil thickness was obtained.

1 Sulfuitol is an acetylene-based surfactant, i.e., 2.4, 7, 9, commercially available from Aerozop Dachf & Chemicals, Inc., Allentown, Pennsylvania.
-tetramethyl-5-decyne-4,7-diol.

2Geigeia® 0 is a substituted imidacilline derivative marketed by CipaGaier.

Example 1 174 parts of toluene diisocyanate were charged into a reaction vessel under a nitrogen gas blanket. 87 parts of methyl ethyl ketoxime were added in 1 hour while maintaining the temperature below 110°F by external cooling.

After the addition was complete, the batch was held at 170'F2 for 1 hour. 60 parts of N-methyljetanolamine was added in 1 hour. The temperature of the exothermic reaction was kept below 220'F by external cooling. After the addition was complete, the batch was
Hold at 20°F for 15 minutes and dilute with 16 parts ethyl cellosolve.

Example V 654 parts of Epon 1001 (75% Nv in xylene) and 1130 parts of POP-0220 were charged into a suitable reaction vessel. The mixture was heated to 3506F and 140 parts of xylene was distilled off under reduced pressure. The batch was cooled to 260OF and 1.1 parts of dimethylbenzylamine was added. i
! ! The batch was held at 260"F for 6 hours for chain extension and then acetylated to below 200"F, at which point 30 parts of N-methylethanolamine and methylisobutyldiketoimine (70% in methylisobutylketone) of diethylenetriamine were added. Solution) 56.7 parts were added.This batch was
83 parts hexyl cellosolve, kept at 50''F for 1 hour,
8.6 parts of dibutyltin dilaurate and 410 parts of the ionizable crosslinking agent of Example (2) were added. Next, this batch was mixed with 100 parts of water, 122 parts of vinegar #1, and 104 parts of Sulfi Tool.
was dispersed in a solution containing 6 parts of GaII amine and 0.6 parts of GaII amine. Dilute 250 parts of active resin with 960 parts of water,
An electrodeposition bath was prepared. 2 on phosphate treated steel panel
Etched at 25 volts for 2 minutes and cured at 180°C for 20 minutes to yield a smooth, hard, effective film about 0.5-0.6 mil thick.

1For-0220 is a poly-casilolactone diol commercially available by Union Carbide Co. Example ■ Epon 829 was mixed with 105211 and Bisphenosim 506.
1 part was charged into a suitable reaction vessel. When the mixture is heated to below 500 ℃, at this point an exothermic reaction occurs and the temperature! +
I made it to 507. The reaction mixture was held at this temperature for 50 minutes, then cooled to 270'F and Pap -0200
50 parts of S and 4 parts of dimethylbenzylamine were added. Keep this batch under 270 for 1-1/2 hours, then 2
Cooling left below 00. 100g of methylethanolamine,
was added and the mixture was kept at f5oy for 1 hour. At this point, 700 parts of the ionizable crosslinking agent of Example I and 175 M of Bexyl Cellosolve were added and after 10 minutes of mixing the batch was dissolved in a solution of 1100 parts of water, 1 part of emso, 12 parts of sulfitol and 0.12 parts of iggyamine. dispersed inside. The resulting product was a stable water-in-oil dispersion.

Example 1 2.4-) 696 parts of luene diisocyanate were charged into a suitable reaction vessel. N-methyljetanolamine 6
57 parts were added dropwise. After 60 minutes, the temperature was raised to 50°C and 100 parts of acetone was added. The addition was completed after 30 minutes, and 100 parts of acetone was further added. At this point, neopentyl glycol 521! was added and the reaction mixture was kept at 50° C. for 60 minutes, and then 87 parts of methyl ethyl ketoxime was added dropwise over 20 minutes. After the addition was complete, the mixture was kept at 45° C. for 60 minutes and then cooled to room temperature. 200 parts of this resin was mixed with 400M of Butyl Cellosolde, 200 parts of Silica Aluminum A, 56 parts of lead silicate, and 60 parts of carbon black. The resulting slurry was then milled in a suitable mill to a Hegman 7 fineness.

To prepare an electrodeposition bath, 200 parts of the above pigment dispersion were added to
640 parts of the resin from Example 2, 960 parts of water and 5 parts of acetic acid were mixed. Phosphate treated panels were coated at 225 volts for 2 minutes and 20 molecules # at 500'F! J hardened.

hsTxx > -177-75 when soaked in 100 below Galt Fog, the panel will fade after 15 days to 1 inch from the scribe mark.
It showed creepage leakage of /3□.

Example ■ 481 parts of Epon 829, 160 parts of bisphenol A, and Empol 1016 (commercially available from Emery, acid value 19)
191 parts of dimer acid No. 3) were charged into a suitable reaction vessel. The mixture was heated to below 660°C, at which point an exothermic reaction occurred and the temperature rose to 400'F. The batch was cooled to below 650°F and held at this temperature for 1 hour. The batch was then cooled to 200°F and 64 parts N,-methylethanolamine and methylisobutyldiketoimine (in methylisoditylketone) of diethylenetriamine were added. 51 parts of a 70% solution of This batch is 25
86 parts of hexyl cellosolve, 10 parts of dibutyltin dilaure) and 52 parts of the crosslinking agent of Example 3.
Added 0 parts. This batch was then mixed with 1200 parts of water, f.
fl: Dispersed in a solution containing 20 parts of acid, 6 parts of Sulfitool 104, and Geigyamine 06M to form a water-in-oil dispersion. To prepare the electrodeposition bath, 250 parts of this dispersion were inverted with 500 parts of water. Phosphated steel panels were coated at 225 volts for 2 minutes and 180 volts
Smooth, approximately 5-0.6 mil thick, cured at ℃ for 20 minutes.
A hard flexible coating was obtained.

Example ■ 670 parts of toluene was charged into a suitable reaction vessel, and 250 parts of toluene was charged.
A mixture of 257 parts of butyl methacrylate, 296 parts of methyl methacrylate, 66 parts of styrene, 146 parts of glycidyl methacrylate and 66 parts of suspended butyl peroctoate was added over a period of 6 hours. 1 hour after the end of the monomer addition. and candy butyl peroctoate 6
260° C. was added and the mixture was held at 260° C. for an additional 2 hours. At this point, diethylenetriamine methyl isobutyl diketoimine (70% solution in methyl isobutyl ketone)
Added 70 parts. Keep this batch under 250 for 1 hour,
Then, 400 parts of the solvent was distilled off, and 50 parts of the crosslinking agent of Example
This batch was mixed with 3,600 parts of water, 80 parts of acetic acid,
Sulfitool 10420 parts and Gaii Ami 2020
of the solution. Add 560 parts of this resin to 186 parts of water.
An electrodeposition bath was prepared by diluting the solution to 0 parts. Phosphate-treated steel panels were coated with 180 port for 2 minutes and 180
Cure for 20 minutes at ℃ to 0.7 mil thick, smooth, hard,
A flexible coating was obtained.

Agent Asamura Hao 4 other people

Claims (1)

[Claims] ill A film-forming resin having a reactive functional group;
1 ( A) an organic diisocyanate having one isocyanate group more reactive than the other;
) reacting with sufficient active hydrogen-containing blocking agent to react with substantially all of the highly reactive isocyanate groups, and (B) at least 2 g! A hydroxyl monofunctional amine having a hydroxyl group of I and at least 1H tertiary amine nitrogen atom is combined with Mi
a b M IJJ solution-blocked polyisocyanate crossagent, wherein the compound is reacted with sufficient of the reaction product (A) to react with J. The inocyanate crosslinking agent becomes at least partially soluble or dispersed by introducing an organic acid into the aqueous composition, with at least one portion of the tertiary nitrogen atoms of the crosslinking agent being dispersed. Part 1 is an aqueous coating composition characterized in that a polyisocyanate crosslinking agent is used which is norotonized so as to ionize the crosslinking agent molecules. (21cA) water; (B) an organic acid having a dissociation constant of at least 10-5; (0) an amine-functional film-forming resin that has been at least partially solubilized by protonation with said organic acid. and (D) a blocked polyisocyanate cross-linking agent which has been at least partially pIre-formed by norotonation of the amine stranded trochanter with the organic polymerase (B); and Garanari S.
The crosslinking agent is (I) (1)! aliphatic, cycloaliphatic and aromatic diisocyanates having one isocyanate group which is more reactive than the other, and their hybrids.
(If) (a) aliphatic, cycloaliphatic and aromatic alkyl monoalcohols, (b) oximes, (C) lactams,
(1)) reacting an active hydrogen-containing blocking agent selected from the group consisting of Liacour and mixtures thereof with sufficient violet to react substantially all of the more reactive isocyanate groups; and ■ an aliphatic , alicyclic and aromatic amines, having at least two hydroxyl groups and at least one tertiary amine nitrogen atom, the drooxy-functional amines of the reaction product (I) sufficient of the reaction product (I) to react substantially all of the free or unblocked isocyanate groups with the hydroxyl groups of the amine; the cross-linking agent is dispersed, at least a portion of the atoms of the cross-linking agent being zolotonized so as to ionize the cross-linking agent molecules (i.e., the cathode supporting Applying a touch-resistant, curable coating composition on the body of IIE7
An aqueous bath composition suitable for use in preparing 1jI.