JPS594617A - Novel epoxy ester resin suitable for thermosettable resin coating composition and novel thermosettable coating composition based on organic solvent - 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 novel epoxy ester resins and novel solvent-based thermosetting coating compositions containing said resins. The present invention also provides for such coating compositions formulated as sprayable high solids coating compositions suitable for use, for example, as automotive solimers to produce coatings that are highly resistant to corrosion, humidity and solvents. Also related.

Solvent-based coating compositions using high molecular weight polymeric resins having crosslinking functionality (eg, molecular weights from about 2,000 to 40,000) and suitable crosslinking agents are known. Typically, such coating compositions are applied to a substrate, such as by spraying, and then cured, by baking the coated substrate at an elevated temperature suitable to drive off the organic solvent and promote the crosslinking reaction. The resulting thermoset coating can provide aesthetic and functional benefits, including corrosion protection for the underlying substrate, even though it is sufficiently moisture and solvent resistant.

Coating compositions containing such high molecular weight polymeric resins typically contain only 25% to 50% solids so that they can be sprayed or otherwise applied to conventional substrates. It is.

The viscosity of higher solids coating compositions is typically too high for this purpose. Conventional epoxy ester-based motor vehicle spray Zolimers, for example, typically have a volatile organic content (rVOcJ') of about 6239/l (5.2 bonds/l).

The elimination of volatile organic solvents during curing of these conventional low solids coating compositions is relatively large, thus making undesirable material handling difficult and increasing cost. Furthermore, large solvent losses and/or solvent recovery equipment make the coating operation quite expensive. In recent years, government regulations regarding hydrocarbon emissions, particularly applicable to automotive coating operations, have mandated a significant reduction in volatile organic content for coating compositions. Thus, for example, in the United States, government guidelines set certain limit lines within which time emissions of volatile organic matter from motor vehicle Norymer coating operations must be reduced within certain specified limits. In order to meet these requirements, low VOC coating compositions can be used in conjunction with emission treatment equipment to achieve specified emission limits. There is a great need for coating compositions that preferably have a VOC lower than government limits, yet can be applied to substrates using known spray application techniques.

In response to these problems, high solids coating compositions have been proposed that utilize low molecular weight polyfunctional adducts or copolymers, typically in combination with polyfunctional crosslinkers. These high solids coating compositions can be applied by spraying with lower VOC than is possible with conventional epoxy ester-based coating compositions or other conventional coating compositions containing, for example, high molecular weight polymer resins. . After application to the substrate, the high solids coating composition is baked at a curing temperature, i.e., an elevated temperature suitable to drive off volatile organics and promote crosslinking and, if applicable, polymerization of the polyfunctional low molecular weight components. Hardened by wood.

Typically, the physical properties of coatings provided by such known high solids coating compositions can differ significantly from the physical properties of cured coatings provided by conventional low solids coating compositions. In particular, cured coatings obtained from known high solids coating compositions may be less flexible, less resistant to solvents, less adherent to the substrate and/or for other reasons. may be inferior in providing modest corrosion protection to the underlying substrate. Therefore, it is suitable for use in high solids solvent-based coating compositions, yet cures to form coatings with physical properties comparable to those obtained from conventional low solids solvent-based coating compositions. It would be highly desirable to provide a coating composition that includes low molecular weight materials that have a high molecular weight.

According to the invention, suitable for use in thermosetting coating compositions,
Moreover, a new low molecular weight crosslinkable epoxy ester resin is provided which is particularly advantageous for use in high solids organic solvent based thermosetting compositions. The epoxy ester resin of the present invention has a number average molecular weight (Mn > about 900 to about 5
000 and comprising Jepoxy P and (1) a first reactant selected from diphenols, dicarboxylic acids and mixtures thereof in a chain extension reaction and (1) a fatty acid in a chain termination esterification. reaction products of chain extension reactions and esterification reactions,
At reaction temperatures reaching at least about 167° C., the epoxy, phenol, dicarboxylic acid carboxyl and fatty acid carboxyl functionalities occur substantially simultaneously in relative proportions of about 1:o to 1:0-0, respectively.
．． 8: Used in an amount of 0.3 to 1 equivalent. Suitable catalysts are preferably used to promote more simultaneous chain extension and esterification reactions.

According to the coating composition aspect of the present invention, the novel organic solvent-based thermosetting resin compositions, in addition to the solvent and optional pigments and additives such as catalysts, flow control agents, etc. Contains epoxy ester resin. In particular, the novel organic solvent-based thermosetting coating compositions have a number average molecular weight (H) of from about 900 to about 5000 and contain geboxide and (1) siphenol, a dicarboxylic acid in a chain extension reaction. and (II) a second reactant comprising a fatty acid in a chain termination esterification reaction, wherein the chain extension reaction and esterification reaction comprises at least about 167 At reaction temperatures reaching C, epoxy functionality, phenol functionality, dicarboxylic acid carboxyl functionality and fatty acid carboxyl functionality occur substantially simultaneously, respectively, in relative proportions of about 1:0 to 1:0 to 0.8:
an epoxy ester resin used in an amount of 0.3 to 1 equivalent, B, a polyfunctional aminoplast crosslinker, and C optionally a number average molecular weight ('Mn) of about 1,000 to 10.
The resin solids of the coating composition is coated with a substantially non-reactive polycarboxy-functional polymeric catalyst with the epoxy ester resin and the polyfunctional aminosilate crosslinker at room temperature up to an O.D.O. % to about 15% by weight.

Particularly preferred compositions of the invention are those formulated as high solids coating compositions suitable for being applied by spraying onto a substrate. Such compositions are particularly useful as Zolimer coatings on bare, unpolished metal surfaces of motor vehicle bodies. As used herein,
High solids coating composition contains volatile organic matter 4071
/1 (6.4 lb/gal) or less is 27°
Approximately 35 in Ford Cup #4 at 0 (80″F')
It gives a viscosity lower than sec.

In accordance with another aspect of the present invention, a method of making a corrosion-resistant, solvent-resistant, and moisture-resistant coating on a substrate includes applying the novel method of the present invention to a substrate.
It is characterized by applying a solvent-based thermosetting coating composition and then exposing the coating to an elevated temperature for a time sufficient to substantially cure the coating layer. Typically, the novel coating compositions of the present invention are coated for a period of time sufficient to produce a cured coating.
For example, from about 15 minutes to about 60 minutes, about 100'0 (212
It can be cured by heating between 260°G (445'F) and about 260°G (445'F). In accordance with a preferred embodiment of the present invention, the coating composition is about 150°C (250°C)
F)) can be sufficiently cured to good coating properties by heating; furthermore, such preferred compositions can be cured to about 60% by heating without substantial loss of such advantageous coating properties.
Can be cured at temperatures up to approximately 200°C (392°F).

The coating compositions of the present invention have been found to be particularly advantageous for use as high solids primer compositions suitable for application by spray techniques.

More particularly, according to the invention, e.g.
l<2.9 lb/gal) to about 503. ! i'/1
High solids coating compositions formulated at low VOCs of up to (4.2 lb/f) have low viscosities ranging from about 15 seconds to about 45 seconds in a Ford Cup #4 at 27°C; Well suited for spray application techniques. High solids coating compositions according to preferred embodiments have vO
C from about 407 g/l to about 443 f! /l (6,
4 Bond/is from Ron to 6.7 pounds/is from Ron) and 2
It can be seen that it has a low viscosity from about 15 seconds to about 25 seconds for Ford Cup #4 at 7°C. Therefore, the coating compositions of the present invention are easier to handle and are less expensive than previously known coating compositions that could be sprayed only at higher VOCs. Additionally, the coating compositions of the present invention can be used to reduce or eliminate emissions treatment and treatment equipment to meet or exceed government guidelines regarding hydrocarbon emissions. Additionally, direct cost benefits are obtained by reducing the amount of hydrocarbon solvent used in the coating composition.

Unlike various previously proposed high solids coating compositions, the coating compositions of the present invention provide the aforementioned low VOC and cure response benefits without sacrificing advantageous physical properties in the cured coating. Conversely, when applied to a metal substrate, such as when applied as an automotive Zolimer coating on bare sheet steel, the cured coating according to the invention is comparable to other commercially available high solids coating compositions of similar properties. It was found that it provides superior adhesion to substrates, superior moisture resistance, and superior corrosion resistance.

It is a significant characteristic aspect of the present invention that the chain extension reaction of Jepoxy P and dicarboxylic acid, diphenol, or a mixture of both and the chain termination esterification reaction of dieboxide and fatty acid are carried out substantially simultaneously. While not wishing to be bound by theory, the esterification reaction of the carboxyl functionality of the fatty acid and the epoxy functionality of the zoeboxide herein is based on the phenolic nature of the siphenol given the inventive reaction conditions specified herein. It can be seen that the chain extension reaction of the hydroxy functionality and the epoxy functionality proceeds at about the same or similar rate, and at exactly about the same or similar rate as the chain extension reaction of the carboxyl functionality and the epoxy functionality of the dicarboxylic acid. Similarly, the reaction of a hydroxyl functionality (as occurred above in the chain extension reaction and chain extension reaction number) with a carboxyl functionality of a fatty acid is much the same as the reaction of such hydroxyl functionality with a carboxyl functionality of a dicarboxylic acid. Proceed at a similar speed.

By carrying out these reactions simultaneously, a resin is produced that contains a mixture of reaction products of different molecular structures, rather than simply a series of analogs of the same structure.

In other words, we do not want to be bound by theory, but
It can be seen here that during the simultaneous chain extension and chain termination reactions, dieboxide and epoxide functional chain extended intermediate reaction products react with dicarboxylic acids, diphenols and fatty acids in a random order. Therefore, each chain-extended reaction product according to a given reaction order in the epoxy ester resin of the present invention will be structurally different from the reaction product of a different reaction order. In addition to reaction products of various molecular structures, the simultaneous reaction of zoepoxides (and epoxy-functional chain-extended intermediate reaction products) with dicarboxylic acids and diphenols and chain-terminating fatty acids, e.g. It has been found to produce product epoxy ester resins with a very broad molecular weight distribution, such as about 12,000 or more. A significant advantage of the present invention, which can now be seen to have resulted in part from this simultaneous reaction, and especially from such different molecular structures and broad molecular weight distributions of the epoxy ester resin reaction products, is the surprising ability of coating compositions containing these resins. It has extremely low viscosity. More particularly, the coating compositions of the present invention are found to have significantly lower viscosities than many comparable commercially available 71 isolid coating compositions for a given solids content (by weight). Accordingly, the coating compositions of the present invention can be sprayed or otherwise applied to substrates at significantly higher solids contents and therefore require significantly lower VOCs. These low viscosities and high solids contents make them very attractive to the industry for all of the aforementioned reasons, including low cost of material handling, low emissions of volatile organics, low cost in accordance with government guidelines, and other related benefits. Significant progress can be made in

The glass transition temperature of the novel epoxy ester resin of the present invention (
The advantageously low Tg) is believed to be another consequence of the very broad molecular weight distribution and different molecular structures. More precisely, it can now be seen that the lower molecular weight portion of the epoxy ester resin and any unreacted monomer act as plasticizer properties for the resin, effectively providing a lower apparent Tg. In any case, it is important that a low Tg is obtained even in the epoxy ester resins of the invention containing high aromatic content. It is known that low Tg provides a superior smoother surface to hardened coated soils. The coating is at its Tg
While the coating is heated and cured after reaching the curing temperature and before being substantially cured, the coating may flow and become smooth. Therefore, a lower Tg provides more time for the coating to flow and smooth, thus improving the surface quality of the cured coating. Additionally, the broader molecular weight distribution of the epoxy ester resin component is believed to contribute in part to the advantageous flexibility of the cured coatings of the present invention. The flexibility of this coating is unexpected given the high weight percentage of aromatic units in the epoxy ester resin. Such high flexibility is particularly advantageous in view of the highly significant cost advantages of aromatic feedstocks over aliphatic feedstocks, along with high aromatic content.

Additionally, aromatics in coating compositions, such as primer compositions for metal substrates, are now believed to be more resistant to hydrolysis than aliphatics. Therefore, and without wishing to be bound by theory, it is now believed that the high aromatic content of the epoxy ester resins of the present invention explains, in part, the superior corrosion protection found to be provided by the novel coatings of the present invention. . This is particularly the case according to preferred embodiments of the invention, discussed further below, in which, for example, a diphenol is used, and the dieboxide reactant and diphenol provide the aromatic units to the resin. Furthermore, it is now seen that the phenolic oxygen introduced into the epoxy ester resin by the chain extension reaction of phenol and epoxy advantageously provides excellent adhesion to metal substrates, such as steel substrates. Thus, the high aromatic content of the cured coating and its excellent adhesion, each enhancing the advantages provided by the other, provide the cured coating of the present invention with superior corrosion protection.

According to the most preferred embodiments of the invention, discussed further below, acyclic aliphatic dicarboxylic acids are used in the synthesis of epoxy ester resins.

According to this embodiment, the epoxy ester resin reaction product contains both aromatic and aliphatic moieties in a random order and distribution. Also, without wishing to be bound by theory, it is now seen that the aromatic units of the diphenol and the aliphatic units of the dicarboxylic acid unit each enhance the benefits of the other in an unexpected and synergistic manner. More particularly, the aliphatic units are believed to impart flexibility to the epoxy ester resin, while the aromatic units impart moisture and corrosion resistance. That is, the epoxy ester resin reaction product provides a cured coating that has both good flexibility and good moisture and corrosion resistance.

Zoepoxide reactants suitable for epoxy ester resins are:
It can be any of a number of diepoxides, including many that are commercially available and will be apparent to those skilled in the art in light of this disclosure.

Finally, however, the choice of reactants to produce the epoxy-ester resin will depend in part on the particular use intended for the coating composition, but terminal diepoxides, ie, diepoxides having two terminal epoxide groups, are generally most preferred. In general, they are more reactive and therefore require reaction conditions that more easily avoid undesirable side reactions, such as epoxy-epoxy reactions and gelation. Preferably, the dieboxide has a number average molecular weight of about 1
00 and about i oooO, more preferably between about 100 and about 600. A large number of such preferred dieboxides are readily commercially available, such as bisphenol-A shrimp chlorophylline epoxy resins, such as the Bpon(TM) series, Shell Chemical Company, Hughston, Texas, and DER (trademark) series, Dow Chemical Company,
It is located in Midland, Michigan. Also preferred are cycloaliphatic zoeboxy resins, such as ebonetutus (gpo
nex ) (trademark) series, Shell Chemical Company, Hughston, Texas, e.g. Resin XB
2793™, Ciba Iggy Corporation, Ardsley, New York, and various acyclic epoxy resins such as 1,4-butanediol diglycidyl ether and 4-vinylcyclohexene dioxide. or cycloaliphatic jepoxy P. Among the above diglycidyl ether bisphenol-A resins or higher molecular weight analogues thereof, such as Epon 828(TM) and Epon 829(TM) of the Epon(TM) series mentioned above, are important due to their cost and commercial availability. Most preferable considering.

The higher molecular weight members of the Epon™ series are suitable for the desired applications of higher molecular weight epoxy ester resins. Generally, however, such higher molecular weight resins provide slightly higher viscosity (or lower solids) coating compositions. Furthermore, Epon series, such as Epon 1001
It should be appreciated that the higher molecular weight analogs of Epon 1004 and Epon 1004 are somewhat less preferred. This is because they have, for example, hydroxyl functionality that can have undesirable side reactions with epoxy functionality. This can result in undesirable resin properties and gelling.

Other suitable geboxides for use in synthesizing the epoxy-ester resins of the present invention are commercially available and will be apparent to those skilled in the art in view of this disclosure. It can also be seen from the foregoing that any mixture of compatible geboxides can be used.

In addition to the diepoxide, part of the epoxy functionality may be provided by any compatible monoepoxy compound or, more suitably, a polyepoxy compound or a mixture of compounds having 6 or more epoxy groups per molecule. I can do it. Suitable polyepoxides include:
For example, there are those having a molecular weight of about 200 to about 800.

The polyepoxide can be essentially any of the known types such as polyglycisol ethers of polyphenols. These can be produced by esterification of polyphenols with epihalohydrins in the presence of alkali.

It will be recognized by those skilled in the art in view of this disclosure that in some cases, particularly where high solids coating compositions are not critical, the use of polyepoxides having higher molecular weights is desirable.

Any such polyepoxide preferably contains free hydroxyl groups in addition to epoxide groups.

Although polyglycidyl ethers of polyphenols can be used, it is often desirable in such compositions to react some of the reactive sites (hydroxyl or, in some cases, epoxy) with a modifier to change the film properties of the resin. . Epoxy resins can be modified, for example, with isocyanate groups containing organic materials or other reactive organic materials.

Other quite useful types of polyepoxides are, for example, the novolac epoxy resins ECN 1235™ and E
Novolac resins such as CN 1273™, Ciba and Iggy Corporation.

In accordance with a preferred embodiment of the present invention, the epoxide compound other than the zoepoxide compound provides no more than about 15%, and most preferably substantially no more than about 15%, of the total epoxide functionality of the reactants required to form the epoxy-ester resin. I won't give it.

There are a large number of commercially available diphenol reactants suitable for the epoxy ester resins of the present invention, many of which will be readily apparent to those skilled in the art in light of this disclosure. Preferred siphenols have the general formula (1), where R is a divalent bonding moiety that is substantially non-reactive with the diepoxide resin. R is a divalent, organic bonding moiety, for example (CH2)
n (where n is preferably from about 1 to about 8), C═O, and the like are preferred, but inorganic moieties such as sulfonyl are also suitable. It has been found that diphenols of this nature give good reactivity with the above-mentioned preferred Jepoxy P, and ultimately give the cured coatings of the invention having excellent physical properties, most notably excellent corrosion protection. It will be apparent to those skilled in the art in view of this disclosure that R must be substantially non-reactive with the fatty acids used in the epoxy ester resin. Particularly preferred diphenols are those of the formula (1) [wherein R has from 1 to about 10 carbon atoms, preferably from 6 to 4 carbon atoms, and most preferably from the general formula (wherein R' and R'' are the same or different, each preferably including hydrogen and lower alkyl of about 1 to 4 carbons, most preferably 1 or 2 carbons, etc. or mixtures of any of these. The siphenol preferably has a number average molecular weight (n) of about 180 and about 500. more preferably between about 180 and about 250.

Diphenols and appropriate fatty acids used with the preferred zoeboxides within this range have been found to provide epoxy ester resins containing a particularly broad molecular weight distribution of mixed reaction products, which resins (discussed above) have low T
It can be seen that the coating compositions of the invention provide particularly advantageous physical properties including g and good corrosion protection. Such diphenols include, for example, the most preferred bisphenol-A1 bisphenol-B, and compatible mixtures of any of these. As used herein, the term diphenol includes compounds containing a single dihydroxy-substituted phenyl ring, such as benzenediol. However, more preferred is the formula (
It is siphenol giving two terminal monohydroxy substituted phenyl rings as in 1). Other examples of diphenols are bis-(4-hydroxy-tert-butylphenyl)-2,2-propane, bis-(2-hydroxy-naphthyl)-methane and 1,5-dihydroxynaphthalene. Other suitable siphenols for the epoxy ester resins of the present invention will be apparent to those skilled in the art in view of this disclosure.

There are a large number of commercially available dicarboxylic acid reactants suitable for the epoxy ester resins of the present invention, many of which will be readily apparent to those skilled in the art in view of this disclosure. Suitable dicarboxylic acids include saturated or unsaturated, cyclic or acyclic aliphatic or aromatic dicarboxylic acids or mixtures thereof. Acyclic aliphatic dicarboxylic acids are generally preferred due to the increased flexibility they provide to the cured coatings of the present invention. Preferred dicarboxylic acids have general formula (1)% formula% (1
) (wherein R″ is a divalent bond moiety that is substantially non-reactive with the dieboxide resin) R/// is the fatty acid used in the epoxy ester resin, the hydroxy functionality (generated in the chain extension reaction), It will be apparent to those skilled in the art in view of this disclosure that it must also be substantially non-reactive with the cross-linking agent used in the coating composition, at least at storage temperatures.
" is preferably a divalent organic bonding moiety. Particularly preferred is R"' preferably having from 4 to 42 carbons, such as (CH2)n, where n is preferably from about 4 to about 42. , < ) linear or branched alkylene or alkylidene moieties, etc., or mixtures thereof. Dicarboxylic acids of this nature provide good reactivity with the preferred zoeboxides mentioned above;
Moreover, it has been found that the final cured coating of the invention has excellent physical properties, most significantly superior flexibility and corrosion protection. The dicarboxylic acid has a number average molecular weight (in) of about 1
45 and about 1000, more preferably about 570. Within this range, dicarboxylic acids used with the preferred geboxides and preferred shiphenols described above and the preferred fatty acids described below have been found to provide epoxy ester resins containing a particularly broad molecular weight distribution of mixed reaction products, and this resin (discussed above) It can be seen that the coating compositions of the present invention have particularly advantageous physical properties including low Tg and good moisture and corrosion protection.

Typical dicarboxylic acids include adipic acid, 6.6-
Zome≠rupentansionic acid, benzene dicarboxylic acid, phenylene diethanoic acid, naphthalene dicarboxylic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, etc. or compatible mixtures of any of these. Dicarboxylic acids according to formula (1) with alkylene chains of less than 4 carbons R'' can be used, such as oxalic acid, malonic acid, succinic acid, glutaric acid, etc., but these provide a slightly lower degree of flexibility. Preferably, dicarboxylic acids provide two terminal carboxyl groups.Similarly, preferred aromatic dicarboxylic acids are those in which the carboxyl groups are further apart, e.g. 1,4- These are benzene-dicarboxylic acid and 2,7-naphthalene-dicarboxylic acid.

The most preferred dicarboxylic acids are the substantially saturated acyclic aliphatic dimer acids known to those skilled in the art and readily available commercially. These are typically dicarboxylic reaction products of fatty acids having from 4 to 22 carbons and a terminal carboxyl group. Of these, the 66 carbon dimer acids are most preferred. This is because the dimer acid provides excellent reactivity with the preferred dieboxides, advantageously provides a broad molecular weight distribution of the epoxy ester reaction product, and ultimately provides the cured coating of the present invention with excellent physical properties. It is from. Additionally, 66 carbon dimer acids may be used, such as Empol 1, each available from Emery Industries, Inc. P1 Cincinnati, Ohio.
014 (trademark), Empol 1016 (trademark) and Oyohienball 1018 (trademark). Most or all commercially available dimer acids contain some percentage, typically from about 5% to 10%,
However, it should also be recognized that in some cases they contain as much as 60% or more of trimer acids and usually smaller proportions of monocarboxylic acids. As used herein, the term "dimer acid" includes such amounts of these materials. Most useful in the present compositions are products that contain mostly dibasic acids and no or small amounts of tribasic and monobasic acids.

It turns out that aliphatic dicarboxylic acids offer further advantages. In particular, without wishing to be bound by theory, it is seen that the epoxy ester resins derived therefrom wet the substrate surface better, thus providing increased adhesion between the substrate and the cured coating. They also flow better and also give a nice smooth surface when cured. It is also seen that the aliphatic units impart increased flexibility to the cured coating as described above, and that this flexibility of the coating imparts increased impact resistance. In this regard, here in the epoxy ester resins according to the preferred embodiments using aliphatic dicarboxylic acids and aliphatic fatty acids, the molecular weight distribution is very broad due to the nearly identical reaction rates of these reactants with dieboxides. Such a very broad molecular weight distribution further increases the flexibility of the cured coating.

If corrosion protection of the substrate is important, it may be preferable to use dicarboxylic acids according to formula (I) above, in which R"' is at least partially aromatic.

As mentioned above, aromatics in coating compositions of the present invention, such as primer compositions for metal substrates, are believed to be more resistant to hydrolysis than aliphatics, thus providing increased corrosion and moisture resistance. It will be done.

In theory, the siphenol and, according to the preferred embodiments described above, each of the soeboxide reactants will contribute aromatic units to the resin, and each will likewise contribute to corrosion and moisture resistance.

Other suitable dicarboxylic acids for the epoxy ester resins of the present invention will be apparent to those skilled in the art in view of this disclosure.

There are therefore many commercially available fatty acids that can be used as chain-terminating esterification reactants for the epoxy ester resins of the present invention. Suitable fatty acids include those derived from or contained in either animal or vegetable oils. Preferred are fatty acids of about 8 to about 18 carbons. Among the fatty acids, preferred are more saturated fatty acids. This is because the olefinic unsaturation of this fatty acid can undergo polymerization-type reactions between such double bonds during the synthesis of the epoxy ester resins of the present invention. However, unsaturated fatty acids such as oleic acid, linoleic acid, lylunic acid, and mixtures of these acids are suitable for use, and many are commercially available and will be apparent to those skilled in the art in view of this disclosure, such as polymeric acids such as hydroquinone. Can be used with suitable inhibitors for type reactions. Additionally, aromatic fatty acids are commercially available and can be used. However, aliphatic fatty acids are preferred in view of the increased coating flexibility they provide. Particularly preferred for use are substantially saturated fatty acids, such as soybean fatty acids, most preferably butyric acid, diurinic acid, palmitic acid, and stearic fatty acids, or mixtures of any of these.

These have been found to be relatively inexpensive and yet provide good reactivity with the preferred zoeboxides mentioned above.

For convenience of use, fatty acids that are semisolid or liquid at room temperature are generally preferred over solid fatty acids.

The epoxy ester resins of the present invention can be made by the reaction conditions detailed herein using techniques that are known and readily apparent to those skilled in the art in light of this disclosure. Chain extension and chain termination reactions occur substantially simultaneously by charging the zoeboxide, cyphenol and/or dicarboxylic acid and fatty acid to a suitable reactor and then heating the mixture. To ensure rapid and/or more complete reaction of dieboxide with carboxyl and phenol functionality, and to ensure that these reactions occur substantially simultaneously at about the same or similar rates, catalysts are typically used. I would like to acknowledge that the existence of Alternatively, other techniques may be used, such as using higher reaction temperatures and/or longer reaction times to provide substantially simultaneous reactions, or relatively large proportions of diphenols (because in the absence of a catalyst, phenolic functionalities (which are believed to be slightly less reactive towards diepoxides than carboxyl functionalities) can be used. However, the use of catalysts is advantageous and preferred in the present invention to provide advantageous epoxy ester resins.

The commercially available Epon 829™, mentioned above, provides a trademarked catalyst. Epon 828 is virtually the same, but
However, it does not provide such a catalyst. Suitable catalysts are commercially available and include epoxy-carboxylic acid/carboxylic acids such as preferred sodium carbonate and lithium neodecanoate, lithium naphthenate, lithium nonanoate, other known organometallic catalysts and tertiary amine catalysts. epoxy
There are any known catalysts or compatible mixtures of any of these for the phenol reaction. Others will be apparent to those skilled in the art in view of this disclosure.

When both diphenol and dicarboxylic acid are used,
The reaction mixture is generally heated to at least about 280"
), preferably at least about 176°C (350"
F). In some cases, an exothermic reaction proceeds in the presence of a catalyst, with or without further heating, and the reaction mixture is then heated from about 196°C to 680°C, depending on batch size and reactor insulation, etc.
°C (380'F to 450'F'). In the absence of a catalyst, such an exotherm is typically not observed and the reaction temperature is preferably about 176°.
C to 196℃ (350"F' to 380'F'
Continuous heating is required to maintain the temperature (up to ). The course of the reaction can be followed by measuring the acid value. After acid number measurements indicate that the reaction is sufficiently complete, preferably at an acid number of 6 or less, the resin can be diluted with a suitable solvent to reduce the viscosity to the desired level. A non-volatile level of 80% was found to be suitable for storage of the coating composition.

When diphenols are used and no dicarboxylic acids are used, the reaction mixture is heated to at least about 175°C (345'F).
) and in the presence of a catalyst, the exothermic reaction usually proceeds with or without further heating. Typically, the reaction mixture will then reach a temperature of about 195°C to 205'0 (380"F' to 400F) depending on part batch size, reactor insulation, etc. In the absence of a catalyst, typically No such exotherm is observed and continuous heating is required.After the acid number measurements indicate that the reaction is sufficiently complete, the desired viscosity is reduced, preferably at an acid number of 6 or less. The resin can be diluted with a suitable solvent to reduce it to the level of .

When a dicarboxylic acid is used and no diphenol is used, the reaction is generally carried out in the presence of a catalyst at a temperature of at least about 165°C.
(280°F), preferably at least about 150°C!
(300'F'). Although not a critical issue, in the case of some dicarboxylic acids that differ significantly from the fatty acids used in the reaction, if the dicarboxylic acids consist of the preferred dimer acids discussed above, approximately 16
Reaction temperatures below 5°C (28 IMF) result in reaction rates for fatty acids and diepoxides that are significantly different from those for dicarboxylic acids and zoepoxides. Typically, the reaction mixture is heated from about 170°C to 190°C ( 640"F
to 370'F) and held at this temperature. An exothermic reaction is observed and the course of the reaction can be followed by measuring the acid number. After acid number measurements indicate that the reaction is sufficiently complete, preferably at an acid number of 7 or less, the resin is treated with a suitable solvent to reduce the viscosity to the desired level for use or storage. Can be diluted.

In said preferred embodiment, the chain extension reaction of the epoxide functionality with the phenol functionality and/or the carboxyl functionality of the dicarboxylic acid proceeds at approximately the same rate as the chain termination reaction of the epoxide functionality with the carboxyl functionality of the fatty acid; Moreover, it should be appreciated that since these reactions are carried out substantially simultaneously to produce the engineered boxyester resins of this invention, the relative proportions of the reactants in the reaction mixture will significantly affect the properties of the product resin. Therefore, when using both a diphenol and a dicarboxylic acid in a chain extension reaction with zoeboxide, the epoxy functionality, phenol functionality, dicarboxylic acid carboxyl functionality, and fatty acid carboxyl functionality are in relative proportions of about 1:0.2 to 0.
．． 6: 0.1 to 0.4: 0.4 to 0.9 is preferable. The reactants are 1 equivalent of epoxy functionality to about 0.4 to 0.6 equivalents of phenol functionality, and about 0.1 to 0.6 equivalents of dicarboxylic acid carboxyl functionality.
More preferably, up to about 0.6 to 0.8 equivalents of fatty acid carboxyl functionality are present. Diepoxide, diphenol, dicarboxylic acid and dicarboxylic acid each have a functional ratio of 1:0.5:0.
Most preferably, 25 is present in a relative amount giving 0.8 equivalents. One most preferred embodiment of the novel epoxy ester resin of the present invention is a novel epoxy ester resin comprising a diglycidyl ether bisphenol-A resin and a bisphenol A% C-18 fatty acid diasteride reaction product and a soybean fatty acid reaction product. In the epoxy ester resin, the components have a relative proportion iL of about 1:0.2 to C1, 4:0, respectively.
．． 6-0.5: Characterized by containing a reaction product used in 0.9-1.2.

When a diphenol is used without a dicarboxylic acid, the epoxy functionality, phenolic functionality and carboxyl functionality are preferably in relative proportions of about 1:0.4 to 1:0.
．． Used in 4-1. The relative proportions in this case range from about 1 equivalent of epoxy functionality to about 0.5 equivalents of phenol functionality to 0.
．． From about 0.5 equivalents to 0 to carboxyl functionality up to 7 equivalents
．． More preferably up to 7 equivalents.

Most preferably, the diepoxide, diphenol and fatty acid are present in relative amounts giving about 1:0.7:0.6 equivalents, respectively.

When dicarboxylic acids are used without diphenols, the epoxy functionality, dicarboxylic acid carboxyl functionality and fatty acid carboxyl functionality preferably have a relative allocation of about i:
o, s~8: Used in 0.3~8.

More preferably, the relative proportions in this case range from about 1"6 to epoxy to about 0.4 to 0.6 to about 0.6 to about 0.4 to dicarboxylic acid carboxyl functionality. The dieboxide, the dicarboxylic acid and the I11 fatty acid are each used in a functional relative quantitative amount of 1:0.4:065 equivalents.Most preferred IM embodiment Ids Jig) Sidyl ether bisphenol-A resin and (a) C-1
The relative proportion of the dimerization reaction product of 8 fatty acids and (1) soybean fatty acid is approximately 1:0.5-0.7 by weight, respectively:
A reaction product of 0.7 to 0.9 is used.

This preferred range of reactant amounts provides the epoxy ester resin with favorable physical properties, most particularly on metal substrates such as bare unpolished automotive body sheet steel (sprayed).
Coating composition with corrosion protection as if applied? I found out that you should give me an I.

In the absence of catalysts for epoxy/phenol and epoxy/carboxy reactions, it is generally preferred to use larger proportions of diphenols within the ranges mentioned above. Some unreacted diphenol is acceptable in the reaction product.

The superior moisture resistance, corrosion protection and other physical properties contemplated by the coating compositions of the present invention are hereby largely demonstrated when using diphenol reactants either alone or with dicarboxylic acids. It is believed that this results from new chemistry that is not of low interest or proposed. More particularly, without wishing to be bound by theory, it is believed that the epoxy ester resins of the present invention may include a substantial portion of phenol-terminated components. That is, while known epoxy adducts proposed for use in coating compositions are reported to be terminated by esterified epoxy groups, the epoxy ester resins of the present invention are now phenolic terminated in a substantial portion. Be considered. This phenomenon is described herein by combining the reaction of a diepoxide reactant with a diphenol-functional reactant and the simultaneous reaction of a carboxyl-functional reactant (i.e. dicarboxylic acid and fatty acid, if present) with the relative proportions of the reactants detailed above. It can be seen that the result is Carboxyl functionality competes with phenolic functionality for reaction with epoxy functionality. This liquid urine is illustrated in Example 110. Therefore (despite the excess of epoxy to phenol in the preferred embodiments described above), reaction products with terminal phenols are present upon depletion of unreacted epoxy functionality. The carboxyl functionality would be expected to react mostly with the pendant hydroxy groups of the chain extension intermediate reaction product. However, such reactions naturally produce water molecules, and slightly more water is introduced as impurities in the reactants during distillation of the epoxy ester resin reaction product. Thus, although a small portion of the dicarboxylic acid (if present) and fatty acid will react with such pendant hydroxy groups, it is expected that the reaction product, i.e., the epoxy ester resin of the present invention, will be in a substantial portion phenol-terminated. It seems clear that much more reacts with the epoxy (competing with the phenolic functionality) than with the epoxy. One of the most important advantages believed to result, in part, from this new chemistry is the superior curing response of the coating compositions of the present invention.

It is believed that the terminal phenolic moieties provide very high reactivity with polyfunctional aminoplast crosslinkers at elevated (curing) temperatures.

The epoxy ester resin described above is used in conjunction with a polyfunctional amitsunolast crosslinker. Suitable crosslinking agents for use in the compositions of the present invention include, for example, alkylated melamine formaldehyde resins having from 1 to about 8 carbon atoms in the alkyl group, as well as many others known to those skilled in the art. There are many materials. Other suitable crosslinking agents will be apparent to those skilled in the art in view of this disclosure. Although many such crosslinking agents are readily available commercially, including, for example, the Resimene® series, Monsando Company, St. Louis, MO, the most preferred are cold cure methylated melamine-formaldehydes. Regimen 717™ is described as a resin.

Additionally, suitable polyfunctional aminoplast crosslinkers can be prepared using conventional techniques. Thus, for example, lower alkanols such as methanol, ethanol, butanol, isobutanol, impropatol, hexanol, 2-ethylhexanol, etc. or mixtures of any of these are reacted with melamine formaldehyde. Preferred crosslinking agents of this type include butylated melamine formaldehyde resins, methylated/butylated formaldehydes, polyalkyl ethers of resins and polymethylolmelamine, among which hexamethoxymethylmelamine resins are preferred due to their relatively low cost and ease of use. Most preferred in view of its commercial availability, its low reactivity with the epoxy ester resins of the invention at normal storage temperatures, and its high reactivity at high curing temperatures. In this regard, preferred polyfunctional aminoplast crosslinkers are substantially non-reactive with the epoxy ester resin at about 60'O or less.

Other suitable melamine crosslinking agents will be apparent to those skilled in the art in view of this disclosure.

The appropriate ratio of polyfunctional aminoplast crosslinker to epoxy ester resin depends on one part depending on the properties desired for the coating to be produced and one part on the coating composition (and then the bake intended to cure the coating composition). It depends on the desired curing response (by schedule) and the desired storage stability, ie, the desired shelf life, of the one-part coating composition. Accordingly, the amount of epoxy ester resin that can be blended with a crosslinking agent to form the coating composition of the present invention can vary considerably. Preferably, the crosslinking agent is used in an amount from about 5 t% to about 40 t%, more preferably from about 20 M to about 60 t%, by weight of total resin solids.

The coating compositions of the present invention can be cured over a wide range of curing temperatures.
It has been found that it provides a cured coating with advantageous physical properties.

More particularly, coating compositions according to preferred embodiments of the present invention cure in about 15 minutes or less at temperatures as low as about 120° C. or less and still cure at elevated temperatures of about 200° C. or more. It has been found that no significant loss of advantageous physical properties occurs for up to about 60 minutes or longer. When considered together with the storage stability of coating compositions, it can be easily seen that the present invention provides a very significant advance in coating composition technology.

The present invention includes the use of a polycarboxy G-capable polymeric catalyst as an optional component of the coating composition of the present invention. The use of polycarboxy-functional polymeric catalysts is further novel and is a highly advantageous aspect of the present invention. Such catalysts can be made by conventional polymerization methods known to those skilled in the art, such as batch polymerization. Thus, polymeric catalysts can be made by conventional techniques, for example, in which monomers, solvent and polymerization initiator are charged to a reactor and then heated to a polymerization temperature for a sufficient time to form a copolymer. . It is preferred that the monomers and the polymerization initiator, such as tert-butyl perbenzoate, are first mixed together, optionally with a small amount of solvent, and then gradually added, for example over a period of several hours, to the refluxing solvent containing further polymerization initiator. . .

The polymerization initiator in the refluxing solvent can be different but compatible with the initiator mixed with the monomer, such as cumene hydroperoxide. Other suitable polymerization initiators are known or will be apparent to those skilled in the art in view of this disclosure.

Preferably, the polymeric catalyst is stored in lined drums. This is because it was found to be somewhat incompatible with steel.

The polymeric catalyst may include any suitable polycarboxy-functional material that is compatible with the other components of the coating composition. Generally, the polymeric catalyst is any polycarboxy-functional compound or mixture of compounds that are substantially compatible with the epoxy ester resin and the polyfunctional aminoplast crosslinker at storage conditions (i.e., typically at room temperature). It can be.

Preferably, the polymeric catalyst has a number average molecular weight (Mn) from about i, o o o to i o, o o o, more preferably from about 1.500 to about 3,000. It has been found that the use of a polymeric catalyst with a higher number average molecular weight, e.g. about 10,000, produces a slightly higher viscosity coating composition, e.g.
When used in appropriate amounts from % to 5% by weight,
This same polymeric catalyst could be used to make vine lid coating compositions. According to a preferred embodiment, the polymeric catalyst comprises (1) a suitable ethylenically unsaturated orocarboxylic acid which provides a double bond for polymerization, such as acrylic acid, methacrylic acid, the two being preferred, butanoic acid; (11) imparting a double bond to the polymerization reaction product and a functionality that is substantially reactive with the epoxy ester resin or multifunctional crosslinking agent of the coating composition at storage temperatures; The polymerization reaction product of any suitable ethylenically unsaturated orocomonomer not provided.

According to such preferred embodiments, polycarboxy functionality is introduced into the polymer as a pendant group on one polymer backbone by copolymerizing a carboxylic acid with a copolymer monomer.

Suitable comonomers include, for example, alkyl acrylates and methacrylates having from 1 to about 8 carbons in the alkyl group, preferably from about 1 to 4 carbons. Representative alkyl acrylates that can be used in the preparation of polymeric catalysts include, for example, isozolobyl acrylate, any butyl acrylate, hexyl acrylate, 2-methylpentyl acrylate, octyl acrylate, and the like, as well as methyl acrylate, acrylic acrylate, etc. Ethyl acrylate, propyl acrylate or a mixture of any of these. Generally preferred are butyl acrylate, butyl methacrylate or mixtures thereof. Preferred comonomers include butyl methacrylate, which is generally the most preferred;
Glycidyl acrylate, glycidyl methacrylate, styrene, any suitable vinyl ether, etc. or compatible mixtures of any of these. Suitable carboxylic acids and comonomers in addition to those listed above are commercially available;
Moreover, it will be obvious to those skilled in the art in view of this disclosure.

In accordance with some preferred embodiments of the present invention, the polymeric catalyst comprises from about 55M to about 80% by weight of copolymerized monomers.
Preferably about 70% by weight of the reaction product, and from about 20% to about 45% by weight of carboxylic acid monomer, preferably about 60% by weight.

According to the present invention, one preferred polymeric catalyst is a 6-polymerization reaction consisting of a polymerization product of about 60% by weight of acrylic acid and about 70% by weight of butyl methacrylate.
- Preferably carried out in the presence of initiators such as butyl and cumene hydroperoxides and the like. Suitable methods for making this and other polymeric catalysts of the invention are detailed in the examples below.

The polymeric catalyst used in the coating composition of the present invention is
One part depends on the desired curing response and one part depends on the desired physical properties of the cured coating. Preferably, while keeping the coating composition vIj sufficiently storage stable for its intended use,
Use sufficient polymeric catalyst to provide a significant improvement in the physical properties of the cured coating. However, as discussed further below, the present invention provides that coating compositions with polymeric catalysts are much more storage stable than similar compositions containing equivalent amounts of known non-polymeric catalysts. Note that this is a significant advantage. It is further noted that the coating compositions of the present invention can use a portion, preferably a small portion, of known non-polymeric catalysts, if any, in conjunction with the aforementioned polymeric catalysts. Non-polymeric catalysts known to those skilled in the art to catalyze such aminosilate cross-linking reactions include, for example, p-)luenesulfonic acid, phosphoric acid, m! phenyl phosphate, butyl phosphate, butyl maleate, etc. or compatible mixtures of any of these. These catalysts are suitable for coating systems intended for low temperature curing schedules. I and (or)
It has been found to be most useful when highly etherified melamine resins, such as hexa(methoxymethyl)melamine, are used, and in amounts determined in part by the intended baking (curing) schedule. It is being (Typically, about 0.2% to about 3.0% violet by weight of total resin solids is used.) In the present invention, the polycarboxy-functional acrylic copolymer catalyst is Most preferably, it is used without any additional non-polymeric catalyst.

Although it is within the skill of the art in view of this disclosure to determine the optimum amount of polymeric catalyst to be used in a coating composition of the present invention intended for a given application, it is believed that the acid level of the epoxy ester resin should be approximately It is typically preferred to use sufficient polymeric catalyst to raise the temperature to a height of 50, more preferably from about 15 to about 65.

Approximately 2 m of resin solid content of jjL aggregate-like catalyst coating composition
% to 100% by weight is generally preferred. In a preferred embodiment of the coating composition of the invention,
More preferably from about 5% to 10q6 of polymeric catalyst;
Approximately 8 inches has been found to be most preferred. Although up to 15% or more can be usefully used, such amounts are -
It is not possible to give the full advantage of storage stability afforded by the use of no preferred amount. The polymeric catalyst is
It can be added to the epoxy ester resin by any known mixing method. Preferably, however, the polymeric catalyst is hot blended, i.e., mixed with the epoxy ester resin at an elevated temperature, e.g., about 105°C (220"F) or higher. Mixing at room temperature results in a slightly cloudy coating composition. However, it is surprisingly found that mixing at elevated temperatures produces clear coating compositions.Hot blended clear coating compositions unexpectedly produce cold blended cloudy compositions. Although higher gloss is of course not desirable, cold-blending these resins and catalysts avoids increasing the heating time and cost of the resins and catalysts. It would be preferable to do so.

- As described in ■, the optional composite catalyst component of the present invention is
This is a significant advantageous aspect of the present invention. More particularly, it has been found that the storage stability of epoxy ester resin coating compositions is increased over similar resin coating compositions using known non-polymeric catalysts. Thus, for example, a coating composition according to a preferred embodiment of the present invention can be subjected to a slight increase in viscosity, such as less than about 5 seconds in a Ford Cuzzo #4 at 27°C, to about 60°C for about 24 hours.

It can be seen that the preferred embodiment of the coating composition increases the viscosity of Ford Cuzzo #4 at 27°C by less than about 10 seconds when exposed to a temperature of about 60°C for about 120 hours.

Surprisingly, in addition to excellent storage stability, the coating compositions of the present invention containing polycarboxy-functional polymeric catalysts can advantageously be cured at low temperatures. Therefore, the present invention σ
The coating compositions of the present invention can be cured in about 15 to 60 minutes at temperatures as low as about 165°C to 165"C! and still produce substantially optimal properties. In fact, the coating compositions of the present invention Even when cured at such lower temperatures, the physical properties of the coatings are comparable to those obtained at higher curing temperatures with some known high solids coating compositions using known non-polymeric catalysts. Among other things, for example, the present invention provides, in particular, according to a preferred embodiment, excellent moisture resistance and corrosion resistance.

Gives hardness, shine and acid resistance. These advantages are illustrated in the examples below. Typically, about 1
Most preferably, the cure time is about 20 minutes at 50°C.

In addition to both excellent storage stability and ability to cure at low temperatures, the coating compositions of the present invention incorporating polycarboxy-functional polymeric catalysts are advantageous when cured at any of a wide range of cure temperatures. It has been found that this method provides a cured coating with excellent physical properties. More particularly, as noted above, coating compositions according to preferred embodiments of the present invention are found to cure at short curing times and advantageously at low temperatures; Accordingly, the coating composition can be cured at elevated temperatures of about 195°C (380'F) or higher for up to about 60 minutes or more without significant loss of advantageous physical properties. Considered in conjunction with the storage stability of coating compositions, it can be readily appreciated that the present invention provides a very significant advance in coating composition technology. More particularly, it will be appreciated that greater flexibility is provided by the coating compositions of the present invention when planning and carrying out curing schedules of the coating compositions.

If the more preferred polycarboxy-functional polymeric catalyst is not used in the coating composition, any of a variety of acid catalysts known to those skilled in the art to catalyze aminoplast crosslinking reactions, such as p-toluenesulfonic acid, phosphoric acid, etc. , phenyl acid phosphate, butyl phosphate, butyl maleate, etc. or compatible mixtures of any of these are preferably used. However, acid catalysts are most useful only for coating compositions intended for low temperature curing schedules and/or with highly etherified melamine resins such as hexa(methoxymethyl)melamine. It is. Such catalysts typically range from about 0.2% to about 3.0% by weight of total resin solids, depending on the baking (curing) schedule determined in part. and more preferably from about 0.4% to about 0.6% by weight. In addition to catalysts, flow control agents, such as zotyl polyacrylates, wetting agents, such as silicones, pigments, pigment dispersants, corrosion inhibitors, such as chromate pigments, all of which are well known to those skilled in the art. can be used in the coating composition of the present invention. Additionally, suitable reactive additives may be used, including, for example, low molecular weight diol flow modifiers and reactive diluents.

It is within the skill of the art to determine the appropriate volatile organic content for a given coating composition and given application of the present invention.

Preferred solvents have relatively low volatility at temperatures well below their boiling point, with low solvent evaporation during storage and/or low K during application of the coating composition to a substrate. Suitable solvent systems include, for example, toluene, methyl ethyl ketone, isobutyl acetate, xylene, cellosolve acetate, acetone and any mixtures thereof. Other solvents that can be used include terpenes, aliphatic and aromatic naphthas. Further suitable solvents are:
They are commercially available and will be apparent to those of skill in the art in view of this disclosure. Generally, it is preferred to use a portion of C-4 to C-6 alcohol solvents such as butanol, pentanol, hexanol, and mixtures of any of these. This is because they suppress the room temperature nigar crosslinking reaction between the polyfunctional aminoplast resin and the epoxy ester resin, thereby improving storage stability. At high temperatures during curing, the alcohol solvent evaporates and thus stops inhibiting the crosslinking reaction. Preferred solvents include, for example, methyl amyl ketone,
or mixtures thereof with C-4 to C-8 alcohols, such as the generally most preferred 1:2 mixture of citanol and methyl amyl ketone, respectively.

Any solvent left in the cured coating must be inert during or after the curing process to avoid adverse effects on the cured coating or other coating layers used with the cured coating. Preferably, the cured coating is substantially free of solvent.

Sufficient solvent is used to reduce the viscosity of the coating composition to a level suitable for storage or application to a substrate in the desired manner.

It has been found that conventional epoxy ester automotive spray-applied primer coating compositions require 540 g/13 volatile organic loading, whereas comparable coating compositions of the present invention require 80' F) requires a VOC of 430 g/-13 or less to give a viscosity of about 18 seconds in Ford Cup #4, which viscosity is suitable for spray application techniques.

27°C (80°C) for the coating composition sprayed onto the substrate.
It is generally preferred to use enough solvent to give a viscosity of from about 18 seconds to about 22 seconds in a #4 Ford cup in 'F'). Of course, it is not necessary to combine the present invention.

Rather, it may have a higher VOC to provide a lower viscosity. Similarly, the coating compositions of the present invention need not be formulated as sprayable compositions. Rather, they may have much higher solids content and viscosity.

In addition to the epoxy ester resin, polyfunctional aminoplast crosslinker and catalyst, flow control agents, if present, such as decyl polyacrylate, wetting agents such as silicones, pigments, pigment dispersants, corrosion inhibitors, Other components can be used, such as chromate pigments, all numerous variations of which are known to those skilled in the art. Additionally, suitable reactive additives may be used, including, for example, low molecular weight diol flow control agents and reactive diluents.

According to another aspect of the invention, a coating is provided on the substrate, which coating contains a crosslinked polymer product after curing of the coating composition of the invention. The coating composition may be a low solids composition, ie, the coating composition may have a high voc v; however, for the reasons discussed above, 71 isolide compositions, ie, those having a low voc w, are generally preferred. . The coating composition can be applied by any conventional method including brushing, dipping, flow coating, spraying, and the like. Spraying is generally preferred for applying the composition, for example as an automotive primer. For the reasons discussed above, the novel epoxy ester resins of the present invention are sometimes advantageous in formulating solid coating compositions. For this purpose, the epoxy ester resin of the present invention has a number average molecular weight (Mn) of about 1000 to about 6.
Preferably, it has up to 000. In this regard, coating compositions of the present invention using the preferred epoxy ester resins, preferred crosslinking agents and preferred polymeric catalysts described above have volatile organic content levels of about 347 g/43 to 47 g/47
Low levels up to 0 fJ/i (from 2.9 lbs/gal to 6.9 lbs/gal), the more preferred range of about 69
Formulations from 5 g/gal to 4709/43 (6.6 lb/gal to 6.9 lb/gal) are also suitable for application to substrates by spraying.

A high enough temperature to cause the crosslinking agent to react with the epoxy ester resin is sufficient to cure the coating composition.

Need to bake for some time. The time and temperature required to cure the coating are interrelated and depend on the specific epoxy ester resin, crosslinking agent, polymeric catalyst, heating medium, and other materials, if any, that make up the coating composition. Depends on quantity. Volatile M machine storage piece 430 g/i
(5,6 bonds/gallon), and selecting the preferred ingredients as described above, the baking time and temperature may alternatively be from about 15 minutes to about 60 minutes and from about 165°C to 165°C (275-F to 325-F). The temperature required for curing may be slightly lower, e.g. approximately 120°C (250°C) for 15 to 60 minutes with the addition of a suitable catalyst.
F)', while the coating composition according to the preferred embodiment of the invention described above has a
It has been found that the best coating results are obtained when cured for 20 minutes at a temperature of . However, this same coating composition can be used for extended periods of time, e.g. about 60 minutes, at about 200'O (690'
F) The ability to withstand high temperatures is a very important advantage of the present invention. Thus, as discussed above, great flexibility is provided in planning and implementing curing schedules for parts coated with the coating compositions of the present invention. Thus, in the assembly of motor vehicles, vehicles that must be kept in a curing oven for long periods of time, for example during unplanned assembly line shutdowns, should be recovered with a cured and intact coating.

High solids coating compositions according to the invention comprising the preferred epoxy ester resins described above, melamine and catalysts (particularly preferred polycarboxy functional polymeric catalysts) are based on conventional epoxy esters. It has been found that it provides a cured coating with corrosion resistance comparable to low solids sprayable coating compositions.

A significant reduction in volatile organic content therefore provides a highly advantageous advance in technology.

The most preferred use of the coating compositions of this invention is as a solid sprayable primer for use on bare metal substrates such as housings of domestic or industrial appliances or automobile bodies. Typically, the primer composition is pigmented and contains any of the pigments normally included in primer compositions and acrylic dispersion overcoats for metal substrates, such as carbon black, iron lithopone oxide, magnesium silicate, silica, barium sulfate. , TlO2sR lead, calcium chromate, strontium chromate, zinc potassium chromate, etc. can be used. This primer can be prepared by known methods such as grinding the pigment into a portion of a curable resin;
It can then be pigmented by adding it to the primer composition.

The pigment to binder ratio of the primer may be as high as 4:1 by weight, depending in part on the condition of the metal substrate. However, it is preferred to use primers having a pigment to binder weight ratio of about 1:1 to 2=1, respectively.

No special means are required for formulating the primer composition of the present invention. For example, these primer compositions may be prepared by simply incorporating the resinous component into a suitable solvent system. Thus, for example, each resinous component can be dissolved in a solvent by appropriate mixing and agitation, and the resulting solutions can then be combined to form the finished primer composition.

The bath medium yarn may be any suitable combination of the above-mentioned bath mediums. For isolid sprayable automotive primers, the solvent preferably accounts for about 25% by weight of the total coating composition.
up to about 65% by weight, although, of course, smaller amounts can be used depending on the desired solids content. For example, a primer with a relatively high solids content may be formulated and then 1! It would be desirable to reduce the Jtm consistency.

The metal substrate can be, for example, aluminum, steel, or phosphated cold rolled steel. However, any metal used as a construction material can be used. The primer composition can be applied to the metal paste in any conventional manner, such as by rolling, brushing, or pouring. A preferred method of applying the primer composition to metal is by spraying. The primer is cured at high temperature by any suitable means, such as a baking oven or a bank of infrared heat lamps. Suitable curing temperatures are discussed above.

Primers are generally thinned to about 60% to about 70% solids for spraying purposes with conventional thinners such as aromatic hydrocarbons, commercial petroleum distillates that are aromatic in nature, and then applied onto the metal base. Spray and cure. The primer is cured at high temperature by any suitable means such as a baking oven or a bank of infrared calothermal lamps. Appropriate curing temperatures are as described above. Curing temperature is approximately 135'
C. to about 165.degree. C. is preferred, but curing temperatures from about 100.degree. C. to about 260.degree. C. can be used if desired.

Example 1 This example illustrates the production of epoxy ester 4it fat according to the present invention. In a suitable reactor, add Epon 829
(Commercial I) Shell Chemical Company (diglycidyl ether of hisphenol-A) 1248 parts, bisphenol-A 642 parts, Emery Industries Inc. 466 parts Emery Industries Inc. (dimer acid) and 1400 parts soybean fatty acid. was loaded. The temperature of the mixture was brought to about 177°C (350'F), at which point an exothermic reaction occurred which raised the temperature to about 193°C (390°F). After 2 hours at this temperature, the acid number was found to be 5.9. The reaction mixture was then cooled to about 149°C (300″F′) and
866 parts of methyl amyl ketone were added.

The resulting resin had a viscosity of Ty2 at a solids content of 80%.

The epoxy ester resins according to the invention from Examples 2 to 5 were prepared generally by the method of Example 1. The components used are shown in Table 1 below. The diepoxide, dicarboxylic acid, fatty acid and diphenol were charged to a suitable reactor along with the catalyst (sodium carbonate) if present. Bring this mixture to about 177°C (650°F).
heated to. At this point, increase the temperature from approximately 188°C to 199°C (370"F' to 390'11i'
) an exothermic reaction occurred. The reaction was continued at this temperature until the acid number dropped below 6. The product was cooled to about 121°C (2500F) and then diluted to 80% nonvolatile content with methyl amyl ketone. In Table 1, all amounts are given in parts by weight.

Table 1 Epon 82911248 1248 D E R33321248 Epon 82831248 Empol 1016' 463 466
463 466 Bisphenol A 342
342 542 642 Linseed oil fatty acids
1400 Pamolyn 2005 1400 Soybean fatty acid 1400
1400 sodium carbonate
1.2 Methyl amyl ketone 863
863 863 B65 non-volatile content %
80.0 79.8 79.6 79.8 Viscosity ”A T% vv acid
Value 5.6 4.9 5.2
5.91゛ Trademark, Shell Chemical Company (Zoepoxide, % Bisphenol-A shrimp chlorohydrin epoxy resin).

2 Trademark, Dow Chemical Company (Jepoxide).

3. Trademark, shell chemical strength; Panny (diepoxide).

4. Trademark, Emery Industries, Inc. (dimer acid).

5. Trademark, Vercules Inc.
Located in Ilmington, PL (light color, color stability, high purity grade linoleic acid).

Example 6 An epoxy ester resin according to the invention is prepared generally according to the method of Example 1. The ingredients used were 1247 g of Epon 829 (trademark, Shell Chemical Company), 152 g of azelaic acid. ! i', bisphenol-A642y, and soybean fatty acid 1400. ? It is.

Zoepoxide, dicarboxylic acid, fatty acid and diphenol are charged to a suitable reactor. This mixture is approximately 177°
G (350°F), at which point the exothermic reaction increases the temperature from about 188°C to 199°C (370°F to 6°C).
up to 90°F). The reaction is continued at this temperature until the acid number falls below 6. The product was then cooled to about 121° C. (250° F.) and then diluted with 785 Il of methylaminosiketone to 78.5 Il of nonvolatile content.
Dilute to % by weight.

The viscosity is Xy2 and the acid value is 6.8.

Example 7 The epoxy ester resin according to the invention is Araldite R
D-2 (trademark) Ciba Geyer Corporation (1,
Diglycidyl ether of 4-butanediol) 994 parts, male Suphenol A642, Empol 1014 (
Trademark) Emery Industries, Inc., by charging 463 parts of incophorated (dimer acid), 1400 parts of soybean fatty acid, and 1.5 parts of sodium carbonate to a suitable reactor. The temperature of the mixture is approximately 177°G.
(350'″F) and at this point the temperature is 193°
An exothermic reaction occurs raising the temperature to 680°F.

After 1 hour at this temperature, the acid number is found to be approximately 5.8. The reaction mixture was then heated to about 149°C (30°C).
0'F) and then add 772 parts of methyl amyl ketone. The resin obtained has a viscosity P at 80% solids content.

Example 8 This example illustrates the production of epoxy ester resins according to the present invention. In a suitable reactor, add Epon 829™ Shell Chemical Company (bisphenol-
1248s of diglycisol, 530 parts of bisphenol-A, and 1186m of soybean fatty acid were charged. bringing the temperature of the mixture to approximately 177°0 (350°F);
At this point an exothermic reaction occurred which raised the temperature to about 196°C (380°F). 60 at this temperature
After minutes, the acid value was found to be zero. The reaction mixture was then cooled to about 300"F' and 741 parts of methyl amyl ketone were added. The resulting resin had a viscosity of Ty2 at 80% solids.

Examples 9 to 12 Epoxy ester resins according to the invention were prepared generally by the method of Example 8. The components used are shown in Table 2 below. The zoJ boxide, dicarboxylate, fatty acid, and diphenol were charged to a suitable reactor trap along with the catalyst (sodium carbonate) if present. Boil this mixture at about 177°0 (350°F).
).

At this point, an exothermic reaction occurred as the temperature was increased from about 188°C to 199°C (from 370'F to 390'F).This reaction continued until the acid number fell below 6.
Continued at this temperature. This product is then added to approx.
It was cooled to 21°C (250'F') and then diluted with methyl amyl ketone to a non-volatile content of 8% by weight.

In Table 2, all amounts are given in parts by weight.

Table 2 Example wrinkle value 0.9 1.1 0.
9 0.91 Trademark, Shell Chemical Company (diepoxides, especially bisphenol-A shrimp chlorohydrin epoxy resins).

2. Trademark, Dow Chemical Company (Zoevoxide).

3 Trademark, Shell Chemical Company (Dieboxide).

4. Trademark, Vercules Inc.
Located in Ilmington, PL (light color, color stable, high purity grade linoleic acid).

Example 13 An epoxy ester resin according to the invention was produced.

In a suitable reactor, add Araldite RD-2™ Ciba®
Geigy Coboration (diglycidyl ether of 1,4-butanediol) 268415, 159 parts of bisphenol-A, 112 parts of soybean fat rR, and 0.6 part of sodium carbonate were charged. Reduce the temperature of the mixture to approximately 177°
0 (350°F), and at this point the temperature was increased to 196°C.
An exothermic reaction occurred which rose to 6°F.

After 1 hour at this temperature, the acid number was found to be 1.2. The reaction mixture is then heated to about 300°F.
), and then 154 parts of methyl amyl-ketone were added. The resulting resin had a solids content of 80% and a viscosity of O.

Example 14 An epoxy ester resin according to the invention was produced.

A suitable reactor was charged with 392 parts of Epon 829™/L Chemical Cumber (diglycidyl ether of bisphenol-A), 174 parts of 4,4'-dihydroxyzophenyl sulfone, and 112 parts of soybean fatty acid. The temperature of the mixture was brought to about 177°C (350″FI), at which point an exothermic reaction occurred which raised the temperature to about 20060°C (692°F).

After 1 hour at this temperature, the acid number was found to be 0.8. The reaction mixture was then heated to approximately 149°C (600″
F') and then 152 parts of methyl amyl ketone were added. The obtained resin has a viscosity of X at a solid content of 80 cm.
It had +.

Example 15 This example illustrates the production of epoxy ester resins according to the present invention. In a suitable reactor, add Epon 829 (
Trademark) Shell Chemical Company (diglycidyl ether of bisphenol-A) 911 parts, Empol 1
104™ Emery Industries, Inc. (dimer acid) and 728 parts of soybean fatty acid were charged. Adjust the temperature of this mixture to approximately 177°C.
(350'F) and at this point the temperature is approximately 196
An exothermic reaction occurred which raised the temperature to 380'F'. After 2 hours at this temperature, the acid number was found to be 5.2. The reaction mixture was then heated to about 149°C.
(30 CI'F), then methyl amyl ketone 2
75 parts and 5 parts of Cellosolve Acetate 2F were added.

The resulting resin had a viscosity of W+ at a solids content of 80%.

Examples 16 to 19 Epoxy ester resins according to the invention were prepared generally by the method of Example 15. The components used are shown in Table 6 below. The diepoxide, fatty acid and dimer acid were charged to a suitable reactor along with the catalyst (sodium carbonate) if present. The mixture was heated to approximately 177°C (3,50'lF'). At this point, the temperature should be increased from about 188°C to 199°C.
An exothermic reaction occurred, bringing the temperature up to 370'F to 390'F.

The reaction was continued at this temperature until the acid number fell below 6. The product is then heated to about 121°C
(250'F) and then diluted with methyl amyl ketone to 80% by weight non-volatile content. In Table 6 all amounts are given in parts by weight.

Table 6 Example Epon 8291500 500 D E R663”,
500 Epon 8283500 Empol 1016' 309 309 3
09 609 Linseed oil fatty acid 400 Pamorin 2005400 Soybean fatty acid 400
400 sodium carbonate
0.5 Methyl amyl ketone 300 3
00 300 300 Non-volatile content% 8
0.0 79.8 79.6 79.8 Viscosity
x x y yy2 acid value 5.2 4-. 8,
5.6 5.81 Trademark, Shell Gummy Co., Ltd. (Dieboxides, especially male Suphenol-A shrimp chlorohydrin epoxy resins).

2 Trademark, Dow Chemical Company, (diepoxide).

3- Trademark, Shell Chemical Company (Diepoxide).

4. Trademark, Emery Industries, Inc. (dimer acid).

5. Trademark, Vercules Inc.
Located in Ilmington, Praue.

Example 20 An epoxy ester resin according to the invention is prepared generally by the method of Example 15. The ingredients used were Epon 829 (Commercial I), Shell Chemical Company 500°g1 Azelain #
109. g and soybean fatty acid 400,? It is. Zoepoxide, fatty acid and dimer acid are charged to a suitable reactor. This mixture is heated to about 177°C! (350'F), at which point the exothermic reaction brings the temperature to about 188°F.
℃ to 199°C (670''F to 390''F). The reaction is continued at this temperature until the acid number falls below 6. This product is then heated to about 121°
C (250”F), then methyl amyl ketone 2
With 84.9, the non-volatile pledge is 78.1 times JI1. Dilute to %. The resin has a viscosity of Y% and an acid value of 4.6.

Example 21 An epoxy ester resin according to the invention was produced.

In a suitable reactor, add 622 parts of Araldye) RD-2(TM) Ciba Geigy Corporation (diglycidyl ether of 1,4-butanediol), 1 Embol.
014(TM) Emery Industries Inc. 564 parts of dimer acid, 72 parts of soybean fatty acid
8 parts and 1.0 part of sodium carbonate were charged. The temperature of the mixture was approximately 177°C (350'F), at which point an exothermic reaction occurred which increased the temperature to 196°C (38Off). After 1 hour at this temperature, the acid number was found to be 5.2. The reaction mixture was then cooled to about 149°C (600°F) and then 500 parts of methyl amyl ketone were added. The resulting resin had a viscosity R at 80% I solids.

Example 22 A millbase, or composition pigment paste, was prepared by milling the following mixture in a ball mill.

Barium hydrochloride 1626 Red pepper 60 Titanium dioxide 105 Silica 75 Strontium chromate 99 Polyethylene wax 48 Xylene 20
0 Toluene 240 2-ethylhexanol 57 Resin of Example 1
264 Examples 23 through 26 were applied in an automotive vehicle assembly operation, each with a paint sprayable pigment applied onto a bare unpolished steel automotive vehicle body panel! A coating composition according to the invention suitable for use as a primer was produced. The coating composition components are shown in Table 4 below. Each coating composition was thinned with methyl amyl ketone in a #4 Ford cup at 27° C. (80° F.) to give the preferred spray viscosity from about 18 seconds to 25 seconds.

It will be appreciated that the use of a desiccant to catalyze the reaction of fatty acid double bonds to provide further crosslinking to the cured resin as in Examples 26, 24 and 25 is optional. In Table 4, all amounts are expressed in parts by weight.

Table 4=! 23 24 25 26 Epoxy ester resin of Example 1 270 270
270 270 acidic phenyl phosphate --
i ------PTE3A
-1---11 Example 22 millpigment
800 800 800 800 Reshimiy (Re
simine)7i7”, 110 110
--- --- Cymel 6252
--- --- 110 -1-Cymel 303"
-1-------936% manganese naphthenate (softener) 4 4 4 ---Butanol 35 65 35 ---1
Trademark, Monsanto Company, St. Louis, Mo. (low temperature high solids methylated melamine-formaldehyde resin crosslinker).

2. Trademark, American Cyanamids, Tunis, New Chassis (highly methylated melamine formaldehyde resin).

3 Trademark, American Cyanamids, New Chassis-Huniin, (hexa(methoxymethyl)melamine).

Examples 27 to 32 Further coatings according to the invention suitable for use as binder-sprayable pigmented zolymers, each for application on bare unpolished steel motor vehicle body panels, e.g. in motor vehicle assembly operations. Compositions are prepared as shown in Table 5 below. Note that the use of desiccant agents, such as in the coating compositions specifically shown in Table 5, is optional. The epoxy ester resin used in each coating composition is identified with reference to manufactured examples. The amount of smoothness is expressed in weight.

Examples 36 through 67 The coating compositions of Examples 26, 24, 25, and 26 were spray applied to bare, unpolished BOnderite steel, cured, and tested for corrosion and moisture resistance.

The curing schedule and test results are shown in Table 6. Corrosion is measured as inches of corrosion from the marking line after 240 hours of salt spray. Moisture resistance is 46°O (110″
Qualitatively evaluated after exposure to condensing humidity at F+).

No. 6 Surface air coating composition 25 25 24 25
Scheduled to cure on 26th 1'5g c 15cr'c
is5°C165°C166°015 minutes 15 minutes 1
5 minutes 15 minutes 60 minutes Corrosion resistance 2/8"2/8"
2/8"2/8"2/8" Moisture Resistance Poor Good Excellent Good Excellent Example 68 through Example 41 High Solids Sprayability for Application onto Bare Unpolished Steel Automotive Body Panels in Automotive Vehicle Assembly Operations, Each Coating compositions according to the invention suitable for use as pigmented zolaimers were prepared. The coating composition components are shown in Table 7 below. Each coating composition was coated with methyl amyl ketone at
Dilute from about 18 seconds to about 25 seconds with a Ford cup #4 at (80'F) to give the preferred spray viscosity. It will be appreciated that the use of a desiccant to catalyze further crosslinking of the cured resin is optional.Section 7
In the tables, all amounts are expressed in parts by weight.

Table 7 Epoxy ester resin of Example 7 270 270 2
70 270 Acidic phenyl phosphate ---'
1 --- ---PT8A
-------11 Example 22 millpigment 8
00 800 800 800 Regimin 717
1 110 110 --- -1-cymel 3252 ---1 ---110---
Cymel 5053 --- --- --- ---
-961 Trademark, Monsanto Company, St. Louis, Missouri (low temperature high solids methylated melamine-formaldehyde resin crosslinker).

2° Trademark, American Cyanamids, Tunis, New Chassis (highly methylated melamine formaldehyde resin).

3 Trademark, American Cyanamids, Uniin, New Chassis, (hexa(methoxymethyl)melamine).

Examples 42 to 47 are each further in accordance with the present invention suitable for use as high solids sprayable pigmented brimers for application, for example, onto bare unpolished steel automotive vehicle body panels in automotive vehicle assembly operations. Coating compositions are prepared as shown in Table 8 below. Note that, as in the coating compositions illustrated in Table 8, the use of a desiccant is optional. The epoxy ester resin used in each coating composition is identified with reference to manufactured examples. All quantities are expressed in parts by weight.

Examples 48 to 52 The coating compositions of Examples 48, 49, 50 and 51 were
It was spray applied to bare, unpolished bonderite steel, cured, and then tested for corrosion and moisture resistance.

The curing schedule and test results are shown in Table 9 below.

Corrosion is measured in inches of corrosion from the scribe line after 240 hours of salt spray. Moisture resistance is 46°O (11
Qualitatively evaluated after exposure to condensing humidity at 0'F).

Table 48 49 5D 51 52 Coating composition 38 58 59 40
41 curing schedule 165℃ 165℃ 165℃
165℃ 166℃15 minutes 15 minutes 15 minutes 15 minutes 60 minutes Corrosion resistance 2/8"2/8" 2/8
″2/8″ 2/8″ Moisture resistance Poor Good Excellent
Good Examples 56 to 56 each produce coating compositions according to the invention suitable for use as bare unpolished steel autopigmented primers in motor vehicle assembly operations. The coating composition components are as follows:
It is shown in Table IJ10. Each coating composition was coated with methyl amyl ketone at 27°C (80°F) in a Ford cup #1.
4 to about 18 to 25 seconds to give the desired spray viscosity. It will be appreciated that, as in Examples 56, 54, and 55, the use of a dessicant to catalyze the reaction of fatty acid double bonds to provide further crosslinking to the cured resin is optional. In Table 10 all amounts are expressed in parts by weight.

Table 10 Epoxy ester resin of Example 15 270 270
270 270 acidic phenyl phosphate --
-1,---PTSA
-------11 Example 22 millpigment 800
800 800 800 Regimin 7171
110 110 ---1 --- Cymel 3252 --- --- 110
--- Cymel 3033 --- ---
--- 961 Trademark, Seven Santo Company, St. Louis, Missouri (low temperature vinelid methylated melamine formaldehyde resin crosslinker).

2 Trademark, American Cyanamids, Tunis, New Chassis (highly methylated melamine formaldehyde resin).

3 Trademark, American Cyanamids, Uniin, New Chassis, (hexa(methoxymethyl)melamine).

Examples 57 through 62 are each suitable for use in automotive vehicle assembly operations, such as for example, as a high solid sprayable pigmented primer for application onto bare unpolished steel automotive vehicle body panels.
Further coating compositions according to the invention are prepared as shown in Table 11 below.

Note that the use of a desiccant, as in the coating compositions specifically shown in Table 11, is optional.

The epoxy ester resin used in each coating composition is identified with reference to manufactured examples. All holdings are expressed in parts by weight.

Examples 66 to 67 The coating compositions of Examples 56, 54, 55 and 56
It was spray applied to bare, unpolished bonderite steel, cured and tested for corrosion and moisture resistance. The curing schedule and test results are shown in Table 12 below. Corrosion is measured as inches of corrosion from the scribe line after 240 hours of salt spray. Moisture resistance is qualitatively evaluated after exposure to condensing humidity at 46°0 (110”F').

Table 12 Example coating composition 5653 54 55 5
6 Corrosion resistance 2/8"2/8"2/8" 2/8
"2/8" Moisture Resistance Poor Good Excellent Good Excellent These examples illustrate the preparation of polymeric catalysts for use in coating compositions according to the present invention. The monomer components and tert-butyl perbenzoate initiator were added in the amounts shown in Table 16 below, along with a small amount of methyl amyl ketone solvent, to refluxing methyl amylctone containing cumene hydroperoxide polymerization initiator over a period of 5 hours. Ta. Following completion of the addition, the mixture was held at 300'F' for approximately 1 hour.

The mixtures of Example 69 and Example 70 were then each treated with a solvent to the desired solids level as shown in Table 16 below.
I paid J shillings. The viscosity and acid number of the polymeric catalyst products are shown in Table 16. Amounts of all ingredients are given in parts by weight.

Table 16 Methyl-amyl ketone 1500 150
0 1500 Butyl methacrylate 10
50 1050 ---Butyl acrylate
- + -1+ 150 steel ---150 --- Acrylic acid 450 300
450 tθrt-butyl perbenzoate 6767
67 Kume/Hydroperoxide 37 6
7 37 Solid content (wt%') 5
0 80 75 Viscosity L
Zfu 24 Acid value 238 152 265 Examples 71 to 7
A coating composition according to the present invention was prepared for use as a solid sprayable pigmented primer for application onto bare unpolished steel automotive vehicle body panels, respectively, in automotive vehicle assembly operations up to 2. . The ingredients of the coating composition are as follows:
It is shown in Table 4. Note that the use of a dessicant to catalyze the reaction of fatty acid double bonds to provide further crosslinking to the cured resin is optional. In Table 14, all component weights are expressed in parts by weight.

Table 14 Epoxy ester resin of Example 1 248 248 Example 68
24 - Polymeric catalyst of Example 69 26 Millbase of Example 22 soi so.

Regimin 7171 110
1106% Manganese naphthenate (desiccant) 44 Butanol 65 651
Trademark, Monsanto Company, St. Louis, Missouri (low temperature high solids methylated melamine-formaldehyde resin crosslinker).

Example 73 Coating composition 7 of Example 71 and Example 72 spray applied to bare unpolished Senderite steel and hardened to provide corrosion and moisture resistance?
test. The hardness schedule for each coating composition is 165°015
It's a minute. Corrosion resistance determined as 11 inches of corrosion from scratch line after salt spray at 240° and 46°
Moisture resistant raw materials qualitatively evaluated after exposure to condensing humidity at c < ii ooF) were excellent for each coating composition;

EXAMPLE 74 The following example illustrates the preparation of the coating composition of the present invention, and specifically describes the method of thermopreparation of a polymeric catalyst and an epoxy ester resin. Example 1
248 parts of the resin of Example 68 and 66 parts of the resin of Example 68 are charged.

The mixture is heated to 104°C (220°F) and then stirred at this temperature for 2 hours. After 2 hours, the mixture was cooled to a room Y product and then mixed with the millpigment 80 of Example 22.
0 parts Resomin 717 (Trademark, Monsanto Capugnie, St. Louis, MO), 100 parts, 4 parts 6% manganese naphthenate desiccant, 65 parts butanol, 6 parts butyl polyacrylate, and Butyl Cellosolve Acetate (Trademark, Union Co., Ltd.). Carnoir Corporation,
(New York, NY) to a previously prepared mixture containing 15 parts χ. This mixture is then diluted with methyl amyl ketone to a viscosity of about 18 seconds in a Ford cup≠4 at 27°C. A number of unpolished Bonderite steel panels were sprayed and then subjected to various temperatures (baking schedule 250'FX 15 minutes, 275'F'X 15 minutes,
300'FX 20 minutes, Ro 25 'F' X Ro 0 minutes, 38
Bake at D'F'X60 minutes). The corrosion resistance of the panels after being exposed to a 240 hour salt spray test is found to be excellent; further panels coated and baked in the above schedule and then overcoated with white enamel have excellent moisture and impact resistance. and adhesion [
Gravelo-meter test]. The coating composition described above has a coating composition of 6Cj'C (140"
After 16 hours in F), the viscosity (Ford cup≠4)
The temperature increased to 60℃ (14℃) after only 2 seconds.
0°F) after 5 days.

Coating compositions according to the invention are suitably prepared by the method of Example 76 using the component tones in the amounts shown in Table 15 below. In each case, the properties of the coating composition and the cured coating made therefrom, in particular the storage stability of the coating composition and the corrosion resistance, moisture resistance, impact resistance and adhesion of the cured coating, of the coating composition of Example 81. It is found that the storage stability is excellent except that it is poor due to the use of acidic phenyl phosphate (i.e., non-polymeric) catalyst therein.

S, I also have 5 drugs.
, Monsando Company, St. Louis, Missouri (low temperature, isolid methylated melamine-formaldehyde resin crosslinker).

2 Trademarks, American Cyanamid Company, Tsane, New Chassis (highly methylated melamine formaldehyde resin).

3ti mark, Union Carbide Corporation,
Located in New York, New York (Ethylene glycol motuptyl ether acetate)
.

Examples 86 to 84 Coating compositions according to the invention suitable for use as high solids sprayable pigmented zolymers for application onto bare unpolished steel automotive vehicle body panels, respectively, in automotive vehicle assembly operations. Manufactured by beggars. Coating composition components are shown in Table 16 below. Note that the use of a desiccant to catalyze the reaction of fatty acid double bonds to provide further crosslinking to the cured resin is optional. In Table 16, all component numbers are expressed in parts by weight.

Table 16 86 84 Epoxy ester resin of Example 8 248 248 Polymeric catalyst of Example 68 24-Example 700 Polymeric catalyst - 26 Millbase of Example 22
801 800 Regimin 7171
110 1106% Manganese naphthenate (desiccant)
4 4 Butanol
65651, trademark Monsando Company, St. Louis, Missouri (low temperature high-thorisomethylated melamine-formaldehyde resin crosslinker).

Example 85 The storage stability of the compositions of Examples 83 and 84 was tested. Each was held at 60 DEG C. (140" F.) for 16 hours. Stability was measured as an increase in 7 odes + 4 seconds at 27 DEG C. (80 DEG F.). The results were as follows.

Coating composition of Example 83 2 seconds Coating composition of Example 84 2 seconds.

Examples 86 to 87 Coating Compositions of Examples 86 and 84 7 were spray applied to bare, unpolished Bonderite steel, cured and tested for corrosion and moisture resistance. The curing schedule and test results are shown in Table 17 below. Corrosion is measured as inches of corrosion from the scribe line after 240 hours of salt spray. Moisture resistance is 46℃ (110'
F') is evaluated qualitatively after exposure to condensed humidity.

Table 17 Two Coating Compositions 86 84 Example 88 Non-inventive, particularly the coating composition of Example 86.
-Compared with Inlid coating composition. Properties of Coating Compositions and Cured Coating Compositions The coated compositions of the present invention have a higher solids content (total density and therefore lower V, O, C) as shown in Table 18 below. It can be seen that although it is applied slowly, it has a significantly lower viscosity IW.

09 10 Example 89 The following example illustrates the preparation of the coating composition of the present invention, and specifically illustrates the hot blending process of mixing a polymeric catalyst and an epoxy ester resin. Into a suitable reactor were charged 248 parts of the resin of Example 8 and 66 parts of the resin of Example 68. This mixture was heated to 104°C (220-'F').
and then stirred at this temperature for 2 hours.

After 2 hours, the mixture was cooled to room temperature and then mixed with 800 parts of the millpigment of Example 22, 4 parts of Resomin 717 (Trade Mark, Monzant Company, St. Louis, Missouri), 4 parts of manganese tinanthenate desiccant, 65 parts of butanol, 6 parts butyl acrylate and butyl cellosolve acetate (trademark, Union Carbide Corporation,
(located in New York, New York) containing 15 parts Z,
Added to previously prepared mixture. Then this mixture begs methyl amyl ketone? It was then diluted to a viscosity of about 18 seconds in a Ford cup≠4 at 27°C. A large number of unpolished Ndellite steel panels were sprayed and then heated to 11 different temperatures (baking schedule: 250'F x 15 minutes, 275-F
X15 minutes, Ro00'FX20 minutes, 325'FX30 minutes,
38D'FX 60 minutes). The corrosion resistance of the panels after exposure to a 240 hour salt spray test was excellent (less than scribe to curvature corrosion). Further panels coated and baked in accordance with the schedule above were overcoated with white enamel. These panels? The above coating composition tested and then exhibited excellent moisture resistance, impact resistance and adhesion (gravelometer test) L0 60'0 (140'
After 16 hours in P), the viscosity increased [I] (foot cup ≠ 4) by only 2 seconds and at 60 ° 0 C 140'
In F), after 5 days there was only 5 seconds of power increase.

Coating compositions according to the invention from Examples 90 to 97 are suitably prepared by the method of Example 89 using the amounts of ingredients shown in Table 19 below. In each case, the properties of the coating composition and of the cured coating made therefrom, in particular the storage stability of the coating composition and the corrosion resistance, moisture resistance, impact resistance and adhesion of the cured coating, are determined according to Example 97. It is found that the storage stability of the coating composition is excellent except for the use of an acidic phenyl phosphate (i.e., non-polymeric) catalyst therein.

Trademark Monsando Company, St. Louis, Missouri (low temperature high solids methylated melamine-formamide resin crosslinker).

2 Trademarks, American Cyanamid Company, Tsuney, New Chassis (highly methylated melamine formamide resin).

'am, Union Carbide Corporation, New York P Jr., New York (Ethylene Glycol Motupyl Ether Acetate).

EXAMPLES A coating composition according to the invention suitable for use as a sprayable pigmented primer for fabric was prepared on each bare unpolished steel automobile body panel in an automobile assembly operation. Coating Composition Ingredients Part 20 below
Shown in the table. Note that the use of a desiccant to catalyze the reaction of fatty acid double bonds to provide further crosslinking to the cured resin is optional. In Table 20, all component amounts are expressed in overlapping sections.

Table 20! 899 Epoxy ester resin of Example 15 248 248 Example 68
24 - Polymeric catalyst of Example 70 - Millbase of Example 22 of 26
801 800 Resomin 717” 1
10 1106% Manganese Heptathenate (Drying Agent) 44 Butanol 65651 Trademark Monsando Company, St. Louis, MO (low temperature vinelid methylated melamine-formaldehyde resin crosslinker).

Example 100 Coating Composition 7 of Examples 98 and 99 was spray applied to bare unpolished Ndellite steel, cured and tested for corrosion and moisture resistance. The curing schedule for each coating composition is 165°015 minutes. Corrosion resistance measured as inches of corrosion from the scribe line after 240 hours salt spray and 46°0 (110″
It can be seen that the moisture resistance qualitatively evaluated after exposure to condensing humidity in F) is excellent for each coating composition.

EXAMPLE 101 The following example illustrates the preparation of the coating composition of the present invention, in particular the hot blending method of mixing with a polymeric catalyst-containing epoxy ester resin. I will explain in detail. A suitable reactor is charged with 248 parts of the resin of Example 15 and 66 parts of the resin of Example 68. This mixture is heated to 104°C (220″F)
and stir at this temperature for 2 hours. After 2 hours, the mixture was cooled to room temperature and then mixed with 800 parts of the millpigment of Example 22, 100 parts of Resomin 717 (Trade Mark, Monsando Company, St. Louis, MO), 4 parts of 6% manganese naphthenate desiccant, 35 parts of butanol. 1 part, 6 parts of butyl polyacrylate and butyl cellosolve acetate (trademark, Union Carbyr Corporation,
New York, New York) containing 15 parts,
Added to previously prepared mixture. The mixture is then diluted with methyl amyl ketone to a viscosity of about 18 seconds in a Four V cup +4 at 27°C. Many unpolished Zendelai l'tM# panels? Spray, then apply at 4 different temperatures (curing schedule: 250ff x 15 minutes, 275"F' x 1
5 minutes, 30 oix 20 minutes, 625'FX 30 minutes, 6
The corrosion resistance of the panels after exposure to a 240 hour salt spray test is found to be excellent. The panels were coated, then baked in the schedule described above and overcoated with white enamel. The above panels exhibit excellent moisture resistance, impact resistance and adhesion (gravelometer test).
Viscosity after 16 hours at 140'F
Only 2 seconds increase in cup≠4) and 60°C! (
14[]”F) a slight increase of 5 seconds after 5 days7
For illustration purposes only.

Coating compositions according to the invention from Examples 102 to 109 are suitably prepared by the method of Example 101 using the ingredients as shown in Table 21 below.

In each case, the properties of the coating composition and the cured coating made therefrom, in particular the storage stability of the coating composition, and the corrosion resistance, moisture resistance, impact resistance and adhesion of the cured coating, were as follows: It can be seen that the storage stability of the compound is excellent except that it is inferior due to the use of 7-enyl acid phosphate (i.e., a non-polymeric catalyst) in it.

Trademark Monsando Company, St. Louis, Missouri (low temperature high solids methylated melamine-formaldehyde resin crosslinker).

2 Trademark, American Cyanamid Company, Tuniin, New Chassis (hypermethylated melamine formaldehyde mJJ1).

3 Trademark, Union Carbide Corporation, New York, New York (Ethylene Glycol Motupyl Ether Acetate).

Example 110 Repeat operation 7 of Example 8 once. Sixty parts of methyl amyl ketone were then stripped from the cooled, diluted reaction mixture. It was found that no significant song water was carried away by this solvent.

INDUSTRIAL APPLICABILITY From the foregoing, it is desirable that the present invention has excellent storage stability7 as a marking composition, especially for automobiles, domestic appliances, etc., and that the coating composition has excellent storage stability7 and is suitable for use on substrates such as metal substrates. Industrial applicability as a solid sol polymer coating composition for other applications where it is desirable to provide excellent moisture and solvent resistance to protect against corrosion, abrasion, etc. is evident. be.

Agent: Haru Asamura Continued from page 1 Priority claim @September 30, 1982 @United States (US)■
430182 @September 30, 1982■United States (US)■431465
・ @September 30, 1982■United States (US)■431467 @September 30, 1982■United States (US)■431468

Claims (1)

Claims: (1) A novel epoxy ester resin suitable for use in a thermosetting resin composition, wherein the epoxy ester resin has a number average molecular weight (Mn) of about 900 to about 5000, and a dieboxide and (1) ) a reaction product of a first reactant selected from diphenols, dicarboxylic acids and mixtures thereof and (II) a fatty acid, wherein the reaction of the zoepoxide with the first reactant and the second reactant comprises at least At reaction temperatures reaching about 167° C., epoxy functionality, phenolic functionality, dicarboxylic acid carboxyl functionality and fatty acid carboxyl functionality occur substantially simultaneously, respectively, in relative proportions of about 0 to 1:0 to 0.8.
: A novel epoxy ester resin composition suitable for thermosetting coating compositions, characterized in that it is used in an amount of 0.3 to 1 equivalent. (2) The epoxy ester resin of claim 1, wherein the zoeboxide has a number average molecular weight of about 100 to 1,000. (3) The zoepoxide is selected from the group consisting of bisphenol-A shrimp chlorohydrin epoxy resin, hydantoin epoxy resin, cyclic and acyclic aliphatic diepoxides, etc., and mixtures of any of these. Epoxy ester resin in item 1. (4) Diphenol has a number average molecular weight of approximately 180 to 500
The epoxy ester resin according to claim 1, comprising: (5) The epoxy ester resin according to claim 1, wherein the diphenol consists of bisphenol-A. (6) The dicarboxylic acid has a number average molecular weight of about 145 to 1
000. (8) The epoxy ester resin of claim 1, wherein the dicarboxylic acid consists essentially of a dimerization reaction product of C-18 fatty acids. Epoxy ester resin according to claim 7. (9) The jepoxy P1, the diphenol, the dicarboxylic acid, and the fatty acid each have a relative quantity of 1:
0.4~0.6: 0.1~0.3: 0.6~0
．． The epoxy ester resin of claim 1 used at 8 equivalents. αQ the zoepoxide consists essentially of a diglycidyl ether bisphenol-A resin, the siphenol consists essentially of bisphenol-A, the dicarboxylic acid consists essentially of a dimer acid reaction product of a C-18 fatty acid, and The dieboxide, diphenol, dicarboxylic acid and fatty acid each have a relative proportion by weight of about 1
: 0.2~0.4=0.6~0.5 : 0.9~1
．． 2. The novel epoxy ester resin according to claim 1, which is used in claim 2. aυ In a novel organic solvent-based thermosetting coating composition, A has a number average molecular weight (Mn) of about 900 to about 5000 and is selected from gepoxide and (1) siphenol, dicarboxylic acids, and mixtures thereof. (1) a reaction product of a first reactant containing a fatty acid and a second reactant containing a fatty acid;
The reaction of the reactants occurs substantially simultaneously at a reaction temperature of at least about 167° C., and the epoxy functionality, phenolic functionality, dicarboxylic acid carboxyl functionality and fatty acid carboxyl functionality are each in relative proportions of about 1:0.
1: 0-0.8: 0.3-1 equivalent of epoxy ester resin, B, polyfunctional aminoplast crosslinking agent, and C. Optionally, number average molecular weight (Mn
) of about 1,000 to 10,000% of the resin solids of the coating composition with a polycarboxy-functional polymeric catalyst that is substantially non-reactive with the epoxy ester resin and the polyfunctional aminoplast crosslinker at room temperature. About 2% by weight to about 1% by weight
Novel organic solvent-based thermosetting coating compositions, characterized in that they contain up to 5% by weight. 12. The solvent-based thermosetting coating composition of claim 11, wherein said diepoxide consists essentially of zoglycyl ether bisphenol-A resin. 12. The solvent-based thermosetting coating composition of claim 11, wherein said diphenol is bisphenol-A. 04) Claim 11, wherein said dicarboxylic acid consists essentially of a dimer acid reaction product of a c-is fatty acid.
Solvent-based thermosetting coating compositions. (1) The solvent-based thermosetting coating composition of claim 14, wherein the fatty acid comprises soybean fatty acid. (1G) The polyfunctional aminoplast crosslinking agent is hexa(methoxymethyl)melamine or the like. and compatible mixtures thereof, wherein αη the polycarboxylic functional polymeric catalyst has a number average molecular weight (Mn) of about 1, 500 to 3,000. (18) wherein said polycarboxyl functional polymeric catalyst has (1
) an ethylenically unsaturated carboxylic acid and (1) an ethylenically unsaturated copolymerized monomer that does not impart functionality to said reaction product that is substantially reactive with said epoxy ester resin or said polyfunctional aminoplast crosslinker at room temperature. 12. The solvent-based thermosetting coating composition of claim 11, which essentially comprises a reaction product of a polymer. → The solvent-based thermoset of claim 18, wherein said polycarboxy-functional polymeric catalyst comprises a polymerization reaction product of about 60% by weight acrylic acid and about 70% by weight zotyl methacrylate. Coating composition. (2G) The solvent-based thermoset coating of claim 11, wherein said polycarboxy-functional polymeric catalyst is used in an amount to raise the acid level of the epoxy ester resin from about 15 to about 35. Composition: Cυ said polycarboxy-functional polymeric catalyst is about 10
A solvent-based thermosetting coating composition according to claim 1, which is mixed with an epoxy ester resin at a temperature of 5°C or higher. (2) In a novel, organic solvent-based thermosetting coating composition having a number average molecular weight (H) of from about 1000 to about OOO and consisting essentially of a diglycidyl ether bisphenol-A resin. (II) dicarboxylic acid consisting essentially of the dimerization reaction product of C-18 fatty acids in the chain extension reaction;
Ill) a fatty acid consisting essentially of a soybean fatty acid in a chain termination esterification reaction; epoxy functionality, phenolic functionality, dicarboxylic acid carboxyl functionality and fatty acid calf
The relative proportion of xyl functionality is approximately 1:0.4 to 0.
．． 6 = 0.1-0.3: Epoxy ester resin, B, polyfunctional aminoplast crosslinker, and C0 number average molecular weight (Horse) used at 0.6-°0.8 equivalents from about 1,000 The resin solids of the coating composition is coated with a polycarboxy-functional polymeric catalyst that is substantially non-reactive with the epoxy ester resin and the polyfunctional aminoplast crosslinker at room temperature, up to about 1.0,000% of the resin solids content of the coating composition.
A novel organic solvent-based thermosetting coating composition comprising from % to about 15% by weight.