JPS5989366A - Thermosettable coating composition based on novel organic solvent - Google Patents

Abstract

(57) [Abstract] 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 engineered xyester resins containing solvent-based thermosetting coating compositions. However, the present invention discloses that this invention is formulated as an e.g. sprayable high solids coating composition suitable for use as an automotive Zolimer to form coatings that are highly resistant to corrosion, humidity and solvents. It also relates to such coating compositions.

High molecular weight (e.g. 2,000 to 4
Solvent-based coating compositions using polymeric resins (up to 0,000) and suitable crosslinking agents are known. Typically, such compositions are applied to a substrate, such as by spray casting, and then cured by baking the coated substrate to drive off the organic solvent and to promote the crosslinking reaction. The resulting thermoset coating, if also sufficiently moisture and solvent resistant, can provide aesthetic and functional benefits, including corrosion protection to the underlying substrate.

Coating compositions containing such cylindrical polymer resins typically contain only 25% to 50% solids so that they can be sprayed or otherwise properly applied to a substrate. It is.

Glaze layers of higher solids coating compositions are typically too expensive for this purpose. Conventional epoxy ester all-based automotive spray primers, for example, typically have a volatile organic content ([vocJ) of about 623.1 V//(5,2
pounds/gallon].

The volatility of these conventional low solids coating compositions is very high! f&, the elimination of the solvent moiety is relatively large, thus making material processing undesirable, difficult, and expensive. In addition, excessive solvent loss and (also fJ: )
Solvent recovery equipment makes the coating operation significantly more expensive. Recently, government regulations on hydrocarbon emissions, particularly applicable to automotive coating operations, have forced a significant reduction in volatile organic content for coated compositions. Thus, for example, in the United States, government guidelines set a deadline by which volatile organic emissions from motor vehicle primer coating operations must be reduced to certain prescribed limits. To meet such guidelines, low VOC coating compositions can be used in conjunction with emission treatment equipment to obtain specified emission limits. Although such processing adds significantly to the cost, there is therefore a great need for coating compositions that have reduced VOa close to government limits and preferably lower, 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 fillers, typically in combination with polyfunctional crosslinking agents.

These Hysoliz P coating compositions have lower VOO? It can be applied by spraying. After application to the substrate, the isolid coating composition is heated to a temperature that drives off the volatile organic content and promotes cross-linking and, in some cases, undercarriage of the polyfunctional low molecular weight component [al]. It can be hardened by baking at a temperature.

Typically, the physical properties of coatings provided by such known Hysoliz V coating compositions can differ significantly from those of cured coatings provided by conventional low solids coating compositions. In particular, the cured coatings obtained from known high solids coating compositions are less flexible, have less solvent resistance, less adhesion to the substrate and/or otherwise have lower corrosion protection to the underlying substrate. It may be inferior in terms of being able to take pictures. Therefore, it is suitable for use in non-lid solvent-based coating compositions, yet forms coatings that, upon curing, have physical properties comparable to those obtained from conventional low-solids solvent-based coating compositions. It would be highly desirable to provide coating compositions that include low molecular weight materials.

It should be noted that many high solids coating compositions, especially the prior art epoxy ester amino resin zolimers, exhibit poor packaging stability, especially in the presence of anticorrosion pigments such as zinc chromate Q). Therefore, the isolid is suitable for use in solvent-based coating compositions, yet not only exhibits good packaging stability or shelf life even in the presence of anticorrosion pigments, but also has a conventional low solids content when cured. g with physical properties comparable to those obtained from solvent-based compositions.
It would be highly desirable to provide a coating composition that includes a low molecular weight material that forms a whole.

It is therefore an object of the present invention to provide new coating compositions containing low molecular weight crosslinkable epoxy ester resins. In this regard, it is a particular object of the present invention to provide novel epoxy ester thermoset coating compositions that have VOCs low enough to meet government guidelines, yet can be applied to substrates by spraying or other known methods. be.

Another object of the invention is to provide a method for forming a coating on a substrate that has advantageous physical properties, such as moisture and solvent resistance and corrosion protection on the underlying substrate. Further aspects and advantages of the invention will be apparent from the following description thereof.

According to the present invention, novel organic solvent-based thermosetting resin/crosslinker compositions include a solvent and an optional pigment;
In addition to additives such as catalysts, flow control agents, blocks containing the Nipoquin Ester 1v1 fat of the present invention and, but not limited to, blocked trifunctional isocyanurates, polyisocyanates, and oligoester-modified blocked isocyanates. Contains topolyisocyanate crosslinking agent. The epoxy ester side resin of the present invention has a number average molecular weight Wr, (
Mn) from about 900 to about 5000, with (i) a first reactant selected from diphenols, dicarboxylic acids, and mixtures thereof in a chain extension reaction; a reaction product of a second reactant comprising a fatty acid, in which the chain extension reaction and the esterification reaction occur substantially simultaneously at a reaction temperature of at least about The fatty acid carboxyl functionality is used in relative proportions of about 1:0 to 1:0-0.8 to O16 to 1 equivalent, respectively. Advantageously, appropriate catalysts are used to promote more simultaneous chain extension and esterification reactions.

Particularly preferred compositions of the invention are those formulated as solid coating compositions suitable for application to a substrate by spraying. Such compositions are particularly useful as primers on bare, unpolished metal surfaces of motor vehicle bodies. As used herein, the solid coating composition has a volatile organic content of about 407.9/l.
! (5,4 lb/gal) or less by 2
It gives a viscosity of less than about 65 seconds in a Ford cup #4 at 7°C (80°F).

In accordance with another aspect of the present invention, a method of forming a corrosion-resistant, solvent-resistant, and moisture-resistant memory on a substrate includes applying the novel solvent-based thermosettable composition of the present invention to a substrate. application and then subjecting the coating to an elevated temperature for a period of time sufficient to substantially cure the coating layer. Typically, the novel coating compositions of the present invention have a temperature of about 100'O (212'F).
and about 230°C (445'F) for a period sufficient to produce a cured coating, such as from about 15 minutes to about 60 minutes. According to a preferred embodiment of the present invention, the coating composition has a temperature of about 120'C (250'F
) can be sufficiently cured to good coating properties by heating for about 15 minutes, but further such preferred compositions can be cured by heating for about 60 minutes without substantially reducing such advantageous coating properties. for a long period of time at approximately 200℃ (692”
F) Add 1 to the hardening at 1.

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 spraying techniques. For example, approximately 347 fj/1 (2,9 lb/
High solids coating compositions formulated at low OCs from about 503 g/1 (462 bonds/gal) to about 1% in Ford Cup #4 at 27°C
It is found to have a low viscosity of 5 seconds to about 45 seconds, making it well suited for spray application techniques. High solids coating compositions according to preferred embodiments have a VOa of about 407 μ/l to about 446 g/l (6.4 bonds/gal to 6.7 bonds/gal) in a Ford Cup #4 at 27°C. It can be seen that the core has a low viscosity from 15 seconds to about 25 seconds. Therefore, the coating composition of the present invention:
It is less expensive than known coating compositions and can be sprayed only at higher OCs.

Additionally, the coating compositions of the present invention can be used to reduce or eliminate emissions treatment agents and equipment to meet or exceed government guidelines regarding hydrocarbon emissions. Additionally, the reduction in hydrocarbon emissions used in the coated composition provides direct cost benefits.

Unlike the various high solids coating compositions previously proposed, the coating compositions of the present invention achieve the aforementioned low VOa and 2. J: Provides the advantage of hardening response. On the contrary, when applied to a metal substrate, such as when applied as an automotive primer coating on bare sheet steel, the cured coating according to the invention is superior to other commercially available high solids coating compositions of similar nature. In comparison, it has been found that it provides excellent adhesion to substrates, excellent moisture resistance, and excellent corrosion resistance.

Other features and advantages of the invention, including preferred embodiments and the best mode of carrying out the invention, will be more apparent from the following detailed description of the invention.

More particularly, the present invention provides novel, organic solvent-based thermosetting coating compositions in which A, number average molecular f.
i (Mn) from about 900 to about 50,001, and (i) a first reactant selected from diphenols, dicarboxylic acids, and mixtures thereof in a chain extension reaction; a reaction product of a second reactant comprising a fatty acid, wherein the chain extension reaction and the esterification reaction occur substantially simultaneously at a reaction temperature of at least about 137°C; The functionality and fatty acid carboxyl functionality are respectively in relative proportions of 1:0 to 1:O to 0.8:0.3 to 1 during curing of the epoxy ester resin, B, said coating composition. upon deblocking of its blocked isocyanate groups at elevated temperatures, reaction between about 0.5 and about 1.6 11J crosslinkers per group on the epoxy ester resin reactive with the crosslinker; The present invention relates to thermosetting coating compositions based on conventional organic solvents that contain a blocked isocyanate crosslinking agent that provides functional inocyanate groups.

Each of the above major components and other components and other aspects of the compositions of the present invention are described in more detail below.

A. The chain extension reaction of the epoxy ester resin dieboxide and the dicarboxylic acid, diphenol, or a mixture thereof and the chain termination esterification reaction of the dieboxide and the fatty acid occur substantially simultaneously. Q. The epoxy ester resin composition of the present invention This is a strikingly characteristic aspect of While not wishing to be bound by theory VC, given the inventive reaction conditions defined herein, the esterification reaction of the carboxyl functionality of the fatty acid and the epoxy functionality of the diepoxide is The chain extension reaction between the phenolic hydroxyl functionality and the epoxy functionality of phenol proceeds at approximately the same rate or at the same rate as the chain extension reaction between the carboxyl reactivity and the epoxy functionality of dicarboxylic acids. Hydroxy functionalities (generated by the chain extension and chain termination reactions mentioned above) are present in the O4, which we now know to proceed at the speed of swimming.
The reaction of the carboxyl functionality of the fatty acid with the carboxyl functionality of the dicarboxylic acid proceeds at almost exactly the same rate as the reaction of such hydroxyl functionality with the carboxyl functionality of the dicarboxylic acid.

By carrying out these reactions simultaneously, a resin is produced that contains not just a series of analogues of the same structure, but a mixture of reaction products of various molecular structures. Desirably, it is now known that during the simultaneous chain extension and chain termination reactions, dieboxide and epoxide functional chain extension intermediate reaction products react with dicarboxylic acids, diphenols and fatty acids in a random order. Therefore, each chain extension reaction product of the epoxy ester resin of the present invention according to a certain reaction order can be combined with a reaction product of a different reaction order F, J:
i14 will be structurally different. In addition to reaction products of various molecular structures, the simultaneous reaction of dieboxides (and epoxy-functional chain-extending intermediate reaction products) with dicarboxylic acids and diphenols and chain-terminating lipids results in sequences of about 600 or less. is believed to yield a product epoxy ester resin 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 derive in part from the simultaneous reactions, particularly the different molecular structures and broad molecular weight distribution of the epoxy ester resin reaction products, is the surprisingly low viscosity of coating compositions containing these resins. It is. More specifically, it can be seen that the coating compositions of the present invention have significantly lower viscosities at a given solids content than many comparable commercially available high solids coating compositions. Accordingly, the coating compositions of the present invention can be sprayed or otherwise applied to a substrate at significantly higher solids contents and therefore have significantly lower VOa
It takes. With such low viscosity and high solids content,
All of the foregoing reasons represent a very significant advance in the industry, including lower costs of material handling, lower emissions of volatile organics, lower costs in accordance with government guidelines, and other related advantages.

The advantageously low glass transition temperature (Tg) of the novel epoxy ester resins of the present invention is believed to be another result of the very broad molecular weight distribution and varied molecular structure. More precisely, it is now understood that the lower molecular weight portion of the epoxy ester resin and any unreacted monomers act as plasticizers for the resin, effectively providing a lower apparent Tg. In any case, the fact that low Tg can be obtained also in these epoxy ester resins of the present invention containing high aromatic content is M powder. It is known that a low Tg provides an excellent smoother surface on the cured coating. During heating to cure the coating, the coating flows after it reaches its Tg and before it is substantially cured at its curing temperature.
Therefore, a lower TgVC allows a longer period of time during which the coating can flow and be smooth, thus improving the surface quality of the cured coating. Additionally, a broader molecular weight distribution of the epoxy ester resin component. is believed to be a hindrance, in part, to the advantageous flexibility of the cured coating of the present invention. The flexibility of this coating is not expected given the high weight percentage of epoxy ester resin Q aromatic units. Such high stability associated with group content is particularly advantageous in view of the very significant cost advantage of aromatic raw materials over aliphatic raw materials.

Additionally, it is now believed that aromatics in coated compositions, such as Zolimer compositions on metal substrates, are more resistant to hydrolysis than aliphatics.

Thus, while again not wishing to be bound by theory, it is now believed that the high aromatic content of the epoxy ester resins of the present invention partially explains the superior corrosion protection found to be provided by the novel coatings of the present invention. It will be done. this is,
Particularly, for example, in accordance with preferred embodiments of the invention discussed further below, a diphenol is used and the geboxide reactant and furthermore the phenol provides the aromatic units to the resin. Furthermore, the epoxy ester ItlI was obtained by chain extension reaction of phenol and epoxy.
It can now be seen that the phenolic oxygen introduced into & advantageously provides excellent adhesion to metal substrates, such as steel substrates. Therefore, the high aromatic content of the cured coating and its excellent adhesion enhance the benefits offered by the other.
1. Provides excellent corrosion protection of uninvented hardened temporary coating.

In accordance with 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 random order and distribution. While again not wishing to be bound by theory, it can now be seen that the aromatic units of the diphenol and the fatty Lj units of the dicarboxylic acid unit each enhance the benefits of the other in a not only predetermined but synergistic manner. . More specifically, it can be seen that the aliphatic units impart flexibility to the epoxy ester resin, whereas the aromatic units impart moisture and corrosion resistance, as discussed above. Thus, the epoxy ester resin reaction product provides a hard coating having both good flexibility and good moisture and corrosion resistance.

The diepoxide reactant suitable for the epoxy ester tree can be any of a large number of diepoxides, including many that are commercially available and that will be apparent to those skilled in the art in light of this disclosure. Ultimately, the selection of reactants for the production of epoxy ester resins will depend in part on the particular use intended for the coating composition, but terminal diepoxides, i.e. dievoxides having two terminal epoxide groups, are generally most preferred. . These are generally more reactive and
Therefore, there is a need for reaction conditions that more easily avoid undesirable side reactions such as epoxy-epoxy reactions and dehydrogenation. Preferably, the diepoxide has a number average molecular weight (n) between about 100 and about 1000, more preferably between about 1[10 and about 600Q]. Many such preferred dieboxides are readily commercially available, such as bisphenol A-modified chlorohydrin epoxy (ηi11, flJ, epon (gpon™)).
] family, Shell Chemical Company, Hughston, Texas, and DFiR(TM) family, Dauk'Mical Company, Midland, Michigan.

Also, cycloaliphatic epoxy resins, such as Ebonex [B
ponex™ series, Hyuston, Texas, hydantoin Epoquine resins, such as Resin
Any of the various acyclic or cycloaliphatic dieboxides, such as 4-butane XN-diol diglycidyl ether and 4-vinylcyclohexene dioxide, are also preferred. Among the above, diglycidyl ether bisphenol A (RJ fat or its higher molecular weight analogues, such as Epon 828 (trademark) of the above-mentioned Epon (trademark) series);
and Epon 829™ are also preferred due to their cost and commercial availability.

The higher molecular weight series of Epon (marked 1 (B)) is suitable for applications where a higher molecular weight epoxy ester resin is desired.In general, however, this higher molecular weight epoxy ester resin has a slightly higher viscosity (sweeter Additionally, it will be appreciated that the higher polymeric members of the Ebon series, such as Epon 1001 and Epon 1004, are less preferred because they have lower solids content.
For example, it has epoxy functionality and hydroxyl functionality that undergoes undesirable side reactions. The result of this is undesirable resin properties and gelling. Other suitable dieboxides for use in the synthesis of 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 dieboxides can be used.

In addition to the dieboxide, the part of the epoxy functionality can be provided by any compatible monoepoxy compound or, more suitably, by a polyepoxy compound or a mixture of compounds having three or more epoxy groups per molecule. can be given by Suitable such polyepoxides include, for example, those having a molecular weight of about 200 to about 800.

The polyepoxide can be essentially any known type, such as polyglycidyl ethers of polyphenols. These can be produced by the ether ratio of polyphenols with halohydrins in the presence of alkali. It will be appreciated by those skilled in the art in view of this disclosure that in some cases, particularly where the solids content of the coating composition is less important, it may be desirable to use higher molecular weight polyepoxides. Preferably, any such polyepoxide contains free hydroxyl groups in addition to epoxide groups.

Polyglycidyl ethers of polyphenols can be used; however, such compositions may include reacting a portion of the warping moieties (hyperoxylic or, in some cases, epoxy) with a modifier to change the film properties of the resin. However, the car is often heavy. The epoxy resin can be modified with, for example, isocyanate group-containing organic materials or other reactive organic materials.

Other quite useful types of polyepoxides are, for example, the novolak epoxy resins EON 12-5 and EO
N 1273 (trademark), a novolac resin manufactured by Civer-Geigy Corporation.

In accordance with a preferred embodiment of the present invention, the epoxide compound other than dieboxide is no more than about 15% of the total epoxide functionality of the reactants used to form the epoxy-ester resin, and most preferably substantially no total epoxide functionality. not give.

There are a large number of commercially available diphenol reactants suitable for the epoxy esters of this invention, many of which will be apparent to those skilled in the art in view of this disclosure.

Preferred diphenols have the general formula (I) (wherein R is 2 which is substantially non-reactive with the dieboxide resin).
The connection part of the value) has f. Preferably, R is a divalent organic linking moiety, such as (OH2)n, where n is preferably from about 1 to about 81, such as C-1, but not an inorganic moiety, such as sulfonyl. is also suitable. Diphenols of this nature have been found to give good reactivity with the preferred dieboxides mentioned above, and ultimately give good physical properties, most notably excellent corrosion protection. In view of this disclosure, it will be apparent to those skilled in the art that R must be substantially non-reactive with the fatty acids used in the epoxy ester resin. Particularly preferred diphenols include:
Formula (I) wherein R is 1 to about 10 carbons, preferably Id 3 to 4 carbons, most preferably the general formula (wherein R' and R are the same) are different, and each is preferred, such as hydrogen and lower alkyl of about 1 to 4 carbons, most preferably 1 or 2 carbons.
or 1 selected from the group containing a mixture of any of these
[selected from the group containing straight-chain or branched alkylene or alkylidene moieties] of a monovalent organic moiety]. Preferably, the diphenol has a number average molecular phosphorus (Mn) between about 180 and about 500, more preferably between about 180 and about 250.

Diphehel and a suitable fatty acid within the range used with the preferred geboxides described above have been found to provide an epoxy ester resin containing a particularly broad molecular coverage of the mixed reaction products, which resins (discussed above) ) is 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-A, bisphenol-B, etc., 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, most preferably t'1 provides two terminal mono-hydroxy substituted phenyl rings as in formula (I)K above. Other examples of diphenols are bis-(4-hydroxy-tert-butylphenyl)-2,2-propane, bis-(2-hydroxy-
They are naphthitreemethane and 1,5-dihydroxynaphthalene. Other suitable diphenols for the epoxy ester resins of the present invention will be apparent to those skilled in the art in light of this disclosure.

There are numerous commercially available dicarboxylic acid reactants suitable for the epoxy ester resins of the present invention, many of which will be 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 in view of the increased flexibility they provide to the cured coatings of the present invention. A favorable dicarboxylic acid has the general formula (formerly HOO
OR''-000H(u) (wherein R'' is a divalent linking moiety that is substantially non-reactive with the diepoxide resin). Considering this disclosure RL/
/ should also be substantially non-reactive with the fatty acids used in the epoxy ester resin, the hydroxy functionality (generated in chain extension reactions) and the cross-linking agents used in the coating composition, at least at storage temperatures. It is clear to the business operator. Preferably, R"' is a divalent organic linking moiety. Particularly preferred, R"' is a straight or branched alkylene or alkylidene moiety, preferably of about 4 to 42 carbon atoms; For example (OH2 Yu(
where n is a dicarboxylic acid selected from the group preferably from about 4 to about 42) and mixtures thereof. It has been found that dicarboxylic acids of this nature give good reactivity with the preferred dieboxides mentioned above, yet ultimately give cured coatings of the invention with excellent physical properties, most significantly superior flexibility and corrosion protection. Ta. Preferably, the dicarboxylic acid has a number average molecule i (Mn) of about 145
and about 1000, more preferably about 570'lr-.

The dicarboxylic acids used in conjunction with the preferred dieboxides and preferred diphenols described in Section 01J, and the preferred fatty acids described below, have been found to provide epoxy ester resins containing mixed reaction products with a particularly broad molecular weight distribution; It can be seen that the compositions of the present invention provide particularly advantageous physical properties including low Tg and good moisture resistance and corrosion protection.

Typical dicarboxylic acids include adipic acid, 6.6-
Dimethylpentanedionic acid, benzenedicarboxylic acid, phenylene dicarboxylic acid, naphthalene dicarboxylic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, etc. or compatible mixtures of any of these. Dicarboxylic acids of the formula (■) (in which R″′ is an alkylene chain of less than 4 carbons), such as evaxalic acid, malonic acid, conolilic acid, and glutaric acid, can all be used; These are less preferred in view of the flexibility of the dicarboxylic acids.Preferably, the dicarboxylic acids provide two terminal carboxyl groups.Similarly, preferred aromatic dicarboxylic acids are those in which the carboxyl groups are further spaced apart. What is there,
For example 1,4-benzene-dicarboxylic acid and 2,7-
Naphthalene-dicarboxylic acid.

The most preferred dicarboxylic acids are substantially saturated acyclic acids known to those skilled in the art and readily commercially available;
It is an aliphatic dimer acid. These are typically dicarboxylation 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 this dimer acid provides excellent reactivity with the preferred dieboxides, provides an epochine ester reaction product with an advantageously broad molecular weight distribution, and finally provides the hard ratio coating of the present invention with excellent physical properties. This is because t, Mk are given. Additionally, 66 carbon dimer acids are readily commercially available. For example, KmpOl 1014
(Trademark), Enball 1016(Trademark) and Enball 1018 (Commercial), each Emery Industries,
Available from Inc., Cincinnati, Ohio. Most of the commercially available dimer acids contain some portion of the trimer acid, typically from about 5% to 10%, often as much as 30% or more, and are As used herein, the term "dimer acid" refers to these Hamura Q
Including those containing such spots. Most useful in the present compositions are products containing dibasic acids as predominant and no or little tribasic and monobasic acids.

Aliphatic dicarboxylic acids are believed to offer additional benefits. In particular, without wishing to be bound by theory, it is believed that this aliphatic dicarboxylic acid derived epoxy ester resin will better wet the substrate surface, thus increasing the overall adhesion between the substrate and the hard coating. I understand now.

These epoxy ester resins also flow better and
Moreover, it provides an excellent smooth surface when cured.

It can also be seen that the lipid 1-family unit imparts a large uJ flexibility to the cured coating as described above, and the flexibility of this coating also imparts a large impact resistance. In this regard, it is now seen that in epoxy ester resins according to 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 and the dieboxide. Such a very broad molecular weight distribution further increases the flexibility of the cured coating.

When corrosion protection for the substrate is important, both formulas (■) (in the formula, R″′
It would be preferred to use a dicarboxylic acid with at least part aromatic). As mentioned above, aromatics in coating compositions of the present invention, such as primer compositions for metal substrates, may be It is believed that each of the diphenols and dievoxides according to the preferred embodiments above imparts aromatic properties to the resin. group units, each of which will contribute equally to corrosion resistance 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 a large number of commercially available fatty acids that can be used as chain-terminating ester ratio 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 these fatty acids, preferred are the more saturated fatty acids. This is because the olefinic unsaturation of the fatty acids is believed to perform polymerization-type reactions between such double bonds during the synthesis of the epoxy ester resins of the present invention. Unsaturated fatty acids such as oleic acid, linoleic acid, lylunic acid, etc. and mixtures of these acids are suitable for use, however, many are commercially available and are not covered by the present disclosure. - Can be used with suitable inhibitors for polymeric type reactions, such as hydroquinone, which will be obvious to the person skilled in the art. However, aromatic fatty acids are commercially available (7 can also be used; however, aliphatic fatty acids 11
/j e ItJ is preferred in view of the increased coating flexibility it provides. Particularly preferred for use are substantially saturated fatty acids such as soybean fatty acids, most preferably, acetic acid, lauric acid, valmitic acid, stearic acid, and the like or mixtures of any of these. These have been found to be relatively inexpensive and yet provide good reactivity with the preferred geboxides 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 prepared by the reaction conditions now defined using techniques known and readily apparent to those skilled in the art in light of this disclosure. dieboxide,
Chain extension and chain termination reactions can be carried out by charging the diphenols, dicarboxylic acids and fatty acids into a suitable reactor and then heating the mixture.
occur virtually simultaneously. Geboxide and carboxyl functionality and phenol functionality quickly and/or
It is usually preferable to have a catalyst present to ensure a more complete reaction and to ensure that these reactions occur substantially simultaneously at about the same or similar rate.
I want to be recognized. Alternatively, other techniques, such as higher reaction temperatures and/or longer reaction times, or a relatively large proportion of diphenol (because in the absence of a catalyst, the phenol functionality is more sensitive to the carboxyl functionality than the rimoshieboxide) (albeit with low reactivity) can be used to give substantially simultaneous reactions.

However, the use of a catalyst has been found to provide useful engineered boxyester resins of the present invention, and is preferred.

Epon 829™, mentioned above as commercially available, is a breeding catalyst. Epon 828™ is substantially the same, but does not provide such a catalyst.

Suitable catalysts are commercially available and include, for example, the preferred sodium carbonate and lithium neodecanoate, lithium naphthenate, lithium nonanoate, other known organometallic catalysts and tertiary amine catalysts, and/or compatibility with any of these. Any of the known catalysts for epoxy-carboxylic acid/epoxy-phenol reactions, such as mixtures. Others will be apparent to those skilled in the art in view of this disclosure.

When both a diphenol and a dicarboxylic acid are used, the reaction mixture generally has a temperature of at least about 127°
280'F), preferably at least about 176°0(3
If present, the exothermic reaction proceeds with or without further heating in the presence of a catalyst, and the reaction mixture is then heated to 50"Ei') in part, depending on batch size and reactor insulation, etc. approximately 193°C to 380°C (380'F to 450'F). In the absence of a catalyst, such exotherms are typically not observed;
Moreover, the reaction temperature is preferably about 176'C to 193°C.
Continuous heating is required to maintain the temperature at (350'F to sso''F'Y!). The progress of the reaction can be followed by measuring the acid number. After it is known to be complete, preferably the acid value is 6.
or less, the resin may be diluted with a suitable solvent to reduce the viscosity to the desired level. A non-volatile level of 80 q6i, I was found to be suitable for storage of the coating composition.

When a diphenol is used and no dicarboxylic acid is used, the reaction mixture is heated to at least about 175°C (645°F).
In the presence of a catalyst σ), the exothermic reaction usually proceeds without further heating or heating.

Typically, the reaction mixture is then heated to about 195"0, depending on the size of the nookute, reactor insulation, etc.
to 205°C (380'F to 400'F). In the absence of a catalyst, such exotherms are typically not observed and continuous heating is required. After this is determined to be satisfactory, the resin may be diluted with a suitable solvent to reduce the viscosity to the desired level, preferably at an acid value of 6 or less.

When a dicarboxylic acid is used and no dienol 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,
If the dicarboxylic acid consists of the preferred dimer acids described above, the reaction temperature is about 165° C. for some dicarboxylic acids that are very different from the fatty acids used in the reaction.
(280"F) will result in reaction rates of fatty acids and diepoxides that are significantly different from those of dicarboxylic acids and dieboxides. Typically, the reaction mixture is heated from about 170"C to 190"C ( 340"F to 67[]"lli") and then held at this temperature. An exothermic reaction is observed, and the progress of the reaction can be monitored by measuring the acid value. By measuring the acid value,
After the reaction is found to be sufficiently complete, preferably at an acid value of 7 or less, the resin is diluted with a suitable solvent to reduce the viscosity to the desired level for its use or storage. It's okay.

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 epoxy functionality with the carboxyl functionality of the fatty acid; Moreover, it should be appreciated that because these reactions are carried out substantially simultaneously to produce the epoxy ester resins of the present invention, the relative proportions of the reactants in the reaction mixture can significantly affect the properties of the product resin. Therefore, when both a diphenol and a dicarboxylic acid are used in a chain extension reaction with a dieboxide, the epoxy functionality, the phenol functionality, the dicarboxylic acid carboxyl functionality, and the fatty acid carboxyl functionality
The doxyl functionality is in a relative ratio of approximately 1:0.2-0.6:
0.1 - 0.4: Preferably used in the range of 0.4 to 0.9. More preferably, the reactants are from about 1 equivalent of epoxy functionality to about 0.4 equivalents of phenol functionality.
up to 6 equivalents, dicarboxylic acid carboxyl functionality from about 1 equivalent to O06 equivalents, fatty acid carboxyl functionality 0
．． It is present to provide from 6 equivalents to 0.8 equivalents. Most preferably, the dieboxide, diphenol, dicarboxylic acid and fatty acid are each about 1:0.5:0
．． 25: Present in a relative amount giving 0.8 equivalents. One preferred embodiment of the novel epoxy ester resin of the present invention comprises a diglycidyl bisphenol-A resin and pifphenol A, a reaction product of a dicarboxylation reaction product of C-18 fatty acid and a reaction product of soybean fatty acid, the components being The relative proportion of heavy goods is approximately 1: 0.2-0.4: 0.3-0
．． 5: Used at 0.9 to 1.2.

When using a diphenol without dicarboxylic M, the epoxy functionality, phenolic functionality and carboxyl functionality are preferably in a ratio of about 41" to about 1:0.4 to 1:0
．． It is preferable to use 4 to 1. More preferably C
The relative proportions in this case are 1 equivalent of epoxy functionality to about 0.5 to 0.7 equivalents of phenol functionality to about 0.5 equivalents to about 0-7 equivalents of carboxyl functionality. . Most preferably, the diepoxide, diphenol and Ij fatty acid have a functional ratio of 1:0.
7: Present in relative amounts giving 0.6 equivalents.

When using dicarboxylic acids without diphenols, the epoxy functionality, dicarboxylic acid carboxyl functionality and fatty acid carboxyl functionality are preferably in relative proportions of 1:
0.3-0.8: Used at 0.3-0.8. Preferably, the relative proportions in this case are 1 equivalent of epoxy functionality to about 0.4 equivalents to 0.6 equivalents of dicarboxylic acid carboxyl functionality to 1 equivalent of fatty acid carboxyl functionality. to 0.6 equivalent. Most preferably, the jepoxy r1 dicarboxylic acid and fatty acid are
The relative amounts of sensuality are 1: 0.4: 0.5, respectively. One most preferred embodiment is a diglycidyl ether bisphenol A resin and (a) O
The relative proportions of the -18 fatty acid 1f/i acid reaction product and (b) soybean fatty acid are approximately 1:0.5 to 0.
7: Reaction production of 0.7-0.9! 1211! Use I.

The epoxy ester resins afforded by these preferred ranges of 1 part reactant have favorable physical properties, most particularly corrosion protection when applied to metal substrates such as bare automobile body sheet steel. It has been found to provide coating compositions having the following properties.

In the absence of catalysts for epoxy/phenol and epoxy/carboxy reactions, it is generally preferred to use a relatively large proportion of the diphenol within the range defined above.
2. Some unreacted diphenol is acceptable in the reaction product.

The superior moisture resistance, corrosion protection, and other physical properties afforded by the coating compositions of the present invention are largely not previously known or proposed when diphenol reactants are used in addition to and to the exclusion of dicarboxylic acids. It is now thought that it originates from the science of fhi.

More specifically, without wishing to be bound by theory, the epoxy esters of the present invention may contain a substantial portion of phenolic end components.

That is, while previously 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 phenolic-terminated in a substantial portion. It is now believed that there is.

This phenomenon is due to the presence of dieboxide reactants and diphenol functional reactants and, at the same time, carboxyl functional reactants (i.e. dicarboxylic acids and fatty acids if present)? being the result of a reaction of the relative proportions of reactants as defined above;
I understand now. Carboxyl functionality competes with phenolic functionality for reaction with epoxy functionality. This phenomenon is illustrated in Example 110. Thus, upon depletion of unreacted epoxy functionality (despite the excess of epoxy with respect to phenol in the preferred embodiments described above) there is a reaction product that converts to terminal phenol. One would have expected it to react with the pendant hydroxy groups of the chain-extending intermediate reaction product. Slightly more water is found than is contributed as an impurity to the reactants.Thus, the receiving moiety of the dicarboxylic acid (V if present) and the fatty acid react with such pendant hydroxy groups, but less than expected. A much larger proportion apparently reacts with the epoxy (in competition with the phenolic functionality) such that the reaction product, i.e., the epoxy ester resin of the present invention, is in substantial part phenol-terminated. One of the most important advantages believed to arise from the chemistry is the superior hardening response of the coating compositions of the present invention. It is thought that this gives a very high reactivity with.

B. Crosslinking Agents The crosslinking agents used in the novel solvent-based coating compositions of this invention include blocked polyisocyanates.

The novel, solvent-based coating compositions of the present invention as a result of using blocked polyisocyanate crosslinkers have excellent storage stability even when anticorrosion pigments such as zinc chromate are used in low concentrations. shows.

As used herein, "blocked polyisocyanate" means any isocyanate group that has been reacted with a substance that prevents the reaction at room temperature with compounds that conventionally react with such groups, and that at least some of the isocyanate groups have been reacted with can undergo a reaction at higher (curing) temperatures,
means an incyanato compound containing two or more incyanato groups. Generally, blocked polyisocyanates can be prepared by reacting a sufficiently dispersed polyisocyanate with an active hydrogen-containing blocking agent to ensure that no free isocyanate groups are present. This blocking agent can be chosen from a large number of materials with active hydrogen, which can be represented by 2BH and are discussed below.

The blocked polyisocyanate crosslinking agent is used in the composition of the present invention so that during deblocking of the blocked isocyanate at the hardening temperature of the composition, the crosslinking agent is added to the film-forming resin of the coating composition as described above. Between about 5 and about 1.6 reactive groups, favorable [7 or about 0.8
and about 1.6 isocyanate groups.

Numerous types of blocked polyisocyanates can be used in the compositions of the present invention.

Particularly suitable blocked polyisocyanates, discussed further below, include blocked polymethylene polyphenol isocyanates, blocked polyisocyanates containing isocyanurate rings, and some oligoester-modified blocked polyisocyanates.

In the production of blocked polyisocyanate crosslinking agents,
Any suitable polyisocyanate can be used. Representative columns include aliphatic compounds such as trimethylene, tetramethylene, pentamethylene, hexamethylene, 1,2-propylene, 1,2-butylene, 2,3-butylene, 1,3-butylene, ethylidene and butylidene diisocyanate. , cycloalkylene compounds such as 1,3-cyclopentane, 1,4-cyclohexane, and 1,2-cyclohexane diisocyanate, m-phenylene, p-
Aromatic compounds such as phenylene, 414'-diphenyl, 1,5-naphthalene, and 1,4-naphthalene diisocyanate, 4,4-diphenylenemethane, 2,4
- or 2,6-tolylene or mixtures thereof, 4
, 117j-aromatic compounds such as 4'-toluidine and 1,4-xylylene diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate and chlorodiphenyl diisocyanate. Substituted aromatic compound, triphenylmethane-4+ 4's 4'-irisocyanate, 1.
3.5-) Liisocyanatebenzene and 2.4.6
-) Triisocyanates such as toluene, tetraisocyanates such as 4,4'-diphenyl-diphenyl-dimethylmethane-2,2',5,5'-tetraisocyanate and trimeric tolylene diisocyanates. There are polymeric polyisocyanates such as polyisocyanates and trimers.

Furthermore, the organic polyincyanates include polyethers that have been reacted with excess polyisocyanate to form isocyanate-terminated prepolymers, as well as fluoropolymers derived from polyols, including polyether polyols or polyester polyols. Good too. The polyols include single polyols such as the glycols of ethylene glycol and propylene glycol and other polyols such as glycerin, trimethylolpropane, pentaerythritol, and mono-ethers and polyethers such as diethylene glycol, tripropylene glycol, i.e. The above Q.) may be an alkylene oxide condensate.

Among the alkylene oxides that can be condensed with these polyols to form polyethers, there are vCij, ethylene oxide, propylene oxy r1 detylene oxide, styrene oxide, and the like. These are generally hydroxyl-terminated polyethers and may be linear or branched. Examples of polyethers include polyoxyethylene glycol, polyoxyprogylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxynonamethylene glycol, polyoxydecamethylene glycol, polyoxydadecamethylene glycol and mixtures thereof. There is. Other types of polyoxyalkylene glycol ethers can be used. Particularly useful polyether polymers include ethylene glycol, diethylene glycol, triethylene glycol, 1. d-Butylene glycol, 1,3-butylene glycol, 1,6-hexanediol and mixtures thereof, glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanediol, pentaerythritol, dipentaerythritol, tri It is derived by reacting polyols such as pentaerythritol, polypentaerythritol, sorbitol, methyl glucoside, sucrose, etc. with alkyleneoxy V such as ethylene oxide, propylene oxide, and mixtures thereof.

A particular class of aromatic polyisocyanates that can be used in the novel solvent-based coating compositions of the present invention are polymethylene polyphenols having the formula: It's Naat. The Upjohn, located in Mazu, Michigan
A compound sold under the trade name f-PAP by The Chemical Company has been found to be particularly useful in the compositions of the present invention, yielding compositions that exhibit the desired toughness in the final cured coating.

The active hydrogen-functional blocking agent to be reacted with the nlJ Re W + diisocyanate can be selected from a large number of blocking agents known to those skilled in the art. Preferred representatives of these blocking agents include (i) aliphatic, cycloaliphatic and aromatic alkyl monoalcohols, (11) hydroxylamines, (iii) oximes, (1) lactams, and selected from the group consisting of Any suitable aliphatic, cycloaliphatic or aromatic alkyl monoalcohol can be used as a blocking agent according to the present invention. For example, methyl alcohol,
Aliphatic alcohols such as ethyl alcohol, chloroethyl alcohol, propyl alcohol, tetyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, methylhexyl alcohol, decyl alcohol, and lauryl alcohol. Can be used.

Suitable cycloaliphatic alcohols include, for example, cyclopentanol, cyclohexanol, etc., but aromatic-
Alkyl alcohols include phenyl carbinol,
Methylphenyl carbinol, etc. A relatively non-volatile monoalcohol having a molecular weight of 1 ton can be used, if desired, to act as a plasticizer in the coating provided by the present invention. Examples of hydroxylamines that can be used as blocking agents include ethanolamine and propatoolamine.

Suitable oxime blocking agents include, for example, methyl ethyl ketone oxime, acetone oxime and cyclohexanone oxime. Among the lactams that can be used as blocking agents are 1IrJ-1-prolactam, -butyrolactam and pyrrolidone, while suitable triatrols include 1.2.4-tria.
R, 1,2.3-benzotriazole, 1,2.3
-) Lyltria-al and 4,5-diphenyl-
There are compounds such as 1,2,6-driasol. Particularly preferred active hydrogen-containing blocking agents are methyl ethyl ketoxime and 2-ethylhexanol.

The above general 4i of blocked polyisocyanate crosslinking agents
l], within the scope of the class, a particular class of blocked polyisocyanate crosslinkers that can be used in the novel solvent-based storage compositions of the present invention are incyanurate ring-containing blocked incyanate compounds. including. Generally, these blocked polyisocyanates are polyisocyanates containing isocyanurate rings). It can be formed by blocking with the blocking agent.

These compounds can be formed by ring-forming trifunctionalization of trifunctional isocyanates. Typically, the reaction does not stop at this stage, but continues through the formation of a multifunctional oligomer or a mixture of such oligomers and a portion of pure trifunctional polyisocyanate. Mixtures of trifunctional products and divine multifunctional oligomers are commercially available.

%, the desired blocked polyisocyanate crosslinking agent has a purity represented by the following formula: It is a blocked form of trifunctional incyanurate. -j- Specifically, this compound is disclosed in Co-pending Application No. 368,178, filed April 14, 1982, the disclosure of which is herein incorporated by reference.

(II), =j-! Goester Modified Blocked Polyisocyanates More specific blocked polyisocyanates useful as crosslinking agents in the novel solvent-based compounding compositions of the present invention are prepared from special classes of oligoester diols and triols. This is an oligoester-modified blocked polyisocyanate. A first type of such olivinister-modified blocked polyisocyanates has one incyanate group that is more reactive than the other, and this more reactive isocyanate group is blocked first with a blocking agent, leaving the remaining The isocyanate groups are then prepared from an organic diisocyanate having inocyanate groups which have been reacted with the hydroxyl functionality of the oligoester diol or triol described above. A second type of oligoester-modified blocked polyisocyanate involves reacting an oligoester diol from an olivinister of the type described above with an excess of an organic diisocyanate to form an inocyanate-terminated sol polymer, and then It can be produced by blocking isocyanate groups with an active hydrogen-containing blocking agent. Each of these materials is particularly useful in the compositions of the present invention and produces a final cured coating composition that exhibits excellent flexibility.

The shaped oligoesters used in the preparation of these crosslinking agents are 19
U.S. Patent No. 4, issued on June 60, 1982.
322.508. Material (1)
Hydroxy-functional oligoesters within the useful class of (II) have a number average molecular weight (Mn) between about 150 and about 6000, preferably between about 2'30 and about 1000;
Has 2 or 6 hydroxyl groups per molecule! 2,
and (Iil) is formed by an ester reaction between a carboxylic acid and an epoxide. The esterification reaction product is composed of (a) a polycarboxylic acid, i.e., an esterification reaction product of a carboxylic acid having two or more carboxyl lid+ and a monoepoxide; (b) a polyepoxide, i.e., two or more carboxyl lids. an esterification reaction product of a compound having an epoxide group with a monocarboxylic acid, preferably a monocarboxylic acid that does not contain ethylenic unsaturation and has no hydroxy functionality, (C) a hydroxy-functional carboxylic acid and a monoepoxy v
-! esterification reaction product of bamboo polyepoxide, preferably monoepoxide, (d) monocarboxylic acid and hydroxy-functional monoepoxide 3
The esterification reaction product is an esterification reaction product selected from the group consisting of an esterification reaction product of an e-oxide or a polyepoxide, preferably a monoepoxide, and a mixture in dimensions (θ)(a) to (d).

As mentioned above, the first type of oligoester-modified blocked polyisocyanate crosslinkers consists of (i) converting an organic diisocyanate having one inocyanate group more reactive than the other to all the more reactive inocyanate groups; to provide a semi-blocked diisocyanate;
(11) is then prepared by reacting this semi-blocked intermediate with the oligoesters discussed above. The organic diisocyanates and active hydrogen-containing blocking agents used in this synthesis are discussed above in connection with the incyanurate ring-containing blocked isocyanate crosslinkers useful in the compositions of the present invention. The organic polyisocyanate-blocking agent adduct intermediate is prepared by reacting enough of the blocking agent with the organic diisocyanate to ensure that one of the two -NCO groups on the diisocyanate reacts. It is formed. The reaction between the organic diisocyanate and the blocking agent is exothermic and therefore the diisocyanate and blocking agent are heated at a temperature of no more than about 80°C, preferably about 80°C to minimize exothermic effects. Preferably, the mixture is mixed at a temperature below 50"C.

This intermediate is then combined with the oligoester diol or triol so as to react substantially all of the free or unblocked polyisocyanate of the diisocyanate/blocking agent intermediate with the hydroxyl groups of the oligoester. will be reacted to. This reaction is desirably conducted at a temperature of about 80'C to 120C.

Also as discussed above, a second type of oligoester-modified blocked polyisocyanate crosslinker useful in the novel, solvent-based coating compositions of the present invention is to convert the excess of organic diincyanate into oligoester-modified blocked polyisocyanate crosslinkers. and the terminal isocyanate groups formed on the resulting prepolymer are then reacted with an active hydrogen-containing blocking agent so as to react with substantially all of the incyanate groups. Manufactured by The diisocyanate starting material is
A sufficient amount of excess is used to ensure that the intermediate is isocyanate terminated. Therefore, it is preferable that the organic diisocyanate and the dihydroxy-functional oligoester are reacted in a molar ratio of greater than 1:1 to 2=1. Numerous diisocyanates of the type mentioned above can be used in the preparation of this intermediate. Although it is not necessary that one isocyanate group be more reactive than the other, the preparation of this type of crosslinker does not preclude the use of such materials.

The coating compositions of the present invention have been found to provide cured coatings having the advantageous physical properties described above over a wide range of cure temperatures. More precisely, the coating composition according to a preferred embodiment of the invention is about 1200C! or lower temperature, for about 15 minutes or less, but still for about 2 [IW of JOoC or higher] for up to about 60 minutes or more for '1' products (J4 r Taken together with the storage stability of coating compositions which have been found to suffer no significant deterioration of their advantageous physical properties, it can be readily appreciated that the present invention represents a very significant advance in coating composition technology. It is within the skill of the art to determine the appropriate volatile organic content for a given coating composition and application of the present invention.

Preferred solvents have relatively low volatility significantly below their boiling point so that solvent evaporation is low during storage and/or application of the coating composition to a substrate. Suitable solvent systems include, for example, toluene, methyl ethyl ketone, isobutyl acetate, xylene, cellosolve acetate and mixtures of any of these.Other solvents that may be used include terpenes, aliphatic and aromatic naphthas. . Further suitable solvents are commercially available and will be apparent to those skilled in the art in view of this disclosure.

Any solvent that may remain in the cured coating must be inert so as not to adversely affect the cured material or other coatings used with the coating during the curing process or thereafter. Preferably, the cured coating is substantially free of solvent.

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

Conventional epoxy ester automotive spray applied primer coating compositions have a volatile organic content of approximately 540 g/l
Comparable coating compositions of the present invention are known to require a temperature of 27°C (80″F) suitable for spray application techniques.
A VOC of 430 i/l or less is required to give a viscosity of about 18 seconds in a Ford cup 7"#4. Generally, for coating compositions cast onto a substrate, 2
Preferably, sufficient solvent is used to give a viscosity of from about 18 seconds to about 22 seconds in a Ford cup #4 at 7°C (80”F). It need not be formulated as a "solid" composition. Rather, the composition may have a higher VOOf to provide a higher image viscosity. Similarly, the coating compositions of the present invention need not be formulated as sprayable compositions. Rather,
This composition may have higher solids content and viscosity.

flow control agents, e.g. polybutyl acrylate, wetting agents,
For example, a large number of silicones, pigments, pigment dispersants, corrosion inhibitors, such as chromate pigments, all known in the art, can be used in the coating compositions of the present invention. Additionally, suitable reactive diluents may be used, including low molecular weight diol flow control agents and reactive diluents. According to another aspect of the invention, a coating is provided on a substrate, the coloration being After curing, the coating composition of the invention contains a crosslinked polymer product. The coating composition may be a low solids composition, ie, the composition may have a high voa H, but is generally a 71 isolid composition, ie, a low Woo? It is preferable to have one. This composition is
It can be applied by any conventional method including brushing, dipping, pouring, spraying, etc. Spraying is generally preferred for applying the composition as an automotive primer. For reasons discussed below, the novel epoxy ester resins of the present invention:
) and is particularly advantageous for the formulation of isolid coating compositions. To this end, the present invention has been developed using the following methods: xyester resin is
Preferably, it has a number average molecular it (Mn) of about 900 to about 5000. In this regard, coating compositions of the present invention using the preferred epoxy ester resins described above have volatile organic content levels from about 347.9// to 467
,! Low content of 9/l trench (from 2.9 bonds/gal to 6.9 bonds/gal), more preferred range 695
It is suitable for application to substrates by spraying even though it is formulated at &/l to 467 g/zl (3.3 py/gallon 3.9 Mnt/gallon).

Hardening of the coating composition requires baking at a sufficiently high temperature for a sufficient time to allow the crosslinking agent to react with the epoxy ester resin. The time and temperature required to cure the coating are interrelated and depend on the particular epoxy ester resin, crosslinker, solvent and other materials, if present, and the amounts of each making up the coating composition. Using a volatile organic content of about 431&/r (3.6 bonds/gallon) and choosing the preferred ingredients described above, baking times and temperatures typically range from about 15 minutes to about 60 minutes and about 135"C, respectively. to 165"'C (275'
-'F to 325'F'). The coating composition according to the preferred embodiment of the invention described above is coated at a temperature of about 150'
C (300"F) VC coatings have been found to give the best coating results when applied for 20 minutes. However, these same coating compositions have been found to give the best coating results when applied for example
The ability to withstand extended periods of approximately 6 u minutes at elevated temperatures (! (390F)) is a significant mold cost advantage of the present invention. Allows great flexibility in both design and implementation.Thus, in automotive assembly, vehicles that are forced to remain in curing ovens for long periods of time during unplanned assembly line shutdowns are hardened and damaged. Collected with untreated coating.

High solids coating compositions according to the invention comprising the novel crosslinkable epoxy ester resins of the invention, in particular the preferred resins described above, and blocked polyisocyanate crosslinkers, especially the preferred materials described above, are based on conventional epoxy esters. It has been found that the present invention provides cured coatings with corrosion resistance comparable to low solids sprayable coating compositions. Therefore, a significant reduction in volatile organic content would represent a highly advantageous advance to the industry.

The most preferred use of the coating compositions of this invention is as a high solids sprayable primer for use on bare metal substrates such as domestic or industrial appliance housings or motor vehicle bodies. Primer compositions are typically pigmented and include carbon black, monoarsenic acid, lithopone, magnesium silicate, silica, barium sulfate, TiO2, yellow lead, calcium chromate, strontium chromate, zinc chromate. Any pigment that is commonly incorporated into Zolimer compositions for metal substrates such as potassium and acrylic dispersion top coats can be used. The primer can be pigmented by known methods, including, for example, grinding the pigment into a portion of the curable resin and then adding it to the primer composition.

The pigment to binder ratio of the primer is preferably as high as 4:1 in coulometric ratio, depending on the condition of the metal substrate. However, the pigment to binder ratio weight is approximately 1 =
It is preferable to use a primer having a ratio of 1 to 2:1.

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

The solvent system can be any suitable combination of the aforementioned organic solvents. For high solids I@mistable automotive solimeers, the solvent preferably comprises a total of about 35% by weight from about 25M of the total coating composition, although of course larger or smaller amounts may be used depending on the desired solids content. can. For example, it may be desirable to formulate the primer at a relatively high solids content and then thin the primer to a spray consistency prior to application.

The metal substrate can be, for example, aluminum, steel, or phosphated cold rolled steel. However, any metal used as a structural material can be used. The primer composition can be applied to the metal substrate by any conventional method such as rolling, brushing, curtaining, etc. A preferred method of applying the fryer composition to metal is by spraying. The primer is cured at elevated temperatures by any convenient means, such as a baking oven or a bank of infrared heat lamps. Suitable curing temperatures are discussed below.

Fryer primers are generally manufactured using conventional thinners such as aromatic hydrocarbons, essentially aromatic commercial petroleum distillates.
It is diluted to about 60% to about 70% for shell spray, then sprayed onto a metal substrate and then cured. The primer is cured at elevated temperatures by any suitable means, such as a baking oven or a bank of infrared heat lamps. The appropriate curing temperature is A
This is il6 of il. The hardening temperature is preferably about 135" (D) to about 165° C., although hardening temperatures from about 100" to about 230° C. can be used if desired.

The invention will be further understood with reference to the detailed examples below. It should be understood that the specific examples are shown by way of illustration and not by way of limitation.

Unless otherwise specified, all references to 1 part are intended to mean all parts by weight.

Liu 1 This example illustrates the production of epoxy ester resin according to the present invention. In a suitable reactor, add Epon 829™ Shell Chemical Company (bisphenol-
1,248 parts of diglycidyl ether of A), 642 parts of bisphenol-A, 466 parts of En4'Neil 1014™ Emery Industries, Incophorated (dimer acid), and 1400 parts of soybean fatty acid were charged. Reduce the temperature of this mixture to approximately 177°
At this point an exothermic reaction occurred which raised the temperature to approximately 193°C (690"F). After 2 hours at this temperature, the acid number was found to be 5.9. The reaction mixture was then heated to about 149°C.
(300-F) and then methyl amyl ketone 8
66 parts were added. The resulting resin had a viscosity of T1/2 at a solid content of 80% and fr.

The epoxy ester resin according to the invention is generally [+11
manufactured by the method. The ingredients used are shown in Table 1 below. Jepoxy V1 dicarboxylic acid, fatty acid and diphenol, along with catalyst (sodium carbonate) if present;
A suitable reactor was charged.

This mixture was heated to approximately 177°C (65D'F). At this point, the temperature should be increased to approximately 188°C to 199°C.
An exothermic reaction occurred at temperatures up to (370"F to 390°F). The reaction was continued at this temperature until the acid number dropped below 6.

The product was cooled to about 121°C (250'T?) and then diluted to 80% nonvolatile content with methyl amyl ketone. In Table 1, the total amount is shown in parts by weight.
t.

Table 1) Siri 2 3 4 5 Epon 829' 1248 1248DBR
IS31”
1248 Epon 8283
1248 Empol 1016'
46ro 46ro 465 463 Bisphenol A 342 342 342
342 Reed f[il II fatty acids 140
0 Pamolyn 2005 14
00 soybean fatty acid
1400 1400 Sodium carbonate
1.2 Methyl amyl ketone 863 863 863 B<53 non-volatile content, CH 80.0 79.8 79.
6 79.8 Viscosity T"/2 T"/'a
V v1/2 acid value 5.6 4.9 5.2
5.9L Commercial Company, Shell Chemical Company (
Chevoxide, especially bisphenol-A epichlorohydrin epoxy resin), 2. Trademark, Dow Chemical Company (Gepoxide), 3. Trademark, Shell Chemical Company (Gevoxide), 4. Trademark, Emery Industries, Inc. Rated (Dimer Acid), 5, Trademark, Vercules Inc., Wilmington, Praue. (Light Color, Color Stable High Purity Grade Linoleic Acid).

1+! I6 The epoxy ester resin according to the present invention is added to a suitable reactor using an Araldye RD-2™ Civer-Geigy®.
Corporation (diglycidyl ether of 1,4-butanediol) 994 parts, bisphenol-A 342 parts, Enball 1014™ Emery Industries, Inc. (reimeric acid) 466 parts, soybean fatty acid 1400 parts and sodium carbonate 1 part. Produced by charging .5 parts. An exothermic reaction occurs which raises the temperature of the mixture to about 177°0 (350°F), at which point the temperature increases by 196'C (380'F) K'. After 1 hour at this temperature, the acid value is approximately 5
．． It turns out that it is 8. The reaction mixture is then cooled to about 300-F and then 772 parts of methyl amyl ketone are added. The resin obtained has a viscosity P1 at 8 υqb solids content.

U7 This section will specifically explain the production of epoxy ester resin according to the present invention. In a suitable reactor, add Epon 829
Cm4M) Shell Chemical Company (31,248 parts of diglycidyl ether of bisphenol-A, 530 parts of bisphenol-A, and 1186 parts of soybean fatty acid were charged. The temperature of the mixture was adjusted to about 177°C (,650"
F) and at this point the temperature was increased to 196 °C (5
An exothermic reaction occurred which raised the temperature to 80°F J. After 60 minutes at this temperature, the acid number was found to be 0. The reactor mass was then cooled to about 149°C (0OO"F) and 741 parts of methyl amyl ketone was added.
The resulting resin has a viscosity of T1/! at 80% solids. It had

Epoxy ester resins according to the invention from Examples 8 to 11 were prepared generally by the method of Example 7. The ingredients used are shown in Table 2 below.

The diexoxide, dicarboxylic acid, fatty acid and diphenol were charged to a suitable reactor along with the catalyst (sodium carbonate) if present. This mixture was heated to approximately 177°C (350°F).
) J.

In this regard, the temperature should be increased from about 188°C to 199°C (
An exothermic reaction occurred from 370'F to 390"F. The reaction was continued at this temperature until the acid number dropped below 6. The product was reduced to 80% non-volatile content with methyl amyl ketone. In Table 2, all the depths are shown in Higashi Ayabe.

Table 2 Example 8 9 10 11 Epon 829'-500500 DER33 Ro2 500 Evo 7B2B"
500 bisphenol h 212 212
212 212 Oil fatty acid in the trench 475 Vamorin 200' 475 Soybean fat I
W acid 475 47
5 Sodium carbonate
0.5 methyl amyl ketone 297 2
97 295 297 Non-volatile content Ch 8
UJI 79.8 79.6 79.8 Hiring
V W X X'/2 acid value
0.9 1.1 0.9 0.91, Shell Chemical Company (Geboxide, especially bisphenol-A epichlorohydrin epoxy resin), 2, Trademark, Dow Chemical Company (Gepoxy V
), 3.Trademark, Shell Chemical Company (Gepoxide), 4.Trademark, Vercules Inc., Wilmington, PR, (Light Color, Color Stable High Purity Gray), + IJ Noric Acid).

Example 12 An epoxy ester resin according to the invention was produced.

In a suitable reactor, add 268 parts of Araldye) RD-2™ Civar x Iggy Corporation (diglycidyl ether of 1,4-7' tandiol), 159 parts of bisphenol-A, 112 parts of soybean fat, and 0.3 parts of sodium carbonate. The parts were charged. This mixture was heated to about 177°0
(350"F), at which point an exothermic reaction occurred which raised the temperature to 196°C (380"F). After 1 hour at this temperature, the acid number was found to be 1.2. The reaction mixture was then heated to about 149°C.
(300”F) and then methyl amyl ketone 13
Added 4 parts. The resulting resin had a viscosity of O at 80% solids.

""Yo An epoxy ester resin according to the invention was produced.

A suitable reactor was charged with 392 parts of Epon 829™ Shell Chemical Company (diglycidyl ether of bisphenol-A), 174 parts of 4,4'-dihydroxydiphenyl sulfone, and 112 parts of soybean fatty acid. The temperature of the mixture was raised to about 177°C (50"F) at which point the temperature was increased to about 200°C (92"F).
An exothermic reaction occurred which increased F). After 1 hour at this temperature, the acid number was found to be 0.8. The reaction mixture was then cooled to about 149°C (OO'F) and then 152 parts of methyl amyl ketone were added. The resulting resin had a viscosity of X+ at 80% solids.

Example 14 This example illustrates the production of an epoxy ester resin according to the present invention. In a suitable reactor, add Epon 829™ Shell Chemical Company (bisphenol-
Diglycidyl ether of A) 911 parts, Empol 10
14(TM) Emery Industries Inc. 564 parts of dimer acid and 7 parts of soybean fatty acid
28 parts were charged. Reduce the temperature of this mixture to approximately 177°C (6
50'F)'f, at which point the temperature is approximately 1
An exothermic reaction occurred which raised the temperature to 96°C (380'F). After 2 hours at this temperature, the acid value was found to be 5.2. The reaction mixture was then heated to about 149°
0 (300"F), then 275 parts of methyl amyl ketone and 275 parts of cellosolve acetate were added. The resulting resin had a viscosity of W +
'I had one.

1+! Epoxy ester resins according to the invention from Example 115 to Example 1B were prepared generally by the method of Example 14. The ingredients used are shown in Table 6 below.

The dieboxide, fatty acid and dimer acid were charged to a suitable reactor along with the catalyst (carbonate) if present. The mixture was heated to about 350°F. At this point, the temperature should be increased from about 188°C to 19°C.
An exothermic temperature increased by K to 9°C (670-F to 390"F'!j) occurred. The reaction was continued at this temperature until the acid number decreased below 6. Then: The product was cooled to about 121°C (250″F) and then diluted to 80% non-volatile content with methyl amyl ketone. In Table 3, the amount of 1-beta is shown in terms of weight.

Table 6 Example 15 16 17 18 Epon 82
9 Upper 500 500DER333
2500 Epon 8283
500 Empol 1016' 509 309
Ro09 309 Linseed oil fatty acid 400 Vamorin 2005400 Soybean fatty acid 400
400 sodium carbonate
0.5 methyl amyl ketone 300
500 300 300 Non-volatile content%
80.0 79.8 79.6 79.8 Viscosity x x y y1 Oxygen value 5
．． 2 4.8 5.6 5.81, Trademark, Shell Chemical Company (Jepoxy-1 especially bisphenol-A shrimp chlorohydrin epoxy resin), 2, Trademark, Dow Chemical Company (Diebogicide), 3, Commercial. a4, Shell Chemical Company (Dieboxide), 4, Trademark, Emery Industries Inc. P (Dimer Acid), 5, Trademark, Vercules Inc., Wilmington, Prairie 0 Shio 1J19 Invention An epoxy ester resin was produced by.

In a suitable reactor, add Araldye) RD-2™ ChipperGeigy Corporation (diglycidyl ether of 1,4-butanediol) 622? J, Emball 1U14 (trademark) Emery Industries Inc. yl? 564 parts of rated (dimer acid), 728 parts of soybean fatty acid, and 1.0 part of IJum carbonate were charged. The temperature of this mixture was increased to approximately 177"C (350"F), at which point the temperature was reduced to 193C (filter 80"F).
An exothermic reaction occurred which increased the temperature to 'F'. After 1 hour at this temperature, the acid number was found to be 5.2. The reaction mixture was then heated to about 149°C (300°C).
'F)K Cooled and then 500 parts of methyl amyl ketone were added. The resulting resin had a viscosity R at a solids content of 80 mm.
The composition pigment paste was prepared by preparing the following mixture in a ball mill: Example 5 (millbase A), Example 11 (millbase B) or Example 1.
It was produced by crushing 14Y with 264 parts of 1 type B (resin paste of pigment mill C).

Composition Barium sulfate 1626 Red radish 60 Titanium dioxide 105 Silica 75 Strontium chromate 99 Polyethylene wax 48 Xylene
200 Toluene 240 2-Ethylhexanol 57 Example 21 A blocked isocyanate crosslinker useful in the compositions of the present invention was prepared. A suitable reactor was charged with 417 parts of PAPIS 80™ from The Upjohn Company (Kalamazoo, Mich.) under a nitrogen blanket.

261 parts of methyl amyl ketoxime was added over 30 minutes keeping the temperature below 210"F by external cooling. After the addition was complete the temperature was kept at 21D'FK for an additional hour.
At this time, complete reaction of incyanato was confirmed by RE. The patch was then diluted with 226 parts of methyl amyl ketone. The resin obtained had a viscosity of Z6'' at a solids content of 75% l'i.

” Shij to I+! Blocked in cyanate crosslinkers useful in the compositions of the present invention up to 125 were prepared from the components shown in Table 4 generally in the manner described in Example 21.

Table 4 Example PAPI -27239'9 Desmojiurue L3 5
25 Methyl amyl ketoxime 174 2
61 87 Penzotriazole 2
6B Methyl amyl ketone 133 150
220 Non-volatile content% 80.0 80
．． 1 75.1 57 Viscosity Zl″l/2Z7
Z2 Zl, Trademark, Mobay Chemical Corporation (Bitts Park, Pennsylvania), 2. Trademark, The Upjohn Company (Kalamazoo, Michigan), 3. Dark [, Mobay Chemical Company (Pennsylvania) , Kalamazoo).

Example 26 Into a suitable reactor, add Hylene T™ EI DuPont de Nemois & Co. (2,4-)ruene diisocyanate) 400
The sample was charged under a nitrogen blanket. 200 parts of methyl ethyl ketoxime were added over 30 minutes while keeping the temperature below 110'F with external cooling. After the addition was complete, the reaction mixture was held at 110"F for an additional hour.

At this point, the Nco conversion was measured to be 50%. Castor oil
l) C D I Custer Oy/l/ (D
, 1. (!astor oll) 1. X, Pencer Kellogg Textron Incorporated)'
All 787 parts of dibutyltin dilaurate and 1 part of dibutyltin dilaurate were added in 60 minutes while keeping the temperature below 210'F. One hour after the end of the addition, the infrared absorption spectrum of the product showed that all incyanate groups were present. was found to have reacted. The batch was then diluted with 346 parts of methyl amyl ketone. The final product had a solids content of 77
．． At 1%, the viscosity was Z4+k.

Example 27 1515 parts of Hylen T™ E.I. DuPont de Nemois & Company (2,4-tolylene diisocyanate) were charged to a reactor under a nitrogen blanket. 757.5 parts of methyl amyl ketoxime were added in 1 hour while keeping the temperature below 110° F. with external cooling. After the addition is complete, let the batch cool for 1 hour.
I kept it at 70'F. At this point, 1.5 parts of dibutyltin dilaurate was added to the reaction mixture and then 1,4-
342 parts of butanediol were added over 1 hour. The temperature of the reaction was kept below 220''F. One hour after the end of the addition, the infrared spectrum of the product showed that all incyanato groups had reacted.

The batch was then diluted with 666 parts of methyl ethyl ketone. The final product had a viscosity of z4+ at a solids content of 80.0%.

Example 28 In a suitable reactor, add 2.4-)luene diincyanate 1
515 parts were charged. 1335 parts of oliyestyl (the reaction product of 7" lobilene oxide and azelaic acid) were added over 2 hours under a nitrogen blanket. The reaction mixture was maintained between 180"F and 200"F during the addition. The reaction product was kept under 200°C for an additional 2 hours, at which point the NC
The O hit rate reached 50%. 757.5 parts of methyl amyl ketoxime was added over 1 hour, during which time the temperature was
It was kept below 210'F. At the end of the addition, 898 parts of methyl ethyl ketone were added to the reaction mixture and the NCo content was 1
Investigated by R. The final product had a viscosity of 23 at a solids content of 80 parts.

Example 29 A blocked isocyanate crosslinker useful in the compositions of the present invention was prepared as follows. 2. 6 moles of 4-tolylene diisocyanate are weighed into a 21 round bottom flask equipped with a stirrer, reflux condenser, temperature side and heating mantle, then 2-ethylhexanol (6 moles) is added dropwise over 40 minutes. did. Temperature the reaction to 50°C using a cold water bath.
The flask was then flushed with dry nitrogen to maintain an inert atmosphere during the reaction. 2
The conversion rate was determined to be 49.7 by measuring the incyanate concentration in the diptylamine solution after a period of time.
%Met. Potassium octoate (0.0% for solids content)
55%) El was added to the flask. An exothermic reaction occurs,
Add 500g of cellosolve acetate and bring the exothermic reaction to 1.
Stopped at 25°C. Temperature # drops and then 10
It was kept at 5°C. After 2 hours, the trimer conversion rate was 198%, and then the reaction was stopped. The crosslinker was purified by repeated recrystallization using cellosolve acetate and hebutane.

Example 30 A blocked isocyanate crosslinking agent useful in the compositions of the present invention was prepared as follows. 2.0 mol of 2,4-tolylene diisocyanate were placed in a round bottom flask equipped as in Example 29, and then methyl ether ketoxime (2.0 mol) was added dropwise over 60 minutes. The temperature was kept above 45°C and the flask was flushed with nitrogen for 7 times. Heat this mixture to 65"O,
Then potassium octoate 0.8. ! 9 (0.15% on solids) was dissolved in xylene 50.9 and then added dropwise to the reaction mixture. After 60 minutes, the temperature rose to 85°C and then 5 oyf more of xylene was added. After 1 hour, the NCo conversion was 91.6. Potassium octoate c0.06'1b) 0. '! RFJ Kishin 1D
DjiK was dissolved and added to the reaction mixture. After 45 minutes, 100% conversion to trimer was obtained. The crosslinker was purified by repeated crystallization using methyl ethyl ketone and heptane.

Shio031 Blocked isocyanate crosslinkers useful in the compositions of the present invention were prepared as follows. Isophorone diisocyaner) 3. [3 moles were weighed into a VC round bottom flask equipped as in Example 29 and then 7 drops of dibutyltin dilaurate melt were added. 6 mol ft of 2-ethylhexanol was added dropwise over 45 minutes. The temperature was kept below 50'C while the flask was flushed with nitrogen. After 1 hour, potassium octoate (0 for solids content)
．． 18%) 2.0 # was added and the reaction temperature was then increased to 80°C in 60 minutes. An additional 2.4 I of potassium octoate was added. After 1 hour at 100C, the infrared spectrum showed no Neo peak, indicating that the reaction had stopped. Crosslinker Recrystallized from Heptane Example 62 A blocked isocyanate crosslinker useful in the compositions of the present invention was prepared as follows. 3.0 moles of inphorone diisocyanate are weighed into a round bottom flask equipped as in Example 29 and then dibutyltin dilaurate 8
Added a drop. Methyl ethyl ketoxime (6,0 mol)
was added dropwise over 1 hour, then the temperature was kept below 50° C. while flushing with nitrogen. After 3D minutes,
The NCO conversion specific gravity ratio was 49.8 qb. Potassium octoate 1.2 g (section 0,13)? In addition, the temperature is 3
Over 0 min it rose to 80' (3.0% potassium octoate was added, then the reaction temperature started to rise to 0
To control the temperature to 120°C, cellosolve acetate (1009f) was added. After 8 hours, the trimer conversion rate was 88.75%, and no further progress was made. cellosolve acetate) 50. ! i' and methyl ethyl ketoxime28. F was added and then the reaction was stopped. The crosslinker was purified by repeated recrystallization from toluene and heptane.

Examples 66 through 40 each produced a coated composition according to the present invention suitable for use as a vinelid sprayable pigmented primer for application onto bare, unpolished steel automotive vehicle body panels in an automotive vehicle assembly operation. Each of the coating compositions shown in Table 5 below was heated with methyl amyl ketone at 27°C < 80°C.
“F) in Ford Cup #4 from about 18 seconds to 25
It was diluted by seconds to give the desired spray viscosity. It can be seen in Table 5 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 as in Column 33, Example 64 and Example 35Vc.
All quantities are shown in heavy weights.

In Example 49-i from Ushio 041, for example, a high solids, sprayable pigmented Zolaimer for application onto unpolished steel automotive vehicle body panels on the ridge in an automotive vehicle assembly operation [7]. Coated compositions according to the invention are further prepared as shown in Table 6 below. Note that the use of a desiccant is optional, as in the coating compositions specifically shown in Table 6. The epoxy ester resin used in each coating composition is identified by reference to the example in which the resin was prepared. All jft 'f- parts by weight.

The coating compositions of Examples 5U through 57 and Examples 33 through 40 were 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 7 below. Corrosion is measured as inches of corrosion from the brush line after a 240 hour Q9 water resistant fog. Moisture resistance is
Qualitatively evaluated after exposure to condensing humidity at 46°(:!(110°F)°).

Examples 5B to 65 Coatings according to the invention suitable for use with high solids sprayable pigmented Zolimer and L7 for application onto bare, unsanded heavy steel automotive vehicle body panels during automotive vehicle assembly operations. A composition was produced. The components of the composition to be contacted are shown in Table 8 below. Each coating composition is diluted with methyl amyl ketone in a #4 Ford cup at 27°C (80'F) for about 18 to 25 seconds to give the desired spray viscosity. It can be seen that the use of a desiccant agent which catalyzes the reaction of the fatty double bonds and further imparts crosslinking to the cured resin is one option.

In Table 8 all amounts are given in parts by weight.

Examples 66 to 74, for example, each coated with a coating composition according to the invention suitable for use as a high-solid P-pigmented pigmented primer for application onto bare, unpolished steel motor vehicle bodies during motor vehicle assembly operations. , produced by Hata et al., as shown in Table 9 below. 9th
It should be noted that the use of desiccants is optional, as in the coating compositions specifically shown in the table. The epoxy ester resins used in each coating composition are determined with reference to the examples in which the resins were manufactured. All amounts are given in parts by weight.

■75 to Example 82 coating compositions from Example 58 to FI+ 65 were applied to the bare,
Unpolished bonderite steel was coated with a similar mist, and then tested for corrosion resistance and humidity. The hardness plan and test results are shown in Table 10 above.
Measured as inches of scribe line corrosion after IJJ salt spray. The erosion resistance was qualitatively evaluated after shaking at 46°G (110″0) and longitudinal humidity VC roughness L7.

411L-□ξj-1L? -Up 901]□"e-
A coating composition according to the present invention suitable for use as a sprayable pigmented primer for application onto stock, unpolished steel motor vehicle body panels was prepared during each motor vehicle assembly operation. The coating composition components are shown in Table 11 below. Each coating composition has methyl amyl ketone,
It was diluted with Ford Katsuzo #4 at 27°C (80″F) from about 18 seconds to 25 seconds to give the desired spray viscosity.

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 86, Shio 1184, and Examples 85, is optional. In Table 11, all quantities are expressed in terms of weight.

Examples 91 to 99'! Coating compositions according to the present invention suitable for use as high solids sprayable pigmented primers for application onto bare, unpolished steel motor vehicle body panels during motor vehicle assembly operations are prepared as follows: Manufactured as shown in Table 12. Note that the use of a desiccant is optional, as in the coating compositions specifically shown in Table 12. The epoxy ester resin used in each coating composition is identified by reference to all examples in which this resin was prepared. All canes are given in parts by weight.

The coating compositions of Examples 100 through 107 e/1186 through Example 90 were 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 16 below. Corrosion is measured as inches of corrosion from the scratch line after 240 hours of salt spray. Moisture resistance is exposed to condensing humidity at 46°G (110'F) [
7 and then qualitatively evaluated.

Display of the 1-1 incident, Mr. W1 Special Agency Director General, 1980, 1985, 1985, 1985, Special #T [i No. I 80910
No. 3 Coating Composition 3, Compensator's IT's 31 Applicant 11
Company Name Ford Motor Company (Name: 04, Generation J!11, 5, Hli Positive Order River) Showa Year Month l' Agency supplementary increase in number + jl Number of J - 567 =

Claims (1)

[Claims] +IIA, a dieboxide and (i) a first reactant selected from dienols, dicarboxylic acids, and mixtures thereof;
and (11) number average molecular needle (Mn) which is a reaction product of fatty Uj acid with a size of about 900 to about 5000? xyester resin (the reaction of the dieboxide with the first reactant and the second reactant occurs substantially simultaneously at a reaction temperature of at least about 135°C; and fatty acid carboxyl functionality in relative proportions of approximately 1:0.2-0.6:(], 1-0.4, respectively)
B, a blocked polyisocyanate crosslinking agent containing at least one incyanate group blocked by reaction with an active hydrogen-containing blocking agent The polyisocyanate crosslinking agent has about 0.5 and about 1.6 polyisocyanate groups per reactive group on the epoxy ester resin during deblocking at the curing temperature of the composition of the blocked isocyanate groups. A novel organic solvent-based thermosetting coating composition characterized in that it consists of: (2) The blocked polyisocyanate is based on the solvent of claim 1, wherein the blocked polyisocyanate is selected from blocked aliphatic, aromatic, cycloalkylene, aliphatic aromatic and nuclear substituted aromatic polyisocyanates. A thermosetting coating composition. (3) The blocked polyisocyanate crosslinking agent is comprised of a blocked polymethylene polyphenol isocyanate having the formula before blocking, where n i , J is equal to 1 to 3. 1. Solvent-based thermosetting coating composition of item 1. (4) The solvent-based thermosetting coating composition of claim 1, wherein the polyisocyanate used to prepare the blocked polyisocyanate crosslinker comprises a polymerized polyisocyanate. (5) The polyisocyanate used in the production of the blocked polyisocyanate crosslinking agent is an isocyanurate ring-containing polyisocyanate produced by ring-forming diisocyanate. Solvent-based thermosetting coating compositions. (6) The blocked polyisocyanate crosslinking agent has the formula (wherein R is selected from the group consisting of aliphatic, cycloaliphatic and aromatic groups and combinations thereof, and 6. A solvent-based thermosetting coating composition according to claim 5, consisting essentially of a blocked trifunctional incyanate represented by (residues of). (7) the polyisocyanate used in the production of the blocked polyisocyanate crosslinker consists of an incyanate-terminated prepolymer prepared by reacting a polyol with an excess of polyisocyanate;
A thermosetting coating composition based entirely on a bath medium according to claim 1. (8) The blocked polyisocyanate crosslinking agent has the formula (A) (i) % (wherein R is selected from the group consisting of aliphatic, cycloaliphatic and aromatic groups and combinations thereof) an organic diisocyanate represented by (11) in which one of the inocyanate groups is more reactive than the other; Claim 1 prepared by reacting with an active hydrogen-containing blocking agent represented by (B) and then reacting the reaction product of (A) with sufficient polyol to react with the remaining incyanato groups. A thermosetting coating composition based on the solvent of paragraph (9) wherein the polyol is (i) a number average molecular paper (
Bodhisattva n) has between about 150 and about 3,000, and (1
1) selected from oligoester diols and triols formed by an esterification reaction between a carboxylic acid and an epoxide, said esterification reaction product being (a)
(b) a polyepoxy P and a monocarboxylic acid containing no ethylenic unsaturation and no hydroxy functionality; (C) a hydroxy-functional carboxylic acid and a monoepoxide; (d) a monocarboxylic acid and a monoepoxide; 8. The solvent-based thermal solvent of claim 8 selected from the group consisting of esterification products of carboxylic acids and hydroxy-functional monoepoxides, and (e) mixtures of (a) to (d). Curable coating composition. 00) The dieboxide is selected from the group consisting of bisphenol-A bichlorocohydrin epoxy resin, hydantoin epoxy resin, cyclic and acyclic aliphatic dieboxides, etc., and any mixtures thereof. The solvent-based thermosetting coating composition of paragraph 4, paragraph 5, paragraph 7 or paragraph 8. αD The dicarboxylic acid consists essentially of the reaction product of a C-18 fatty acid. Claims 1 and 4
The solvent-based thermosetting coating composition of paragraph 5, paragraph 7 or paragraph 8. (121) The solvent-based thermoset coating composition of claim 11, wherein said fatty acid consists essentially of soybean fatty acid. θ3) said dieboxide consists essentially of diglycidyl ether bisphenol-A resin. and the diphenol consists essentially of the dimer acid reaction product of C-18 fatty acids, the diepoxide, the diphenol, the dicarboxylic acid and the fatty acid, respectively, in relative proportions by weight of 1:0.
．． 2-0.4: O, used in 6-0.520.9-1.2, claims 1, 4, 5
The solvent-based thermosetting coating composition of paragraph 7 or paragraph 8.