CA1307607C

CA1307607C - Reactive coatings comprising and acid-functional compound, an anhydride-functional compound, and epoxy-functional compound and a hydroxy-functional compound

Info

Publication number: CA1307607C
Application number: CA000583103A
Authority: CA
Inventors: Rodney M. Harris; Sandra H. Angelo; Mohamad D. Shalati; James A. Marquart
Original assignee: Sherwin Williams Co
Current assignee: Sherwin Williams Co
Priority date: 1987-11-16
Filing date: 1988-11-15
Publication date: 1992-09-15
Anticipated expiration: 2009-09-15
Also published as: DE3884757T2; US4871806A; EP0316873A2; DE3884757D1; EP0316873B1; JPH02625A; EP0316873A3

Abstract

ABSTRACT
Curable compositions which comprise:
(i) an acid-functional compound having an average of at least two carboxylic acid groups per molecule; and (ii) an anhydride-functional compound having an average of at least two cyclic carboxylic acid anhydride groups per molecule; and (iii) an epoxy-functional compound having an average of at least one epoxy group per molecule; and (iv) a hydroxy-functional compound having an average of at least two hydroxyl groups per molecule;
wherein at least one of the compounds (i), (ii), (iii) or (iv) comprises a film forming polymer.

Description

REACTIVE COATINGS COMPRISINC
AN ACID-FUNCTI-NAL COMPOUND, AN ANHYDRIDE-FUNCTIONAL COMPOUND, AN EPOXY-FUNCTIONAL COMPOUND
AND A HYDROXY-FUNCTIONAL COMPOUND
BACKGROUND OF THE INVENTION
1. Field of the Invention.
ThLs inventlon relat~c to novel reactive coating~ whlch can be cured at room temperature or force dried at temperatures r~ng-ing up to about 3SO~F. The coatings may be utilized a~ primcrs, topcoats or a~ clearcoats nnd/~r basecoats in clearcoct/basecoat compositions. Th0 combination of carboxyllc acid-functional com-pounds, anhydride-functional compounds, epoxy-functional com-pounds and hydroxy-functional compounds providQs ~ast reacting, durable coatings which minimize the toxicity problem~ which m~y be associated with other low temperature curing 3ys$em8.

2. Deccription of the Prior Art.

One common prior ~rt approach to high performanc~ low temperature curing coatings has involved two-component coatings comprisin~ resctive i~ocyanates nd activa hydrogen-containing compound~ ~uch as hydroxyl-containing polymers or amino-containing polymer~ to produco polyurethane or polyurea coatings.

Althou~h these m~terials h~ve excellent perform~nce and cure at low t~mperature~, th~ isocyan~tes may, under some conditions, be relatively h~zardoua to handle.
Coa~ing compo~ltion~ comprisin~ reacti~ combin~tions of ~5 epoxy-containing compounds ~nd compoundR having ~cid or amine .
functionality ar~ known in the art. Similarly, coating compo~i-tions comprising cyclic 3nhydride~ and hydroxy-functional com--.~ .
:

`:

: ' ' ' ' ' '~

.

- 1 307~7 pounds are also known in the art. The prior art has not, ho~ever, taught ~he combination of anhydride-functional compounds, acid-funGtional compounds, epoxy-functional compounds and hydroxy-functional compounds to provide low temperature curing coatings having excellent durability and performance.
BRIEF SUMMARY OF THE_INV~NTION
This invention involves a curable composition which comprises: (i) an acid-functional compound whi~h has an average of at least two ~arboxylic acid groups per molecule and is prepared by reacting a hydroxy-functional polymer with at least one cyclic anhydride to form acid and ester groups; (ii~ an anhydride-functional compound having an average of at least two cyclic carboxylic acid anhydride groups per molecule; (iii) an epoxy-functional compoun~ having an average of at last one epoxy group per molecule; and (iv) a hydroxy-functional compound having an average of at least two hydroxyl groups per molecule; wherein at least one of the compounds (i), (ii), (iii) or (lv) comprises a film forming polymer. The compound (lii) is different from ~he compound tiv). The term "compound" is used in its broadast sense to include monom~rs, oligomers and polymers. The tarm "film forming polymer" means any polymeric material that can form a film from evaporation of any carrier or solvent.
In its most preferred formulation, this invention relates to curable composi~ions wherein the acid-functional compound is a polymer ob~ained by the half-ester reaction of a ~ - 2 -, .

.

1 307b~7 hydroxy-functional polymer with a cyclic carboxylic acid anhydride, and wherein the anhydride-functional compound is a free radical addition polymeriæation product of at least one unsaturated monomer having anhydride functionality and at least one other ethylenically unsaturated monomer, and wh~rein the epoxy-~.,`' . ;:
,~
l ~ ~

~ 2a -~,''', ~ ' ., ,' ,.

. .

~ 307607 1 functional compound is an epoxy compound haYing ~n average o~ at le~8t two epoxy group8 per molecule f and wherein the hydroxy-functionAl compound i~ the addition polymerlzation reaction product of ~t le~st one unsaturRt~d monomer having hydroxy functionality and st lea~t one other athylenically un~aturAted monomer.
It is especi~.lly preferred to utilize the curable composi-tion of thls inv~ntion in combination with about 5 to ~bout 80~
by weight of an inert solvent. It i8 convenl~nt to provide the co~ting composition a~ a multicomponent ~ystem which i~ reactive upon mixlng the components. EspeciAlly preferred i8 a two-compon~nt ~ystam wherein the anhydride-functlonal compound ~nd the ~cid-function21 compound are combined in one package and the epoxy-functional compound and th~ hydroxy-functlonsl compound provide a ~econd package. The two packageo cAn then be mix~d together to provide the curable coatings immediately prior to application.
In one preferred application, this inv~ntion relates to coated ~ubstrate~ having a multi-layer dacorativ~ and/or protec-a tive co~ting ~hich comprl~os:
(a) a b~ecoat comprising a pigmented film-forming polymer; ~nd tb) a tr~n~parent clearcoat compri~lng a film-forming polymer applied to th0 surface of the b~ecost compo3ition; -; wherein the clearco~t and/or the ba~ecoat compri~e~ tho curabl~ -compo~itions o ~his invent~on.

~ 3 1 3û76~7 ~2795-1~7 DETAIL~D DESCRIPTION OF THE INVENTION
1. ACID-FUNCTIONAL COMPQUNDS
The acid-functional compounds which are useful in the practice of this invention should have an averar~e of at least two, and preferably at least three, carboxylic acid groups per molecule. Al~hou~h low molecular weight dlacids and polyacids such as phthalic acid, succinic a~idr adipic acid, azelaic acid, maleic acid, fumaric acid, trimellitlc acld and trimesic acid could al~ernatively be u~ilized in the practice of ~his invention, it is especially preferred to utilize polymeric acid-functional compound~.

:

"~ , - 4 ."
"
,~, ,. .
;
:

" 1 307607 t Prefer~bly the acid-function~l polymer will ha~o a number aver~ge molecul~r weight of ~t lea3t about 400. Typicel number average molecular weight~ of the carboxylic acid-functional polymers will range from ~bout 500 to about 30,000. Repr~senta-S tive acid-function~l polymers include ~crylica, polye~ters and polymers prepared by the re~ction of anhydrides with hydroxy-functional polymer8 ~ di~cussed more fully below.

I.A. Carbo~ylic ~cid-functional polymers prepared by the half-ester forming reaction of anhydrides ~nd hydroxy-functional polymers.
Especi~lly preferred in the pr~ctice of this lnvention cre carboxylic acid-functional polymer~ prepared by the half-ester reaction of cyclic carboxylic acld anhydrlde~ and hydroxy-function~l polym~r~. The hclf-~ter re~ction invol~oo ehe ring opening of the cycllc anhydride by reaction with ~ hydroxyl group S - on the hydroxy-functional polymer to fGrm one e~ter group and one ~cid group.
Typically, the hydroxy-functional polymers will ha~e number average molecular weight~ o~ at leaat about 400 ~nd typ~cAI
number av~rage molecul~r w~ighto will range from ~bout 400 to about 30,000, and ~p~ci~lly 1,000 to ~bout 15,000. Method~ of prep4ring hydroxy-functionAl polym~rs are well known in the are flnd the method of prep~ration of the hydroxy-~unctionAl molecule or polymer i~ not critical to the practice of thi~ invention.
Representative polymero whlch can b~ reacted with ~nhydrldes to produce the acid-~unction~l polymer~ include the hydroxy-functional polyether~, polyeY~er~, Acrylics, polyur~th~neo, poly-: - 5 -1 caprol~ctone~, ~tc. as generally di~cua~ed ln Sections l.A.I.
through l.A.5. below.
l.A.l. Polyether polyols are well known in tho ~rt ~nd are conveniently prepared by the reaction of ~ diol or polyol wlth ~he corr~spondlng slkyle~e oxide. Those materials are comm~rcially avall~bla ~nd may be prepared by a known proces~ such a~, for example, the proces~s described in ~yclo ed~a of Chemical_Technol~y Volume 7 p~gas 257-262, publi~hed by Interscience Publiah~rs, Inc., 1951. Repre3ent~tive example~ include the polypropylsne ether glycol~ and polyethylene ether glycola such ~R thos~
~rketed ~8 Ni~x~ Polyol~ fro~ Unlon Cerbide Corporation.
l.A.2. Another uceful cla88 of hydroxy-functionnl polymers cre those prep~red by cond~ns~tion polymerization resction techniqueo as are well known In the ~rt. Rapresen-tative condens~tion polymerization reactions includs poly-estera prepared by the condonsaeion of polyhytric Alcohols ; and polycarlboxylic ucid~ or anhydrldo~, with or wlthout ~he r inclusion o~ drying oil, semi-drying oil, or non-drying oil `~)0 fatty ~cidG. By adjuating the otolchiometry of the ~Icohol~
and th~ scid~ whil~ maint~ining an exce6~ of hydroxyl groups, hydroxy-function~l poly~sters can bz re~dlly pro-duced to provido a wide rang~ of desired mol~cular weights ~nd p~rform~nce ch~r~ct~ri~tic~.
S The polyester polyolo are derived from on~.or more ~ro-matic and/or eliphatic polyc~rboxylic acid3a the ~nhydride~
thereof, and one or more al~iphatic and/or aromatlc polyols.
.';:

''~"

1 The carboxyllc acids include the ~atur~ted ~nd un~aturnted polycurbo~ylic acid~ and the derlv~tive~ thereof, auch a8 : maleic acid, fumaric acid, succinic ~cid, adipic acid, azelaic acid, ~nd dicyclopentadiene disarboxylic acid. The carboxylic ~cids ~180 include the aromatlc polycarboxyllc acids, 6uch a~ phthalic acid, isophthalic scid, terephthalic ~c~d, etc. Anhydride~ such ~ maleic ~nhydride, phthalic ~nhydrlde, trimellitic anhydride, or Nadic Methyl Anhydrlde (brand n~me for methylbicyclo[2.2.1]heptene-2,3-dic~rboxylic anhydride i~omer~) c~n al~o be u~ed.
: Repre~entative ~atur~ted ~nd uneatur~ted polyols which can be reacted in ~toichiom~tric exce~ with ~he c~rboxyllc acids to prod~ce hydroxy functional polyeoter~ includ~ diol3 . such as ethylene glycol, dipropylene glycol, 2,2,4-trimethyl 1,3-pent~nediol, neopentyl glycol, 1,2-propanediol, 1,3-prop~nediol, 1,4-butanediol, 1,3-but~nediol, 2,3-butcnediol, 1,5-pentane~diol, 1,6-hex~nediol, 2,2-dim~thy~-1,3-propanediol, 1,4-cyclohexanedimoth~nol, 1,2-cyclohexansdimeth~nol, 1,3-cyclohexanedimeth~nol, 1,4-bi~(2-hydroxyethoxy)cyclohexsne, trimethylene glycol, tetra-methylene ~Iycol, pent~ethylene glycol, hexamethylene glycol, decdmethylene glycol, diethylene glycol, triethylene glycol, tetr~ethylene glycol, norbornylene glycol, 1,4-benzenedimethcnol, 1,4-benzen~dl~th~nol, 2,4-dimethyl-2-i ethylenehexane-193-diol, 2-butene-194-diol, and polyol~ sush a~ trimethylolethsne, trimethylolpropane, trimethylolhsxane, , ": :
',:

~ , ,~
., .

triethylolprop~ne, 1,2,4-butanetriol, glycerol, pent~-erythritol, dipentaerythritol, etc.
TypicRlly, the re~ction between the polyols and the polycarbo~ylic ~cids i8 conducted ~t ~bout 120C to ~bout 200C in the presence of ~n ~st~rific~tio~ c~taly~t ~uch a8 dlb~tyl tin oxlde.
l.A.3. Additionally, hydroxy-functionAl polymers can be prepared by the ring opening resction of epoxides and/or polyepoxides with prim~ry or, pref~rably, ~econdary am~ns~
or polyamines to produce hydroxy-function~l paly~&rs. Rspre-sent~tive amine~ ~nd polyamines include eth~nol ~mine, ~N-methylethanol amine, timethyl ~min~, ethylen~ diamine, isophorone di~mine, etc. Repres~ntative polyepoxides include tho~e preplred by condensing ~ polyhydric alcohol or polyhydric phenol with ~n epihalohydrin, such ~ epichloro-hydrin, usuAlly under alkuline conditions. Som~ of these conden~ation products arc ~vailable commer~ially under ehe desigllationo EPON or DRH from Shell Chemical Company, and methods of preparat1on are ropre~entatively taught in U.S.
patents 2,592,560; 2,5~2,985 ~nd 2,694,694.
I.A.4. Oth0r useful hydroxy-function~l polymers c~n be prepared by the re~ctlon of an exce~s of ~t leA~t one polyol, such a~ tho~e repre~ent~ively de~cri~d in Section l.A.2 above, wlth polyi~ocyanateo to produce hydroxy-S functional ureth~nes. Repredentatlve polyi~ocyan~tes h~ving-two or more isocy~nate group~ per molecule inclu~e the ~liph~tic compounds ~uch a~ ethylene, trimethyl~ne, r~ 8 -.

. , , ~,. . ..

1 ~07607 tetrsmethylens, psntamethylene, hex~methylsn#, 1,2-propylene, 1,2-butglene, 2,3-butylene, 1,3-butylene, ethylidene and butylidene dii60cyanates; the cycloalkylene compound3 auch ~

3-isocyan~tomethyl-3,5,5-trimethylcyclohexyllsocyanate, and the 1,3-cyclopentane, 1,3-cyclohexAne, ~nd 1,2-cycloh~x~ns diisocyanates; the aromatic compound~ such a~ m-phenylene, p-ph~nyl~n~, 4,4'-diph~nyl, 1,5-n~phth~len~ and 1,4 n~phthalene dilsocy~n~te~; th~ aliphatic-~romatlc com-pounds such a~ 4,4'-diphenylen~ methane, 2,4- or 2,6-toluene, or mixture~ ther~of, 4,4'-toluldino, and 1,4-xylylens dilqocyanate3; the nuclear sub~t$tut~d sromatic compounds such a~ diAnisidine diisocy~nate, 4,4'-diphenyl~ther dii~ocy~nste ~nd chlorodiphenylene 15 - diisocyanato; tha trilsocyanat~s ~uch a8 triphenyl methane-4,4',4''-trii~ocy~nate, 1,3,5-triisocyAnate benzene and 2,4,6-triioocyanate toluene; and tho tetr~isocyan2te~
such 8g 4,4'-diphenyl-dim~thyl meth~ne-2,2'-5,5'-tetr~i~ocyanate; th2 polymeriz~d polyl~ocyan~teA such ~8 tolylene diisocyanate dlm0rs and trimers, und othor vsriou~ polyisocyanates containing biuret, ur~th~ne, ~nd/or allophsnate linkages. The polyi~ocy~n~tes ~nd the polyols sre ~yplcAlly reacted ~t ` temperature3 of 25~C to about 150C to form the hydroxy-functionul polymers.
l.A.5. U~ful hydroxy-unction~1 polymers c~n al~o be -conveniently pr~pared by fr~ rsdical polymerlzction tech-1 niques such a8 in the produceion of acryl~c reaina. ~he polymer~ sre typically prepared by the addition polymariza-tion of one or more monomers. At least one of the monomers will contain, or can be reacted to produce, a re~ctive S hydroxyl group. Repre~entatlve hydroxy-functional monomer~
include 2-hydroxyethyl scrylQte, 2-hydroxyethyl meth-acryl~te, 2-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxybutyl acrylAte, 4-hydro~ypantyl acryl~te, 2-hydroxyethyl tO ethacrylate, 3-hydroxybutyl meth~crylate, 2-hydroxyethyl chloroacrylate, diethylene glycol methacrylatc, tetra-ethylene glycol acrylate, par~-vinyl benzyl alcohol, etc.
Typical ly the hydroxy-functional monomer~ would b3 copolymer-ized with one or more monomers havin~ ethylenic uncatur~tion such ~:
(i3 esters of scrylic, methacrylic, crotonic, tiglic, or other un~aturAted scid~ ~uch ag: methyl acrylate, ethyl'acrylate, propyl acrylate, isopropyl ~crylate, butyl ~crylato, isobutyl acrylate, ethylhexyl acrylste, 0 amyl ncrylnte, 3,5,5-trimethylhe`xyl acryl~te, methyl methacrylate, ethyl methacrylate, propyl methccrylate, dimethyl~minoethyl methacrylate, isobornyl me~h-acryl~te, ~thyl ti~l~te, methyl crotonste, ethyl croton~e, etc.;
(ii) vinyl compounds ~uch a~ vinyl acetate, vinyl propi-on~te, vinyl butyr~te, vinyl i~obutyr~te, vinyl benzo-~te! ~inyl m-chlorobenzo~te,~vinyl p-methoxybenzoate, ` ~ - 1 0 -., . I

.~ ,., ~ .
.'~ ' - .
~ ~ .
.

vinyl ~lpha-chloroacet~te, vinyl toluene, vinyl chloride, etc.;
(iii) styrene-based m~terials ~uch a~ styrene, ~lphd-methyl ~tyrene, ~lpha-ethyl ~tyrene, alpha-bromo ~tyrene, 2,6-dichlsro~tyrene, etc.;
(iv) ~llyl compounds such ~8 allyl chloride, ~llyl ~cetate, ~llyl benæoate, ~llyl methacrylate, etc., (v) other copolymerizable un~turated monomer~ auch ~
ethylene, ~crylonitrile, meth~crylonitrile, dimethyl m~leate, isopropenyl acetate, i~opropenyl isobutyrete, acrylamide, meth~crylamlde, and dienes such B~ 1,3-butadionel etc.
The polymer~ are Gonveniently prepared by conventional free r~dical ~d~ieion polymeriz~tion techniques. Yrequantly, the 15 - polymeriz~tion will be c~t~lyzed by convention~l c3~1y~ts known in the art to 8enQr~te a free radlcal such ~8 azobis(isobjutyronitrile), cumene hydroperoxide, t-butyl perbenzoate, utc. Typically, th~ ~crylic monomere ~re heuted in the presence of the cat~lyst ~t temper~tures 0 ranging from ~bout 35C to ~bout 200C, snd e~peci~lly 75C
to 150C, to ~ffect the poly~erization. The molecul~r weight of th~ polymer can be controlled, if de~lred, by the monomer o~lYction, rescticn temperature and time, ~nd/or the use o~ chain tr~n~er a~ent~ ~ is well known in the ~rt.
EspeciaIly pref~rred polymers in the practice of thi~ -invention for re~ction with the cyclic anhydride to produce the carboxylic acid-functional polym~rs are hydroxy- ;
:

~: .

.

--- ` 1 307607 function~l polyesters and hydroxy-functional Ycrylic polymers. An e~pecl~lly preferred hydroxy-functional polymer i~ the addition polymerization reaction product of (a) 5 to 100, and e~peci~lly 10 to about 40, weight percent S of a hydroxy-functional ~thylenically un~tur~t~d monomerand (b) 0 to 95, and e3pecially 60 to about 90, weight percent of ~t leaat one other ethylenicQlly una~tur~tod monomer copolymerizablq with the hydroxy-function~l monomer.
The cyclic carboxylic acid anhydrldea u~ful in the pr~ctice 1~ of this invention to produc¢ the carbo.~ylic acid-function~l h~lf-ester product by r~action with the hydroxy-function~l compound cAn bq any monomeric aliph~tic or ~romatic cyclic anhydrid~
h~ving one anhydride group per ~olecula. RepreRentati~
Anhydrid~s include, pht-h~lic anhydride, 3-nitrophthalic~
: ~5 - anhydrid~, 4-nitrophthalic ~nhydrid~, 3-flourophthalie ~nhydride, 4-chlorophthalic anhydride, tetr~chlorophthalic anhydride, tetra-bromophthalic anhydride, totr~hydrophthalic anhydride, hexahydro-~ phthalic anhydrilde, m~thylhexahydrophth~lic anhydrid~, 3uccinic ; nnhydride, dodec~nyl~uccinic snhydrlde, octyl~uccinic anhydrite, maleic anhydrid~, dichloromaleic anhydrid~, glutaric anhydride, sdipic anhydride, chlorendic ~nhydride, it~conic anhydride, citraconic ~nhydride, endo-methylenetetr~hyd~ophth~lic anhydride, cyclohexan~-1,2-dic~rboxyllc anhydride, 4-cyclohexene-1,2-dlc~rboxylic ~nhydride, i 4-methyl-4-cyclohex~ne-1,2~dicarboxylic ~nhydride, 5-norbornene-2,~-dicarboxylic Inhydride, 1,4-Gycloh~adiene-1,2-dicarboxylic anhydride, 1,3-cyclopentanedicarboxylic ~nhydride, diglycolic ,,~, ' ~', ' ' -,: .
:, :~.
,: ,,. ~ .
. , 1 acid snhydride, etc. Maleic anhydride i~ especiAlly preferred because of its reactivity and rel~tively lo~ cost. Other useful anhydride~ include those ~nhydrides hsving a free carboxyl ~roup in ~ddition to th~ anhydride group such ~ trimellitlc anhydride, aconitic anhydride, 2,6,7-naphthalene tric~rboxylic anhydride, 1,2,4-butane tricarboxylic anhydride, 1,3,4-cyclopsntane tri-carboxylic ~nhydride, etc.
The re~ct~on of th~ hydroxy-functionul compound ~nd the cyclic anhydride should normally b# conduc~ed at ~qmper~ture~
0 les~ than about 75Z, preferably le~ than 65C, and most preferably between abou~ 35C to 60C. The reaction temperaturn i~ maintained until the reacti~n haD proce~dad to providD ~he de~ired ~moune of half-ester groupa on the acid-functional compound. NormGlly, a~ a convanient meaaure af the extent of ~he reaction, the reaction will be continued until no change in the amount of re~idu~l unreacted anhydride can be obsorvat, and wlll generally involye reacting at least about 70~, and preferably at least 952, of the available anhydrld~. If the oub~aquont ond usc of the acid-functional polymer can tolarate ~he remaining free 'O anhydride, if ~ny, no ~eparation or removal of the exce~
unreacted anhydride io neces~ary. If tha 0nd u8e of the acid-functional polymer require~ that it be free of ~ny unreacted anhydride, the reaction can be continued until ~ub~t~nti~lly all of tha anhydride ha~ reactad, or the free anhydride may be removed by vacuum distillation or other technf quas W811 known in the art.

, . .. ~ , 1 The level of anhydride reacted with the hydroxy functional compound need only be sufflcient to p~ovide the final de~ired acid value of the acid functional compound. Typic~lly the rccc-tion would be conducted by admi~ing the polyol and the anhydride at levels to provid~ flt le~8t about 0.3 ~nd normally about 0.7 to 1.0 ~nhydride groups for each hydroxyl group. ~y conducting the re~ction at temperature3 less than sbout 75C the c~rboxylic Acid groups formed a~ part of the half-e~ter are not appr~ciably recc-tive with the hydroxyl groups themselves and 80 they do not com-tO pete with the ring opening half-e~ter react$on of the remaining anhydride~.
In order to cond~ct the re~ctio~ at the~e rsl~tively lo~
temp~ratures, it 1~ preferred to utilize ~n esterification cata-lyst. The catalyct should be present in sufficient amount to cstalyze the re~ction and typically will be pre en~ at ~ level of at lea~t about .Olg, and normally from about .05X to about 3.0%, based upon ~he weight of the cyclic anhydride. Catalyst~ which are u~eful in t~e ecter~icstion r~actlon of the anhydride with the hydroxy-functional mol~cule include mineral acid~ such 88 hydrochloric acid ~nd ~ulfuric acid; alkal~ met~l hydroxid~ such as ~odium hydroxide; tin compounds such a~ st~nnous octoete, or dibutyltin oxide; aliphatic or aromatic ~mine~, especi~lly ter tiary alkyl aminea, such aa triethylamine; and aromatic hetero-cyclic amines ~uch a~ N-methyl imidazole and th~ like. E~pe-!S ci~lly preferred are N-methyl imid~zole and ~riethyl~mine.
Although the resction between the hydroxy-functional com pound ~nt the anhydride can be conducted in the absence of 801-, : .

1 vent if the m~terial~ are liquid at the reactlon temp~rsture, it i5 normAlly preferred to conduct the reaction in the pre~ence of an inert ~olvent such as esters, keton~s, eth~rs or ~rom~tic hydrocarbon~. If deslred, the ~cid-functional molecule can be utili~ed a~ the solvent ~olution, or, opti~n~lly, all or p~rt of the inert solvant may be removet, e.g. by distillatisn, after the reaction i8 completed.
After the reaction i~ co~ple~d, it i~ frequently d~slrable to add 8 low molecular weight alcohol solvent, ~uch A8 $~obut~nol or isopropanol, to the acid-functional at a lev~l vf about 5 to 35 percent by w~ight to pro~ide stabiliæation on storage.
O l.B. Carboxylic Acid-Functional Polymer~
Prep~red From Un~atur~ted Acid-Functionnl Monomers.
Useful acid-~unction~l polymers can also be con~enlently prepared by addltio~ polymeriz~t~on techniqu~e ~uch sa in tho production of ~cryllc re4ins. The acid-functional polymers are routinely prep~red by the free radical addition polymerization of unsaturated acid~ such a~ maleic Acid, acrylic acid, meth~crylic acid, crotonlc acid, etc. ~long with one or more un~tur~ted monomers. Reprecontative monomers include the ester~ of uneaturated acido, vinyl compound6, styrene-based materidls, allyl compound~ and othcr copolymerizable monomers ao r~pre~entatively t~ught in Section l.A.5. of thi~ cpecificAtion.
The monomer~ which are cG-polymerized with the un~turatod ~cid ~hould b- free o~ ~ny functionality which could re~ct wlth the acid ~roups during th~ polym~rization.
l.C. C~rboxylic Acld-Functional Polym~rs Prepared Fro~ Polyole and Polyacid~.
Other useful acid-functions1 polym~r~ includQ polye~t~r polymers obtained from the reaction of one or mora arom~ic :::
.

1 And/or ~liphatic carboxylic acids or their anhydride~ ~nd one or more aliph~tic and/or aromatic polyols wherein the scid function-~lity is pre~ent In a stoichiometric excess over tha hydroxy func-tion~lity. Representaeive carboxylic acid~ and polyols include ~ho~e li~ted in Section l.A.2. of thi~ specification.
2. ANHYDRIDE-FUNCTIONAL COMPOUNDS.
The anhydride-functional compound~ which ar~ u~eful in the practice of this invention can be any aliphatlc or arom~tic com-pound having at lea~t two cyclic carboxyllc acid anhydride groups in the molecule. Polym~rlc anhydrides h~vlng numbur 3v~raga molecular weights between 500 and 7,000 are mo~t u~eful. E8pe-cially preferred in the practice of this invention i~ the u8e of free radical addition polymers, 3uch as acrylic polymors, having anhydride functionality. These are convenlently prepared ~8 i8 well known in the art by the polymerization under fre~ radical addition polymerization conditiono of at lea~t one unsaturHted monomer havin~ anhytride functionality, such 88 m~ anhydride, citraconic anhytrite, itaconic anhydrid~, propenyl succinic anhydride, etc. optionally with other ethyl~ni-cally uns~turAted !0 monomers such a8 tho e~ters of un~aturated ~cids, vinyl compounds, ~tyrene-based mat~rlala, ~llyl compound~ ~nd other copolymerizablo monomers, ~11 as repreaentatively t~ught in Section l.A.5. of thi~ ~peclficatlon. The monomora whish are copolymerized with tha un~turatet anhydride ~hould, of course, - 5 be free of ~ny functiDnality which could react with the anhydride-~roup~durin~g the polymerization. The anhydrid~-funct~onal polymers can be conveniently prep~red by conventional fros :

, 1 r~dical ~ddition polymeriz~tion techniques. Typically the polymeriz~eion ~ill be conducted in an inert solven~ and in th~
pre3enc~ of ~ catalyst lt temper~tures r~nging fr~m 35C to about 200C. The ~nhydride-function~l polymers should comprise at lea~t 5% by w~ight of the anhydride. An aspeci~lly pr~ferrad ~nhydrlde-function~l free radical addition polymer compri~e~ the fre~ radical addition polymeriz~tion product of (~) 5 to 40, and e3pecially 15 to about 25, weight percent of an ethylenically un~aturated monoanhydridQ ~nd ~b~ 60 to 95, ~nd e3p~clally 75 to about 85, weigh~ percent of at l~a~t one other ethylenically un~atur~ted monomer copolymurizable with the ethyl~nically un~aturat~d anhydrid~.
Other polyanhydrides, in flddition to the acrylic polymeric anhydride~ prepared by ~ free radical ~ddition procesa, c~n also ba utilized in the pr~ctice of thl~ Invention. E~ter anhydrides can be prepar~d, a~ i~ known in the art, by the reaction of e.g.
trimellltic ~nhydride with polyols. OCher representativo, suitable polyan~ydride~ include poly-functional cyclic dianhydrides cuch a~ cyclopentano te~racsrboxylic ~cid disnhydride, diphenyl-ether tetracarboxylic acid di~nhydrid~, 1,2,3,4,-but~ne tetrac~rboxyllc ac~d di~nhydrlde, a~d the benzo-phenon~ tetr~carboxylic disnhydride~ ~uch a~ 3~3~414~-benzophenone totracarboxylic di~nhydride, ~nd 2,bromo-3,3',4,4'-benzophenone tetr~carboxylic acid dianhydride. Trianhydride~
~uch a8~ th~ benz~ne ant cyclohexene hexac~rboxylic acid trianhydrides ar~ alco u~eful.

''' , ~ -, . ,, -`" 1 307607 Addition~lly, u~eful polyanhydrides c~n be pr~p~red by th~
maleiniz~tion of polyun~aturated compound~ such aa uns~turated rubber~, unsaturae~d oils and un~aturated hydrocarbons.
3. EPOXY-FUNCTIONAL COMPOUNDS.
The coatings of thi~ invention al~o require th~ u~e of at least one epoxy-function~l compound. The epoxy compounds can be monoepoxies or, prefer~bly, ~ polyepoxide having ~n ~vsrag~ of ~t le~st two epoxy ~roups per ~olecule.

Representaeive u~eful monoepexides in~lude the mono~lyc~dyl ethers of aliph~tic or aromatic alcohols ~uch a~ butyl glycldyl ether, oc~yl glycidyl ether, nonyl glycidyl ether, decyl glycldyl ether, dodecyl glycidyl ether, p-tert-butylphenyl glycidyl ether, and o-cresyl glyc~dyl ether. Monoepoxy esters ~uch aa tha glycidyl ester of ver~atic acid (commercially availcbla a~
CARDURA~ E from ~h~ll Chemical Company), or the glycldyl esters of other acids auch as tertlflry-nonanoic acid, terti~ry-decanoic acid, tertiary-undecanoic acid, etc. ar~ al80 uaeful. Similarly, if desired, un~aturated monoepoxy esters such a8 glycidyl acrylate, glycidyl methacryl~te o~ glycidyl l~urate could be u3ed.
~0 Additionally, monoepoxidized oils can al80 be uoed.
: Other uaeful monoepoxi~s includ~ ~tyrens oxide, cyclohaxene oxide, 1,2-butene oxite, 2,3-butene oxide, 1,2-penten~ oxid~, 1,2-hept~n~ oxide, l,~-octene oxide, 1,2-non~n~ oxide, 1,2-decene oxide, and the lik~. -~5 It i~ only nece~sary thae the monoepoxide compounds havs a suffici~ntly low ~olstility to rem~in in the co~ting compo~lon `
: : under the applic~ble conditions of cure.
' 1 Polyepoxide~ are e6pecially preferred in th0 re~ctlve coatings of this invention. Especially preferr~d ar the poly-functional epoxy compounds, due to their reactivity and durabil-ity, are the polyepoxy-functional cycloaliphatic ~poxies.
Preferably, the cycloaliphatic epoxie~ will have ~ number average molecular weight lea~ than about 2,000 to minimize the viscosity.
The cycloaliphatlc epoxies are conveniently prepared by methods well known in the art 3uch ~s epoxldatlon of dlene~ or polyenes, or the epoxid~tion of unsatur~ted esters by resction with a peracid such ~ peracetic and/or performic acid.
Commercial ex~mples of representative preferret cycloali-phatic epoxies include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclo-hexane carboxylete (e.g. "ERL-4221" fro~ Union CRrblde Corp.);
bi~(3,4-epoxycyclohexylmethyl)adipate (e.g. "ERL-4299" from Union lS - C~rbide Corporstion); 3,4-epoxy-6-methylcycloh~xylmethyl 3,4-epoxy-6-methylcyclohex~ne carboxyl~te (e.g. "ERL-4201" from Union Carbide Corp.); bi~(3,4-epoxy-6-methylcyclohexylmethyl)adipate (e-8- "ERL-4289" from Union Carbide Corp.);
bis(2,3-epoxycyclopentyl~ ether (e.g. "ERL-0400" from Union Carbide Corp.); dip~nteno dioxide (e~g. "ERL-4269" from Union Carbide Corp.); 2-(3,4-epoxycyclohexyl-5, 5-spiro-3,4-tpoxy) cyclohexsnq-metadlox~ne (e.g. "ERL-4234" from Union Carbide Corp.~. Other commercially avail2ble cycloaliphatic epoxies are availcble from Ciba-Geigy Co{poration such ~8 CY 192, a cyclo-~5 allphatic diglycidyl e~er epoxy resin having an epoxy equivalent weight of about 154. The m~nufacture of representatlve cycloali-; ~ 19 -' .
~ .

-``` 1 307607 1 phatic epoxie~ i8 taught ln YarioUs patents including U.S.
2,884,408, 3,027,357 and 3,247,144.
Other polyepoxide~ potentially useful in the practices of this invention include aliphatic and aromatic polyepoxie~, such as those prepared by the reaction of an aliphatic polyol or poly-hydric phenol and ~n epih~lohydrin. Other useful epoxies include epoxidized oils ~nt acrylic polymer~ derived from ethylenically un~eturated epoxy-function~l monomer~ auch n3 glycidyl acryl~te or glycldyl meth~crylate in combination with other cspolym~riz-able monomers such as those li~ted in l.A.5 above.
4. HYDROXY-FUNCTIONAL COMPOVN3S.
The hydroxy-functio~l compounds which are u8~ul in the practice of this invention ~hould have an average of at leQ~t two hydroxyl groups per moleculo. Although low molecul~r weight diols and polyols ~uch e~ propylene glycol, 1,6-hex~nediol, tri-ethanol-amine end pentaerythritol can be utilized in the practice of this invention, it i~ especially preferred to utilize poly-meric hydroxy-fuhctional compound~ auch a~ polyethsra, poly-e ters, ncrylic~, polyurethanes, polycaprolactone~, etc.
0 Preferably the hydroxy-functionnl polymer will h~ve a number average molecular weight of at leest ebout 400. Typical nu~ber aver~ge molecular weigbts will range from Ibout 400 to about 30,000, nnt e~pecially l,000 to ~bout 15,000. In order to pro-vide the faste~t rate of reaceion during cure it ia preferred in ; the pr-ctice of thia invention to utilize hydroxy-function~l com-pounds having predominantly, and preferably all, prim~ry hydroxy functionality.

.. . .
1 Representstlve hydroxy-functional polymers are t~ught in Sections l.A.l. through l.A.5. of this spec$fication. Especially preferred as the hydroxy-functional polymer i8 a hydroxy-functional polymer compri6ing the addition polymerization of (a) S 10 to about 60 ~eight percent of a hydroxy-functional ethylen-ically unsaturated monomer and (b) 40 to about 90 weight percent of at least one ethylenically unsaturated monomer copolymerizable with the hydroxy-functional monomer.
The ratio~ of anhyJride to acid to epoxy to hydroxyl groups can he widely vAried within the practice of this invention as long a~ at least some of each group is present in the reactive coating. It 13 preferred, howov~r, to provide about 0.05 to ~bout 3.0 acld groups and about 0.5 to about 4.0 epoxy groups and ~bout 0.05 to 6.0 hydroxyl groups for each anhydrida group in the lS reactive system. It i9 especially preferred to provide 1.0 to about 2-.0 acid groups and 1.0 to about 3.0 epoxy groups and about 1.0 to about 4.0 hydroxyl groups for each anhydride group.
At lea~t one of the hydroxy-function~l compound, th~ ~cid-functional compound, the epoxy-functional compound, o~ the 0 anhydride-function~l compound should be a film-forming polymer, and each of the compound~ ~hould be mutually soluble wlth ~he other compounds. If de~ired, more than one of any of the acid-functional, ~nhydrite-functional, epoxy-functional or hydroxy-functional compound~ could b~ utilized in a single coatlng formulation.
The coating~ cf this invention can be cured ~t temperatures ranging from about room temperature up to about 350F. The ':~
., ,:

1 co~tlngs can be used a~ clear coatings or they may contain pig-ments ~ well known in the art. Repre~entotive opacifying pigment6 include whlte pigments such a~ titanium dioxide, zinc oxide, antimony oxide, etc. and organic or inorganic chrom~tic S pigments ~uch ~8 iron oxide, carbon black, phthalocyanine blue, etc. The coatin~s may also conteln ext~nder p$gments ~uch as calcium carbonate, clay, ~ilica, talc, ets.
; The coating~ may al~o contain other ~dditive~ such a8 flow agents, cataly~ts, diluents, solvents, ultraviol~t light absorbers, etc.
It i~ especially preferred ln the prectice of this in~ention to include a cataly~t for the reaction of anhydr~de groups and hydroxyl group~ and al~o a c~taly~t for the reaction of epoxy and acid groups. It i~ especially preferr~d ln the practice of this invention to utllize tertlary amlnes and especially N-methyl~mida~ole a8 a catalyst for the snhydride/hydroxyl reac-tion. The cat~lyot for the anhydride/hydroxyl r~action will typically be pre~qnt ~t a l~vel of at l~st O.OlS by weight of the anhydride compound and preferably 1.0 to ebout 5.02.
0 Tertlary amino~, secondary amine~ ~uch as ethyl i~idezole, quaternary ~mmonlum 8~1ts, nucleophllic catalysts, such as lithium iodlde, phosphonium salts, and pho~phine~ ~uch as triphenyl phoophino ~rc especlally u~eful a~ cataly~t3 for epoxy/acid recctlon~. The cataly~t ~or the epoxy/acld reectlon ~5 will typically be pre~ent at a level of at lea~t 0.012 by ~eight of the total acid-functional compound and epoxy-function~l compound and will be present at O.l to ibout 3.02~ -, 1 Since the curable compositions of thi~ invention are typic-~lly provided as multi-package systems which must be mlxed together prior to use, the pigments, c~talysts and other addi-tives can be conveniently added to ~ny or all of the indivldual S package~
The coating~ of this invention may typicclly be applied to any substrate such metal, plsstic, wood, glas~, synthetic fiber~, etc. by brushing, dipping, roll coating, flow co~ting, ~praying or other method conventionally employed in the coating industry.
One preferred applic~tion of tha cur~ble co~tings of this invention relates to their u~e a~ cle~rco~ts and/or b~sQcoat~ in clearcoat/basecoat formulation3.
Clearcoat/basecoat ~y~tems are ~ell known, espsci~lly in the automobile indu~try where it is especially useful to ~pply a IS pigmented b~secoat, which may cont~in m~tallic pigment~, to c sub~trate and allow it to form a polymer fllm followed by ths spplic~tion of a clearco~t which wlll not mix with or have ~ny appreci~ble sol~ent attack upon thc previously applied b~seco~t.
The basecont composition may be any ~f the polym~r0 known to be O useful in coatine compo3itions including the reactive compo~i-tion~ of thi~ invention.
One useful polymer basecoat includes tha acrylic ~ddition polymers, particularly polymers or copolymsr~ of one or more alkyl esters of ~crylic acîd or methacrylic acid, optlonally together with one or more other ethyIenically uns~turated monomers. These polymers may be of either the thermoplastic type or the thermosetting, crosslinking ~ype which cont~in hydroxyI or ~ .

i, , .
''''' , amine or other re~ctive functionality which can be cro~slinked.
Suitsble acrylic e~ter~ for either typ~ of polymer include methyl methacrylQte, ethyl methacryl~te, propyl methacrylate, butyl meth-~cryl~te, ethyl acryl~te, butyl acrylate, vinyl ~cetate, acrylo-nitrile, acrylamide, etc. Where the polymer~ are required to bo of the crosslinking type, suitable functional monomers which can be used in addition to those already mentioned include acrylic or methacrylic acld, hydroxy ethyl acrylate, 2-hydroxy propyl meth-acrylate, glycidyl acrylat~, tertiary-butyl ~mino ethyl meth-acryl~te, etc. The baseco~t composltion may, in ~uch a c~e, also contain a cro~linking agent ~ch 88 ~ polyisocyanate a poly-epoxide, or a nitrog~n re~in ~uch ~8 ~ condensate of an ~ldehyde such a8 formaldehyde wLth a nitrogeneous compound such B8 urea, melamine or benzoguanamine or ~ lower alkyl ether of such.~ con-densate. Other polymers useful ln the basecoAt composition lnclude-vinyl copolymers ~uch a~ copolymer~ of vinyl eaters of inorgAnic or orFanic acids, 3uch as vinyl chloride, vinyl ace-tate, vinyl prOpionatQ, etc., which copolymcr~ m~y option~lly be partially hydrolyzed 80 as to introduce vinyl alcohol units.
Other polymer~ useful in the manufacture of the ba~eco~t includc alkyd ro~ina or poly~ters which c~n be prepared in 8 known msnner by the conton~ation of polyhydric alcohols and poly-carboxylic acids, ~lth or without the inclusion of na~ural dryin~
oil fatty acido a~ d~cribed elsewhere in this ~pecification.
~5 The polyesters or Alkyds may contain a proportion of free hydroxyl sndtor carboxyl groups which are availsble for resction, if de~ired with suitable cro~slinking ~gentR a~ discuss~d above.
.
- ~4 -:
,:
.~ .

. .
If d~sired, the b~ecoat compo~ition may al80 contain minor amounta of a cellulose estçr, to fllter the drying or visco~lty ch~racteristics of the basecoat.
Typically, the basecoat will include pigments conYentLonally S used for CoRting compo6ition~ and after being applied to a sub-strate, which may or may not previously have been primed, the basecoat will be allowed sufficient time to form a polymer film which will not be lifted during the application of the cleArcoat.
The clearco~t i8 then ~pplied to the ~urface of the basecoat, and the ~ystem can be &llowed to dry or, if desired, can be force dried by baking the costed substrate at temperature~ eypically ranging up to about 250F.
Typically, the clssrcoat m~y contain ultraYiol2t light absorbers ~uc~ ~8 hindered phenols or hindered amlnes at ~ level - ranging up to about 62 by weight of the vehicle solidD a~ i3 well known in the art. Tha clearcoat can be applied by any applicatLon method known in the art, but prefer~bly will be spr~y applied. If desired, multiple layers of basecoat andlor clearcoat can be applied. Typically, both the baseco~t dnd the clearco~ will each be ~pplied to g$ve a dry film thickness o~
about 0.01 to aboùt 6.0, and e3peclally about 0.5 to about 3.0 mils.
The following 0xamples have been selected to illustrate spe-cific embodiments and pr~ctice3 of ~dvan~age to ~ more complete S underætanding of the invention. Unlea~ otherwi~e atated, "p~rt~"
means p~rts-by-weight ~nd "percent" i~ percent-by-weight. The :

- 25 - .

.

numeric r~ting~ for solvent resi~tance (MEK rubs), wet adhesion, and sslt ~pray are on e scale of 0-10, 10 beat.
In each of the clearcoat/b~6ecoat formulations described in Example~ 6 through 15 the prlmer was G.8.P.X etching primer fil-S ler (2-component vinyl-butyral baaed primer commercially avail-able from The Sherwin-William~ Comp~ny) and the basecoat wa~
Acrylyd~ acrylic enamel (a lacquer-like coatin~ commerclally avsilable from The Sherwin-William~ Company). The primer, the b~secoat and the cl~arcoat were applied to provid~ dry film thick-nssses of 1.0, 1.0 and 2.0 ~ respeetlvely.
EXAMPLE I
PREPARATION OF ANHYDRIDE-FUNCTIONAL ACRYLIC POLYMER
A 4 neck, round bottomed fla~k equipped with m~chanicel ~tirrar, r~flux conden~er, thermomet~er9 nitrogen inl~t and fluid metering pump W~8 charged with 1472 parts xylene, 240 parts maleic ~nhydride and heated to reflux (139C) under nitrogen. A
; monomer mixture of 480 p8rt8 i~obutyl methacrylate, 720 part~
butyl acrylate,'720 part~ methyl me~hacrylate, 120 p~st3 m~leic a`nhydride and 60 parts t-butyl perbenzoate were then m~tered lnto the reaction over a 3-hour period. H~lfway through th2 addition, an additional 120 p~rts of mal~ic anhydrid~ wa~ ch~rg~d to the reaction v~el ~nd monomer addition wa~ continued. After refluxing the r~action mixture for an additional 15 minutes, 12 p8rt8 of t-butyl p~rbenzo~t~ in 128 part~ xylene wese added over 45 minute~. Heeting w~ continued for ~ hours at reflux. The resulting xylene ~oluble anhydride-function~l re~in was 61.2Z
' ;

`~ 1 307607 1 solids, had A Gardner Holdt visco6ity of 24.5, an ~cid value of116.5, ~nd A den~ity of Rpproximately 8.6 pounds per gallon.

CARBOXY-FUNCTIONAL ACRYLIC POLYMER
A carboxy-functional acrylic polymer wa6 prep~red by charging a reaction vsssel equipped with a mechanical ~tirrsr, reflux condenser, thermom~ter, nitrogen inlet and fluid metering pump with 1621.2 parts xylene which wn~ then heated the ~olvent to 120~C under nitrogen. A monomer mlxture compo~ed of 1013.2 10 ~ p~rt~ hgdroxy ethyl ~ryl~te, 1013.2 part~ Tone M-100 (trade na~--of Union Carbid~'~ hydroxy acrylic/c~prolactone adduct believed to be the reaction product of 1 mole of hydro~y ethyl acryl~t~
and 2 mole~ of csprol~ctone), 2~37.2 parts methyl me~hacryl~te, 3242.1 p~rts isobutyl methacrylate, 81.1 part~ Vazo 67 ~tr~dsmark lS for E. I. duPont initiator believed to be 2,2'-azobis(2-methylbutyronitr1lc)) and 6352.9 parto xylene wa~
metered into th~ reaceion vessel over ~ perlod of 3 hour~ whlle maint~inin~ the temperature of the re~ctlon vec~l at 120C.
After the monomer mix addition wa~ completed, ~h~ tqmperatura of !0 the reaction mixture WA~ r~l~ed to reflux ~137C) and 20.3 p~rt~
Vazo 67 in 131.4 part~ xylene W~8 added over ~ perfod of 30 minutes. Reflux temperature wa8 maintained for one additional hour. After cooling the reaction mixture to room temper~ture, 1144.4 pflrt~ msleic anhydride ~nd 114404 p~rta xylene were ~dded.
S The polymeric ~olu~ion W~8 heated to 60C ~nd 10.8 p~rts trie~hyl amine waa added. The reaction mixture was stirred and m~intained at 60C for approxim~tely 6 hour~. The resulting carboxylic -- 27 ~

,~
' acid~function~1 acryllc polymer hRd a thsoretic~l percent ~olidr of 48.1, H Gartncr Holdt viscoslty of V-, snd an acit equivalent weight of 790.

HYDROXY-FUNCTIONAL ACRYLIC POLYMER
A hydroxy-functio~al polymer was pr~psr~d by initi~lly ch~rging ~ polymerlz~tlon re~ctor aqulpped wlth a m~hanical ~tirr~r, ~ wnter cooled condenser, nitrog~n inl~t, water trap, thermometer, hesting m~ntl~ and fluid met~ring pump with 172.5 p~rt~ of n-butyl acetate. Ths reaction veas~ ho~ted to approxim~t~ly 237F nnd a monomer premix compo~et of 96.2 part~
of methyl meth~cryl~ 3.0 parts of butyl a~rylHt~, 58 p.art~ of hydroxy ethyl m~thacrylate~ 54 p,arts styrena and an inltiator premixture composad o 11.5 parts of n-butyl ~cet~te ~nd 5.7 ~ part~ of Vazo 67 w~s metsred ~imultaneou~ly into the polymeriz~-tion re~ctor at ~ const~nt r~te ov~r ~pproximately 4 hours. The reaction temper~ture was m~intained for an ~dditional 2 houra after th~ addition W~8 completed and cooled for one hour. The resulting hydroxy-function~l polymer h~d ~ number ~vera~ mol9c-'O ular welght of sppr~xlm~tely 9,600.
EXAM _ _ ANHYDRIDE-FUNCTIONAL ACRYLIC POLYMER
A reac~ion vqssol aquipped a8 {n Exampl~ I w~a charg~d with 6,624 psrts of xyl~n~, 648 p~r~o of m~ anhyt~id~ ~nd he~d to refl~x under n~trogcn. To this h~ted solution a monomor mix-tu,re of 5,616 p~rt~ butyl acryl~te, 3,024 partB methylmeth- , -~crylat~, 540 p~rts m~leic anhydrlde ~nd 270 part~ of t-butyl .
~ ~ 20 -.. - . . - ...

"` 1 307607 peroctonte was metered into the re~ction v0ssel at a constant rate over 8 3-hour time period. At 1 hour and at 2 hours into the monomer flddition, heatin~ and monomer addition were stopped and the reactor was charged with 540 parts and 432 pBrtB of malelc anhydri~e respectively. Heating wa3 resumed to reflux and the monomer ~ddltion wa8 continued. The reaction mi~ture wn~
mnintained at reflux temperature for nn additional 15 minute~
after the completion of all of the monomer addition. A solueiOn of 54 parts of t-butyl peroctoate in 576 parta xylene wa~ added to the reaction over a 45~minute p~riod. The r~action was held at reflux or an additional 2 hours and then allow2d to cool to room temperature to obt~in an anhydride-function~l polymer hsvlng a number avernge molecular we~ght of about 1,800 and a free maleic anhydr.ide content of le88 than 0.1%. This polymer had an - average of about 3.6 anhydride groups per molecuie.

, PREPARATION OF CLEAR COATING
A curable clesr co~tlng wac prepared according to tho following reclp~:

o '. .

;~

' .
, Raw Materi~l Parts-Bv-Weizht Hydroxy-Functional Acryllc Recin of Example 3 170.31 ERL 42211 54.46 Acid-Function~1 Polymer of Ex~mple 2 430.84 Xylcn~ 37.56 Tol.uene 43.44 Byk 3002 2.5 20~ N-Mathylimidazole/
1~ Methyl Isobutyl Ketone 4.78 20% Triphenylpho~phine/
Toluene 13.19 Tinuvin 2923 2.95 202 Tinu~in 32a4/Tsluene 24.59 Anhydrid~-Fun~tional Polymor of ~ Example 1 44.35 Vnion Carbid~ tradem~rk for 3,4-epoxycyclohexylmathyl 3,4-epoxycyclohexane c~r~oxyl~te 2flow control agent ~old by Byk-Mallnkrodt (T J
trademark of Ciba--Geigy for dl[4(2,2,6,6-tetramothyl pi~rdinyl)]'oebscate light stab$1izer trsde~ark'of Cib~-Geigy for 2-(2-hydroxy-3,5~diterti~ry amyl-phenol)-2H-benzotrlazole This co~ting formulation r~pre~ent~d ~pproxi~tely 3.0 hydroxyl group~, about 3.0 ~poxy groups and 2.0 c~rboxyl$c acid group~ Xor each anhydrid~ group. The triphenylpho~phine c~talyst wa~ pre~ent a~ ~pproximately 1~ on epoxy and cnrboxylic acld solid~, ~nd the N-methylimidazols i8 preaent a~ approxi~tely 3 . 5~ of the anhydride rssin~ ~olid~.
The clesr coatings wer~ ~pplied to metAl aub~tr~te~ immedi-at~ly aftar mixing and allowed to Air dry. The co~t~d filma : ~ 30 -: ~ .

``` ~ 307607 exhibited ~ Koni~ Pendulum Hardneso number of 12 sfter sne d~y, 45 after ~aven days and 72 after 35 day~. The cured films had good solvent r~sistance, excellent resistance to humldity (170 hours) and to salt ~pray (170 hours).

A curable clear coatlng intcnded for u8e over ~ ba~ecoat/
pri~r syst~m wa~ prepared according to th0 followlng recipe:
Raw Materials P~rts Carboxylic Acid-Functional Polymer of Example 2 ~22.72 ERL 4221 53.22 Anhydrlde-Functional Polymer of Example l 44.08 Hydroxy-Functional Polymer of Example 3 163.02 Xylene 198.81 ~y~ 300 . 2.5 20% N-Methylimid~zole/Methyl Isobutyl Katone 4.70 20% Tinuvin 328¦Tolu0ne 24.05 Tinuvin 292 ', 2.89 Thi~ clear formulation represene~ 3.0 hydroxyl groupa, 3.0 epoxy groups snd 2.0 carboxylic acid groups por esch ~nhydride group. The N-mcthylimid~zole cata~yst i~ pre~ent At ~bout 3.5 based on the anhydride re3in ~olids. Th~s coating w~ reduced with suit~ble ~olv~nto and spr~y applied over tha primer ~nd base-co-t on iron phosphate tre~ted cold rolled ~te~l. The co~ting !5 system was allowed to a~blent cure 24 hour~ before te~tin8.
The resultant film exhi~itad a Konig Pendulum H~rdne~s reading of 9 s~ter one d~y, 21 ater one week and 30 aft2r four .~_ ~ 31 -~ ~ . ` ` . .
: ~

,~ , - .
:' :

' '' ' , `` ~ 307~07 weeks. The coating exhibited solvent resistance of 2 flfter one dny and 9 Rfter four week~. A 20 glos~ readin8 of 84 and fl dis-tinctness of im~e re~dlng o 92 W88 obtained. S~lt spr~y re~ist-ance at 170 hour~ of expo~ure to 5~ sfllt spray solution was excellent.

Exampl e ~ 7 - 15 . Exnmples 7 - 15 were carri~t out by a similar procedure to ehat de~crlbed for Example 6 except for the modifications described in the table below. Th~ nnhydride-function~l polymer 1~ used in Examples 7 - 15 i8 tha~ described in Example 4.

!5 ~ 32 -.
, '~ ..............

:

., .
~,i ` - -``` 1 307607 a~ ~ _ ~ _ ~_ o~
O ~ C~ ~ O ~ O ~ ;r 0~ ~5 ~ O U~ o r~ u~ ~
s _ ~_ o o O O
_ . _ O-- O ~ O ~ C~ r 0 ~ a) u~ u~ ~ o .

,~ 0 _ .~ C`l ~ ~ C'J o U~ ~
o ~ o ~ O ~ O ~ ~ CO ~ ~ ~ ~ ~ ~ U~ ~D

~
I~ ~ C~
~o ~ ~ "~ C.) O-- O ~ O-- O ~ ~ ~ C~ 0 . ~ ,~ ,~ ~ 0 o o o ~-- o -- o ~ c~ o ~ a~

r~ o o _ ~ `Q ~o _ ~ o-- o-- o-- o-- o ~o ~ o ~ ~ C~
D _ ~_ ~ 0 ~O ~
E-~
O O O O
~ ,_ U') _ O O
o C~i o C~ i o ~ o _ ~0 O O O O
O ~ O--~ O--~ O--~ -- I~ ~J C~l ~ ~ r~ Ul _ 00 ~ U~ ~ U~ ~

O '-- O-- O--~ O
~ 0 ~ .
C~ _ O
~0 ~ O '~
_ ~ 3 0 V )-n. : v ~ V ~ * U ~ ~: C
~o ~ C ~ C C n ~
X 0 _, ~ ~ ~ o _ ~ ~ ul _ ~ .1 ~ ~ 1 rl al P. t: 1~ '~ O ~ rl C P~ D
X ~ E -- ~ ~ ~ ~ o ~ .,~
~r~ ar O ~ ~ cr 1~ a~ z ~ ~ F-~ o 1~
o ~ ~ o o ~ ~u ¢
~ ~ ~ Q ~ Q ~: 3 U'3 : :
,. ~:
,, ~`
- ~ 3 3 ^

.
.
.

.

ExamDles 16 - 19 .. A , _ Examples 16 19 were prepared by mixing the component~ to provide the equlvalent and welght ratio6 identifi~d in the Table below and ~pplying the coating6 to iron phoqphate treated cold rolled steel substrates ~nd baking the coat~d ~ubstrate~ for 30 minutes at 180F. In the T~ble below the epoxy compound ~as ERL-4221, the ~cid-functional polymer wa3 that of E~mple 2, the hydroxy-functlon~l polymer waa th2t of Exempl~ 3, ~nd th~

anhydride-functional polymer waa that of Ex~mple 4.
Table 2 BAKED EXAMPLES

Wei~ht and Equivalent Ratios Epoxy/COOH Equiv~lents 1.5/1 1.4/1 1.5/1 1.5/1 OH/ANH Equiv~lent~ 3.0/1 2.0/1 2.5/1 2.5/1 Z Epoxy/COOH Solid867g 50% 90~ 10 % OH/ANH Solldo 33~ 50g 10~ 90 RESULTS
KONIG P~NDULUM HARDNESS
I Day 66 57 54 78 1 Week 109 92 114 102 4 Weeks 128 111 134 110 MEK
1 Day 3 4 5 7 1 W~3ek 4 5 6 7 0 4 Weeks 5 5 6 7 20 Glo~ 94 92 93 94 HUMIDITY
Wet Adhe~ion 10 10 10 10 Blushing 7 10 10 0 Glo~s Retention-Post 1 hr 98X 99~ 1002 24~ -SALT SPRAY
; Scribe Creepag~ (mm) 6 4 6 5 Scribe Corrosion 6 7 4 4 While this Invention ha~ been described by a ~pecific num4er ,, .

~ 34 -'' ,. ' . .

.
;~;
:'1' ~,. .

~"` 1 307607 of embodimqnt8, it i~ obvious that other variation~ and modlfic~-tions may b~ mad~ without dep~rting from the spirit and sc~pe of the invention ~ ~e~ forth in the appended claims.

~; 10 ~ ' 15 - :
.

.

S

:35 - :

~ ~ ,. ..

,:., :~

:~: ' ~ , '' . -, . ' ' ' -

Claims

1. A curable composition which comprises:
(i) an acid-functional compound which has an average of at least two carboxylic acid groups per molecule and is prepared by reacting a hydroxy-functional polymer with at least one cyclic anhydride to form acid and ester groups;
(ii) an anhydride-functional compound having an average of at least two cyclic carboxylic acid anhydride groups per molecule;
(iii) an epoxy-functional compound having an average of at least one epoxy group per molecule; and (iv) a hydroxy-functional compound having an average of at least two hydroxyl groups per molecule;
wherein at least one of the compounds (i), (ii), (iii) or (iv) comprises a film forming polymer; and the compound (iii) is different from the compound (iv).

2. The composition of claim 1, wherein the acid-functional compound has a number average molecular weight of at least about 400.

3. The composition of claim 1, wherein the acid-functional compound is prepared by a half-ester reaction of a hydroxy-functional polymer having a number average molecular weight of 400 to 30,000 and a monomeric aliphatic or aromatic carboxylic acid cyclic anhydride having one anhydride group per molecule.

4. The composition of claim 3, wherein the hydroxy-functional polymer is a polyether polyol or a polyester polyol.

5. The composition of claim 3, wherein the hydroxy-functional polymer comprises the addition - 36a -polymerization reaction product of (a) 10 to about 60 weight percent of a hydroxy-functional ethylenically unsaturated monomer and (b) 40 to about 90 weight percent of at least one ethylenically unsaturated monomer copolymerizable with the hydroxy-functional monomer.

6. The composition of claim 5 further characterized in that the cyclic anhydride is maleic anhydride.

7. The composition of claim l further characterized in that the anhydride-functional compound is an anhydride-functional polymer having a number average weight of at least about 500.

8. The composition of claim 7 further characterized in that the anhydride-functional polymer is the addition polymerization reaction product of at least one unsaturated monomer having anhydride functionality.

9. The composition of claim 8 further characterized in that the anhydride-functiona1 polymer is the additon polymerization reaction product of (a) 5 to 40 weight percent of an ethylen-ically unsaturated monoanhydride and (b) 60 to 95 weight percent of at least one other ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated anhydride.

10. The composition of claim 9 further characterized in that the monoanhydride is maleic anhydride.

11. The composition of claim l further characterized in that the epoxy-functional compound is a monoepoxide.

12. The composition of claim 1 further characterized in that the epoxy-functional compound has an average of at least two epoxy groups per molecule.

13. The composition of claim 12 further characterized in that the epoxy-functional compound is a cycloaliphatic epoxy.

14. The composition of claim 13 further characterized in that the epoxy compound is selected from the group consisting of 3,4-epoxy cyclohexylmethyl 3,4-epoxycyclohexane carboxylate;
3,4-epoxy 6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexane carboxylate; bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; bis 2,3-epoxycyclopentyl) ether; dipentene dioxide;
2-(3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy) cyclohexane-metadioxane; and bis(3,4-epoxycyclohexylmethyl)adipate.

15. The composition of claim 1 further characterized in that the hydroxy-functional compound is a hydroxy-functional polymer having a number average molecular weight of at least about 400.

16. The composition of claim 15 further characterized in that the hydroxy-functional polymer is selected from the group consisting of hydroxy-functional polyethers, polyesters, acrylic polymers, polyurethanes, and polycaprolactones.

17. The composition of claim 15 further characterized in that the hydroxy-functional polymer is an addition polymerization reac-tion product of (a) 10 to about 60 weight percent of a hydroxy-functional ethylenically unsaturated monomer and (b) 40 to about 90 weight percent of at least one ethylenically unsaturated monomer copolymerizable with the hydroxy-functional monomer.

18. The composition of claim 1 further characterized in that it also incorporates a catalyst for the reaction of acid groups and epoxy groups.

19. The composition of claim 18 further characterized in that the catalyst is triphenyl phosphine.

20. The composition of claim 1 further characterized in that it also incorporates a catalyst for the reaction of anhydride and hydroxyl groups.

21. The composition of claim 20 further characterized in that the catalyst is a tertiary amine.

22. The composition of claim 21 further characterized in that the tertiary amine is N-methylimidazole.

23. The composition of claim 1 further characterized in that compounds (i), (ii), (iii) and (iv) are each present at a level to provide about 0.05 to about 3.0 acid groups and about 0.5 to about 4.0 epoxy groups and about 0.05 to about 6.0 hydroxyl groups for each anhydride group.

24. The composition of claim 23 further characterized in that compounds (i), (ii), (iii) and (iv) are each present at a level to provide 1.0 to 2.0 acid groups and 1.0 to 3.0 epoxy groups and 1.0 to 4.0 hydroxyl groups for each anhydride group.

25. A curable composition which comprises:

(i) an acid-functional polymer having an average of at least two carboxylic acid groups per molecule and wherein the polymer is obtained by the half-ester reac-tion of a hydroxy-functional polymer with a cyclic carboxylic acid anhydride; and (ii) an anhydride-functional polymer having an average of at least two cyclic carboxylic acid anhydride groups per molecule and wherein the anhydride-functional polymer is the addition polymerizatlon reaction product of (a) 5 to about 40 weight percent of an ethylenically unsaturated monoanhydride and (b) 60 to about 95 weight percent of at least one other ethylenically unsaturated monomer copolymerizable with the ehtylenically unsatur-ated anhydride; and (iii) an epoxy-functiona1 compound having an average of at least two cycloaliphatic epoxy groups per molecule; and (iv) a hydroxy-functional polymer having an average of at least two hydroxyl groups per molecule.

26. The composition of claim 25 further characterized in that the hydroxy-functional polymer which is reacted with the cyclic carboxylic acid anhydride comprises the addition polymerization reaction product of (a) 10 to about 60 weight percent of a hydroxy-functional ethylenically unsaturated monomer and (b) 40 to about 90 weight percent of at least one ethylenically unsaturated monomer copolymrizable with the hydroxy-functional monomer.

27. The composition o-f claim 26 further characterized in that the cyclic carboxylic acid anhydride is maleic anhydride.

28. The composition of claim 25 further characterized in that the anhydride-functional compound is an anhydride-functional polymer having a number average weight of at least about 500.

29. The composition of claim 28 further characterized in that the anhydride-functional polymer has a number average mole-cular weight of 500 to 7,000 and is the addition polymerization reaction product of (a) 15 to 25 weight percent of an ethylenical-ly unsaturated monoanhydride and (b) 75 to 85 weight percent of at least one other ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated anhydride.

30. The composition of claim 29 further characterized in that the monoanhydride is maleic anhydride.

31. The composition of claim 25 further characterized in that the epoxy compound is selected from the group consisting of 3,4-epoxy cyclohexylmethyl 3,4-epoxycyclohexane carboxylate; 3,4-epoxy 6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexane carboxylate; bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate;
bis(2,3-epoxycyclopentyl) ether; dipentene dioxide; 2-(3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy)cyclohexane-metadioxane; and bis(3,4-epoxycyclohexylmethyl)adipate.

32. The composition of claim 25 further characterized in that the hydroxy-functional polymer is a hydroxy-functional polymer having a number average molecular weight of at least About 400.

33. The composition of claim 32 further characterized in that the hydroxy functional polymer is an addition polymerization reac-tion product of (a) 10 to about 60 weight percent of a hydroxy-functional ethylenically unsaturated monomer and (b) 40 to about 90 weight percent of at least one ethylenically unsaturated monomer copolymerizable with the hydroxy-functional monomer.

34. The composition of claim 25 further characterized in that it also incorporates a catalyst for the reaction of acid groups and epoxy groups.

35. The composition of claim 34 further characterized in that the catalyst is triphenyl phosphine.

36. The composition of claim 25 further characterized in that it also incorporates a catalyst for the reaction of anhydride and hydroxyl groups.

37. The composition of claim 36 further characterized in that the catalyst is a tertiary amine.

38. The composition of claim 37 further characterized in that the tertiary amino is N-methylimidazole.

39. The composition of claim 25 further characterized in that compounds (i), (ii), (iii) and (iv) are each present at a level to provide about 0.05 to about 3.0 acid groups and about 0.5 to about 4.0 epoxy groups and about 0.05 to about 6.0 hydroxyl groups for each anhydride group.

40. The composition of claim 39 further characterized in that compounds (i), (ii), (iii) and (iv) are each present at a level to provide 1.0 to 2.0 acid groups and 1.0 to 3.0 epoxy groups and 1.0 to 4.0 hydroxyl groups for each anhydride group.

41. A substrate coated with a multi-layer decorative or protective coating, which comprises:
(a) a base coat comprising a pigmented film-forming polymer; and (b) a transparent clear coat comprising a film-forming polymer applied to the surface of the base coat composition;
in which at least one of the clear coat and the base coat is formed from a multicomponent curable composition which is reactive upon mixing of its components, the curable composition comprising.
(i) an acid-functional compound which has an average of at least two carboxylic acid groups per molecule and is prepared by reacting a hydroxy-functional polymer with at least one cyclic anhydride to form acid and ester groups;
(ii) an anhydride-functional compound having an average of at least two cyclic carboxylic acid anhydride groups per molecule;
(iii) an epoxy-functional compound having an average of at lea t one epoxy group per molecule; and (iv) a hydroxy-functional compound having an average of at least two hydroxyl groups per molecule;

wherein at least one of the compounds (i), (ii), (iii) or (iv) comprises a film forming polymer; and the compound (iii) is different form the compound (iv).

- 43a -

42. The coated substrate of claim 41 further characterized in that the epoxy-functional compound has an average of at least two epoxy groups per molecule.

43. The coated substrate of claim 42 further characterized in that the epoxy-functional compound is a cycloaliphatic epoxy.

44. In a substrate coated with a multi-layer decorative and/or protective coating which comprises:
(a) a basecoat comprising a pigmented film-forming polymer;
and (b) a transparent clearcoat comprising a film-forming polymer applied to the surface of the basecoat composition;
the improvement which comprises utilizing as the clearcoat and/or the basecoat a multicomponent curable composition which is reactive upon mixing of the components, wherein the curable composition comprises:
(i) an acid functional polymer having an average of at least two carboxylic acid groups per molecule and wherein the polymer 18 obtained by the half-eater reac-tion of a hydroxy-functional polymer with a cyclic carboxylic acid anhydride; and (ii) an anhydride-functional polymer having an average of at least two cyclic carboxylic acid anhydride groups per molecule and wherein the anhydride-functional polymer is the addition polymerization reaction product of (a) 5 to about 40 weight percent of an ethylenically unsaturated monoanhydride and (b) 60 to about 95 weight percent of at least one other ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated anhydride; and (iii) an epoxy-functional compound having an average of at least two cycloaliphatic epoxy groups per molecule; and (iv) a hydroxy-functional polymer having an average of at least two hydroxyl groups per molecule.

45. The composition of any one of claims 1 to 24, which is a multi-package system comprising a first package which contains the anhydride-functional compound (ii) and the acid functional compound (i) and a second package which contains the epoxy-functional compound (iii) and the hydroxy-functional compound (iv), so that the packages may be mixed together immediately prior to use of the composition whereby the compounds react and cure.

46. The composition of any one of claims 25 to 40, wherein at least one of the polymers (i), (ii), and (iv) is a film forming polymer; the composition is contained in a multi-package system comprising a first package which contains the anhydride-functional polymer (ii) and the acid-functional polymer (i) and a second package which contains the epoxy-functional compound (iii) and the hydroxy-functional polymer (iv), so that the packages may be mixed together immediately prior to use of the composition whereby the compounds react and cure.