CA2181191A1 - Body putty resin - Google Patents

Abstract

A body putty resin composition of the present invention comprises 20 to 50 weight percent of a reactive component which becomes an integral part of the composition on curing, and 50 to 80 weight percent of a polyester formed from an .alpha.,.beta.-unsaturated dibasic acid and/or anhydride, one or more of a polyhydric alcohol, a combination of a polyhydric alcohol and dicyclopentadiene, or dicyclopentadienyl alcohol, and optionally a saturated dibasic acid and/or anhydride, wherein the ratio of total number of equivalents of hydroxy to total number of equivalents of acid is about 0.5 to 1.2 and wherein from about 15 to 60 percent of the .alpha.,.beta.-unsaturated dibasic acid and/or anhydride is available to react with the reactive component.

Description

21 ~ l t ~ ~
~10 95119379 P~

BODY PUlT~ RESIN
Related A.,`-The present application is a ~ i.."-in-part of U.S. Serial No.
08/182,467, filed January 13, 1994, the disclosure of which is illCu herein by reference in its entirety.
Field and B;.~4". ~ ' of the Invention This invention relates to a body putty resin .~ ;.,., The body putty resm r-.-~ ; ., of the present invention exhibits adherence to metallic surfaces such as zinc-coated (galvanized) metals, and thus is particularly adapted for use m repairing automobile bodies.
Dents, gouges and other surface i.. ~.Llliii~,~ of ).. ~ r body parts are routmely fixed or repaired with either metallic solders or various plastic materials. Metallic solders are disfavored because ~rplir~ir~n thereof is difficult and requires a great deal of skill. Exemplary plastic materials are a putty composed of a thermoset resin (e.g., an ~ ' polyester resin or an 15 epoxy vinyl ester), fillers, promoters, catalysts and other additives. The putty is allowed tû harden and is ~L.,~.l... lly sanded to conform to the desired contour of the ~ ~( ' '- body part. Standard body putty has successfully been used to repair damaged steel surfaces of automobile bodies. However, rust and corrosion have i l~ ;ly become major problems for -L ~ whose 20 bodies are .. ri.. I- -c~ from mild steel (i.e., low carbon steel).

WO95~19379 2~ 8 1 1 q i .~
In order to minimize corrosion, the automobile industry is replacing mild steel with zinc-coated (galvanized) steel. It has been found tnat standard body putties that are typically used for mild steel have poor adhesion to galvanized steel. Thus, an urgent need exists for a means of improving the 5 adhesion of automobile body putties to galvanized steel.
For example, U.S. Patent No. 5,169,723 to Forster proposes that a chemically etched surface of galvanized stee~ provides improved adhesion for a polyester resin based automobile body putty. The etching solution comprises a metal salt that is more CI~ LIU~U~ Vt: than zinc. The putty is applied to the lû etched surface and after curing is sanded to conform to the desired contour of the automobile body.
U.S. Patent No. 4,525,427 to Bayha et al. relates to a polyester ;. . capable of forming a thin film that adheres to metal and plastic substrates, such as steel, and are IJa~ ,uldlly useful in repairing automobile 15 bodies. These ..,."l..,~:';...,~ are referred to as "body putty prirners". Bayha further proposes tbat the metallic surface may also be chemically etched to maximize adhesion of surfacing materials to the metal surface. However, body shops tend to want to avoid CULU~IUII1~ the galvanized surface by sanding into the metal or etching the surface in view of car-maker warranty limit~rinn~,20 especially as it includes amother labor step. Other l,UlUI)O~i~iUll:~ and methods for repairing automobile body parts are proposed m, for example, U.S. Patent Nos. 4,531,275 to Kelly, 4,732,633 to Pokorny, and 4,308,118 to Dudgeon.
Despite the general availability of various plastic materials and methods for repairing automobile body parts, there contirlues to be a need for 25 ~ IU.~ L~ in body putty resin C., 'l"~ , and palLi~ ulally m the adhesion thereof to zmc-coated (galvanized) metal. Moreover, such a body putty resin must be capable of providing a coating which is flexible. A body putty which is more flexible will be less likely to be dislodged from the automobile due to cohesive failure.

2181 ~91 ~;o s~tls37s r~ n., Surnmairv of the Invention With the foregoing in mind, it is an object of the invention to provide a body putty resin ~ J~ ll which has improved adherence to metal surfaces and ~ U.~lly zinc-coated (galvanized) metal surfaces.
s 5 It is a feature of the present invention to provide a flexible body putty resin .. ,~ il ", It is another feature of the present invention to provide a body putty resin ~ which provides a surface with improved sandability.
It is another feature of the present invention to provide a body putty resm Culll~v~iliull which does not require the galvanized metal surface to be CUIII!JIUIIIi~CI~ to effect adhesion of the resin CUIIIIJU~i~iUII to the metal surface.
These and other objects, features and advantages are provided by the body putty resrn ~."..~ ;(,.. of the present invention which comprises 20 to S0 weight percent of a reactive component which becomes an integral part of the 15 ~.~\mrt~citinn on curing, and 50 to 80 weight percent of a polyester formed from an cv,~ dibasic acid and/or anhydride, one or more of a polyhydric alcohol, a c.,...l,~ i..., of a polyhydric alcohol and ~i~y~ li ,., or Y~ .IYI alcohol, and optionally a saturated dibasic acid and/or anhydride, wherein the ratio of total number of equivalents of hydroxy to total 20 number of equivalents of acid is about O.S to 1.2, and preferably 0.8 to 1.2, and wherein from about lS to 60 percent of the c~ dibasic acid and/or anhydride is available to react with the reactive c--mr~n.ont Typically, the resin ~.,...l..,~;l;.", comprises S0 to 80 weight percent of polyester formed from about 30 to 40 weight percent of an (Y"~-l ' 25 diacid and/or arlhydride, 30 to 40 weight percent of di~y- l"~ 1; ,. 7 and 20to 30 weight percent of a polyhydric alcohol; and 20 to S0 weight percent of a reactive component which becomes an integral part of the uu~ Ju~;lio~ on currng. The body putty cr.mr-citi~n can include fillers, pigments, thixotropic additives, l~hII-UII~iIIg materials, and various other ~u..~ Liul~l additives.
In another, .. I,o l;.~,. .. 1 the present invention provides a body putty resrn c~ - comprising 20 to 50 weight percent of a reactive component which becûmes an integral part of the . .",.l, .~ on curing; and S0 to 80 ... .. . . _ _ _ .. . _ _ _ . _ _ _ .

218~ql WO 95119379 . ~_I/U_ '.'l .

weight percent of a polyester formed from an cY,~-l ' dibasic acid and/or anhydride, a polyhydric alcohol and ~ y~ ;. ."~ or derivative thereof, and optionally a saturated dibasic andlor anhydride, wherein a nadic moiety is formed between the o~ ul~d~uldl~d dibasic acid and/or anhydride 5 and ~;y~ l;- ,.. formed from di~y~lu~ Lddiene or derivative thereof, wherein the ratio of total number of equivalents of hydroxy to total number of equivalents of acid is about 0.5 to 1.2, and preferably 0.8 to 1.2, and wherein from about 15 to 60 percent of the ~ l.rl~11 dibasic acid and/or anhydride is available to react with the reactive C~mrr~nl nt The present invention also provides a galvanized metal surface adhered to which is a body putty resin CUIu~O~i~iull comprising 20 to 50 weight percent of a reactive component which becomes an integral part of the ~,ulllpO~iLiull oncuring, and 50 to 80 weight percent of a polyester formed from an dibasic acid andlor anhydride, one or more of a polyhydric 15 alcohol, a ,"",l, ,-~;.", of a polyhydric alcohol and di~yl-lu~llLddi~lle~ ordi~,y ~ l;. ..,yl alcohol, and optionally a saturated dibasic acid andlor anhydride, wherein the ratio of total number of equivalents of hydroxy to total number of equivalents of acid is about 0.~ to 1.2, and preferably 0.8 to 1.2, and wherein from about 15 to 60 percent of the cY,~-u~ LIll ' dibasic acid 20 andlor anhydride is available to react with the reactive component.
The term "galvanized" is irltended to relate to zinc-coated metal.
Galvanized metal is commonly used to protect rust-prone metal such as the steel used m automobile bodies. The surface of galvanized metal used in the . ~m~il~ imdustry typically is coated with zinc or a zinc alloy to about 50 to 25 70glm~. It is this type galvanized metal to which the present invention is iLUlally directed, although it is u~ ,' ' to use the body put~y resin CUIll~u~iLiOll of the present invention with other metallic surfaces.
The present invention also provides a method of repairmg a damaged galvanized metal surface. The method comprises catalyzing the curitlg of one of the above-described body putty resin .. ,1,.,~;l;.,.. ~, applying the curing body putty resin ~ to the damaged metal surface; and subjectmg the ....... .. .. . ......... ....... . . ... .. . . .. _ .. . ,, _ . . , ,,, _ _ _ _ 2181 1~
~10 95/19379 P~
S
damaged metal surface having the body putty applied thereto to conditions sufficient to cure the body putty and to finish the damaged metal surface.
Brief Description of the DravnnrJg Y Figure 1 is a ~.~c~liv~ view of an automobile having a metal surface adhered to which the body putty resin ~ of the present invention is bemg applied.
Figure 2 is a cross-sectional view talcen along line 2-2 of Figure 1.
D` ' ' ` Degcriu~iQn of the Inventi~
The present invention will now be described more fully hereinafter.
10 This invention may, however, be embodied in many different forms and should not be construed as limited to the ~ ùdilll~llL set forth herein; rather, this r~ ,ol1;.ll. .,l is providcd so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those slcilled in the art.
In accordance with the present invention, a body putty resin ~r~".l."~ ", lS has been found having improved adhesion to metal surfaces and particularly galvanized metal surfaces. The body putty resin cr~mrr~ririr~n of the present invention also provides a flexible surface when cured and is less lilcely to be dislodged from the automobile due to cohesive failure. Moreover, the body putty resin c~ can be easily sanded in that the dusting is greater, 20 naunely, more of the cured resin .:~....l.n~;l;..., is removed with each sanding.
As ~-- .,---~-;~- J above, the body putty resm Culll~u~iLiull of the present imvention comprises 20 to 50 weight percent of a reactive component which becomes an integral part of the c.~ ;li.... on curing, and 50 to 80 weight percent of a polyester formed from an cY,~ dibasic acid and/or 25 anhydride, one or more of a polyhydric alcohol, a l,Ulllllill~iUll of a polyhydric alcohol and di-y~ lvl~ .I;r .~f:, or di~y- ~ l; rl alcohol, and optionally a saturated dibasic acid and/or anhydride, wherein the ratio of total number of equivalents of hydroxy to total rlumber of equivalents of acid is about 0.5 to 1 2, and preferably 0.8 to 12, and wherein from about 15 to 60 percent of the 2 1 ~
wo 95119379 r~

,,~-, ' dibasic acid and/or anhydride is available to react with the reacti~e Culll,ul ' In one ~l~ùdilll.,llL, tbe resin c-~mr--~itir~n comprises 50 to 80 weight percent of polyester formed from about 30 to 40 weight percent of an "~-5 1 ' diacid and/or anhydride, 30 to 40 weight percent ofdiuy. 1~ ;. , and 20 to 30 weight percent of a polyhydric alcohol; and 20 to 50 weight percent of a reactive component which becomes an integral part of the c~ ,., on curing In another rllll10~1;lll. .1l, the body putty resin ~;ulll,uu~iLioll comprises 20 10 to 50 weight percent of a reactive component which becomes an integral part of the l,UI~o~;Liul- on curing; and 50 to 80 weight percent of a polyester formed from an ,~ . ' dibasic acid and/or arlhydride, a polyhydric alcohol and di~y~ l~lu . - i;. .IG or derivative thereof, and optionally a saturated dibasic and/or anhydride, wherein a nadic moiety is formed between the ,,~-15 1 ' dibasic acid and/or anhydride and ~Y'll-r " formed from di~y~ u ~ i;.... or derivative thereof, wherein the ratio of total number of equivalents of hydroxy to total number of equivalents of acid is aboue 0.5 to 1.2, and preferably 0.8 to 1.2, and wherein from about 15 to 60 percent of the ,~ ' dibasic acid and/or arlhydride is available to react with the 20 reactive culllr Suitable ,~ .",~ i dibasic acids include maleic, fumaric, itaconic, chloromaleic, citraconic, and like acids arld/or anhydrides. Maleic acid and maleic arlhydride are preferred particularly when the formation of the tladic moiety is desired The amount of "B-I ' dibasic acid and/or 25 anhydride available for reaction with the reactive component is believed to be critical to the adhesion of the body putty resin in that the high amount of ' dibasic acid or anhydride results in a high reactivity The balance of any diacids or arlhydrides employed to modify the reactivity and properties of the polyester may be either saturated or of the non-cY,~-u..a~Luld~ed type, and 30 may be, for eAample, phthalic, isophthalic, terephthalic, LeLIdl~ydlu~llLlldlic, or teLId~,hlululullillalic acid, meLl.yl.ll.,~l dllydlu~ Lllalic acid (nadic acid),¦IGAd.l~lulu~l-lo-~ll~Lllyl.,.l~..~.-dl-yll-u~l-Lhdlic acid or low-molecular weight . .. . _ . .. . _ . _ _ . ... . .. ... . ... . ... . . .

2 ~ 7 1 ~0 95/19379 r~
aliphatic ~i~,albuAylic acids, such as succinic, adipic or diglycolic acid, or their anhydrides.
The resultrng resin ~-"..l.o~;l;."~ can have an end-capped di~.y~.lu~ ' '' moiety or can have a nadic moiety. The term "nadic moiety"
e 5 relates to the adduct formed between the ce,~-l i dibasic acid and/or anhydride (e.g., maleic anhydride) and cyrl~ derived from ~i.y- l l- ."A,I;. . In operation, one mole of di~y- I~ e cracks to produce two moles of cycl..~ .lr which in turn add across the double bonds of two moles of, for example, maleic acid derived from the ring opening 10 of maeieic anhydride. Another option is to use nadic acid or anhydride, and react it directly with the glycol. This is contrasted to an l'end-capping di~y~luL~ Lddi~ moiety" wherein during processing the elevated klulJ~IaLu of the reaction mixture are high enough to obtain a maleic anhydride-di y ~ ..."...l;.... adduct but low enough to avoid cracking di~yulu~llLddi~lle,15 and to avoid maleic acid i~,.." ;,;,.~ to fu naric acid. Typically, the cracking .l~lalulc is about 140C or higher.
Suitable polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, di~lu~yl~llc glycol, 1,3-butanediol, 1,4-butanediol, 1,3 hPY~ riinl, neopentyl glycol, methyl-~ 1,3-butylene glycol, 1,6-20 hP~ n~ iinl, neopentyl glycol, ethylene oxide adduct of bisphenol, and propyleneoxide adduct of bisphenol. The use of ;li~y. l. .~ in forming . ,. ,~
polyester is well known (~, for example, U.S. Patent No. 3,347,~04 to 7imm~rm~, the disclosure of which is ill ull,l ' herein by reference in its entirety). Derivatives of ~i.y~lu~llL~Ii~ can also be used such as 25 dicy~ l; alcohols if an end-capping moiety is desired. It is noted that the ratio of total number of equivalents of hydroxy to total number of c~ alcllL~ of acid is preferably 0.~ to 1.2 when maleic acid is not used and 0.5 to 1.2 when maleic acid is used.
The phrase "reactive component which becomes an integral part" is 30 intended to relate to a component that during curing (poly.". .;,~i.,.,) of the polyester becomes crosslinked into the polymer. This is to be contrasted to the use of solvents that are merely added as processing aids such as to dilute the .

wo95119379 . 1~. IIL ''t resin rnmpncilinn so that the resin can be applied as a coating such as described in U.S. Patent No. 4,525,427 to Bayha et al. or the use of wate} to form an emulsion such as described in U.S. Patent Nos. 4,447,577 and 4,551,489 to Bayha. The solvents in these patents are intended to be flashed off and do not 5 become an integral part of the polyester resin. Additionally, it is noted that the resins of Bayha are end-capped di~ r resins Suitable reactive ~ include acrylates such as Li~ /' , Styrene, vinyl toluene, divi~lyllJ~ , diallyl phthalaoe, and styrene-derivatives such as chlorostyrene.
The body putty ~.~.. I.n~;li,.,. can include a tertiary amine promoter.
Nonhydroxy functior~al tertiary amines include dil~ l~lilil,." diethylaniline, and dirnethyl-p-toluidine, and are typically mixed into the resin .,.~
Hydroxy-functional tertiary amine promoters include p-tolyl ,I;. :I....,. ,I ~ I; ~ ~ or n~-tolyl .1; 1~ and may be ill~:ul~ul..~d intû the polyester backbone 15 via r~l~ ;ri- ~ with acid end groups or can be simply mixed into the resin The curing of the body putty resin ~.. I.. ~;l;.. can be catalyzed by free radical perûxide initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, t-butyl l~dlu~ u~i~, t-butyl !,."l , and others known in the 20 art. Those skilled in the art will recognize that certain peroxide initiators will require that a metallic salt such as cobalt o~ r ' be blended into the resin to effect cure. Various types and . .. :.,-l;.. ~ of quinone (and other) types of inhibitors rnay be used to obtain the required gel time with free radical peroxide initiators.
The body putty resin .. I.. ~;li. can further include fillers, pigments and dyes, stabilizers, thixotropic additives and various other additives. Suitable fillers include calcium carbonate, clay, talc, alumina hydrate, kaolin. silica sand, mica, and the like. Preferably, the amount of filler in the resin culll,uuD;Lioi~ ranges from about 40 to 70 percent by weight. Suitable thixotropic 30 agents include activated silicas, castor oil derivatives, activated clay Ulh ULIU~;~D, and the like.

2181 ~91 ~) 95/19379 _9_ Reinforcing materials can also be included. A wide variety of rUl~,illg materials are available and include glass fibers, glass microballoons,carbon fibers, sisal fibers, Kevlar~ fibers, asbestos fibers, cotton fibers, steel fibers, and the like.
5 In operation, the body putty resin ci".,~ . is formed by reacting the individual c..,.~ together using known techniques. The resin composition is prepared in a reactor vessel equipped with a mPrh~nir~l stirrer, a condenser and an inert gas (e.g., nitrogen) inlet. The order of reaction will vary depending whether an end-capping di~ 1;. ."~ moiety or a nadic moiety 10 is desired. For example, if an end-capping moiety is desired, ~liLy' l.,l,. .,lAfliPn,~
or derivatives thereof and optional water if an anhydride form of the ' dibasic acid is used, are added to the vessel followed by adding the lY,3- ' dibasic acid and/or anhydride in a controlled manner such that the heat of the exotherm does not elevate the batch t~ a~UlC beyond about 15 125C. The t~ J.ld~Ul~ is maintained at about 125C for about 2 hours. The polyhydric alcohol and optional tertiary amine promoter are added before raising the L~ .lalu.~ to about 205C. The batch is cooled and the inhibitor and reactive component are added. The mixture is then cooled to about 25C.
The curing of the curable body putty resin ~ i,." is catalyzed using, for 20 example, using a free radical peroxide initiator.
If a nadic moiey is desired, the polyhydric alcohol (e.g., diethylene glycol) is added to the vessel in a controlled manner and heated to about 80C.
The c~,~ . ' dibasic acid and/or anhydride is added while limiting the batch i lll~ a~ul~ to about 130C. The vessel is heated to about 210C. The 25 L~ .ldt~.~ is cooled to about 170C and the di~y. ll,. .,1 -1;- Ir is added. The batch is held at 170C for about one hour to crack the uyl l~ . The mixture is then cooled to about 25C. The curing of the curable body putty resin cl~rr,~iti~n is catalyzed using, for example, using a free radical peroxide initiator.
As shown in Figures 1 and 2, the curmg body putty resin CUlu,uu~;Liull 10 is applied to a damaged metal surface 20 such as an WO 95/lg379 ~ J., 5'~ ~

automobile 30 fender. The resin Co~ )O~;Liull is permitted to cure and the damaged metal surface is finished such as by sanding and paintmg.
A cured body putty made with the body putty resin composition of the present invention provides rapid sandability (less than 20 mimutes after 5 catalyzation of putty made witb it) and superior adhesion properties perrAitting the artisan to sand the borders of the cured putty down to a "feathered-edge."
This is the region of di~a~ illg putty thickness grading into the ~UIIUUII~lillgd metal. Cured putties made with the resin of the present invention cease to be solvent sensitive (an important aspect of adhesion) in the feather-10 edge region in less than ~0 minutes following catalyzation of the putty. Incontrast, u.al-~.Ai~ body putties will remain solvent sensitive in the feather-edge region beyond 18 hours. If the repaired area is painted while still solventsensitive m the feather-edge region, the paint solvents will dislodge the putty film from the galvanized metal substrate causing peeling. Peeling, in turn, 15 costs the body shop time and labor to rework the area of repair. The putty has improved flexibility ~ il,uLIlly when it has a nadic moiety. The more flexible a pntty, tbe less likely it will disengage from the _ -' lP Additionally, the pntty is softer.
The following examples are illustrative of tbe present invention, and are 20 not to be construed as limiting thereof~

218~
~jo ss/1s37s P~ ,., 5. ~: ~
h:~AMPI .F~
EsamQle 1 A resin Culu~u~iliull comprising the following is prepared.
~QmPosiffQD ~QI~ Wgt % ~, vi.y. 1~.1,. .,IA.I;. .Ir 70 38.0 water 7 0.5 maleic anhydride 100 40.3 p-tolyl I;- :l -- ,n~ ;IlP 2 1.6 ethylene glycol 77 19.6 10 The resin c~ is prepared in a reactor vessel equipped with a mrrh7,nir~1 stirrer, a condenser and a nitrogen gas rnlet in the following manner. The vi.,y~ liPne and water are added under a nitrogen blanket to the Yessel and heated, with stirring, to 95C. Maleic anhydride is added in acontrolled manner such that the heat of exotherm does not elevate the batch 15 L~ J".aiul~ beyond about 125C. Following the addition of the maleic anhydride, the batch t~ u,~ is maintained at about 125C for about two hours. ~ liUII in this mamner maximizes the formation to the maleic-di~ r~ "~ r ester. The ethylene glycol andp-tolyl ~I;r~ ll;llP are then added before raising the reaction t~ -aLulc to 205C and processing the 20 polymer to its endpoint ~lrtP~minrd by a Gardner-Holdt viscosiy of S-T and acid number 8-15 at 67 percent IIUI.YOI~L;L~ in inhibited styrene. The batch is then cooled to 190C to slow tbe reaction. The batch is then blended with 50 ppm l.~llu~uiu~u..., inbibitor and syrene (reactive c.~mp~nPr~t~ such that the mixture is maintamed below 80C and such that the final lullv~ s content 25 of the mixture is about 65 percent by weight. The mixture is then cooled to 25C. The resulting resin when ~.UIII~JVUIIV~li with talc filler and catalyzed with benzoyl peroxide is easily sanded.
.

2 1 ~
WO9~/19379 ,~,1/.,."S.'~

Example 2 In order to evaluate the addition of no di~y. l..l~f .~ iPnP~ a resin f."",l.n~.~;.,., comprising the following is p}epared.
C~, '" Moles Wgt %
5diethylene glycol 105 49 9 p-tolyl l;~ 2 1.7 phthalic anhydride 20 13 .3 maleic anhydride 80 35.1 The resin ...,,,I..)~;li(.,, is prepared in a reactor vessel equipped as in Example 1.
10 The diethylene glycol andp-tolyl II;rlll--l(ll,lll,ill~ are added to the veSsel, with stirring, under a nitrogen blanket and heated to about 80C. Flaked phthalic anhydride is added through a powder funnel over about 20 minutes. The maleic anhydride (molten) is added in four equal portions over a one-hour period to limit the batch ~I~ flLUI~ (due to exotherm) to about 130C. The 15 reaction ~III,U~ UIC is then raised to 220C and the polymer is processed to its endpoint flPt~prminp~ by a Gardner-Holdt viscosity of J-K and an acid number of 10-14 at 67 percent IIUUVUIG~ in inhibited styrene. The batch is then cooled to 190C to slow the reaction. The batch is then blended with 50 ppm llydluuluillu.._ inhibitor in styrene (reactive component) such that the mixture is 20 maintained below 80C and such that the final llùll~uld~ ,il content of the mixture is about 65 percent by weight. The mixture is then cooled to 25C.
Example 3 ;n order to fl . - ~ - the formation of a nadic moiety, a resin ~"..~I,n~ comprismg the followmg is prepared.
25C; ~ . ' Moles Wgt %
diethylene glycol 60 28.5 propylene glycol 46 15.7 maleic anhydride 100 44.0 (.I;.. y I -~ r 20 11. 8 30 The resm ~ . :';.... is prepared in a reactor vessel equipped as in Exa~nple 1.
The diethylene glycol and propylene glycol are added to the vessel under a nitrogen blarlket, with stirring, and heated to about 80C. The maleic . _ _ _ _ . _ . , -2181 ~91 ~o ss/~937s ~ .J~5,.

anhydride is added in four equal portions over a one-hour period to limit the batch ~ U~ UlC (due to exotherm) to about 130C. The batch lc~ alulc is then raised to 210C and processed to the point at which the Gardner-Holdt viscosity is about S-T and the acid number of 10-20 at 67 percent ll~,..v.,I.~ s5 in inhibited styrene. The batch is then cooled to about 170C. The ~i~. 1."). ." .1;. ..f is now metered into the reactor over a one-hour period.
Processmg in this manmer maximr~es formation of the nadic moiety (maleic-cy~l~p! nf~if nf adduct) as each mole of di~ l .l~f 1; If- crdcks to produce two moles of ~,~ ;.... which in turn add across the double bonds of two 10 moles of maleic anhydride. Following addition of the ~ ;y. I..l.f .I~ .lf, fhe batch is held at 170C for one hour before cooling to slow the reaction. The batch is then blended with 50 ppm hydroqumone inhibitor and styrene (reactive c- r t) such that the mixture is mamtained below 80C and such that the final IIVIIv~)ldtil~ content of the mixture is about 65 percent by weight.
15 Finally, the batch is cooled to 25C. After cooling, 0.6 percent by weight (of polyester plus styrene) of ~i~u~ ul;liul~ is blended into the product.
E:xample 4 A resin Cull-~oDiliul~ comprismg the followmg is prepared.
C , ' Moles Wgt %
20maleic anhydride 1.0 40.5 li~. I.. l,, .. ~ .1;, .~f_ 0.32 18.8 diethylene glycol 0.69 30.2 ethylene glycol 0.41 10.5 The resin U~ r ''' is prepared according to the procedure outlined in 25Example 3 above.
Exam~le S
A resim ~ ;.,.. comprising the following is prepared.
Composition Moles W~ %
diethylene glycol 105 50.8 30 phthalic anhydride 20 13.5 maleic anhydride 80 35.7 .. _ _ . . . .

21 8~ lql woss/Ls37s r~,. s -The resin ~ is prepared in a reactor vessel equipped as in Example l.
The diethylene glycol is added to the vessel under a nitrogen blanket, with stirring, heated to about 80C. Flaked phthalic anhydride is added through a powder fimnel over about 20 mmutes. The maleic anhydride (molten) is then 5 added in four equal portions over a one-hour period to limit the batch ~ C (due to exotherm) to about 130C. The reaction L..,.~,.,.aLul~ is raised to 220C and the polymer is processed to its endpoint determined by a Gardner-Holdt viscosity of about J-K and an acid number of about 10-20 at 67 percent ~vllvvl~ in inhibited styrene. The batch is then cooled to 190C
10 to slow the reaction. The batch is then blended with 50 ppm ll~dlvuuil~vllc-inhibitor in styrene such that the mixture is maintained below 80C and such tbat the final l~vll~vld~ ,s content of the mixture is about 65 percent by weight.
Frnally, the batch is cooled to 25C. After cooling, 0.5 percent by weight (of polyester plus styrene) of dilll~Lllylallilillc is blended into the product.
Exam~le 6 A resin . ~ .r~ " comprising the following is prepared.
C . " Moles W~t %
diethylene glycol 105 46.
phthalic anhydride 60 37.1 maleic anhydride 40 16.4 The resin ~:v~ v~ihv.l is prepared according to the procedure outlined in Example 5 above.
C: ~ dt;~, Example I
A resin c..,..~ .... comprising the following is prepared.
ComDosition Moles W~t %
diethylene glycol 105 45 .6 phthalic anhydride 70 42.4 maleic anhydride 30 12.0 The resin ~ ,. is prepared according to the procedure outlined in 30 E~ample 5, above.

2 1 ~
~1 95~9379 r~

ComParative T~'..~,m~
A resin ~...."~ l comprising the following is prepared.
~ Moles W t %
diethylene glycol 105 44.6 5phthalic anhydride 80 47.5 maleic anhydride 20 7.9 The resim c,. ,l,..~;li.. is prepared according to the procedure outlined in Example 5, above.
Putty resins prepared in a manner similar to Comparative Example 2 are 10 typical of the vast majority of resins currently utilized in automobile body putties.
A~lh~cion Evp~ on ProcedlJre Each resin is adjusted to 500 centipoise viscosity with styrene and also adjusted with inhibitor (i.e., l~dlu4uu- m~) such that a putty prepared from it 15 would yield a putty gel time of 4 to 6 minutes (at 25C) when catalyzed with 2 percent by weight of 50 percent berlzoyl peroxide paste. In each case, a ratioof 40 parts resin to 60 parts of talc (i.e., Vertal-92 from Lomas T...~ IIAI) isused.
All putties are catalyzed as described and applied to the substrate 20 (solvent wiped, not sanded) at a thickness of about 1/16". Suitable substrates include automaker certified galvanized metal test panels such as "90E," "EGA,"
"E60," "45E" obtainable from Advanced Coatings Technology, Hillsdale, Michigan. The galvanized coating on these range from pure zinc to zinc alloys which are applied from 50 to 70 g/m2. The "GM 90E" type is used as the 25 standard as it is identified as havrng the greatest zinc content and thus proved to be the most difficult upon which to achieve adhesion.
The putties are checked for adhesion (30 minutes after catalyzation and overnight) by bending the metal panel over the edge of a table to a 90 angle.
The cured putty is then chipped away from the creased area of the substrate. If 30 pieces of the putty could be removed leaving no film of putty remaining on the substrate, the sample is considered to have undergone adhesive failure.
, _ _ , _ , _ . , .,, , , ,, .... .. , . ,, . ,,, , ., .... , . , .. ,,, , . ,,,, . , ,,, . ,,, _ 2 ~ ~ 1 1 9 1 wo 95/19379 -16- r.., Cohesive failure is ~ when a film of putty remained on the substrate. The samples are considered to have 1~ ,,.lr~l true adhesion only if this remarning film was not solvent-sensitive (could not be wiped clean with a solvent soaked rag).
The relevance of solvent sensitivity to adhesion is ,' ' in the feather-edge area durmg the painting phase of the auto repair process as described earlier.
The putty systems appearing in Table I below are identifled by the rèsin prepared rn each of the above examples.
Table I
Putty Adhesion ~ Adhesion Cl W~t % Maleic 30 Mins. ? Overni~ht?
Example 1 40.3 YES YES
Example 2 35.1 YES YES
15Example 3 44.0 YES YES
Example 5 35.7 YES YES
Example 6 16.4 YES YES
Comparative Example 1 12.0 NO NO
20Comparative Example 2 7.9 NO NO
Thus, all putties prepared from resins formulated with greater than 15 percent maleic anhydride by weight ~' ~~ ' adhesion to the galvanized metal substrate by the 30 minute mark. r,..l}~ lvl~, allowing putties of 25 Comparative Examples 1 and 2 to cure overnight did not erlhance adhesion u.l..~ll,,e.
C~ i.. Example 3 A resin ~ according to Example 1 of U.S. Patent No. 4,525,427 to Bayha et al. is prepared. This , ~ is a prrmer and 30 includes toluene as a solvent. In order to evaluate the wllllJoi~lliol~ as a body 2 1 8 1 i 9 1 ~`0 95/19379 P~

putty, the resin ~ is c.. ~ with talc in a 40/60 ratio. The putty is catalyzed using 2 percent by weight of a 50 percent benzoyl peroxide catalyst. The putty is then applied to a thickness of 1/16 inch to a galvani~ed metal substrate. It sagged and did not dry for several days. There is no 5 adhesion. Thus, the, , is not useful as body putty resin and must be applied as a thin primer coating.
C' ~ dti.., ~Y~nple 4 An end-capped resin ~.,,.,l..,-:l;..l~ comprising the following is prepared.
C~ , ' ~ W~t %
10maleic anhydride 1.0 40.0 ~li~. I.. ~,. . - li. .Ir 0.32 18.1 water 0.52 3.7 diethylene glycol 0.69 29.8 ethylene glycol 0.41 10.1 The processing and thinning procedures used are identical to those described in "Method 2" of U.S. Patent No. 4,525,427 to Bayha et al. In this way an end-capped resin can be prepared and compared to a resin having a nadic moiety (Example 4).
5~ . _ Qf T i~uid Properties The liquid properties of the Comparative Example 4 and Example 4 are compared.
I'' , d1,i . .
EY~ample 4 ~ ' 4 Weight % styrene 67 67 25 Viscosity (centipoise) 720 445 SPI gel time (mins) ~.1 5.7 Cure mterval 1.7 5.8 Peak exotherm, F 421 307 The difference in viscosity is due to the difference m chemical structures of the 30 polymers. The differences in SPI gel time, Cure Interval and Peak Exotherm WO95tlg379 r~ .s.

illustrate the lower reactivity of the body putty resin of Example 4. Lowe}
reactivity results in less crosslink density and a more flexible but tough putty.
C~ . Qf Physical Properties These resins were compared for physical properties following c.. ll,u.. ~ with body putty fillers to simulate a typical "li~ hL" putty formula used in the U.S. market:
Material Wei.~ht%
Resin 50 DMA 0.2 Talc 44 TiO2 2.4 Fumes Silica 0.6 Glass Microspheres 3 Dimethylaniline (DMA) is a promoter necessary to effect cure with benzoyl 15 peroxide paste (common putty catalyst). TiO2 is added to lighten the color of putties. Fumed silica provides desired rheological behavior. Glass lllil,lUi~ Iower the putty density.
Both putties are catalyzed with 2% of 50% active benzoyl peroxide catalyst paste, pressed between glass plates set 0.25 imch apart and allowed to 20 cure overnight at ambient t..ll~ Lul~. Specimens of each are then cut and tested on an Instron using ASTM procedures for flexural properties. The following results are ~ --""- ;, ~ in Table II:
Table II
C~ . .~1i . ~, l~xample 4 Resin ExamDle 4 Barcol hardness 15-17 0 Shore D hardness 100+ 70-75 Flexural Strength, psi 396~ 2929 Flexural Modulus, psi x 10~ 6.77 3.42 30Flexural Toughness, in.#/in3 2.19 6.2 Barcol hardness is an index of an higher range than Shore D hardness.
Flexural modulus is a measure of relative stiffness. Flexural toughness is a 2~B~
~1095/19379 r~ l~o~,c measure of the extent to which a material will absorb energy without fracture.
The above data clearly show that cured putty made with the resin having a nadic moiety is much mo}e flexible and softer than that made with the ~U~ iUII~I resin ~-r~ lilir.~ in Bayha et al., U.S. Patent No. 4,525,427.
5 These properties have critical impact on puty l~lr,.l,.d~ and Ill_.kri~
ac~c~l,ilily. The more flexible a putty is, the less likely it will be dislodgedfrom the ~ltnmokil~ Moreover, the surface can be rapidly sanded.
In the ~ " and examples, there have been disclosed preferred . ."I-o-l;"~. ~t~ of the invention. Although specific terms are employed, they are 10 used in a generic amd descriptive sense only and not for the purpose of limitation, the scope of the invention being defined by the following claims.

,,,, j : ' ! ' '

Claims (34)

CLAIMS:

1. A curable body putty resin composition suitable for use in repairing metal surfaces, the body putty resin composition comprising:
20 to 50 weight percent of a reactive component which becomes an integral part of the composition on curing, and 50 to 80 weight percent of a polyester formed from an .alpha.,.beta.-unsaturateddibasic acid and/or anhydride, one or more of a polyhydric alcohol, a combination of a polyhydric alcohol and dicyclopentadiene, or dicyclopentadienyl alcohol, and optionally a saturated dibasic acid and/or anhydride, wherein the ratio of totalnumber of equivalents of hydroxy to total number of equivalents of acid is about0.5 to 1.2 and wherein from about 15 to 60 percent of the .alpha.,.beta.-unsaturated dibasic acid and/or anhydride is available to react with the reactive component such that the reactive component becomes cross linked into the polyester upon curing of the resin.

2. A body putty resin composition according to Claim 1 wherein the .alpha.,.beta.-unsaturated dibasic acid is maleic acid and the .alpha.,.beta.-unsaturated dibasic anhydride is maleic anhydride.

3. A body putty resin composition according to Claim 1 wherein the reactive component is styrene.

4. A body putty resin composition according to Claim 1 wherein the polyhydric alcohol is a glycol.

5. A body putty resin composition according to Claim 4 wherein the glycol is one or more of the glycols selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol,1,4-butanediol, 1,3 hexanediol, neopentyl glycol, methylpentanediol, 1,3-butylene glycol, 1,6-hexanediol, neopentyl glycol, ethylene oxide adduct of bisphenol, and propylene oxide adduct of bisphenol.

6. A body putty resin composition according to Claim 1 further including a tertiary amine promoter.

7. A body putty resin composition according to Claim 6 wherein the tertiary amine promoter is one or more amines selected from the group consistingof dimethylaniline, diethylaniline, dimethyl-p-toluidine, p-tolyl diethanolamine, and m-tolyl diethanolamine.

8. A body putty resin composition according to Claim 1 further including a free radical peroxide initiator.

9. A curable body putty resin composition suitable for use in repairing metal surfaces, the body putty resin composition comprising:
20 to 50 weight percent of a reactive component which becomes an integral part of the composition on curing; and 50 to 80 weight percent of a polyester formed from an .alpha.,.beta.-unsaturated dibasic acid and/or anhydride, a polyhydric alcohol and dicyclopentadiene or derivative thereof, and optionally a saturated dibasic and/or anhydride, wherein a nadic moiety is formed between the .alpha.,.beta.-unsaturated dibasic acid and/or anhydride and cyclopentadiene formed from dicyclopentadiene or derivative thereof, wherein the ratio of total number of equivalents of hydroxy to total number of equivalents of acid is about 0.5 to 1.2 and wherein from about 15 to 60 percent of the .alpha.,.beta.-unsaturated dibasic acid and/or anhydride is available to react with the reactive component such that thereactive component become cross-linked into the polyester upon curing of the resin.

10. A curable body putty resin according to Claim 9 wherein the .alpha.,.beta.-unsaturated dibasic acid is maleic acid and the anhydride is maleic anhydride.

11. A curable body putty resin according to Claim 9 wherein the reactive component is styrene.

12. A curable body putty resin according to Claim 9 wherein the polyhydric alcohol is a glycol.

13. A curable body putty resin according to Claim 12 wherein the glycol is one or more of the glycols selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3 hexanediol, neopentyl glycol, methylpentanediol, 1,3-butylene glycol, 1,6-hexanediol, neopentyl glycol, ethylene oxide adduct of bisphenol and propylene oxide adduct of bisphenol.

14. A curable body putty resin according to Claim 9 further including a tertiary amine promoter.

15. A curable body putty resin according to Claim 14 wherein the tertiary amine promoter is one or more amines selected from the group consisting of dimethylaniline, diethylaniline, dimethyl-p-toluidine, p-tolyl diethanolamine, and m-tolyl diethanolamine.

16. A curable body putty resin according to Claim 9 further including a free radical peroxide initiator.

17. A galvanized metal surface adhered to which is a cured body putty resin composition comprising:
20 to 50 weight percent of a reactive component which becomes an integral part of the composition on curing, and 50 to 80 weight percent of a polyester formed from an .alpha.,.beta.-unsaturateddibasic acid and/or anhydride, one or more of a polyhydric alcohol, a combination of a polyhydric alcohol and dicyclopentadiene, or dicyclopentadienyl alcohol, and optionally a saturated dibasic acid and/or anhydride, wherein the ratio of total number of equivalents of hydroxy to total number of equivalents of acid is about 0.5 to 1.2 and wherein from about 15 to 60 percent of the .alpha.,.beta.-unsaturated dibasic acid and/or anhydride is available to react with the reactive component such that the reactive component becomes cross-linked into the polyester upon curing of the resin.

18. A galvanized metal surface according to Claim 17 wherein the .alpha.,.beta.-unsaturated dibasic acid is maleic acid and the .alpha.,.beta.-unsaturated dibasic anhydride is maleic anhydride.

19. A galvanized metal surface according to according to Claim 17 wherein the reactive component is styrene.

20. A galvanized metal surface according to Claim 17 wherein the polyhydric alcohol is a glycol.

21. A galvanized metal surface according to Claim 20 wherein the glycol is one or more of the glycols selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol,1,4-butanediol, 1,3 hexanediol, neopentyl glycol, methylpentanediol, 1,3-butylene glycol, 1,6-hexanediol, neopentyl glycol, ethylene oxide adduct of bisphenol andpropylene oxide adduct of bisphenol.

22. A galvanized metal surface according to Claim 17 wherein the body putty resin composition further includes a tertiary amine promoter.

23. A galvanized metal surface according to Claim 22 wherein the tertiary amine promoter is one or more amines selected from the group consistingof dimethylaniline, diethylaniline, dimethyl-p-toluidine, p-tolyl diethanolamine, and m-tolyl diethanolamine.

24. A galvanized metal surface according to Claim 17 wherein the body putty resin composition further includes a free radical peroxide initiator.

25. A galvanized metal surface according to Claim 17 wherein a nadic moiety is formed between the .alpha.,.beta.-unsaturated dibasic acid and/or anhydride and cyclopentadiene derived from dicyclopentadiene.

26. A method of repairing a damaged metal surface comprising the steps of (a) catalyzing the curing of a body putty resin composition comprising 20 to 50 weight percent of a reactive component which becomes an integral part of the composition on curing, and 50 to 80 weight percent of a polyester formed from an .alpha.,.beta.-unsaturated dibasic acid and/or anhydride, one or more of a polyhydric alcohol, a combination of a polyhydric alcohol and dicyclopentadiene,or dicyclopentadienyl alcohol, and optionally a saturated dibasic acid and/or anhydride, wherein the ratio of total number of equivalents of hydroxy to total number of equivalents of acid is about 0.5 to 1.2 and wherein from about 15 to 60 percent of the .alpha.,.beta.-unsaturated dibasic acid and/or anhydride is available to react with the reactive component such that the reactive component becomes cross-linked into the polyester upon curing of the resin;
(b) applying the curing body putty resin composition to the damaged metal surface; and (c) subjecting the damaged metal surface having the body putty resin applied thereto to conditions sufficient to cure the body putty resin and to finish the damaged metal surface.

27. A method according to Claim 26 wherein the .alpha.,.beta.-unsaturated dibasic acid is maleic acid and the .alpha.,.beta.-unsaturated dibasic anhydride is maleic anhydride.

28. A method according to Claim 26 wherein the reactive component is styrene.

29. A method according to Claim 26 wherein the polyhydric alcohol is a glycol.

30. A method according to Claim 29 wherein the glycol is one or more of the glycols selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3 hexanediol, neopentyl glycol, methylpentanediol, 1,3-butylene glycol, 1,6-hexanediol, neopentyl glycol, ethylene oxide adduct of bisphenol, and propylene oxide adduct of bisphenol.

31. A method according to Claim 26 wherein the body putty resin composition further includes a tertiary amine promoter.

32. A method according to Claim 31 wherein the tertiary amine promoter is one or more amines selected from the group consisting of dimethylaniline, diethylaniline, dimethyl-p-toluidine, p-tolyl diethanolamine, and m-tolyl diethanolamine.

33. A method according to Claim 26 wherein the body putty resin composition further includes a free radical peroxide initiator.

34. A method according to Claim 26 wherein the body putty resin composition catalyzed in step (a) includes forming a nadic moiety between the .alpha.,.beta.-unsaturated dibasic acid and/or anhydride and cyclopentadiene derived from dicyclopentadiene.