CA2185456A1 - Polymeric vehicle for high solids coatings - Google Patents

Abstract

This invention relates to a polymeric vehicle which is effective for providing a high solids formulated coating composition. The polymeric vehicle comprises a blend of at least one nonmesogenic substantially linear oligoester diol and at least one hardener which is a mesogenic polyol, phenolic ester alcohol or crystalline polyol, which blend is effective for reaction with a crosslinker which is reactive with the nonmesogenic oligoester and hardener.

Description

~ wos6l23034 21~5456 P ll u yrlT.~l~Tr ~Trr.~ FOR lrTI' ~ ~O~ID8 COATII~G~
mis Arrl;r~A~t;nn is a rontin~ ti~n-In-Part S application of a Contin~ t;~n-In-Part Application, Serial No. 08/477,091, riled June 7, i9g5, which i5 a f-nn~in~l~tion_In-part Arrl i~ inn 0~ Serial No.
PCT/US95/01058 which is _ Cnnt; n~ tion-In-Part ^rr~ ;r~inn 0~ Serial No. 08/186,429. miS invention 10 is directed to polymeric vehicles _nd rormulated coating compositions ror coating binders which are high in solids and minimi 70 the use of organic solvents to erfect viscosities which permit the application of such poly_eric vehicles or ~ coating compositions 15 to a ~a~Late _g _ protective paint by existing ~;ial application T'i . Mo~e parti r-ll ~rl y, this invention is directed to polymeric vehicles and rormulated coating compositions which compositions include a ~ ic ~ lly linear oligoester diol, a hardener and croCcl inkor. These compositions are very high in solids and low in vol2tile organic -, and provide a coating bind~r with ~xL.~ -ly good ~ilm properties.
~ A~ OF ~IS l!RIOR AR!I! A~ID P~ u, One Or the primary _ in paint is the "film former" that provides a film for the protective function for a ~uLaLLate coated with the paint. Film for_ing of liguid paints include resins which have required organic solvents to provide the resinfi with suitable viscosities such that the paint can be applied by existing ~ ;lal application e~i- . U~e of organic solvents, however, raises at least two problems. In the past and poton~i~lly in the future, P~:~LV- I-P~ shortages mitigate against the use of organic solvent in great volumes. Second, enviL~ 1 concern mitigates against the use of organic solvents and requires such use be m;n;m;7Ocl.
SUBSTITUTE SHEET (RULE ~6) W096l23034 2 1 85456 EnviL, J~l concern has become increasingly t Lz~llL. This concern not only extends to Lvo.tiOn of the environment for itF own sake, but extends to public safety a6 to both living and working S conditions. Volatile organic ~ 6i ntlc resulting from coating compositions which are applied and used by industry and by the - n~ public are not only often lnrl~c~nt, but also contribute to pl,~ ;CA1 smog.
G~v~ - have est~hl; Ch~d regulations setting forth gl~ l; n~lc relating to volatile organic _ ' -(VOC8) which m~y be released to the a ' :. The U.S. Envi~ ~ 1 Protection Agency (EPA) has QSt~hli~h~d gU -3al inA~ limiting the a~ount of VOCs released to th~ lli , e, such ~ 1 in--c being - - 1 ~d for adoption or having been adopted by various states cf the United Stateg. G-ic3~1;n~-c r~lating to Voc~, such as thos~ of the EPA, and ~nvi-l L~l c~ are particular7y pertinent to the paint and industrial coating industry which uses

2 0 organic solvents which are emitted into the ~ e .
To reduce organic solvent content and VoCs, r-,;~L. I~ . hnve developed high solids coating compositions and p_: ed coating com~ositions. High solids compositions generally are liquid and are 2S ~to~i~n~d to minim;7e solvents. Powdered coating Compositions are solid powders and generally eliminate solvents. While each h~ve alv~--L_~e~, each coating composition has di~_.lv~ L..~e~.
Coating compositions which include high solids 30 polymeric vehicles based upon polyesters have become popular. In high solid polyesters as opposed to ~6U~IV- .1 icm~ compositions which use organic solvents, high - ~ Pc ~ weight g--n~ l l y needs to be achieved during crnccl ;nl~tn~ rather than being attained from the 35 basic polyester polymer. Hence, high solids polyesters normally supply a greater number of renctive sites (p~ n~nl-ly hydroYyl groups) available for SU~STITUTE SHEET ~RULE 2~i~

WO 96/23034 2 1 ~ 5 4 5 6 P~ , h cro~ ; nki n~. The resultant polymers typically exhibit 70-80% solids-weight when reacted 8~ n;rh;l LLically with i~c~y~,n~ Le crn~S~l 1nk~r~1, but rL_~uel~Lly yield empirical solids up to 18% lower, when cros~l; nk~-~l with 5 -l~m;n~ re8ing. De8pite their reduced use of organic - solvents, high solids polyester coating compositions c~n be ~L~ ed on the same T~;~ L and be employed in many of the same ArFl;r~t;nnll as lower solids "c~ l ;nn~ polyester coating compositions.
10 Further, a~ a result Or their m~ny ~LL~ LLs such ~8 ease o~ .r _LuLing and use, low volatile ~m;clRinn-:, reduced energy requirements, greater ~pplication ~f~ nry, lower hAnrll ;ng and storage costs, and excellent physical ~L~,~eLLies, high solids polyester 15 coating compositions have enjoyed t,~ 1 Ar growth in .ur~.cLuL~ and use. They still reguire organic E~olvents, however, and are a source of VOCs.
Powder coatings and W-curable ct)atings are ;; rAhl~ ultrahigh or 100% solids coatings . However, 20 there are limitations as to the t~-~hn;~ and the '?T';. t which are used to apply the E~ d composition .
To reduce solvent content and VOCs in polymeric vehicles and formulated coating compositions for 25 paints, r6see.~.,1..:L have been driven by three major objectives: controlling the reactivity of the film forming ~ - in the paint keeping the viscosity of the s~ in the paint low to m;n;m;7e the organic solvents in the paint and to keep the VOCs in 30 the paint at the lowest poP:~:;hlt~ level; and keeping the - in the paint at a low volatility to m;n;m;
VOCs .
one way to reduce Vocs is to further reduce organic solvent content and increase the solids level 35 of the coating composition to an ultra high solids level. High viscosity is a major problem which needs to be solved in ultrahigh solids coatings. In high SUbSTITUTE SHEET (RULE 26) w0 96123034 2 1 8 5 4 ~ 6 ~ L l ~

solids polyester coatings, the viscosity of aLed polyester 6~1U~ nq depends on several variables. Mnlec~lAr weight and - lec~llAr weight distribution are two 1 _ L~-IL factors. According to 5 polymer physics theory, the visco5ity of polymers in the liquid 6tate depends mainly on the averaqe Ar weight and the t _LUL~:, SO it is dD~irAh~e to reduce average lP~--llAr veight for solventless polyester coating. The ma~or factor 10 controlling num er average ~ ~-lAr weight (M~) of a polyester is the mole ratio of dibasic acid/diol or polyol. A dibasic acid to diol or polyol ratio o~ the order o~ 2: 3 is typical. However, 10s8 of polyol during the pro~ rl ion o~ the polyester can result in a significantly higher number average l~lllAr weight than predicted from the starting ratio. It is n~n~qqAry to add gome eYtra glycol to te for 1088. Further, in ultra high solids co8tin~ the low clllAr weight ~r~ lnn of re~-in in the polymeric vehicle may be volatile enough to ~ L~t~ when a thin ~ilm is baked. Such loss has to be counted as part o~
the VOC ~mi Rsinnl3.
The number of fllnr~ ;onAl groups per molecule also affects the viscosity because of 11YdLO~ bonding.
Most n 7; ~, or polymers require hi~h functionality to achieve a highly croqql lnk~-d film and r~-Aqn~Ahl~ Tgs to have adequat~ film properties for most applications.
The high fllnr~ ionAllty tends to increase the viscosity ~lqnlflcAntly.
An object of the invention is to ~rovide a polymeric vehicle which will reduce o~ eliminate VoCs.
Another object of this invention is to provide polymeric vehicles which are not only low in VOCs, but which provide coating binders with good film properties such as hardness and impact resistance.
SWSTITUTE SHEET (~ULE 26~
_ _ _, ,, , . . . . . _,,, _ _, W0 96/23034 2 1 ~ 5 4 5 6 Yet Another object of this invention is to control the viscosity to low levels at a spec; 1'ic shear rate of a liquid polymeric vehicle or li~uid formulated coating composition without using orgnnic solvents or water for 5 such control.
Further, objects and ~1vAl.t~s of the invention will be found by L~ L~ C~ to the following description .
8~aRY OF T~
The invention provides a liquid polymeric vehicle which may be a sol~tinn or a tli~pPrsi~An and which polymeric vehicle is errective for providing a high solids ~ormulated coating composition. The polymeric 15 vehicle comprises a blend Or at least one - , ;A
suL~ ;Ally linear oligoester diol and at least one hardener which is a - , ;c polyol, rhPnnl;~ ester alcohol (PHEA) or a crystalline polyol which blend i5 Qrrective for reaction with a cros~l;nkPr which is 20 reactive with the - ~ oligoe :ter and hardener.
In general the viscosity of the polymeric vehicle which ~n- ltl~lPs a blend of the oligoester, haLdel~er and cro~sl;nkor will be in the range o~ rrom about 0.1 to about 20 Pa.s at from about 20-C to about 60 C at a 25 shear rate of about 1000 sec.~1 in the absence of organic solvent. The polymeric vehic;e comprises from about 10 to About 50 weight percent haL le~lel, based upon the, ; na~l weight Or the harl~ , oligoester and croA-~:l ;nkPr, from about 15 to about 50 weight 30 percent oligoester and from about 10 to about 40 weight percent cro~l; nkPr. Ir the hald~l~eI is a , ; c polyol, the - - , ; ~ polyol is present in an amount erfective to provide the polymeric vehicle from about 5 to about 50 weight percent , ;~ groups, based upon 35 the weight of the -~ polyol.
The oligoester diol and/or mixture of such diols has a number average lec~lAr weight in the range of SUBSTITUTE SHEET (R~ILE 26i W0 96t23034 2 1 8 5 4 5 6 P~

rrOm about 275 to sbout 3000 and a polyA~cp~sity index of not ~ore than about 2 . 6 and preferably not more than about 2.2. The ol l~o~Qt~r diol is liquid below about 50 C when in th~ environment of the h~rA~n~r and 5 crn~ nlr~r The oli~o~Qt~r is y ~l :L-I I ;A11Y linear which means it also may be linear. The oligoester diol has a main longitudinal chain which ha~ chain ~~_ having the DLL~ uL~s --CH2--, --O--, --C(=O)-- and to a limited extent may have ~ ~- with 2.LL~1~.;LUL_S
10 - (R) CH- and - (R) 2C- wherein R is methyl, ethyl, propyl, isopropyl, isobutyl or normal butyl. The main longitudinal chain is terminatQd with hydroxyl groups, or a hydroxyl group may be on R if R i8 within four carbon atoms Or the ~ ~rmin~l carbon o~ the main 15 longitudinal chain. The oligoester dlol should not on average contain more than one branch (def ined by R
nbove) per l~c~l e of diol residue in the main chain.
}lenc~, an oligoester made from a mixture of ne~ ..Lyl glycol and let~l y linear diol must have at least 50 20 mole percent of the total diol residue of ~ _ 1 et~ly linear diol residue in the mnin chain of the oligoester. E~rther, not morQ than about 896 of the number of l~.dL~Y~ atoms along the mnin longitudinal chain may be substituted with carbon Atoms.
25 Altern~tively, the brAn~h~n~ by virtue Or substitution _uch as R should not permit the branching index, as defined below, to be more than about 0.12. Generally R
will be methyl.
In one aspect the haL~ L is a , ic polyol 30 which has two or more hydroxyl groups and which forms a dispersion or a 5nl utinn with the oligoester when it is a part or the formulated coating compo~ ition. The polyol has - - ~, i c groups selected from the group consisting Or general .C~ ~A': I, II and III as 35 set forth ~elow:
.

SUBSTI~lJTE SHEET (RULE 263 w0 96123034 2 1 8 5 4 5 6 P~

I
/~\ or covalently bonded ~' ~ combinations of general _ _ c formula I;
II
o Q Q or covalently bonded combinations of general -- _ d formula II;

nnd co~binations o~ F~ I and II;
III

, ~ _ ; ns-t i rmC: of R;

wherein 30 A is selected ~rom the group consisting of o o CH3 -0--C-, -c-o-, -CH~N- , -N--CH--, -0-CHz-, -CH2-0-, -C3N-,

3 5 Cl H~
-N--C-, covalent bond, SUBSTITUTE SHEET l~ULE 26) wo 96/23034 2 1 8 5 ~ ~ 6 8 A .~ J ~.. . C ~
O O O
Il 11 11 -O-C C-O- and -O-C H
\ / \ /
5 c~c C5 / \ / \
H H C-O-Il 11 B ls sol~ct~l from the group consisting of -OC-, -C-O-, Cl H3 ICH3 -CH-N-, -N~CH-, -O-CH2-, -CH2-O-, -C=N-, -N=C-, covalent bond, O o o Il 11 11 2 0 -o-C C-O- -O-C H
\ / \ /
C=C , C~C
/ \ / \
H H H C-O-ll o O o o o _ o ~ o_ ~ o~o- Il--- --v---X~

wherein c - ~m integer from 2 to 8;
d ~ 1 or 2:
u = A;
x-- A; and g; an integer from 1 to 3.
In another;, l.alll aspect, the hardener in the polymeric vehicle and the formulated c:oating composition i5 a crystalline polyol which has two or more hydroxyl SUBSTITUTE SHEET (RULE 26) ~ wos6l23034 2 1 ~ 5 4 5 6 .~
groups, 5 to 200 carbon atoms, a nu_ber average lec~llAr weight (Mn) in the range of from about 400 to 4000 and a polytl;qp~rsity index of not more than about 2.6 and prefer~bly not more t_an about 2 . 2 . The crystalline 5 polyol i6 in~lllhle in the formulated coating composition at storage and at arrl;rA~inn, but is miqr.;h1e in the polymeric vehicle at the in1~n~ b~king t~ _LUL~ of the ~ormulated coating composition which provides the coating binder.
In yet another i Lel~L aspect, the haL~ L may be a PHEA which is a phonr~l; r ester alcohol which ; nrl 11~Dq at least two ester 1 ;nl~ , at least one aliphatic hydroxyl group and at least one hydroYyl group extending from an aromatic ring of the le~le (a rh~no1ic 15 hydroxyl group). G~n~rAlly the ND or number average - lec~lAr weight for a PHEA is in the range of about 250 to about 1200. The ph~nnl ;C ester alcohol may be the reaction product of 1I~dL~ Yb~IIZOiC ac_d, such as para l~lLu~y}J~::llzoic acid, and a monoglycidyl c _ -' having a lec~lAr weight in the range Or from about 150 to 1000 such as the monoglycidyl ' with the f ormula o 1l 2 5 CH2 - C~CH2 -OCCR~
where R L~JLe se:llLs a mixture of aliphatic groups. Nost preferably the three R groups in the glycidyl have a total Or 8 carbon atoms and which the glycidyl 30 ~ ' is ~,ially available rrOm Exxon rh~m;r~l Company under the ; ' - Glydexx-. In this aspect, the PHEa has the ~LL~I~.;LUL~
o )~o~OJ~
E10 C,H"
HO

SUBSTITUTE SHEET (RULE 26) W0 96/23034 2 1 8 5 4 5 6 r~

In paint t~chn~oCJy, it i8 known that linearity i8 a~sociated with the ~ln~l~cirAhle eharacteristic of eryst~ll;nity, but linQarity has not been a5sociated with 5 the Ao~ci1-Ahl~ eha,__LeListie of low viseosity. Many linear oligoester diols are erystalline at from about 25-C to about 50'C, making problematic their formulation into eoating eompositions. In these ease6, it may be desirable to eopolymerize the linear with 10 }~rA. I 0cl - to reduee eryEt~l1in;ty. It has been found that },~ d n~ however, tend to inerease viseosity. Henee, the proportion of b,~ ed ~ D
eopolymerized into an ~ 1 i 3 - - or polymer for a polymeric v~hicle ~hould be ll~in;mi~ l to the lowest level that will 15 prevent eryst~l 1; 7ation of the ol~; or polymer for the polymerie vehiele for the eoating composition. In this connection, it has been surprisingly found that linear or DUL~ t;Ally linear aliphatic oligoester diols, A8 defined herein, have low viF,cosities relative 20 to their - lec~lAr weight. It also has been ~ound that these oligoester diols exhibit shear th;nninAj at high shear rates. In croe~Cl ~nkod COl!ltin~C~ such diols qonQ~Ally produce eoatings~ that are too soft for most uses. It has been found, however, that the properties of 25 these coatings may be onh~nA~ocl to use~ul levels by hlon~l;nj a h~d~ -_L that i8 a diol or polyol and which is crystalline, a PHEA and/or in~ o~: -- 3 - j~A, grOUP8~
with the ~ -~, ic~ ol ig-:~oct-n- diol and crnscl ;nkor.
~e have diDc~ r- d that this blend may be made without 30 increasing the viscosity o~ the blend 80 much that it can not be applied to a D~D~L~e.
}lence in another aspect, the invention provides a method for controlling the viscosity of the polymeric vehicle at a sp~oc i f i 1~ shear rate by eontrolling the 35 relative amounts of D~J~DI_~.L;Ally linear ~ ic oligoester diol and ~alde.~ , ic polyol, PEIEA
and/or crystalline polyol) sueh that when the SU8STITUTE SHEET (RULE 261 .

~ W096123034 2 1 8 5 4 5 ~ P-~U~

- oligoester diol and hardener are inPc~
with a cross- inker, the blend of the oligoester diol, 11~ de..eL and crrc~l;nlrp~ will be in relative amounts cfrective to provide a coating binder which will have a 5 hardness of at least about B at a binder ~ hirl~n~CE Or about one mil. In An i La~l- aspect, the polymeric vehicle Or the invention will provide ~ coating binder with a hardness o~ at leact about H. ~he viscosity of the blend will be in the range of from about 0.1 to about 10 20 Pa.s at about 20 to about 60-C to provide a shear rate of at least about 1, 000 and preferably in the range of about 1, 000 to about 1 X 106 sec.-l in the absence of organic solvent.
I~ ~ L OF T~
"Polyester" means a polymer which has -CO- linkages in the main chain of the polymer. nol i ~, '~ ~eans a that is a polymer, but has a number average weight not greater than about 10,000 uith or without repeating - c units. "Non-ol i, lc" is a _ that does not have repeating monomer units along a main chain. "crncp~] inkpr~l means a di- or polyfunctional ~,laf~ce cr~n~Ainin~ fllnt~inn~l groups thAt are capable of forming covalent bonds with hydroxyl groups that are present on the oligoe-;ter diol and hald~l~e~ which ;is the -, - ic polyol and/or crystalline polyol. Amino resins, polyisocyanate and epoxy resins are mel3bers of this class; -lAminP resins are a sub-class of amino resins. The croCcl inkinq agent may be a blend, hence, there may be more than one u~-a--~e which forms a blend of ~ a-lces which forms covalent bonds with the hydroxyl groups of the oligoester and 35 ll~ldeeL. "Polymeric vehicle~ means polymeric and resinous ~ in the formulated coating, i.e., before film formation, in~ linq but not limited to the l l y linear ol i ~op~pm diol, J i c polyol, SU~STITUTE SHEET ~RULE 261 Wo 96/23034 2 ~ 8 5 4 5 6 crystalline polyol and croC~ l ~nkor. "Coating binder"
means the polymeric part of the film of the coating after solvent has evt ~Lc~d a~ter baking and after crn~2lel 1nklng, "Formulated coating composition" means the 5 polymeric vehicle and optional solvents, as well as ri~ ~ catalysts and additives which may optionally be added to impart dQsirable application ~ h~r~rtPristic3 to the formulated coating and ~ -ir~hll? properties such as opacity and color to the f ilm As used herein "high solids" means at least or more than about 7S weight percent solids under AS~N test D-2369-92 A "high solids formulated coating composition"
or high solids polymeric vehicle means a nnn~5~ Po ~
composition ~-nnl ~inin~ at least or more than about 75 15 weight percent solids as per ASq~M test D-2369-92 In r~spect to a high solids polymeric vehicle according to the invention, the polymeric vehicle composition has a viscosity of not greater than about 0 3 Pa s at a shear rate Or about 25 sec ~1 at a t _ ~LuLe of about 30 C
20 Generally the ~l 1 P~Pd coating composition according to the invention will not have more than about 200 g/L VOCs under ASTM test D-3960-93 ''Polydi~rPr~ity index" tPDI) means the weight average le~ r weight (N") divided by the nu~ber 25 average molecular weight (N"), PDI--4/M"
"VOC" means volatile organic ~ "Low VOC"
means less than about 200 grams VOCs per liter of polymeric vehicle not ;n~ Aln7 water l'SuLn~ lly linear oligoester diol" means an 30 aliphatic diol that has a main longitudinal chain which has chain ~ s having the ~ uLe8 -CH2-, -0-, -C(=O)- and to a limited extent may have 8-, Is with the 8~LU ~UL~S -(R)CH- and -(R)2C- wherein R is methyl, Qthyl, propyl, isopropyl, isobutyl or normal butyl me 35 main longitudinal chain is terminated with a hydroxyl group, or alternatively, a hydroxyl group may be on R ir R is within four carbon atoms Or the tPrmin~l carbon atom SUBSTITUTE SHEET (RULE 26) w096/23034 2 1 8 5 4 5 6 r~ ,.. L
Or the main longitudinal chain. Most often R will be methyl. The oligoester diol should not on average contain more than one branch (defined by R ~bove) per 1 eC~ll e Or diol residue in the main chain. A
5 ~,..1.,,~_..1 ;Al ly linear oligoester diol may be completely linear and is made by polymerizing linear ~9;CArh~Yyiic acids such as HOOC(CH2)nCOOH with linear diols such as HO(CH2)"0H. The re~ction miYture may contain, however, a proportion or n~ c~ln , usually diols which 10 bear hrAn~ hPs (~uch as R 6et forth above) which are usually methyl. Not more than about 8 percent of the number of hy-lLuy~:l.s along the main chain Or the oligoester can be substituted with carbon atoms.
Alternatively, the ol ;go~2t~r diol will have a branching5 index, as de~ined below, of not more than about 0.12.
The hrAn-~hin~ indeY is defined a ~
branching index -- (C, + 2Cd) Bl ;
C, + C, + 2Cd Where C~ -- the average number of line~r ~_ per n l i; ~ lec 25 C, -- the average number Or g~
with single h~ per ~-lecl~l e;
Cd = the aver~ge number of ~ ~s with double l~ c per - l~rlllc;
Bl - the average length, in carbon and oxygen atoms, of ~
"Diol" is a ~ or ol ;-0 with two hydroxyl groups. "Polyol" is a - ' or nl ;S ~~~ with two or more hydroYyl groups. As used herein, "polymerll means a - polymer with repeating - ic units as described herein and ~ n~ A~ 0l i ~_ a~ described herein.
nSolvent" means an organic solvent.
~Organic solvent" means a liquid which includes but is not limited to carbon and 1~dL~ which liquid has a boiling point in the range of from about 30-c to about SUBSTITUTE SHEET (~ULE 26) W096l23034 2 ! 8 5 4 5 6 r ~

3~0-C at ~bout one a; ~ UL-.2.
"Volatile organic _ __ n are described by the U.S. EnviL 1 Protection Agency at 40 C.F.R. 51.000 of the Federal r~ nnc of the Hnited States of 5 America as any ~ ' of carbon, ~Y~ in~ carbon 'rl~ carbon dioYide, r-rh~n;r acid, ~
cArhi~ or ~ o -~t~, and ~ ; .;alL~..a~ e, which par~r;rAt~ in _i ,' ic ~ o. 1 --j~A1 ro~C~inn~:.
This ; nr] llAo-l any such organic ~ _ ' other than 10 than ~ollowing, which have been ~ o~m;n~d to have ne~l ;q;hl~o phofrrh~ rAl reactivity: acetone; methane;
~thane; methylene chloride (dichloromethane); 1,1,1-trichloroethane (methyl chloroform); ' ,1, l-trichloro-2 , 2 , 2-trirluoroethane ( CFC-113 ): trichlorof 1UOL , Lhane 15 (CFC-ll); dichloro~;fl~ n~ (CFC-12);
chlorn~ ~~ (CFC-22); trifluoromethane (FC-23);
1,2-dichloro-1,1,2,2-te~ fl~ L}.~n~. (CFC-114);
chlc,L~,l, l Afl~loroethane (CFC-115); l,;,l-trifluoro 2,2-dichloroethane (HCFC-123); 1,1,1,2-te~r~fl~nroethane tHF-20 134a); l,l-dichloro l-flucLv~:Ll-al.c (HCFC-141b); l-chloro 1 , l-di f luoroethane (HCFC-14 2b); 2 -chloro-1 , 1 , 1 , 2 -te~ rAfl~n~oe Ll-alie (HCFC-124); pon~Afl-~rroethane (HFC-125); 1,1,2,2-tetraflu~L-_L~-~sne (HFC-'.34); 1,1,1-trifluuL~ Ll.ane (HFC-143a); l,l-difluoroethane (HFC-25 152a); and perfluuL~,..aLL,o~ _ ~ which fall intothese classes:
(i) Cyclic, ~Lall~ d~ or linear, completely fluorinated alkanes;
(ii) Cyclic, ~ od, or linear, cnr-r~letoly fluorinated 30 ethers with no ul.__LuL_tions;
(iii) Cyclic, ~ od~ or linear, letoly fluorinated tertiary amines with no u~ LuLaLions; and (iv) Sulrur containing perfluoro~AArhnn~ with no ul~aLuLations and with sulfur bonds only to carbon and 35 fluorine. Water i8 not a VOC.
"Film" is formed by application of the formulated coating composition to a base or ~uLaLLate~ ~vapOl~tiOn SUBSTITUTE SHEET (kULE 26~

W096123034 2 ~ ) /1 5 ~ r~
of solvent, i~ present, and croQ~l 1nk;n~, "Di~r~-si~n" in respect to a polymeric vehicle, r 1 ~t~d coating composition, or ~ s thereo~
means that the composition must include a liquid and 5 particles which particles are ~l~tec tAhle by dynamic light s~;~L~eLing.
"Soluble" means a liquid dissolved in a liquid or a solid dissolved in a liquid. nM; ~c;h~e" means a liquid which is dissolved or is soluble in a liquid.
"Dissolved" in respect to a polymeric vehicle, r~ lAt~l coating composition or thereof means that the material which is dissolved does not exist in a liquid in particulate form having at least about 5 weight percent particles having ~ s greater than 15 about 30n~ which are as ~ by dynamic light ing.
"Adduct of ' r~nD" means the product of an addition reaction between a An-- with another with a flln -t ~ onA 1 group reactive with the 2 0 oxirane, such as a hydroxyl group .
nl~ - ; r~ refers to ' , ol; s ;- or polymers which do not have the f 1 A I, II and III
dQfined above as - _ ;n in an amount of more than above 5 weight percent based upon the weight of the The polymeric vehicle comprises a blend of a ~~-~ ;c g ~ 1 ;Ally linear oligoester diol and a hardener which is a --- ~ ;c polyol, PHEA and/or a crystalline polyol which blend is effective for a 30 reaction with a cr~ Ql ink~r which is reactive with the D~DI- L;Ally linear oligoester and haL.l~,.~r. In general the viscosity of the polymeric vehicle which inn~ a blend of the oligoester, hal~"el and cro~cl;nk~r will be in the range of from 35 about 0.1 to abcut 20 Pa.D at from abut 20-C to about 60 C at a shear rate of about 1000 sec. . -1 in the absence of organic solvent, each ingredient being in an amount SUBSTITUTE SHEET (RULE 26) W096/23034 2 1 8 5 4 5 6 ~ .L.., --16 ~
effective for providing a polymQric vehicle which will provide a coating binder with a pencil hardness of at lQast about B when applied to a DuL;~LLOLe at ~h;rkr~ of about l mil dry. In an i La~lL aE;pect, the polymeric 5 vehicle provides a coating binder having a pencil hal.L.ess of at least about H at a thirkn~5 of 1 mil dry.
The polymeric vehicle comprises from about lO to about 50 weight percent hA r ~lrl~ r ~ based upon the combined wQight of the h~SLd~ L, ol i~o~ L and cro~ nkor~ from 10 about lS to about SO weight percent oligoester diol and from bout 10 to _bout 40 weight percent cr^~l ink~r. If the haL.l~ L is a ~ _, i c polyol, the - ~ ~ , ~; c polyol is present in ~n amount effective to provide the polymeric vehicle with from about 5 to about 50 weight5 percent , ic groups, based upon the weight of the i c polyol . If the h~ lel.-I i8 a blend of - - - - i r. polyol and a cry~t~ n~- polyol, the ratio of - _ ; c polyol ~nd crystalline polyol and amount of the blend are in amcunts effective for prnviding the 20 polymeric vehicle which provides a coating binder having a pencil hardness of at least about B when applied to a D~L~L<lLe at a thirkn~ of about 1 m:il dry.
The r~uL~ Al l y linear oligoester diol has a number averaqe ~ c~lAr weight in the rJ~nge of from 25 about 275 to zlbcut 3000 and a polydis~ersity index of not more than about 2.6 ~nd preferably not more than 2.2. It h~s a main longitudinal chnin which h~s chain ~, ' having the .~LLU~,LUL~ -CE2-, -O-, -C(~O)-, -(R)CH- and - (R) 2C- wherein R is as described above with R generally 30 being methyl. The oligoester diol sho~ld not on average contain more than one branch (defined by R above) per l~c~ of diol residue in the main chain. Not more than about 8 percent of the }~dLog~l~8 along the main chain o~ the oligoester diol may be substituted with a 35 carbon to provide the branching such as the methyl and Qthyl hr~nrh~nq. The branching should be m;nim;79d to the lowest level that will prevent cr~rstallization of the . SUBST~TUTE SHEET (RULE 26) -~ WO 96123034 ~ 4 5 6 . ~
oligoester diol at ' ~LUL~ _bove the intonrlP~l application temperature of the polymeric vehicle and rc 1 At~d coating composition. This t~ ~u~ t: is - usually ~rom about 25 C to about 50 C ~nd preferably 5 above about 0-C. The ol ~oa~tPr diol is liquid below about 50 C when in the environment o~ the hardener and crn~Cl ;nkDr.
The use of an nl i~oPctPr in the polymeric vehicle i5 Lc~IL becau_e it has a low viscosity, as a part of0 the polymeric vehicle but has a -~fficiPntly low tion rate such that the oligoester has at least about 93 weight percent solids when tested by AS~rN D-2369. This min;mi 7~'' the VOC content of the oligoester where the VOCs result from the lec~llAr weight fractions5 of the oligoester that ev~ Lc~te upon baking.
The D ~ n~;Ally linear ol~oPctPr diol may be made by esterifying linear ~lir~rhnYylic acids such as HOOC(CH2)~COOH (where n-- 2 to 14) with linear diols such as ~O(CHj)",OH (where m = 2 to 16) using t~rhn;Tl~C such as 20 catalyzed direct ester; f irat;nn, cata;yzed L.~..De .Le.ification or a catalyzed P~tPr; fication reaction using dicyclohexylr~rho~li im;~lP (DCC) . Zinc acetate may be used as a catalyst in the L-..nDeDLerification reaction and a solu~;nn of p-25 ~ nll~Anaclll t:nn;r acid in pyridine may be used as ac~talyst in the reaction using DCC. I)iols which may be used to make the DuLDI - I ;Al ly linear oligoester diol include 1, 3-propane diol, 1, 4-butAna~l; nl ~ 1~ 5-1~ - '; ol, l, c~ h~ lP~l; n~ n~ PA; ~l, diethylene 30 glycol, triethylene glycol and te L-- - thylene glycol.
Diacids which may be used to make the DuL~ t; A l l y linear oligoester diol include adipic acid, glutaric ~cid, azelaic llcid, d~r~n~;nir acid, and dn~l~c-An~;oic acid. These ~ are ~ l-tal y linear and will 35 provide l PtPl y linear oligoester diols . Completely linear oligoester diols do not have any branching at all.
SUBST~TUTE SHEET (RULE 26~

W096/23034 ~ 1 85456 h7hile the nl i~od-t~r diol~l of this invention may be l~t~ly linear, they only have to he DuLD~ ially linear and - with some brAnrh; nAJ may be mixed with the completely linenr - - . r l~-q of ~ -5 which may be mixed with the lin~ar to form -uL31 - 1 iAl ly linear oligoester diols are l,3-bU1 Anc-8;nl, 2--ethyl-l G 11~ ,~; nl~ 2,2,4--~r;- y~p~tAAn~rl; nl~
ne~ yl glycol, HOOCCH(CH3)r~,r~r rOr~R, and 2-ethyl-2-n-butyl--1,3--pr^rAna~l;nl .
The 3UbD~A~'I inlly linear oligoester diols also may be made by the catalyzed t _ - - e~ lf ication reaction of the C-J' L~ e6ter of the diacid with the diols as described above. The ..u~ l;nA~ esters of the diacids include dimethyl azeleate, dimethyl glutarate, dimethyl 15 adipate, dimethyl tlD~rAnc~rl;o~te and dimethyl d~ or.te. Mixtures of two or more of the acids or e~cters thereof and two or more diolD may be c ~L~I Lc..-erified and may be used to make the E~"L3l~- l ;Ally linear nli~o~qt~-r diol. r l~q of such 20 mixtures includc~ a C~ A .sa~ ied mixture of dimethyl Azele_te with 1,4 ~uI~ ; o l and l,G i~ _ nn-l;ol: a CV~ D~ lfied mixture of dimethyl _zeleate and dimethyl adipate (1:1 molar ratio) and 1,4 ~u~ l;nl which mixture provides a viscosity of 0.72 Pa.s at 3 rpm 25 at 25'C; a c;~LL..s~3~erified mixture of dimethyl azeleate and diethyl d~ I ';oate (1:1 molar ratio) with the dLols 1,4 ~ r~l1ol~ diethylene glycol and 1,10-~eCAn~l;o~ (2:i:1 molar ratio). Typical linear oliy~,eD~,3 which may be used in the invention have the 30 general rC lAq:
HO(CH2)CO[C(=O~ (cH2)7c(=o)o(cH2)n]xoH
where n= 2 to 12 and x= 1 to 5:
3 5 ~2 .,OC ~ CH2 t OC ( O ) ( C~H2 ) 7 C ( o ) o~T, ~, o~ T2 ] X OH
where x= 1 to 5; and SU~STITUTE SHET (WLE 26) ~ WO 96n3034 2 1 8 5 4 5 6 r ~

HO(C112)~0tC('O) (CH2)l0C(=O)O(CH2)~]XOH
where x~ 1 to 4.
Even ed diacids (acids having even numbers of carbon atoms) tend to provide o~ with melting 5 points which are too high, except when used as mixtures.
Hence, acids which have an odd number of carbon atoms are preferred.
In a ~L-=~eLLe d: i- o~ the invention, the linear oligoester diol in the polymeric 10 vehicle has the general formula HO(CH2)~--[OOC(CH2)nCOO(CH2),]pO--H
wherein p>l and <6, m = 2 to 16, n = 0 to 12. In respect 15 to this aspect of the invention, it has been f ound that oligoester diols where p - 2, m = 4, ~ and 10 and n = 4 and 7 are part;cl~lArly uDeful. The oligoester diol where m -- 7 and n = 4 has a single, broad melting point at about 40-C and its viscosity is low, Duch as 0.2 Pa.s at 20 50-C.
A suLD~Ar~ 11 1 y linear ,1; JO~_t~r diol which is useful in the invention has the gener~l formula ~AJ~T~2~2-t-OOC(CH2)7~00~T,CTT2 CH]X0-H

~7hen x is about 2, the ol;, has a branching index of about 0 . 097 . T~is monomer is an example of a DL~LAr~L;Ally linear monomer which has small branches which, while not ;nt~n~l;nAJ to be bound by any theory, ._dv.. ~J~ ly ~ill D~yLeSS the melting point of the oligoester diol.
Oligoester diols may be made by the catalyzed LL_..) e.,LeLlfication reaction o~ mixed dimethyl esters of AJlutAric, adipic ~nd azelaic acids with 1,4-butanediol or 1~3-~ILA ~ . The use of mixed acids provides another pl~ l. Le for D~JLeDsing the melting point of the SUBSTITUTE SHEET (RlJLE 26) W0 96/23034 2 1 8 5 4 5 6 ~ L ~ ~

oligoQster diol. Where oligoeDter dic,ls were synth~ ed with mixed dimethyl esters and 1, 4 b~ 7; ol, the viscosity of the liquid monomer ranges from about 0 . 245 to about 4.6 Pa.s at 25-C., when it h~s a number average 5 ~ Ar weight ranging from about 300 to about 1600.
Where 1,3--butAnsAinl was substituted for 1,4--butAn~A;A~l, the viscosity of this li~uid monomer ranges from about 0.2g5 Pa.s to about 2.92 Pa.s at 25-C., when it has a number average -~le~ lAr weight ranginS from about 350 to 10 about 930.
The amount of hr~Annhinj in the oligoester diol to effect a melting point rAA~ t~nA and crystallinity r~ i nr- as described above varies with the particular combination of "linear" - D and the characteristics 15 of the branched . As a ~road rule, the mole ratio of t~e b~ d diol to linear diol should not need to exceed 1:1 for ~ 3 1 diols having a single methyl side chain, 8UCh as 1,2 r~LVlAnrAi~Al, or 0.67:1 for ~ LA l ~d diols having an ethyl side c~lain, such as a 1,2-20 butAn~A~o~ or two methyl side chains, such as n~v~e~.Lylglycol.
In the aspect o~ the invention where the polymeric vehicle in~AlllA~_ a o-, in polyol haLde~L which has two or more hydroxyl groups, the A~ A, hardener forms 25 a ~;AP~rA;nn or a solution with the oligoester diol when it i8 a part of the formulated coating composition. When the ~, ic polyol forms a dispersion in the rormulated coating composition, the number average lAn~l l~ weight of the -- ; ;~A~ polyol is in the ran~Je of from about 186 30 to about 4000 and has a polydispersity index of not more than about 2 . 6 and preferably not more than about 2 . 2 .
When the - , i c polyol forms a solu~ i on in the formulated coating composition, the molecular weight of t_e - , ~c polyol is in the range of from about 186 to 35 about 1000 and has a poly~ per~ity index of not more than about 2 . 6 and preferably not more than about 2 . 2 .
The ~ ~c, ; A polyol has - - , i r. groups selected from SUBSTITUTE SHEET (RULE 26) ~ w096/23034 21 85456 P~

the group consi6ting of general ~ 1AC I, II and III as set forth above.
In the aspoct when the I~A1~1al~ar is a mesogenic - polyol and the - - ~c, ; ~ polyol is in SAl ~t j nn in the 5 formulated coating composition, the ~ polyol in the formulated coating composition is present in an amount effectiYe to provide the polymeric vehicle with from about 10 to about 50 weight percent ; i~ groups based upon the ~eight of the - - ~ i c polyol .
Where the - -, i~ polyol ic i;cr~rs~d in the f~ 1 At~d coating composition, the - - , ; c polyol comprises from about 5 to about 50 weight percent - , i groups based upon the weight of the - - , ;
polyol .
In either aspect, however, in general the ratio by weight percent of the r , ; t~ polyol to oligoester diol ia in the range of from about 5/95 to about 50/50 and preferably from about 10/90 to about :~0/70.
In an; L~.t aspect of the invention the - ~, ; r! polyol has the general formula R-F-E-F-R (Formula IV) wherein E is selected ~rom the group consisting of ~G~, _~C~C~ lmd ~ C~ G~O~
and G is sDl ec~ od from the group consisting of -COo-, -ooC-, -CH20-, -~CH2-, -N~C-, and -C--N-. R' is selected from the group -CH3 and -H.
F is selected ~rom the group con~isting of -o-, -coO-and -OOC-. R is an aliphatic C1 to C3~ group which has at least one hydroxyl group. Any hydroxyl group which is a part of R is not in an alpha position to F, or in other words is spaced from F hy at least one carbon atom.
SUBSTITUTE SHEET [RIJLE 26) W096123~34 21 ~54 5~ r ~

In another i ~a~-L aapcct, the , ;c polyol has the general formula R-F-E-F-R
wherein E is 8~ 1 from the group consisting of ~ G ~, T~ O ~ li ~ ~1 ~ C ~ C ~ C ~
R ', G and F are as set rorth above and R is the adduct of a ~ rnn~ having not more than 25 carbon atoms.
A particularly u~eful 'rnn-- to terminate a diol, ~ n~ ; ng the diol having the general 10 ~ormula IV, has the general for~ula O O
CH2-CHCH2-OCR3 ' ' .
R" LC yLC5~ a miYture Or aliphatic groups the three R' ' groups in the oxirane having a total of 8 carbon atoms. An adduct o~ the latter oYiral~e is particularly userul as R in the general formula R-F-E-F-R. The latter oYirane is ~,ially available ~rom the ~SYYOn ~`h~-mir:~l Comp~my under the name of GlydeYY N-10~ ence, when E
and F are such that their combination provides Il_ 0~ 0--11 ~ --30 and GlydexY N-10- (as an adduct~ terminates each end of the E, F combination to provide the R of the general ~ormula R-F-E-F-R for one ~ diol, a particularly p~ cfeL ~ ~f , l r~ o~ having thf following formula is provided.
SUBSTITUTE SHEET (RULE 26 ~ wo 96123034 2 ~ 5 6 R,~CH2rCH-cH2{~a~ ~CH2lH-CH2~R, R2 R~
Rl + R2 + R3 = C8HI~
The polymeric vehicle comprises a blend of the 5 linear oligoester diol and t~e - , i c polyol of the general formula R-F-E-F-R (IV) or ~ r:~n~ adduct terminated diols of formula R-F-E-F-R ~s set forth above.
The ~ , ;r diol or polyols as set ~orth in formula IV are made by reacting a - - , ; c diol such as O O
HO~ C--0~ 0-- C~ OH
with an h~lo~n~tc-~ alcohol such as BrtCH2)6-O~ to provide an aliphatic terminated - - , ; r diol as set 20 forth in formul~ IV. Aliphatic terminated diols may be derived from epoxies such as Glydexx rl-lo6 by reacting a diol with t_e epoxy to provide t_e ; r polyol as follows.

SUBSTITUTE SHEET (RULE 26) .

W0 96/~3034 2 1 8 5 ~ 5 6 r ~ c ~

H~OH
1 ar(CH~OH
HO-(CH,),~H,),-OH (1) l G~
o OH O OH
R,C~CH,~:H,~(CH~,~CII,),~CH,-C-CH,~CR, (2) H H
M~Oqc-n~c diols l and 2 above may also serve as useful haL ~ L ~ .
In another aspect of the invention, the hardener is a crystalline polyol which may be an ol;, or D~ay be nnnnl i ic and which polyol which consists Q-:c--nt~Ally of carbon, lly~lLu~ oxygen and nitrogen atoms, has two or more hydroxyl groups and has from 5 to about 200 carbon atoms. I~ it has nitrogen atoms, these atoms will be a part of an amide, urea or amidine group. If the crystalline polyol is an nl i; , it has a number ~verage lec~l Ar weight in the range of ~rom about 400 to about 4000 and a po ydispersity index of not more th~n about 2. 6 and preferably not more than about 2 . 2 . I~ the crystalline polyol is not ol ~-o ic~ the crystalline polyol has a molecular weight in the range ~rom 120 to about 500.
Crystalline polyols of the invention are non-rh~nnl~ rh~l~nli~ means that, in the aspect of the invention where the crystalline polyol cnnt~; nc an aromatic ring such as a benzene ring, the crystalline polyol does not have hydroxyl groups attached directly to the benzene ring.
The crystalline polyol is ~i i cr~rsrcl in the polymeric vehicle and the formulated coating SUBSTITUTE SHEET (RULE 26~

~ wos6l23~34 21 8 545 6 r~ L

composition and has a soll~hi 1 i ty in the formulated coating composition of not more than about 10 g/L at from about O-C to about 40-C. The crystalline polyol i~ a liquid and is nl r-lhl e with the formulated coating 5 composition at a ~ _LUL~= of at lea~t ahout 80 C, ~nd preferably in the range o~ from ~hout lOO-C to about 175-C. The crystalline polyol displays one or more first order transitions at ~rom about 80-C to about 175-C by DSC and displays crystallinity by WAXS.
10 It is incolllh~e in the formulated coating composition at storage and at ArFl icA1-inn~ but is miscible in the polymeric vehicle at the ln1-c-nrl ~ baking t _ aLure of the formulated coating composition which provides the coating binder. Prefer2bly the crystalline polyol has 15 a melting point o~ from about 5-C to about 40-C lower than the i nl-e-n.~-~d baking ~ , ~u~ ~ of the ~ormul2ted coating composition or the curing ' , aLuLe of the polymeric vehicle. The latter baking t~ aLuLe gene-~Ally ranges from About 70 to 2bout 175-C.
20 r l~c of crystalline polyols include the following.
O O
HO(CH~)n[~01~3-CO(CH~)n-]~-OH
25 where n = 2 through 12 and x = 1 through 20. Useful hardeners having the latter general formula include O O
HO{(CH,.);Ol O-CO-1(CH,);OH

and lOGT
SUBSTITUTE SHEET (RULE 26) W096/23034 21 ~ 5~56 r ~

O O
HO-[(CH~)~o~O~O-CO-l~(CH~ -OH
C(CH20H)~ and RC(CH20H)3 are crystalline polyols where R i8 methyl, ethyl, propyl and butyl.
Another crystalline polyol is HOCH2 (CHOH) ~CH20H.
YQt another eYample of a crystalline polyol is o HOCH2CH2~ 1 ~CH2CH,OH
OlN~O

10 The polydi~persity index of the .,ub~ .. Lially linear oligoester may be obtained by ~7yn1hPqi7in~ the ol ~, through a direct esterification reaction, a LLA~ L-rification reaction or by an esterification reaction using ~ La..L~ s,uch as dicycloheYyl~Arho~i ;mifl- (DCC) . Careful use of these t~rhntT~es can yield ~LUI_U-;LS with a polydispersity index as low as 1. 4 . The polydispersity index of the oligoester and the mesogenic polyol may be lowered to lQvels below 1.4 by purification of th~: oligoester product such as by eYtraction of the volatile low l~c~ r weight fr~rtirn~ or by vacuum stripping of cuch frArt1--n~. using these t.~-hniA,~ a poly~ r-rRity indeY of 1.1 or even lower may he .-htA i n_Cl -The cro-Ql i nk_r may be solid, but generally is a li~uid. In either CiLI Lal-~e, the cr~-,#-l i nk_r i5 mi~cihle or soluble in a blend of oligoester diol and SLIBSTITUTE SMEET (RULE 26) wo 96/23034 2 1 8 5 4 5 6 Pcr/uS96/00982 hardener without rai5ing the viscosity of the blend of the oligoester diol/h7 r ~1 ~ ~ /cros-l i nk_r or the f 1 A~tPd coating composition aoove the range of from about 0.1 to about 20 Pa.s at about 20 to 60 C at a 5 shear rate of at least 1000 sec.~l in the absence of organic solvent. The croCCl inkPr has a f~lnnt;nnAl ity which i8 reactive with active l.y~uq~ns such as the hydroxyl groups of the oli~,^~t-r and hardener and should be effective to provide a coating binder with a 10 h~ of at least about B and in an i kl..L
arpect, at least about H at a binder t~ nPc~ of about 1 mil.
To provide an effective coating binder, the polymeric vehicle comprises at least about a 15 st ,i~-hil ic amount of cr^---l in~Pr which will react with the hydroxyls of the ol i~o-~tP~ and hardener. The croC--l inkPr may be a polyiso~;y,lllate which generally are not blocked because blo~ in~ will raise the viscosity of the iSG~;y~ te such that it will not be fl.n.-ti~-20 or useful in the rrAr~ti~-e of the invention. Amino resins (usually made from Am;~in_c, ureas or amides by reaction with f~ ldPhyde and ~ i 6e~l ~ Lly usually with an alcohol) also may be used a~ a crOccl ink-r which will react with the hydroYyls of the linear 25 oligoester and hardener which is a polyol. The cro~Clink-r has an average fUn~-tinnAl ty reactive with the hydroxyls of the oligoester and hal-lel~e~ of greater than about 2.4. When it is a liguid, the crOccl inkPr generally has a viscosity of less than about 3.0 Pa.s 30 at about 25~C, c-ntin~-c to be a liguid at about lO C, and is micrihlP- with the oligoester and hardener.
Suitable crnccl inkPrE~ include, but are not limited to - ~ Ami n- for~ _hyde types such as hexakis t y ~ yl) 1 Amino resin (H~qMM) (sold as "Cymel 35 303" and ~ ei ~ 747") and other amino resins as described in Wicks, Jones and Pappas "~rganic Coatings:
Science and T-chnnlo~y" PP 83-103, Wl' ~y Interscience, SUBSTITUTE SHEET (RULE 26) W0 96/23034 2 ~ 8 5 4 5 6 1992. Additionally, as previously st~ted, the cro~l;nkDr ma~ be solid under certain conditions as long as it is soluble in the oligoester diol/hardener blend and does not increase the viscosity of the 5 oligoester diol/hardener/ crn~l i nkD~ blend or formulated coating composition above t~.e aforedescribed range. These cro~ nk~ s include a hexakis '' y '' 1) lAmino (E~) resin'which sometimes appears as a solid, is highly alkylated and has the 10 general formula:
N(CH20CH~)2 N~N
(CH,OCH2)2N N N(CH20CH,)2 The l~tter HN~[ resin appears as a waxy solid with a melting point in the range of about 30~C and is sold by Cytec rholn~r~l Compzmy under the name Cy~el 300. A
15 similar ~ m; nD resin which sometimes appears to be a solid at about 25-C and which can be used in the invention is a highly - ic, highly methylolated h ' ylolated lAminD ~n~ hyde resin which is aold by r~ o rhomicAl Comp~ny under the designation 20 HM-2612.
A part-~lA~ly useful cro~ nl~D~ includes a blend o~ polyis~ nates based on 1~ ~' ylene diisouy~,~O.Le (sold as Luxate XHD 0700 by Olin Corporation) and thought to be a mixture of the 25 following ~,L~uL,lLæa S~JBSTITUTE SHEET ~RUIE 26) 21 85~56 (ON,~O O
r~ oc~ N N ~ NCO
oc~ ~ \ 11/
Particularly useful croQ~l; nkPr8 are blends of polyiso~,y~i-ates and - 1 Ami n-~- . A particularly useful blend comprises a blend of - - 1 rlmi nc- and Luxate~
5 XHD 0700 in a ratio such as 2.0 parts - lAminP to 0.65 Luxate to 0 . 22 Luxate- also is a particularly useful cr~s~l ;nkPr.
Propertie6 of the coating binder:; resulting from the use of amino resin cro~ nk~r5 a}so may be 10 ~ u~-d with hardeners additional to the aiuLcdes~Llbed - --, ic polyol, crystalline polyol 2nd PHEAS. These additional haL~ eL~ include polyurethane diols. These diols include the uLeLl.a~.è diols K-FLEX
VE 320-100- and K-FLEX VD 320W from l~ing Industries.
15 K-FLEX UD320-100 is a 100% polyurethane-diol with hydroxyl eguivalent weight 160, viscosity 7.0 Pa.s at 50 C. Its -LLU-,LULe is thought to be EIO(CH2)60CONH(CH2~6NHCOO(CH2)60H. K-FLEX UD-320W has the same :S~LU~;~ULC as K-FLEX UD320-100, is a polyurethane-20 diol con~in;n~ about 10% by weight o~ water withhydroxyl eguivalent weight 178, viscosity 8.0 Pa.s at 25-C. Elardeners such as diesters of neu}Jt..Lyl glycol (NPG) and paral.~.lLu~yLc..~oic acid (PH~A) which diesters are hereinafter referred to as AY-l, also are useful 25 additional hard.:..c~ for the coating composition, ~C~pe.~Ally ir small amounts of organic solvents are used in the fo~ulated coating composition. A
SUBSIIT`UTE SHEET (RIJLE 26) W0 96/23034 2 1 8 5 4 ~ 6 particularly useful hArt~^- P~ which i8 a diester of NPG
~nd PHBA has the ~LLUULUL~
O CH, O
HO~1!~CH~1-CH~H
CH, Bec~use amino resinE~ by them~elv~s without additives such as t_e aroL~ '- ibed additional h~rdeners may not gLve desired f ilm pr~perties, the above-irl~nt;f~Pd additional ha~ L~" are particularly useful with polymeric vehicles which include amino resins. Each of the _, ' of the polymeric vehicle are in amounts effective for providing it with the aruL- ~e~uLlbed viscosity range and are effective ~or providing a coating binder with ~ pencil hardness Or at least about B at a th~nl~nPqs of about 1 mil dry.
lS l~ _~cat_E~ pr~vid~ eY~Pl 1 ~nt ~ilm propertie~ but may ~horten the pot life of the polymeric vehicle or ~ormulated coating composition.
The reaction between the oligoester, hardener and the croRRl~nkPr which provides the coating binder generally is a catalyzed reaction. ~rypical catalysts for isocyc.l.ate crnCRl; nk; n~ rP~c~ 1 nnq include soluble tin catalysts such as dibutyl tin dilaurate and tertiary amines such as ~iA7~hicyclot2.2.2] octane and zinc salts of organic acids. Typic~l cataly6ts for the as amino resin croq-qllnk;n~ roA~t;nnc include para toluene ~ulfonic acid tp-TSA), dodecyl benzene sulfonic acid and dinonyl na1hrhAl~nP diR~ nnic ac d. Typically the catalyst comprises from a_out 0.3 to a~out 1.5 weight percent o~ the blend of oligoester and crncqlinkpr~
30 based upon the weight of the oligoester, crossl; nkPr and catalyst.
The method of controlling the vis~osity of the polymeric vehicle and ~ormulated coating composition at SUBSTITUTE SHEET (flULE 26~
_ _ .. _ . .. . . _ ..... .... ...... _ . _ .. . .. _ . .... ..... . =

-Wo 96123034 a particular shear rate iB practiced } y providing the coating composition with the .~UID~ Ally linear oligoester diol having the chain ~- with the ~LL~-UL-~8 -CH2-, -0-, -C(~0)-, -(R)CH- and -(R)2C-5 (wherein R is methyl, ethyl propyl, isopropyl, isobutylor normal butyl; or providing the branc hing index as a~oresaid), which nl; ~o~ct~ diol i~ ithin the ler~lAr range and viscosity range as aforesaid with the oligoester also having a poly~ r~-rsity index of 10 not more than a~out 2 . 6 and preferably not more than 2 . 2 and preferably below about 1. 8 and mixing the oligoester with the hardener and a crsCcl ;nl~r with the fllnr~ ~nnAl ;ty z~nd viscosity as aforesaid. MA;nt51;n;
the DuLDL~..Lial linearity of the oligoester, 15 l~~;ntA;n;n~ the polyrl;cpersity index of the oligoester and h~L~ L and also providing a cro~ l; nk~r which is miscible or soluble with the oligoester and h_rdener, and has the fllnr~ionAl ~ty and viscosity as aforesaid permits control of the viscosity oi the 20 coating composition which m;n;m;7~c the use of organic solvents in a way and in an amount heretofore not previously knowd.
The formulated coating compositions are made by mixing the polymeric vehicle with pigments, catalysts 25 and additives such as dei~ ~" pigment dispersants, anticrating agents and rheology ~;f~rc. The t~l coating compositions have a viscosity of not more than about 1. 2 Pa . s at about 50 C at shear rates which may range from about 1 sec.-1 to about 100, OOo 30 sec.~~ r~n~;n~ upon the ;n~n~ ~r3 method o~
application. The formulated coating composition may be applied to a DULlDLL~Lte by spraying (which has very high shear rates), dipping (which has a low shear rate such as about 1 sec.~l), roll coating, brushing (which may 35 have shear rates of from about 1000 to about 20, ooo sec.~l) or using other known application ~; and thereafter ~h~ t~; n~ the coating composition by the SUBSTITUTE SHEET (RULE 261 _ _ _ . _ . . _ _ . . _ _ . . .

21 ~5~56 wo 96/23034 -32-application of heat in the t~ ULe range of from about 20-C to about 300-C for about 0.5 to about 60 minutes.
The following ~ 1 aS ~Qt forth compositions 5 according to the invention and how to practice the method of the invention.
~L~ I
The -- --, ; a diol having th~ formula R,~H~-CH-CH24~ 34-CH,lH-CH,-o~ R, R~ R
Rl+R2+R3 -- C~Hl7 was made as follows.
In a 100 ml, 3-neck flask P~ ped with a ~agnetic lS stirrer, a ~ , a I or and a nitrogen gas inlet are placed 7.0 g (0.02 mol) of bis (4'-11~1LUAYL~ ZUY1) 1~4--diI~1LU~YL~ e~ 10.0 g (0. 04epoxy group e~uiv. ) of glycidyl nacAa~ te, 20 g of N-methyl pyrrolidone (NMP) and 0.085 g of Bu~NICl-. The 20 ~lask is flushed with N2 and heated to 160-C slowly (about 1 hr. ) and kept at this t c~LlLe for 2 hrs.
After cooling, the solution of the product is poured into 30 m~ of dichlu~ ---. The solution is washed with water three times in a separatin~ funnel. The 25 phases are separated and diclo~ ~nP is reraoved with a rotary ~a~uLaLor. The residue is dried under vacuum at 80-C for 12 hrs. Yield is 15.3 g [90% based on bis (4' h~dLu..yLèl.zcyl) 1,4 1.~ lLu..yL~ ..e] of resin. By gel permeation ~I,L~ ,I.Y (GPC): N~ = 1070 , ~, =
30 1390, PDI -- 1.3.
SL~STITUTE SHEET ~RULE 26) _ w0 ~6l23034 2 1 ~ 5 4 5 6 r r~YPT ~
innnr ~A~ n~,t~
Linear adipates h~ving the general formula HO- t (CH2 ) ~-OCO- (CH2 ) ~-OCO ] 2- (CH2 ) ~~~
n 6, 7, 8, 9 and 10 are made as followa via the following re2ction 2 ClOC- ( CH2 ) ~ -COCl+ 3HO ( CH2 ) ~-O}I >
HO- t ( CH2 ) ~-OCO- ( CH2 ) ~ -OCO ] 2 - ( CH2 ) ~-OH .
A lOO-mL U~ ne~ u..~ };u~ flask is0 ~ irped with _ i~! gtirrer, t - te~, nitrogen y inlet and plastic tube. Adipoyl chloride (8.33g, 2 mols~, 7 diol (n in diol = 7, g.02g, 3 mols) and pyridine (2.1 mols) are charged into the flaslc.
The mixture is heated up to 70-C and then kept this 15 , LULC for three hours. At the ~ ~LUL~: of 70-C, nitrogen is bubbled through the melted mixture to blow out the hydrochloric acid. The hydrochloric acid (HCl) is liberated through a plastic l:ube into 100 mL
of water. when the ~ t; nl~ of the solution is 20 0.09N, which d~t~rmin~rl by titration Or 0.5N NaOH, then the reaction, ~ is raised to 180-C for another three hours. After reaction, the product is cooled to room t~ c~LU~:. A white, semi-solid paste is obtained. The product i5 washed with water three times 25 and dried under vacuum. Yield of the product t7 diol-adipate) is 13.2g (95%) . The number ~verage ~ ec~l Ar weight N~ is 1,744 and ~" i8 3,126.
The reaction of 10 diol with adipoyl chloride f~ the s2me ~r~ duL. as used for the 7 diol-30 adipate used. The difference is that the product is washed with water first and then washed with -nol.
The chAr~tPristics of the P~dUC;L~ were d~1 ~rm;nCd by IR, DSC and GPC.
The melting points were studied by rAril 1 Ary 35 TempII-TAl .rAt~/y Devices and DSC to investigate the transition proce~is and thermal behavior.
SllBSTITUTE SHEET~RULE 26~

wo 96/73~34 2 1 ~ 5 4 5 6 . ~l/U~

TablQ 1. The melting points o~ a~r3t~.
6 diol- 7 diol- 8 diol- 9 diol- 10 diol-S~adip~to ~dip~lte /IdipAte adip~te adipdte ~E~P I~
5Melting 83-C - 64-C - 62-C -Pointa 120-C 85-C 65.6-C 68-C
DSC
Melting 38-C -Point~ 45-C
10High Poly~er 58-C 67-C 74-C
M.P.~
15 * me melting points of high polymers were from lite~LuLe.
Table 2. M~C'll~r weight distr;hutinn~ were measured by GPC and are as rOllow8: ;
7-dlol-adipate lO diol-adipate M" 1744 2578 1~ 3126 4532 N"/N" 1.79 1.76 Viscositie wer~ ~ by b th Hercules ~i-25 Shear vi- ' and Brook~ield low shear vil ~ -.
me results are t~ t~l below.
Table 3. me viscosity of 7 diol-adipate at different shQar rates ts~l) and t- ~ LuL~n on Bro~kf~ld 30 v1-Viscosity (Pa. 8~ *
LuL~2 at various shear rate (-C) 3.4 5-1 6.8 5-1 17 5-1 34 æ~
35 40 0.565 0.561 0.542 60 0.231 0.228 0.224 0.222 80 0. 113 0 . 112 0. 110 0 . 109 100 0 . 066 0 . 068 0 . 064 0 . 062 40 * milli Pascal-sec.
SUBSTITUTE SHEET (RULE 26 wog6n3034 2 1 8 5 4 5 ~

Bec~use the Bro~ d v; ' can measure the viscosities only at the low she~r rates, the viscosities also were - ._d on a Hercules Hi-Shear v~ ~- ' to inV~t1 g~t~ their rh ~ 1 behavior at S the high shear rates. The results are sho~n in Table

4.
Table 4. The viscosities o~ 7 diol-adipate vs. shear rates at various t LUL'~.-- on Hercules Hi-Shear 10V1 r Sh~-r Vi co~ity ~ P~
c)50--57-C 60--66-C 70--74-C 80--81-C 90--91-C
157500 0 . 135 0 . 11 0 . 087 0 . 071 0 . 070 10000 0 . 132 0 . 108 0 . 086 0 . 069 0 . 068 12500 0 . 131 0 . 105 0 . 084 0 . 068 0 . 067 15000 0 . 127 0 . 104 0 . 083 0 . 066 0 . 066 20000 0 . 122 0 . 101 0 . 081 0 . 066 0 . 065 2025000 0.1'15 0.099 0.078 0.065 0.064 30000 0 . 114 0 . 096 0 . 077 0 . 063 0 . 062 35000 0.113 0.095 0.077 0.063 0.062 40000 0.115 0.096 0.078 0.063 0.063 42069 0.117 0.098 0.078 0.064 0.064 2540000 0.123 0.104 0.081 0.067 0.067 35000 0.14 0.116 0.089 0.071 0.071 30000 0 . 159 0 . 126 0 . 093 0 . 074 0 . 074 25000 0 . 18 0 . 136 0 . 1 0 . 077 0 . 077 20000 0.198 0.149 0.105 0.079 0.079 3015000 0.218 0.156 0.108 0.082 0.082 12500 0.225 0.161 0.108 0.083 0.083 7500 0.235 0.165 0.11 0.083 0.083 ' milli Pascal-sec.
35 *Due to poor t, aLuLc control of the Hercules v1r -~r, the ' ~ILULC 0~ mea~uL~ ~ is given as a range. In general, the, , - c~tuLæ in~ se~
during the experiment.
SU8STITUTE SHEET (RU.E 26) W096/23034 2 1 ~ 5 ~ 5 6 1~111 Jiao ~

The visco6ities o~ th~ 10 diol-adipate were studied on a Hercules Hi-Shear v;~ ' . Results are shown in Ta7Dle 5.

5 Ta~le 5. The viscosities of 10 diol-adipate vs.
t _ L ~si and shear rates.
Sh~r Rato~ V; ~c^~ i ti ~- Vi ~o~it i ~ Vi~co~itie~
ec.1 ~Pa.~) ~p~ Pa.~) Vi~ -;t~
at 75 - at 85 - at g5 - ~Pa.is) 78-C 87-C 96-C at 105-C
10 7500 0 . 086 0 . 068 0 . 06 0 . 051 10000 0 . 084 0 . 068 0 . OS9 0 . 0502 12500 0 . 083 0 . 067 0 . 059 0 . 05 15000 0 . 082 0 . 066 0 . 059 0 . 0495 20000 0.080 0.064 0.058 0.0492 15 25000 0.078 0.063 0.057 0.049 30000 0.'077 0.063 0.056 0.049 35000 0.076 0.062 0.056 0.048 40000 0.077 0.063 0.056 0.049 42069 0.078 0.063 0.056 0.049 20 40000 0.081 0.066 0.058 0.05 35000 0.087 0.069 0.06 0.052 30000 0 . 093 0 . 072 0 . 062 0 . 054 25000 0. 098 0 . 075 0. 065 0 . 055 20000 0.102 0.077 0.067 0.056 25 15000 0. 106 0 . 079 0 . 068 0 . 057 12500 0.107 0.079 0.068 0.058 7500 0, 107 0 . 079 0 068 0 . 058 * milli Pascal-sec.

L T~- - AY~ t~
Linear azeleates having the general formula HO ~ - ( CH2 ) O-OCO- ( CH2 ) 7 -OCO ] 2 - ( CH2 ) D-OH
n ~ 4, 6, 8, 9, 10 and 12 35 are made as follows via the following reaction:
2 HOOC(CH 2)7COOH + 3 HO-(CH 2)oOH ~
HO ~--( CH2 ) a ~OCO~ ( C}~2 ) 7 ~OCO ] 2 ~ ( CH2 ) o~OH
SUBSTITUTE Sl IEET (RULE 26~

2.1 85456 The method and ~ i in this synthesis were the same as that used in gynthoR i 7; n~ adipates . The ~JLU~ dULe: uged i5 the same as that used ~or synthesis or 7 diol-adipate as described under ~a).
Because acid chlorides are e~pensive ~or large - scale synthesis, diacids are used to replace acid chlorides to obtain similar pL~nlU~.iLii with less cost.
The reaction is indicated below.
2 HOOC(CH 2)7CO-OH + 3 HO-(CH 2)~OH
HO- [ - ( CH2 ) L-OCO- ( CH2 ) 7 -OCO ] 2- ( CH2 ) L~OH
n = 4, 6, 8, 10, 12 A 500-mL LI~L~ n~_k, ~uu.d ~.~L~ flask is eq~irp ii with ~ nir~l stirrer, Dean-Stark trap, ~,,,"1...~_" I' ' t snd nitrogen inlet. Azelaic acid (95g, 2 mols), 1~4-~ inl (68.23g, 3 mols) and para toluene ~ frnir acid are charged into the flask, and xylene (2% o~ total wt. ) is u~ed for reflux. The 20 miYture i5 heated up to 160-C (below the boiling points of diols). The t _ atUL~ is held at 160-C for five hours until 17 mL water is c~ rt~. Then the ~ u,~ is raised to 180-C for on~ hour. When the acid value of 4 diol-azeleate is less than 10, the 25 reaction is topped and a white semi-solid paste is obtained. Yield of this product (4 diol azeleate) is 155g (95%) . The acid nu7~ber (A.V. ) 2 . The - le~ll Ar weight (NL) 1508; M,: 2528.
The ~ L;rn of other diols and Azelaic acid 30 follow the s~me ~ du.~ that 4 diol-azeleate used.
The di~f~al~ce is the initial reaction ~ : ~LUL~. In cach ca~e, the initial L ~ is held at the t aLuL~ below the boiling points of diols.
The rh~rArt~ristic of these PL~1U~ Ls was 35 ~et~rmin~cl by IR, GPC, NNR and DSC.
The melting point of A7Alf-At--~ is as follows.
SUBSTITUTE SHEET (RULE 26) _ _ _ _ _ . _ _ W0 96123034 ~ 1 ~3 5 4 5 6 r~ L . .

Tabl~ 6. The melting point o~ linear oligoester diols.
Samplea 4 diol- 6 diol- 8 diol- 10 diol- 12 diol-~z~le~te Azeloate ~zeleate ~zeleate azeleAte Melting Pointa 30-e-37-e 34-e-56-e 34-e-48-e 36-c-ss-c 34-c-63-c S
A eomparison of the melting points of adipate and n~ te iB ghown in Table 7.

Table 7. The melting point of 7,4 ~nd 4,7 diols.
7 diol-~dip~te Sample~ 4 diol-~zeleate 4 diol- from ~cid (B) I~zelc~te ~A) chloride Meltin~ Point~ 30-c. - 3s-c. 33-c. - 3s-c. 3s-c. - 40-c.
A: azeleate synth~ from diol and aeid ehloride.
B: azel~ate 5yn~h~e;~cl from diol and diaeid.
Th~ ln~ r weight distr;htlt lnn~ of azeleates w~re as ~ollows.
Table 8.
4 diol-~zeleate 6 diol-azele~te 10 diol-Azeleate Mn 1508 2054 2864 M" 2528 3681 4751 M~/Mn 1.67 1.79 1.65 SUSSTITUTE SHEET lRULE 26) ~ wog6n3034 21 8 5 4 5 ~ r~,u~6~
A7~1 1~nte8 The viscosities of ~7~ was also studied on BroA~ LVDV-II+. The results are tabulated below.
5 TablQ 9. The viscosity of 4 diol-A7~P~ at dif~erent ~h~ar rates ( 8-l ) and t _D .
Viscos ity ( PA . 8 ) *
at various heAr rates 10 Temp. (-C) 3.4 8-l 6.8 8-l 17 8-l 34 8-30 0. 486 0 . 483 0 . 475 40 0.2g7 0.289 0.282 0.272 50 0 . 171 0. 171 0 . 169 0 . 167 83 0.054 0.053 0.052 0.051 15 104 0 . 03 0 . 029 0 . 029 0 . 029 * Pascal ~e~ .a8 When the viscosity in Table 9 was measured at 20 30-C, the 4 diol-azeleate was mostly liquid but cAnt~ln~d an estimated lOS o~ r~l~d crystalline material .
Table 10. The viscosity of 6 diol-~ at a 25 variety of tr ~ LuL~:~ and shear rates.
Viscosity (Pa. 8 *
at va ious shear -ates ~emp. (-C) 1.7 8-l 3.4 æ~l 6.8 8-30 50 3.047 70 1.416 1.416 80 0. 966 0 . 960 0 . 951 lO0 0 . 594 0 . 564 0 . 546 ~ Pascal aac;~,..d~

SUSSTITUTE SHEET (PILE 26) WO 96n3034 2 1 ~ 5 ~ 5 6 Tnble 11. The vi8c08ity 0~ 8 alol-azeleate at di~ferent t ' _E and shoar r~tes.
Viscosity (Pa. s) *
~t various ~hear r~te Temp. (-C) 3.4 8-l 6.8 5-1 17 8-l 34 8-50 0 . 192 0. 191 0 . 185 0 . 182 60 0 . 165 0 . 159 0 . 148 0 . 136 80 0 . 06g 0 . 063 0 . 061 o . 059 10 100 0 . 039 0 . 038 0 . 037 0 . 036 * Pa~cal la_v.,~l~
Table 12. me viscosity o~ 10 diol-azeleate at 15 di~erQnt t~ ~ ItU~ and shear rates.
Viscosity ~Pa.s) *
at various ~hear rates Temp. (-C) 3.4 8-l 6.8 8-~ 17 ~-l 34 8-~
20 60 0 . 192 0 . 185 0. 178 0 . 174 80 0 . 086 0 . 084 0 . 083 0 . 083 100 O.OS 0.048 0.047 0.046 * Pascal s cv,,~s Table 13. me viscosity o~ 12 diol-azeleate at various t ~ ' ~ s and shear ratefi.
Vi~co~ity (Pa. 8) *
at various ~hear rates Temp. (-C) 3,4 8-1 6.8 8-l 17 8-1 34 s-60 0.435 0.415 0.405 80 0 . 081 0 . 078 0 . 077 0 . 0762 35 100 0 . 045 0 . 042 0. 0396 0 . 0393 Pascal ~a_v"d4 SUBSTITUTE SHEET ~RIJLE 26 W0 96/23034 2 1 ~ 5 4 5 ~ 6 1 (c) ~ t~ collt~inina A T~if~ t-: 1 Polyol For ~UL~ ~ of comparison with F ~ L~ ly linear nll~ ~ A-^l~-t ~ ~nn~n~n;n~ a trifunctional polyol baged on tr~ ylolpropane (TMP) triol (Cl) are 5 made via the rollowing r~lrtirn:
C2H,C (CH20H) 3 + HOOC (CH 2 ) ~COOH
C2H5 ( CH20H) 2CH200C- ( CH2 ) 7 -OCO-CH2-C ( CH20H2 ) -CH2 -CH3 A 200-mL ~ n~- k, ~uu-l ~c L~ flask is eT~rpe~l with r- ' ~r~l stirrer, Dean-Stark trap, c~ F- ~ th~ L~r and nitrogen inlet. Azelaic ~cid (50g, 1 mol), trimethylolpropane (~rNP 68 . 56g of 72.46g, 2mol) and boric acid (0.4% of total wt.) or p-TSA (0.2% of total wt.) are charged into the flask, and xy-lene (3% of total wt. ) is used for reflux. The mixture is heatcd to 140- C and held for six hours.
When water that is rol 1 Prt~Pd in a Dean-Stark trap reaches 90% Or the t_eoretical amount, the rest of the I r; ' ' ylolpropane (4g) is added to the flask and heating is cnrl~1n~Qd for another two hours, then the reaction ia stopped. A LLa~ z.L- ,-L viscous lis~uid is obtained. Yield of the product (Cl) is 107 g (95%).
Acid number (A.V.) :5.
A7Pl~i~tP~S rnnt~inirl~ a tr;fllnr~nn~l polyol based on TMP triol and 1,4- hnt~nP~7iol (C2) are made via the following reaction:
HO(CH2)~0H+HOOC(CH2)~COOH+C2HsC(CH20H)3 >
C2H~C(CH20H)2CH200C(CH2)~-OCO-(CH2)2CH20H
The reacticn follows the same ~ lu~ a that Cl used. Diol, azQlaic acid, 90% of T~lP, and boric acid or p-TSA were charged into the flask at the initial 2~tage. A~ter ~ix hours, the rest of the lOS TMP is added into the flask. A ~ r ,.,L liquid is oht~nP~. Yield of the product (C2) ~ras 106g (96%).
A.V.: 2 . SUBSTITUTE SHEET (RULE 26) W0 96/23034 2 ~ 8 5 4 5 6 . ~ , h. ~
Azeleate~ Cnnt";n;n~ a tr;flln~-~;nnJ~l polyol (Cl, C2) had the rollowing ~ Ar weight distribution.
~1 ~
Nn 1286 1509 5 Mw 3101 3180 ~ 2.41 2.11 Table 14. The~viscosity of Cl at the di~ferent t ~- and she~r rates.
Shear Rat~s Viscosity (Pa.s) * at different ~Lu eE:
10 (Vs) 80-C 90-C lOO-C 150-C
0 . 4 0 . 749 0 . 709 0 . 509 0 . 4 09 2 0.509 0.309 0.216 0.124 4 o . 464 o . 287 0 . 184 0 . 066 7 . 9 0 . 451 0 . 267 0 . 171 0 . 045 15 * Pnscal 3 ao~
Tnble 15. The viscosity of C2 at the differênt ~ and shear rates.
Shear Rates Viscosity (Pa.s) * at dirferent t ~ -7 e~Lu ~E
20 (V8) 27-C 35-C 40-C 50~C
0 . 9 1 . 704 0 . 972 0 . 719 0 . 44 1 . 7 1. 65 0 . 948 0 . 696 0 . 391 3 . 4 1 . 64 0 . 939 0 . 687 0 . 384

6.8 ----- 0.916 0.685 0.384 25 * Pascal ~ Cu~
It can be seen that these azeleates cnntA;n;n~ a Irlfl~n~t;nnAl polyol have DUbDI'-''l ;Ally higher viscosities than the linear A~l A~t~- and additives described above (compare Tables 3, 9-13 with Tables 14-30 15) at a given t~ UL~:. The lec~ll Ar weights ofthe linear and bL~r.~,l.ed nl; ~ are generally e.
SUBSTITUTE SI~EET (RIJLE 26) Wo 96/23034 2 1 8 5 4 5 6 ~ U~ '.'L

Is~S III
t~rj ~ls L$near ~ oP~t~-r diols (4 diol-~zeleate and 7 5 diol-_dip~te) and a7~ P ~ ta;n~nj a trifunctional polyol (C2) described in Example II are used as or as a reactive diluent in coating rormulations.
Hexa(~ yl) 7am;n~ resin (PP~-10 747), a ~ully methylolated, ic 7~m~nP resin in which hexakis (- t y yl) - l ~m; no is a L~ l ive :~LLu~;LuLe and hexa(alk~,.y ~' yl) --lam~nP resin (~P~ 755), a methylolated and butylolated --lam;nP resin in which hexakis 15 (all.L,y yl) - l~m;nP resin is a l~ L' r ,IL_t ive ~LLU~LUL~: were obtained from r- rhPm;.-~l Company.
The h~ lene biuret resin (D- N-3200), which i8 aliphatic polyis~.;ya.lates, was obtained from Niles Corpor_tion. R-Flex 128- (K128) _nd K-Flex 1886 (K188), which are proprietary diols wl~re obtained from King Industries, Norwalk, ~ nnP ~irtlt. K-Flex 188 has the ~ L U~. LUL ~
O o HC--CH2 ~ CH; ~ 1 - ~CH2)n _ C--O--CH2 ~CH2--CH n--5--7 K-Flex 128 also is a polyester made f~om a cyclohexyldiol, but it has a lower le~ r weight 30 than K-Flex 188. Surface additives, BYR 341 and BYK
701 were obtained from BYK Chemie. Polyester resin 5778 (PS 5778) was nht~ P~7 from Cargill, InC. p-T~ q~lfnn;~- acid - .~lL-te (p-T;A) and methyl-ethyl-ketone (MER) were obtained from Aldrich rh-m;r:~l 35 Company. All tl7e materials were used as received.
SU~STITUTE SHEET (RULE 2~

wo 96/23034 2 1 8 5 4 5 6 ~ ~111 Ji'~ ~

First, all the diols or polyols are charged into small glass bottles, then, the dlol miYtures are heated up to 50-C or 60-C (dar~nA;n~ on the tran6ition t a~ULc8 of aiols) until they became h~
5 The diol miYtures âre well stirred in the h- , -state. An amino resin (R747 or R755) i8 added into the polyol mixtures that had already cooled to room t~uL~. The catalyst, p-TSA, i~ rlrst dissolved into small amount ~about 0.5 ml) of acetone, and then 10 i8 added into a well-miYed coating miYture. After the catalyst i8 added, the formulations are well stirred agaln.
The surface of each u lLL- ~t~d ~teel Q-panel is cleansd with acetone or Yylene three times.
CoAt;n~ are ~L~Le:d by drawing down on u.-LLcated ~teel Q-panels with a #30 wi~ . ..L..~æd, d~e-h .-' ..11 bar.
~t~n~R applied are ~ tcd in the t- _ aLUiLæ range from 40~C to 60 C, ~le, steel panels and draw-down bar also are preheated to about 40-C or 50-C.
ThQn the coated panels are baked in 150-C oven for 30 mlnutes . Dry rilm l h; rl-n-~ was 25 + 5 um.
Viscositiés are - .d on a ~r~n~ Pld LVDVII+
vi~r ~' ~T'1~Ped with thermal celln. Samples ---- ~d lnrl~l~QA polyol, CrnRRl 1nlror and catalyst.
The fllm properties ar~ tested between two hours ~nd three days after CrnRRl ;nkin~. Pencil ha~ ass, reverse impact and forward impact resistance were c~ according to ASTN D3363, D2794. During the impact r~e-; Rt~nre test, coating rilms did not have any initlally fallure, however, fllms displayed failures at the test spots three days aft~r thQ tests. NEK
r~ R~ ~nre is tested by a piece of Rim-wipe paper ~ ULC.~ with NFiK solvent and is L~ L~ed as the number of double rubs. The ,-l~e~ e Or the film is 35 A~t~rmi~n~A~ by vi8ual evaluation. Film th~rl~noqc is _d by a magnetic coating fh;rlrn~RR gauge (Nikrotest). EYcept for formulations 2 and 4, the SUBSTINTE SltEET ~RULE 26~

~ wos6n3034 2185456 ~ c~

~ollowing ~ 1 ?~ted coating compositions are made to ahow that rilms in l:cc~,Lda~ with the invention are harder and tougher. F~ 1 Ati ~ 2 and 4 are not in n~iic~ with the invention, but are for , ~ e-tive 5 ~u.
tb) ~At'l-- For~
tlo~ F'~lm csst ~t S0-C~
partQ
10 4, 7 (7 diol) Adipate of EYample IIa 70 P^^; - ~ 747 30 P-TSA 0 . 5 Surface additive (BYK-341) 0.1 Solvent None P.. _ _L~ r FormylAation 1 Viscosity at 40-C 0.4 Pa.s Irh i rlrn^-lc 25 ~m Forward Impact Resistance 140 in-lb Reverse Impact Resistance 80 in-lb Pencil Hardness X-HB
NER Resistance >200 rubs 601id content (llO-C, 30 min.) 97%
~rp--ArAn~e ~rAn^~p^rency, gloss 25 ~ Ati~- 2. (F~lm ml~t b~ ~Qt at 40-C to 50-C) ~E~
4,7(7 diol) Adipate of E~cample IIa 20 3-Ring - - --, ; n ~^,1; ~ of EYa~ple I 50 P~^i-- - 747 30 30 P-TSA 0 . 5 Surface additive (BYR-341) 0 . 4 Solvent None FLO8 ~ 1 Or FC 1~ f 1~ 2 .
Viscosity at 40-C 0.8 Pa.s 35 ~hirl~n^~^ 25 ,um Forward Impact Resistance 160 in-lb Reverse Impact Resistance 160 in-lb SUBSTITUTE S~IEET (RU~E 26~

Wo 96l23034 --4 6--Pencil TT~ " 4H-3H
MEK R~ciCIt~-n-~" >200 rubs Solid content (llO-C, 30 min. ) 95%
~rp~--An~e 1-rAncpArenCy~ gloss tion 3. ~F~lm cast at 30-C) Part~

7,4 AzelQate of Example IIb 20 3-Ring J 1.~ ol i ~ o~ Example I 50 ~ _i - 747 30 10 P--TSA o. 5 6urface additive (BYR-341) 0 . 4 Solvent None E1VU_LLl~ o~ For~la~irn 3.
Viscosity at 40-C 0.8 Pa.s 15 Thlt~lrn~cc 25 ,um Forward Impact Pec; C~nræ 160 in-lb R~verse Impact Resistance 160 in-lb Poncil Ha~'l~ 4H-3H
MER Resistance >200 rubs 20 Solid content (llO-C, 30 min. ) 95%
~L~l~n~ e L c~ ~L~ll~y, glo~s Fo~nulation ~. ~F~l_ ca~t at roo~ t _ .,L....~
Azeleate of Example IIc 7 0 25 P--Ci - 747 30 P-TSA ~ 5 Surface additive ( BYK-341) 0 .1 Solvent None Plvv_~ Ll~s of Ft ~
30 Vlscosity at 27-C 1.35 Pa.s 'rhif~l-n~cc 25 ,um Forward Impact Resistance 120 in-lb Reverse Impact Resistance 60 in-lb Pencil Har~ness 4H

35 MEK Resistance >200 ruvs Solid content (llO-C, 30 min. ) 95%
A~e~LAIloe transparency, gloss SUBSTITUTE SHEET (RULE 26) -~ Wo 96123034 2 1 8 5 4 5 6 - -F~ ion 5. tFilm cla~t ~t 30 -C or 40 -C) P~ts Azele~te of EYample IIc 50 3-Rlng ~ ;~, nl i j C of Example I 20 ~ ; 7 4 7 3 o P-TSA 0 . 5 Surface additive (BYK-341) 0. 4 Solvent None P~ le~ or J~c l~tlon 5.
Viscosity at 40-C 1 Pa.s Th~r-~nP-;a 25 ,um Forward Impact Resistance 140 in-lb Reverse Impact Resistance 8 0 in-lb Pencil Hardness 4H
MEK Resistance >200 rubs Solid content (llO C, 30 min. ) 95%
Appearance transparency, gloss (a) ~t~- For~ 7 ~rith l.3.s-Tri~7 ~2-1.~ V~Y1 ~thVl) c~ r~ ~ciC ~
4--Diol A7Al ~Ate (4DA) (M, = 695) (30 g) is placed in a 100-mL beaker and heated to 150-C on a hotplate.
THECA (6 g) is placed in another 100-_L beaker and heated at 150 C in an oven until it melts, then it is poured into hot liquid 4DA under fast l--gn~t;~
stirring. The mixture is cooled down to room L~e under m~n~t;r stirring. M~lAmin~ resins r -; - 755 or 797 were added at a r~tio of 65/35 (4DA~ -lAminP). The mixture was then stirred for 40 hour8. r -; ~ 797 is methylolated --1Amin~
~nrr-7~hyde resin having as its principal reactive group --N-- (CH20CH~)2. It rnnt~in~ 20 weight % o~ a polyol additive. It totals 92% golid~ ht.
SIJBS7. 11UTE SHEE7, (RULE 261 W096/23034 2 1 8 5 4 5 6 ~ l~L
--~8--Table 16 . Film properties of cn~ i ng_ made from 4-fiinl~7010~te (MD ~ 695) with ~HECA.
Formulation No. 1 2 3 R~ 755 % 35 35 35 5(4DA/TE~CA ~ 4/1) % 65 65 65 p-TSA % 1.0 1.0 1.0 Di #p~r#inn time in hours 3 40 40 Viscosity mPa.s at 1025-C 620 g50 ---2 n ~u~u~y ethanol NO NO 10% of wt. oi~
solids weight Baking temp. for 30 minutes 150-C 150-C 150-C
Pencil Hardness HB 2H 2H-3H
15~lho$inn OB lB 2B
Direct impact lb-in. 40 60 60 Film ~ rough surf ac- good good 20 !~!h~ c~ct of aatalYst ~inonvlnaD~th-l-n~ ~sulfonic ~oi~ ~DNND8A) Two formulations were made with 12 . 5% THECA
using DNNDSA as a catalyst. DNNDSA i5 a liquid and i5 ~asy to mix into the resin. The properties are listed 25 in Table 17. It W~8 ~ound that the use of DNNDSA
u.~d gla88 and l~veling and that, when formulated with ~o~ 797, the coating ~ilm had the best i, u~ L in film properties, the ha~ e~ was 2H-3H
and ~h~Fzinn was 3B on untreated panels.

SUaSTlTLlTE SHEET (RULE 26 21 85456 ~
wo 96~3034 Table 17. Film properties of coA~in~ made from 4-A1 ~1~70~eAte (N~ - 695) with TÆCA using DNNDSA as cataly~t.
5 TEI13CA % 12 . 5 12, 5 4DA % 50 50 vPe~- - 755 & 797S 3?.5 (755) 37-5 (797) DNNDSA % 1. 0 1. O
Baking temp./30 minutes 150'C 138'C
10T~ 2E1 2H-3}1 ~'7hP~!inn on untre~ted steel panel OB-lB 3B
AAhQc~inn on primed steel panel 5B 5B

SPI~ I~r 20 1~ Form~ n Or ~-~Lol ~ol~ t~ = 695~ with th~
6t~T
4-Diol A70l-o~t~o (DA) (~ = 695) (30 g) is placed in a 100-mL beaker and heated on a hotplate to 120'C. 6GT (6-glycol-te~ Lt,~l~te, 3 g) is placed in 25 an aluminum dish and heated at 130'C in an oven until it melts, then it is poured into liquid 4DA. The mixture is cooled down to room tr aLl~L~ under _ 3tic stirring. MPl~m;n~ resinR 755 or 797 are added at ratio o~ 65/35 (4DA/ -lAminp:. me m ixture is 3 0 then stirred ~or 2 hours .
.
SUBSTIIUTE SHET (RUL~
.

Wo 96l23034 ~ 1 8 5 4 5 6 Table 18. Properties of coatings made fro~ 4-diol A7~1~at~ 695) with 10% of 6GT.
(4DA/6GT -- 10/1, % 60 517.o~i ~ 755, ~ 40 p-TSA % of wt. of total solids 1. 0 Viscosity mPa.s * (40 hr. st-rring) at 25-C RPN ~ 50 spindle #64 1800 Direct i~pact in . -lb . 6 0 10Pencil hardness HB
Solvent r~ t~n~-e >200 A~h~Rinn OB
* milli Pascal-sec.
15 Table 19. Viscosity of 4-diol azeleate (Mn = 695) with 10% 6GT using different shear rate at 25-C.
Shear Rate 100 50 20 10 5 2.5 1.0 R~M
20 mP~.s 1442 1782 2269 3899 5879 94599 18600 * milli Pas al-se .
Spindle LV #64.
E~allPLE V
25 l~) Fnrm~ tion of 4-dlol ~lont~ ~M = 550) with t~e 7~ -r~ ~ ~ D - ~r~rh I tol .
A saturated Eol utinn of D-~orbitol in water (109~ by weight of D-sorbitol) wa~ added into the resin (Oligomer/797 - 65/35~ under stirring. The D-sorbitol 30 was not ~p~ 1 and ~ with water for~ed a rluffy 8"';r~ i nr~ in the ~olution.
SUBSTIME SHEET (~UL~

21 ~5~56 W0 96123034 r~

Table 20. Properties of coatlngs mad~. from 4DA (N" =
550) with D-Sorbitol.
D-sorbitol % 6 . 5 ~wt of D-sorbitol 5(dissolved in water~
4ADA ~t 5 8 . 5 P~l:i - 797 % 35 p-TSA % 1. 6 Baking t~ c~tULe/30 min. 138-C
Pencil hardness 2H
~hP~ n 4B
Film ~ L.. ~e yellow, transparent l~LaMPLD VI
8Ynthe~is of ~n oli~oester ~liol which i~ the re~ction Dro~uct Or 1,~ L~ liol nn~ a m~ of l~imethYl ~tors Or ~IOOC (~17) _COO~ Ci~lS, n = 3, ~ ~nd 7 in 1 m~ r r~tio ~MP=520).
l~e materials used for the synthesis of oligoester diols were as follows. Dimethyl azelate was obtained from Aldrich and redistilled, the distilled diester was ~ ~ ~ of dimethyl ester~ of heptanedioic (1.8%), octanedioic (4.1%), azelaic (83.6%), dPI-AnP~l1oi~ (3.5%) and lln~lPCAnolliOiC (7.1%) acids, as dPtermi nPd by GC/MS . Dimethyl glutarate and dimethyl adipate were obtained from Du Pont, as "DBE-5" and "DBE-3", respectively, they are reported to be mixtures of the dimethyl esters of s~rlnic (SA), glutaric (GA), and adipic (AA) acids in the following proportions:
DBE--3: SA, <1%: GA, 5--15 %; AA, 85--95%;
DBE-5: dimethyl glutarate >98 . 5% .
DBE-3 and DBE-5 are liquids at 25-C. ~nd solids at O-C.
1~4-butAnP~ 1 (99%) and zinc acetate dihydrate (98%) were obtained from Aldrich t`hPmi~l Co.
In a 500-ml four-neck fla~k equipped with stirrer, Dean-Stark trap, c~m~lPnl:Pr, thl- Ler and SU~STlTUrE SHEET ~RUL~ 26) .

~v0 96n3034 2 1 8 5 4 5 ~ P~

nitrogen inlet, were placed dimethyl ~zelate (108 g., 0.5 mol), DBE-i (87 g., 0.5 mol), DBE-5 (80 g., 0.5 mol), 1,4 ~U~ Ai~l (270 g., 3.0 ~ol), zinc acetate dihydrate (1.0~ g., 0.29~ of total ~ cLa~lL weight).
5 Thl3 stirred mixture was heated by an electrothermal heating mantle with a controller from 150-C. to 170-C.
~or 3 hours, and then heated to 200-C~ and r~;nt~inPd rOr 1 hour. About 9S% of the theoretical amount of -1, the by ~L~du L o~ the transesterification, 10 was rollec~P<l in the Dean-Stark trap. The t~ ~LUL~=
was raised from 200-C. to 220-C., and nitrogen was ~ed slowly through the l,~cLa..Ls to remove 1,~ ~uL~nediol, the L~ iL~dU-,~ of the co-pol~u ~ Lion. Oligoester-diols with dif.:erent lec~ll Ar weights were obtained by5 removing samples at different intervals.
me oligoester diol (MD~520) was mixed with a ha~d~ and cro~ nkPr as described below.

$UBSTITUTE SHEET ~RULE 261 Wo s6/23034 2 1 8 5 ~ 5 6 (a) Fon~ulations of oligoester diol of VI with h~clPT~ r 6GT
Table 21.
OligoL_Lel-diol VI ~a) VI a VI a 5~ 520) ~ ) ( ) Wt~ 4.9 g ~ lcft a~ left ~irdener 6GT n % of Diol. 20~ n CYmel 1135 ~9~ of 66~ n lODiol~
5~1 r~ 24000~ n Lux~te XND 0700 ~
o~ Diol~ --- 1096 "
Solvent ~ - --- 5~s 15BYK-077 0,5 ~Defo8mer~
DIIIIDSA~
P~nel ~ aa left a3 left Film thickne J O . 9 - 1. 0 0 . 9 - 1 . 0 0 . 8 - 0 . 9 20~mil~
Direct I3p~ct (lb- ~120 >120 >120 in~
ReverJe Implct <80, -40 -80, >40 <80, >40 25Pencil Hardneas lN - 211 2N lN - 2N
~E~ Rub ReJi~tance >200 >200 >200 Adhe~ion lB - 2B 3B - 4B 3B - 4B
,~ rJ~rre Tran~parent Tran~p~re TranQparent nt * 6-glycol-te~ te ~r~ Lc.y- of the total weight ~ Q-PHOS is ~ mark under whlch pho5phated stee1 panels are sold. These panels were. U8 d in th tests described herein. e e SUBSTITUTE SHEET ~RULE ~

W096/23034 _54_ r~llLv,~.'l -- 1..1~, of oll~o~ t~r ~lol of r 1~ wlth 1'"~!~. Jr 10GT.
10 GT is O O
HO{(CH~-;O10-CO~ CI~I;OH

Table 22.

Oligv~ liol VI VI VI
(M" 520) Wt/ 4 . 9 g ~ left aa left Nardener 10GT " "
15a o~ Diol. 25G r ~
Cymel 1135 (% o~ 66a " "
Diol ) Sol~pen~e 24000~ la n Lux~te XHD 0700 (~
20of Diol) --- 10a "
Solvent (~ -- 5a BYI~-077 0 . 5a 0 , 5% 0 . 5a (Defoamer) ~
DNNDSA~- la 1~ la 25Panel Q-PHOS R-36- as left a~ lQft Film th' kn 0 8 - 0.9 1.0 - 1 (mLl ~ LC e ~ .1 0 . 8 Direct ImpAct (lb- >120 >120 >120 in) 30Rever~e I~p~lct <80, -40 >80, >4C <80, >40 (lb-in) Pencil Hardne~ lN - 2H 2H lH - 2H
MEI~ Rub Reei~t~nce >200 >200 >200 Adhesion lB - ZB 3B - 4B 3B - 4B
357~rp~1rJ-n~-e Tran~parent Tran p~re Transparent nt * r~ n~e o~ the total weight.
Dinonyl n~rhth~ n~ disulfonic acid.

SUBSrlTUTE SHEET (RULE 26) ~ W096/23034 2 1 8 54 56 l..tl- - or n~ Bt-r ~ l Or R~ e ~ with r ~v,.~, T~vle 23.
5Oligv__L-5L-i~ol VI ~ (a) VI ~a) (MD ~7C) ~t/ 4.8 g " "
Ei~rdencr THEC~ "
~ of Diol. 20~ " "
10 Cymel 1135 ( ~c o~ 66~ " "
Diol ) Solapenae 24000 Lux~te XND 0~00 (~
of Diol) --- 10~ "
15Solvent (ME$) ~ --- 5 BYI~-077 0 . 5~ 0 . 5~ 0 . 5 (De~oa~er~
D~ND5A~
Panel Q-PNOS R-36- aa l~ft aJ le~t 20Film thickneaa 0.7 - 0.8 0.8 - 0.9 0.8 Direct Imp~ct (lb- -120 >120 ?120 Ln) ReverJe Imp~ct <60 -60 -60 25(lo-in) Pencil HardneaJ 5H 5H 5H
Ru~v Re~ tance >200 >200 >200 A~heaion 5B 5B 5B
ArpA: - Tr.n~pAr~r~f Tr~nap~re TrAn~pAr~.nt nt P~ ht~ of the total weight.
' Dinonylnapthalene disulfonic acid.
SUBSTITUTE SHEET (RU~E æ~

Claims (47)

WHAT IS CLAIMED IS

1. A polymeric vehicle which is effective for providing a formulated coating composition having at least about 75 weight % solids, the polymeric vehicle comprising:
at least one nonmesogenic substantially linear oligoester diol having a number average molecular weight in the range of from about 275 to about 3000 and a polydispersity index of not more than about 2.6;
at least one hardener selected from the group consisting of a mesogenic polyol, a crystalline polyol, a phenolic ester alcohol and mixtures thereof; and at least one crosslinker which is reactive with the substantially linear oligoester diol and hardener, the mesogenic polyol having a number average molecular weight in the range of from about 186 to about 4000, a polydispersity index of not more than about 2.6 and comprising from about 5 to about 50 weight percent mesogens, based upon the weight of the mesogenic polyol, the crystalline polyol being oligomeric or nonoligomeric and having from 5 to about 200 carbon atoms, the oligomeric crystalline polyol having a number average molecular weight in the range of from about 400 to about 4000, the nonoligomeric polyol having a molecular weight in the range of from 120 to about 500, and a solubility in the formulated coating composition of not more than 10 g/L at a temperature range of from about 0°C to about 40°C, the phenolic ester alcohol having at least two ester groups; at least one aliphatic hydroxy group and at least one phenolic hydroxy group, the oligoester diol, hardener and crosslinker being in a ratio effective to provide a mixture of the oligoester diol, the hardener and crosslinker with a viscosity in the range of from about 0.1 to about 20 Pa.s at from about 20°C to about 60°C at a shear rate of about 1000 seconds-1.

2. A polymeric vehicle as recited in claim 1 wherein the mesogenic polyol has mesogen selected from the group consisting of formulas I, II and III, wherein I
or covalently bonded combinations of general formula I;
II
or covalently bonded combinations of general formula II;

and combinations of Formulae I and II, III
or or covalent combinations of general formula III;
wherein A is selected from the group consisting of , , -CH=N-, -N=CH-, -O-CH2-, -CH2-O-, , , covalent bond, and , B is selected from the group consisting of , , -CH=N-, -N=CH-, -O-CH2-, -CH2-O-, , , covalent bond, , , , or wherein c = an integer from 2 to 8;
d = 1 or 2;
u = A;
x = A; and q = integer from 1 to 3.

3. A polymeric vehicle as recited in claim 1 wherein the oligoester diol is terminated with hydroxyl groups and has a longitudinal chain having chain segments with the structures selected from the group consisting of -CH2-, -O-, -C(=O)-, -(R)CH-, -(R)2C- wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, isobutyl and normal butyl and not more than about 8 percent of the number of hydrogens which would be bonded to carbon atoms along the longitudinal chain are substituted with R.

4. A polymeric vehicle as recited in claims 1, 2 or 3 wherein the polymeric vehicle comprises from about 15 to about 50 weight percent oligoester diol, from about 10 to about 50 weight percent hardener and from about 10 to about 40 weight percent crosslinker.

5. A polymeric vehicle as recited in claim 1 wherein the crystalline polyol consists essentially of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen atoms, the nitrogen atom forming a part of a nitrogen group selected from the group consisting of an amide group, an urea group and an amidine group.

6. A polymeric vehicle as recited in claims 1, 2, 3 or 5 wherein the substantially linear oligoester polyol has a branching index of not more than about 0.12 wherein the branching index is defined by the formula branching index = ;
Where C1 = the average number of linear segments per oligomer molecule;
C? = the average number of segements with single branches per molecule;

Cd = the average number of segments with double branches per molecule;
B1 = the average length, in carbon and oxygen atoms, of branches.

7. A polymeric vehicle as recited in claims 1, 3 or 5 wherein the crystalline polyol has a melting point of from about 5°C to about 40°C below a baking temperature which ranges from about 70 to about 175°C.

8. A polymeric vehicle as recited in claim 1 wherein the oligoester diol has the general formula HO(CH2)m-[OOC(CH2)nCOO(CH2)m]pO-H
wherein p > 1 and < 6, m = 2 to 16, n = 0 to 12.

9. A polymeric vehicle as recited in claims 1, 2 or 3 wherein the mesogenic polyol has the general formula Ro-F-E-F-Ro wherein E is selected from the group consisting of , and G is selected from the group consisting of -COO-, -OOC-, -CH2O-, -OCH2-, , and ;
wherein R' is selected from the group consistlng of - CH3 and H;
F is selected from the group consisting of -O-, -COO- and -OOC-; Ro is an aliphatic group having from 4 to 30 carbons and at least one hydroxyl group; and wherein any hydroxyl group included in Ro is spaced from F by at least one carbon atom.

10. A polymeric vehicle as recited in claim 9 wherein Ro is an adduct of a monoxirane having not more than about 25 carbon atoms.

11. A polymeric vehicle as recited in claims 1, 2 or 3 wherein the mesogenic polyol has a number average molecular weight in the range of from about 186 to about 4000, a polydispersity index of not more than about 2.6 and is effective for forming a dispersion in the formulated coating composition.

12. A polymeric vehicle as recited in claims 1, 2 or 3 wherein the mesogenic polyol has a number average molecular weight in the range of from about 186 to about 1000, a polydispersity index of not more than about 2.6 and is effective for forming a solution in the formulated coating composition.

13. A polymeric vehicle as recited in claims 1, 2, 3 or 5 wherein the crosslinker has an average functionality which is reactive with the hydroxyls of the oligoester diol and hardener which average functionality is more than about 2.4.

14. A polymeric vehicle as recited in claim 4 wherein the crystalline polyol consists essentially of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen atoms, the nitrogen atom forming a part of a nitrogen group selected from the group consisting of an amide group, an urea group and an amidine group.

15. A polymeric vehicle as recited in claim 4 wherein the crystalline polyol has a melting point of from about 5°C to about 40°C below a baking temperature which ranges from about 70 to about 175°C.

16. A formulated coating composition having at least about 75 weight % solids, the formulated coating composition comprising:
a polymeric vehicle and an organic solvent, the polymeric vehicle comprising at least one nonmesogenic substantially linear oligoester diol having a number average molecular weight in the range of from about 275 to about 3000 and a polydispersity index of not more than about 2.6, at least one hardener selected from the group consisting of a mesogenic polyol, a crystalline polyol, a phenolic ester alcohol and mixtures thereof, and a crosslinker which is reactive with the substantially linear oligoester diol and hardener, the mesogenic polyol having a number average molecular weight in the range of from about 186 to about 4000 and a polydispersity index of not more than 2.6 if it is dispersed in the formulated coating composition and a number average molecular weight of from about 186 to 1000 and a polydispersity index of not more than about 2.6 if it is a solution in the formulated coating composition, and the mesogenic polyol comprising from about 10 to about 50 weight percent mesogens, based upon the weight of the mesogenic polyol, if it is in solution in the formulated coating composition and comprising from about 5 to about 50 weight percent mesogens, based upon the weight of the mesogenic polyol, if it is dispersed in the formulated coating composition, the crystalline polyol having oligomeric or nonoligomeric and having from 5 to about 200 carbon atoms, the oligomeric crystalline polyol having a number average molecular weight in the range of from about 400 to about 4000, the nonoligomeric polyol having a molecular weight in the range of from 120 to about 500, and a solubility in the formulated coating composition of not more than 10 g/L at a temperature range of from about 0°C to about 40°C, the phenolic ester alcohol having at least two ester groups; at least one aliphatic hydroxy group and at least one phenolic hydroxy group, the oligoester diol, hardener and crosslinker being in a ratio effective to provide a mixture of the oligoester diol, the hardener and crosslinker with a viscosity in the range of from about 0.1 to about 20 Pa.s at from about 20°C to about 60°C at a shear rate of about 1000 seconds-1.

17. A formulated coating composition as recited in Claim 16 wherein the oligoester diol, the hardener and the crosslinker are in a ratio effective to provide the coating binder having a pencil hardness of at least about B when applied to a substrate at a thickness of about 1 mil dry.

18. A formulated coating composition as recited in claims 16 or 17 wherein the mesogenic polyol has mesogens selected from the group consisting of formulas I, II, and III wherein I
or covalently bonded combinations of general formula I;
II
or covalently bonded combinations of general formula II;
and combinations of formulas I and II, and III
or covalent or combinations of general formula III;

wherein A is selected from the group consisting of , , -CH=N-, -N=CH-, -O-CH2-, -CH-O-, , , covalent bond, and , B is selected from the group consisting of , , -CH=N-, -N=CH-, -O-CH2-, -CH2-O-, , , covalent bond, , , ,or wherein c = an integer from 2 to 8;
d = 1 or 2;
u = A;
x = A; and q- integer from 1 to 3.

19. A formulated coating composition as recited in claim 16 wherein the oligoester diol has a longitudinal chain having chain segements with the structures selected rrom the group consisting of -CH2-, -O-, -C(=O)-, -(R)CH-, -(R)2C- wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, normal butyl and isobutyl and not more than 8 percent of the number of hydrogens which would be bonded to carbon atoms along the longitudinal chain are substituted with R, wherein the main longitudinal chain is terminated with hydroxyl group or R is substituted with hydroxyl group if R is not more than four carbons of a terminal carbon of the longitudinal chain.

20. A formulated coating composition as recited in claims 16, 17 or 19 wherein the polymeric vehicle comprises from about 15 to about 50 weight percent oligoester diol, from about 10 to about 50 weight percent hardener and from about 10 to about 40 weight percent crosslinker.

21. A formulated coating composition as recited in claim 16 wherein the crystalline polyol consists essentially of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen atoms, the nitrogen atom forming a part of a nitrogen group selected from the group consisting of an amide group, an urea group and an amidine group.

22. A formulated coating composition as recited in claims 16, 17, 19 or 21 wherein the substantially linear oligoester polyol has a branching index of not more than about 0.12 wherein the branching index is defined by the formula branching index = ;

Where C1 = the average number of linear segments per oligomer molecule;
C? = the average number of segments with single branched per molecule;
Cd = the average number of segments with double branched per molecule;
B1 = the average length, in carbon and oxygen atoms, of branches.

23. A formulated coating composition as recited in claims 16, 19 or 21 wherein the crystalline polyol has a melting point of from about 5°C to about 40°C below a baking temperature which ranges from about 70 to about 175°C.

24. A formulated coating composition as recited in claims 16, 17 or 19 wherein the composition further includes a catalyst.

25 A formulated coating composition as recited in claim 19 wherein the composition further includes a catalyst.

26 A method for providing a polymeric vehicle with a viscosity in the range of from about 0.1 to about 20 Pa.s at a shear rate of about 1,000 seconds-1 at a temperature range of from about 20°C to at least about 60°C, the method comprising:
mixing at least one nonmesogenic substantially linear oligoester diol, at least one hardener and at least one crosslinker, the substantially linear oligoester diol having a number average molecular weight in the range of from about 275 to about 3000 and a polydispersity index of not more than about 2.6, the hardener selected from the group consisting of a mesogenic polyol, a crystalline polyol, a phenolic ester alcohol and mixtures thereof, the crosslinker being reactive with the substantially linear oligoester diol and hardener, the mesogenic polyol having a number average molecular weight in the range of from about 186 to about 4000, a polydispersity index of not more than about 2.6 and comprising from about 5 to about 50 weight percent mesogens, based upon the weight of the mesogenic polyol, the crystalline polyol being oligomeric or nonoligomeric and having from 5 to about 200 carbon atoms, the oligomeric crystalline polyol having a number average molecular weight in the range of from about 400 to about 4000, the nonoligomeric polyol having a molecular weight in the range of from 120 to about 500, the phenolic ester alcohol having at least two ester groups: at least one aliphatic hydroxy group and at least one phenolic hydroxy group, the oligoester diol, hardener and crosslinker being mixed in a ratio effective to provide a mixture of the oligoester diol, the hardener and crosslinker with a viseosity in the range of from about 0.1 to about 20 Pa.s at from about 20°C to about 60°C at a shear rate of at least about 1000 second-1.

27. A method as recited in claim 26 wherein the mesogenic polyol has mesogenic groups selected from the group consisting of formulas I, II, and III wherein I
or covalently bonded combinations of general formula I;

II or covalently bonded combinations of general formula II;

and combinationE of formulas I, II and III

or covalent or combinations of general formula III;

wherein A is selected from the group consisting of , , -CH=N-, -N=CH-, -O-CH2-, -CH2-O-, , , covalent bond, and , B is selected from the group consisting of , , -CH=N-, -N=CH-, -O-CH2-, -CH2-O-, , , covalent bond, , , , or v = wherein c = an integer from 2 to 8;
d = 1 or 2;
u = A;
x = A; and q = integer from 1 to 3.

28. A method as recited in claim 26 wherein the oligoester diol has a longitudinal chain having chain segments with the structures selected from the group consisting of -CH2-, -O-, -C(=O)-, -(R)CH-, -(R)2C-wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, normal butyl and isobutyl and not more than 8 percent of the number of hydrogens which would be bonded to carbon atoms along the longitudinal chain are substituted with R, wherein the main longitudinal chain is terminated with hydroxyl group or R is substituted with hydroxyl group if R is not more than four carbons of a terminal carbon of the longitudinal chain.

29. A method as recited in claims 26, 27 or 28 wherein the polymeric vehicle comprises from about 15 to about 50 weight percent oligoester diol, from about 10 to about 50 weight percent hardener and from about 10 to about 40 weight percent crosslinker.

30. A polymeric vehicle comprising:
a blend of a nonmesogenic substantially linear oligoester diol having a number average molecular weight in the range of from about 275 to about 3000 and a polydispersity index of not more than about 2.6 and a hardener selected from the group consisting of a mesogenic polyol, a crystalline polyol, a phenolic ester alcohol and mixtures thereof, the blend effective for crosslinking through a crosslinker which is reactive with the substantially linear oligoester diol and hardener, the mesogenic polyol having a number average molecular weight in the range of from about 186 to about 4000, a polydispersity index of not more than about 2.6 and comprising from about 5 to about 50 weight percent mesogens, based upon the weight of the mesogenic polyol, the crystalline polyol being oligomeric or nonoligomeric and having from 5 to about 200 carbon atoms, the oligomeric crystalline polyol having a number average molecular weight in the range of from about 400 to about 4000, the nonoligomeric polyol having a molecular weight in the range of from 120 to about 500, and a solubility in the formulated coating composition of not more than 10 g/L at a temperature range of from about 0°C to about 40°C, the phenolic ester alcohol having at least two ester groups; at least one aliphatic hydroxy group and at least one phenolic hydroxy group, the oligoester diol and the hardener being in a ratio effective to provide a mixture comprising the oligoester diol, the hardener and a crosslinker with a viscosity in the range of from about 0.1 to about 20 Pa.s at from about 20°C to about 60°C at a shear rate of about 1000 seconds-1.

31. A polymeric vehicle as recited in Claim 30 wherein the oligoester diol, the hardener and the crosslinker are in a ratio effective to provide a coating binder having a pencil hardness of at least about B when applied to a substrate at about one mil dry.

32. A polymeric vehicle as recited in claim 30 or 31 wherein the mesogenic polyol has mesogen selected from the group consisting of formulas I, II, and III, wherein I

or covalently bonded combinations of general formula I;

II
or covalently bonded combinations of general formula II;

and combinations of formulas I, II and III

or covalent combinations of or general formula III;

wherein A is selected from the group consisting of , , -CH=N- , -N=CH-, -O-CH2-, -CH2-O-, , , covalent bond, and , B is selected from the group consisting of , , -CH=N-, -N=CH-, -O-CH2-, -CH2-O-, , , covalent bond, , , ,or V = wherein c = an integer from 2 to 8;
d = 1 or 2;
u = A;
x = A; and q = integer from 1 to 3.

33. A polymeric vehicle as recited in claim 30 or 31 wherein the oligoester diol is terminated with hydroxyl groups and has a longitudinal chain having chain segments with the structures selected from the group consisting of -CH2-, -O-, -C(=O)-, -(R)CH-, -(R)2C-wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, normal butyl and isobutyl and not more than 8 percent of the number of ens which would be bonded to carbon atoms along the longitudinal chain are substituted with R, wherein the main longitudinal chain is terminated with hydroxyl group or R is substituted with hydroxyl group if R is not more than four carbons of a terminal carbon of the longitudinal chain.

34. A polymeric vehicle as recited in claim 30 wherein the crystalline polyol consists essentially of atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen atoms, the nitrogen atom forming a part of a nitrogen group selected from the group consisting of an amide group, an urea group and an amidine group.

35. A polymeric vehicle as recited in claims 30, 31 or 34 wherein the substantially linear oligoester polyol has a branching index of not more than about 0.12 wherein the branching index is defined by the formula branching index = ;

Where C1 = the average number of linear segments per oligomer molecule;
C3 = the average number of segments with single branches per molecule;
Cd = the average number of segments with double branches per molecule;

B1 = the average length, in sarbon and oxygen atoms, of branches.

36. A polymeric vehicle as recited in claim 35 wherein the mesogenic polyol has mesogen selected from the group consisting of formulas I, II, and III, wherein I

or covalently bonded combinations of general formula I;

II
or covalently bonded combinations of general formula II;
and combinations of formulas I, II and III
or covalent combinations of or general formula III;
wherein A is selected from the group consisting of , , -CH=N- , -N=CH-, -O-CH2--, -CH2-O-, , , covalent bond, and B is selected from the group consisting of -CH=N-, -N=CH-, -O-CH2-, -CH2-O-, , covalent bond, , , or v = wherein c = an integer from 2 to 8;
d = 1 or 2;
u = A;
x = A; and q = integer from 1 to 3.

37. A polymeric vehicle as recited in claim 36 wherein the polydispersity index of the oligoester diol is not more than 1.8.

38. A polymeric vehicle as recited in claims 30, 31 or 34 wherein the crystalline polyol has a melting point of from about 5°C to about 40°C below a baking temperature which ranges from about 70 to about 175°C.

39. A polymeric vehicle as recited in claim 30 or 31 wherein the oligoester diol has the general formula HO(CH2)m-[OOC(CH2)nCOO(CH2)m]pO-H
wherein p > 1 and < 6, m = 2 to 16, n = 0 to 12.

40. A polymeric vehicle as recited in claims 30 or 31 wherein the mesogenic polyol has the general formula Ro-F-E-F-Ro wherein E is selected from the group consisting of G is selected from the group consisting of -COO-, -OOC-, -CH2O-, -OCH2-, and wherein R' is selected from the group consisting of - CH3 and H;
F is selected from the group consisting of -O-, -COO- and -OOC-; Ro is an aliphatic group having from 4 to 30 carbons and at least one hydroxyl group; and wherein any hydroxyl group included in Ro is spaced from F by at least one carbon atom.

41. A polymeric vehicle as recited in claim 40 wherein the oligoester diol is terminated with hydroxyl groups and has a longitudinal chain having chain segments with the structures selected from the group consisting of -CH2-, -O-, -C(=O)-, -(R)CH-, -(R)2C- wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, normal butyl and isobutyl and not more than 8 percent of the number of hydrogens which would be bonded to carbon atoms along the longitudinal chain are substituted with R, wherein the main longitudinal chain is terminated with hydroxyl group or R is substituted with hydroxyl group if R is not more than four carbons of a terminal carbon of the longitudinal chain.

42. A polymeric vehicle as recited in claim 40 wherein Ro is an adduct of a monoxirane having not more than about 25 carbon atoms.

43. A polymeric vehicle as recited in claim 32 wherein the mesogenic polyol has a number average molecular weight in the range of from about 186 to about 4000, a polydispersity index of not more than about 2. 6 and is effective for forming a dispersion in the formulated coating composition.

44. A polymeric vehicle as recited in claim 32 wherein the mesogenic polyol has a number average molecular weight in the range of from about 186 to about 1000, a polydispersity index of not more than about 2. 6 and is effective for forming a solution in the formulated coating composition.

45. A polymeric vehicle as recited in claim 34 wherein the crystalline polyol has a melting point of from about 5°C to about 40°C below a baking temperature which ranges from about 70 to about 175°C.

46. A polymeric vehicle as recited in claims 30, 43, 44 or 45 wherein the oligoester has a polydispersity index of not more than 1.8 and the oligoester diol and the hardener being in a ratio effective to provide a mixture comprising the oligoester diol, hardener and a crosslinker, which mixture will provide a coating binder having a pencil hardness of at least about H when applied to a substrate at about one mil dry.

47. A polymeric vehicle as recited in claim 46 wherein the mesogenic polyol has mesogen selected from the group consisting of formulas I, II, and III, wherein I

or covalently bonded combinations of general formula I;
II

or covalently bonded combinations of general formula II;
and combinations of formulas I, II and III
or covalent combinations of or general formula III;

wherein A is selected from the group consisting of , , -CH=N- , -N=CH-=, -O-CH2-, -CH2-O-, , , covalent bond, and B is selected from the group consisting of , , -CH=N-, -N=CH-, -O-CH2-, -CH2-O-, , , covalent bond, , , or v= wherein c = an integer from 2 to 8;
d = 1 or 2;
u = A;
x = A; and q= integer from 1 to 3.