CA2185454A1 - Polymeric vehicle effective for providing solventless coating compositions - Google Patents

Abstract

This invention relates to a polymeric vehicle which reduces or eliminates VOCs in coating compositions by providing a formulated coating composition which does not require an organic solvent for application to a substrate. The polymeric vehicle of the invention comprises at least one linear oligoester diol effective for cross-linking with a cross-linker, and having a number average molecular weight within controlled limits of a polydispersity index effective for controlling the viscosity of the polymeric vehicle.

Description

=

prlTvM~RTC VEEICLE ~ S~;LlvlS FOR ~UVll.~lNl:i SOLVEIITLESS
COATING COMPOSITIO~S
FIELD OF T~E lNVl~ lUN
This application is a Continuation-In-Part 5 application of U.S. Application Serial No. 08/487, 962, which is a Continuation-In-Part application of Serial No.
PCT/US95/01053 which is a Continuation-In-Part application of Serial No. 08/186, 430. The present invention relates to a blend of ingredients which is 10 effective for providing a formulated coating composition without the addition of organic solvent to provide a composition which may be applied to a substrate as a protective paint by existing commercial application equipment. More particularly, this invention is directed 15 to a polymeric vehicle which is a blend of a linear oligoester diol having a number average molecular weight in the range of from about 275 to about 1200 and a crosslinker, a solventless formulated coating composition made from the polymeric vehicle, a coating binder made 20 from the solventless formulated coating composition and a method of controlling the viscosities of the polymeric vehicle and formulated coating composition.
U~L~_ OF T~E PRIOR ART A~ r~
One of the primary components in paint is the 25 "film former'T that provides a film for the protective function for a substrate coated with the paint. Film forming components of liquid paint include resins which have required organic solve~ts to provide the resins with suitable viscosities such that the paint can be applied 30 by existing commercial application equipment. Use of organic solvents, however, raises at least two problems.
In the past and potentially in the future, petrochemical shortages mitigate against the use of organic solvent in great volumes. Second, environmental concern mitigates 35 against the use of organic solvents.
Environmental concern has become increasingly - important. This concern not only extends to preservation of the environment for its own sake, but extends to Wos6n303s 21 ~ 54 54 r~ 4l ~
puolic safety as to both living and working conditions.
Volatile organic emissions resulting from coating compositions which are applied and used by industry and by the consuming public are not only often unp~easant, but also contribute to photochemical smog. Govfrnmfntc have established regulations setting forth guidelines relating to volatile organic compounds ~VOCs) which may be released to the atmosphere . The U. S . Environmental Protection Agency (EPA) has established guidelines limiting the amount of VOCs released to the atmosphere, such guidelines being scheduled for adoptlon or having been adopted by various states of the United States.
Guidelines relating to VOCs, such as those of the EPA, and environmental concerns are particularly pertinent to the paint and industrial coating industry which uses organic solvents which are emitted into the atmosphere.
To reduce organic solvent content and VoCs, researchers have developed high solids coating compositions and powdered coating compositions. High solids compositions generally are liquid and are designed to minimize solvents. Powdered coating compositions are solid powders and generally eliminate solvents. While each have advantages, each coating composition has disadvantages .
Coating compositions which include high solids polymeric vehicles based upon polyesters have become popular. In high solid polyesters as opposed to " conventional" compositions which use organic solventS, high molecular weight generally needs to be achieved during crossl;nking rather than being attained from the basic polyester polymer. Hence, high solids polyesters normally supply a greater number of reactive sites (prf' 'n~ntly hydroxyl groups) available for crosslinking. The resultant polymers typically exhibit 70-80% solids-weight when reacted stoichiometrically with isocyanate crosslinkers, but frequently yield empirical solids up to 12% lower, when crosslinked with melamine , , , . . , .. ... . , .. , . , . , . _ .

wo96n3035 2 1 8 5 4 5 4 PCT~S96/01141 resins. Despite their reduced use of organic solvents, high solids polyester coating compositions could be produced on the same equipment and be employed in many of the same applications as lower solids "conventional"
5 polyester coating compositions. Further, as a result of their many strengths such as ease of manufacturing and use, low volatile emissions, reduced energy requirements, greater application efficiency, lower handling and storage costs, and excellent physical properties, high lO solids polyester coating compositions have enjoyed spectacular growth in manufacture and use. They still require organic solvents, however, and are a source of VOCs .
Powder coatings and W-curable coatings are 15 desirable ultrahigh or 100% solids coatings. However, there are limitations as to the techniques and the equipment which is used to apply the powdered and W-curable compositions.
To reduce solvent content and VOCs in polymeric 20 vehicles and formulated coating compositions for paints, researchers have been driven by three major objectives:
controlling the reactivity of the film forming components in the paint; keeping the viscosity of the components in the paint low to minimize the organic solvents in the 25 paint and to keep the VOCs in the paint at the lowest possible level; and keeping the components in the paint at a low volatility to minimize VOCs.
IIigh viscosity is a maj or problem which needs to be solved in ultrahigh or lO0~ solids coatings. In 30 high solids polyester coatings, the viscosity of concentrated polyester solutions depends on several variables. Molecular weight and molecular weight distribution are two important factors. According to polymer physics theory, the viscosity of polymers in the 35 liquid state depends mainly on the average molecular weight and the temperature, so it is desirable to reduce average molecular weight for solventless polyester Wo 96/2303s 2 1 8 5 4 5 4 PCT/US96/01141 coating. The major factor controlling molecular weight (Mn) of a polyester is the mole ratio of dibasic acid/diol or polyol. A dibasic acid to diol or polyol ratio of the order of 2: 3 is typical. However, loss of polyol during the production of the polyester ca~ result in a significantly higher molecular weight than predicted from the starting ratio. It is necessary to add some extra glycol to compensate for loss. In very high solids coatings, the low molecular weight fraction of resin may be volatile cnough to evaporate when a thin film is baked. Such loss has to be counted as part of the VOC
emissions .
The number of functional groups per I;Lolecu~e also affects the viscosity because of hydrogen bonding.
Most oligomers or polymers require high functionality to achieve a highly crosslinked film and reasonable Tgs to have adequate film properties for most applications. The high functionality tends to increase the viscosity signif icantly .
An object of the invention is to provide a polymeric vehicle which will reduce or eliminate VOCs in coating compositions by providing a polymeric vehicle which is effective for providing a formulated coating composition which does not require orga~ic solvent to reduce the viscosity of the formulated coating composition for application of the formulated coating composition .
~nother obj ect of this invention is to provide polymeric vehicles which are not only low in VOCs and effective in providing solventless ~ormulated coating compositions, but which provide coating binders with good film properties such as hardness and impact resistance.
Yet another obj ect of this invention is to control the viscosity to low levels at a specific application shear rate of a liquid polymeric vehicle or a liquid formulated coating composition without using -orga~ic solvents or water for such control.
Further, obje~ts and adv~ntages of the invention will be found by reference to the following description.
.

Wo 96l23035 2 ~ 8 5 4 5 4 PCT~S96~1141 SUM~RY OF TEIE lNV' '`l.LlU..
The invention provides a liquid polymeric vehicle which is effective for providing a formulated coating composition which does not require the addition 5 of organic solvent to obtain a viscosity such that the formulated coating composition may be applied by existing commercial application equipment. The invention also provides a way of controlling the viscosity of the polymeric vehicle at a specific shear rate using linear 10 oligoester diols having a number average molecular weight within controlled limits of a polydispersity index, a linearity and a molecular weight limitation which are effective for controlling the viscosity of the polymeric vehicle .
The invention provides a polymeric vehicle which has at least about 92 weight percent solids and which comprises at least one linear oligoester diol having a number average molecular weight in the range of from about 275 to about 1200 which is effective for 20 reaction with a crosslinker. The linear oligoester diol and/or mixture of such diols has a polydispersity index (MW/Mn) of less than about 2.6, preferably less than 2.2, preferably in the range of from about 1.4 to about 1.8, and most preferably less than about 1.4, and a viscosity 25 in the range of from about 0.1 to about 1.2 Pa.s at a temperature in the range of from about 20C to about 50C
as measured on a Brookfield thermocell viscometer model DV-II+ using a SC9-~1 spindle at 6 rpm. The use of a linear oligoester or mixture of such oligoesters in the 30 polymeric vehicle is important because it has a low viscosity and has a sufficiently low evaporation rate such that the oligoester has at least about 93 weight percent solids when tested by ASTM test D-2369-92. This minimizes the VOC content of the oligoester since only a 35 small fraction of the material will evaporate upon baking. Generally, when the crosslinker is added even a lower fraction of the oligomer will evaporate during 21 854~
W0 96~303s P~ 0ll4l baking because part of the volatile material reacts with the cros s l inker .
The crosslinker may be a solid, but generally i8 a liquid. In either circumstance, the crosslinker is 5 miscible or soluble in a blend of oligoester diol and crosslinker withsut raising the viscosity of the blend of the oligoester diol/crosslinke~ or the formulated coating composition above the range of from about 0.1 to about 20 Pa.s at about 20 to about 60C at a shear rate of at 10 least 1000 sec.~' without organic solvent.
The crosslinker has an average functionality of greater than about 2.4, and preferably greater than about 2.9, a viscosity of less than about 3.0 Pa.s at about 25C when it is a li~uid, preferably is a liquid at about 15 10C, and a has functionality which is reactive with the hydroxyl groups oi- the oligoester. The polymeric vehicle comprises at least about a stoichiometric amount of crosslinker which will react with the hydroxyls of the-linear oligoester diol. A catalyst such as a soluble tin 20 compound for polyisocyanates or an acid for~amino resins generally should be used in an amount effective to effect the reactio~ between the oligoester diol and the crosslinker. In the aspect of the invention which includes amino resins as the crosslinking agent, the 25 invention is effective for providing a polymeric vehicle which will have at least asout 80, preferably about 88 to about 90 and most preferably at least about 92 weight percent solids. Since no solvent is added, the volatile material comprises primarily crosslinking reaction by-30 products and traces of volatile materials and impuritiespresent in the resinous and other components of the formulation. When the crosslinking reaction does not evolve volatile by-products, for example the aspect of the invention which includes a polyisocyanate a8 a 35 crossl ;nkin~ agent, the invention is effective for providing a polymeric vehicle which will have at least about 97 weight percent solids and typically about 99 .... . . . _ ... = = . _ . . _ . , . .... . , _ _ _ _ . . .. .

~ wog6n303s 2 1 8 5454 ~ 0l,4l weight percent solids. In this connection, the aforedescribed polymeric vehicles, and formulated coating compositions based thereon, may be less than 100 weight percent solids without the addition of organic solvents 5 because low molecular weight fractions of the oligoester which forms the polymeric vehicle may evaporate or otherwise originate from the polymeric vehicle and become a VOC with the application of heat for a thermoset into a coating binder.
In a very important aspect of the invention, the crosslinker blended with the linear oligoester diol is a polyisocyanate or is a blend which comprises a polyisocyanate and melamine in amounts effective to achieve desired hardnesses, impact resistance and 15 adhesion for the coating binder.
In an important aspect of the invention, the polymeric vehicle has a viscosity of not more than about 1. 2 Pa . s at the temperature of application, which is usually not more than about 50C and is preferably about 20 25C. ~he polymeric vehicle preferably has a viccosity of not more than about 0.8 Pa.s at 25C to provide a coating binder having a pencil hardness of at least about B.
2 5 L~ ,.. OF T~E ~
"Polyester" means a polymer which has -C (=O) O- linkages in the main chain of the polymer.
"Oligomer" means a compound that is a polymer, but has a number average weight not greater than about 10, 000 with 30 or without repeating monomeric units. "Crosslinking agent" means a di- or polyfunctio~al substance containing functional groups that are capable of forming covalent bonds with hydroxyl groups that are present on the oligoester diol. The crosslinking agent may be a blend;
35 hence, there may be more than one substance which forms a blend of substances which form covalent bonds with the hydroxyl groups of the oligoester diol. ArLino resins and W096/23035 21 85454 PCrlUS96101141 polyisocyanates are memoers o~ this class. "Polymeric vehicle" means polymeric and resinous components in the formulated coating, i.e., before film formation, including but not limited to the linear oligoester diol 5 and crosslinking agent. "Coating binder" means the polymeric part of the film of=the coating after solvent has evaporated and after crosslinking. "Formulated coating" composition means the polymeric vehicle and optional solvents, as well as pigments, catalysts and l0 additives which may optionally be added to impart desirable application characteristics to the formulated coating and desirable properties such as opacity and color to the film. "VOC" means volatile organic compounds .
As used herein a linear" means that the oligomer has a main longitudinal chain that is substantially without any side chain or group extending therefrom such that the longitudinal chain has only the chain segments having the structures -CH2-, -O- and -C (=O) - with the longitudinal chain being terminated with -OH groups. In this context, a substantially without" means that the oligoester does not have more than about 3 percent of chain segments, other than -CHz-, -O- and -C (=O) - and the terminating hydroxyl group, with a branch extending from them. Further, side chains should not raise the viscosity of the oligomer above the viscosity range of from about 0 . l to about l . 2 Pa. s at a temperature irr :the range of from about 20C to about 50C as measured on a Brookfield viscometer madel DV-II~ using a SC4-31 spindle at 6 rpm.
"Diol" is a compound or oligomer with two hydroxyl groups. "Polyol" is a compound or oligomer with two or more hydroxyl groups.
"Solvent" means an organic solvent.
"Organic solvent" means a liquid which includes but is not limited to carbon arid hydrogen and ha~ a Wo96/23035 2 1 8 54 5 4 .~ ,0,l4l g boiling point in the range of from about 30C to about 300C at about one atmosphere pressure.
"Dissolved" in respect to a polymeric vehicle, 5 formulated coating composition or components 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 diameters greater than about 30nM which are as measured by dynamic light l O s cattering .
"Soluble" means a liquid dissolved in a liquid or a solid dissolved in a liquid.
"Miscible" means a liquid which is dissolved or is soluble in a liquid.
"Polydispersity index" (PDI) means the weight average molecular weight (Mw) divided by the number average molecular weight (Mn), PDI=MW/Mn.
"Volatile organic compounds" are defined by the U.S. Environmental Protection Agency at 40 C.F.R. 51.000 of the Federal Regulations of the IJnited States of America as any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium carbonate, which participates in atmospheric photochemical reactions.
This includes any such organic compound other than then following, which have been determined to have negligible photochemical reactivity: acetonei methane;
ethane; methylene chloride (dichloromethane); 1,1,1-trichloroethane (methyl chloroform); l, l, 1-trichloro-2, 2, 2-trifluoroethane (CFC-113); trichlorofluoromethane (CFC-ll); dichlorodifluoromethane (CFC-12);
chlorodifluoromethane (CFC-22); trifluoromethane (FC-23);
1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-llg);
chloropentafluoroethane (CFC-115); 1,1,1-trifluoro 2,2-dichloroethane (HCFC-123); 1, 1, 1, 2-tetrafluoroethane (HF-134a); 1,1-dichloro 1-fluoroethane (HCFC-141b); l-chloro 1, l-difluoroethane (HCFC-142b); 2-chloro-1, 1,1, 2-WO 96l23035 2 ~ 8 5 4 5 4 PCrlUS96101141 tetrafluoroethane (HCFC-124); pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1-trifluoroethane (HFC-143a); 1,1-difluoroethane (HFC-152a); and perfluorocarbon compounds which fall into 5 these classes:
(i) Cyclic, branched, or linear, completely fluorinated al kanes;
(ii) Cyclic, branched, or linear, completely fluorinated ethers with no unsaturations;
10 (iii) Cyclic, branched, or linear, completely fluorinated tertiary amines with no unsaturations; and (iv) Sulfur containing perfluorocarbons with no unsaturations and with sulfur bonds only to carbon and fluorine. Water is not a VOC.
A "film" is formed by application of the formulated coating composition to a base or substrate, evaporation of solvent, if present, and crosslinking.
According to the invention, the liquid polymeric vehicle has at least about 80 to about 92 20 weight percent solids and comprises at least one linear oligoester diol having a number average molecuIar weight i~ the range of from about 275 to about 1200 which is effective for reaction with a crosslinker. The polymeric vehicle is thermosetting with the thermoset being 25 achieved by the reaction of the linear oligoester diol and crosslinker with the application of heat. The latter reaction provides a coating binder of a paint coating.
The oligoester diol ~Lay be liquid or solid at about 25C, but if it is a solid it has a melting point of below 30 about 50C, preferably below about 40C. The melting point is most preferably below about 10C. The melting point of the oligoester diol is usually reduced after~ it is mixed with the crossl i nk~r. Even so, it may be neC~Re~ry in some cases to heat the coating composition 35 to melt crystalline oligomers before its application.=
Control of the viscosity of the oligoester diol comes from at least two sources. First, the oligoester is _ _ _ _ _ , ... . .. ..... . . . . ... . .. . .

Wo 96/23035 2 1 8 5 4 5 4 PCrNS96/01141 linear with its main chain having only chain segments having the structures -CH2-, -O- and -C(=O)- and the main chain being terminated with -OH groups. The linear longitudinal chain of the oligomer is substantially 5 without any side chain or group. This linearity reduces the viscosity of the oligoester relative to an Qligomer even with relatively small amounts of branching. As previously noted in this application "substantially without" means that the oligomer does not have more than l0 about 3 weight percent of the chain segments, other than -CH2-, -O- and -C (=0) - and the terminating hydroxyl group, with a branch extending therefrom. Side chains, if they exist, should not raise the viscosity of the oligoester above the range of about 0 . l to about l . 2 Pa . s as set 15 forth above. Second, the number average molecular weight of the oligoester is controlled such that the oligoester has at most a small low molecular weight fraction which will be a source for evaporation or VOCs upon the application of heat for the thermosetting of the coating 20 binder. In this connection the linear oligoester diol has a polydispersity index (MW/M~) of less than 2 . 6, preferably less than about 2.2 and preferably in the range of from about l.g to about 1.8, and most preferably less than about l . 4 . Relative to its molecular weight 25 the oligoester diol has a low viscosity ~about 0.l to about l . 2 Pa. s as set forth above) on the Brookfield viscometer which produces a shear rate of about 2 sec.~1.
The slow evaporation rate of the oligoester, its linearity and the control of the number average molecular 30 weight such that unreacted monomers and oligoesters with molecular weights below about 250 are minimized are important factors such that the viscosity of the oligoester and the polymeric vehicle are sufficiently low to permit a formulated coating composition with a useable 35 viscosity that permits its application without the addition of organic solvents.

wO96n3035 21 85454 PCrrUS96/0114~ ~
The polydispersity index of the linear :
oligoester may be obtained by synthesizing the oligomer through a direct catalyzed esterification reaction, a catalyzed transesterification reaction or by a catalyzed 5 esterification reaction using reactants such as dicyclohexyl-carbodiimide (DCC). Zinc acetate may be used as a catalyst in the transesterification reaction and a solution of p-toluenesulfonic acid in pyridine may be used as a catalyst in the reaction using DCC. Careful 10 use of these techrliques can yield products with a polydispersity index as low as 1. 4. The polydispersity index may be lowered to levels below 1.4 by purification of the oligoester product such as by extraction of the volatile low molecular weight fractions or by vacuum 15 stripping of suck fractions. Using these techniques a polydispersity index of 1.1 or even lower may be obtained. Typical oligoester diols include the reaction products of linear aliphatic dicarboxcylic acids having not more than about 16 carbon atoms or esters thereof 20 such as azelaic acid, glutaric acid, adipic acid, decanedioic acid, dodecanedioic acid, succinic acid, dimethyl azeleate, dimethyl glutarate, dimethyl succinate, dimethyl adipate, dimethyl decanedioate and dimethyl dodecandioate with one or more linear..diols 25 having not more than about 16 carbon atoms such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, diethylene glycol, triethylene glycol and tetraethylene glycol. As used herein, linear aliphatic dicarboxycylic acid means 30 an acid with divalent segments having only the structures -CH2-, -O- and -C (=O) - terminated with -COOH. As used herein linear diol means a diol with segments having the structures -CHz- and -O- terminated with -OH. Mixtures of the acids or esters thereof and diols may be 35 cotransesterified and may be used to achieve certain melting points and molecular weights. Examples of such mintures include a cotransesterified mixture of dimethyl . . ~

w096/23035 -13- PCIIUS96101141 .
azeleate with equal weights of 1, 4-butanediol and 1, 6-hexanediol which provide5 a product having a viscosity of 0.65 Pa.s at 30Ci a cotransesterified mixture of dimethyl azeleate and dimethyl adipate (1:1 molar ratio) and 1,4-butanediol with ~n=920 which mixture provides a viscosity of 0.72 Pa.s at 6 rpm at 25C; a cotransesterified mixture of dimethyl azeleate and diethyl dorler~nerl~oate ~1:1 molar ratio) with the diols 1, 4-butanediol, diethylene glycol and 1,10-decanediol (2 :1:1 molar ratio) . A particularly useful oligoester diol may be prepared from 1, 9-butanediol and a mixture of the dimethyl esters of HOOC(CH2)"COOH, n=3, 4 and 7 in a 1:1:1 molar ratio to provide oligoester diols with number average molecular weights such as 310 and 520. Typical linear oligoesters which may be used in the invention have the general formulas:
HO (CH2) n [OC (=O) (CH2) 7C (=O) O (CH2) n]XOH
where n= 2 to 12 and x= 1 to 5;
HOCH,CH2OCH2CH2 [OC (=O) (CH2) 7C (=O) OCH2CH2OCH2C7,~2] XOH
2 0 where x= 1 to 5; and HO (CH2), [OC (=O) (CH2) 1~C (=O) O (CH2) ~]XOH
where x=1 to 4.
Even nu7~7bered diacids (acids having even nu7nbers of carbon atoms) tend to provide oligomers with melting points which are too high, except when used in mixtures.
For example, an oligomer made from 1,4-butanediol and dimethyl dodecanedioate has a melting point of 60 to 65C
and is poorly suited for use in solventless lir~uid coatings. Hence, acids which have an odd number of carbon atoms are preferred in a single acid type of composition and as a substantial component o~ a mixture.
Xowever, mixtures of different diacids and diols wherein the mixture includes a diacid and/or diol with an even num7ber of carbon atoms may be used.
The oligoester diol may be a mixture of the chemically same or different oligoester diols which have W096/2303s 21 8~454 J~ 41 ~

differing number average molecular weights and which number average molecular weights are in the range of from about 275 to about 1200. In an important aspect, oligoester diols having the same chemical formula, but with differing number average molecular weights, are mixed to provide a polymeric vehicle according to the invention. Such mixtures may be used to improve the properties of the coating binder or the polymeric vehicle. For example, oligoester diols having the same formulas, but for number average molecular weight, when mixed to provide a blend of oligomers comprising 20 weight percent oi~ an oligomer having an Mn of about 500 and 80 weight percent of an o1igomer having an Mr~ of about 300 improves the impact resistance of a coating binder over a coating binder which is made using exclusively an oligomer which has an Mn of about 300. Such blends of oligomers increase the PDI of the oligomeric diol such that the oligomeric blend used in a polymeric vehicle may approach 2. 6. In general, without such blends, however, PDI of the oligoester diol used in the polymeric vehicles according to the invention should not have a PDI of more than about 2 . 2 . Further, the lower the PDI while retaining coating properties, the better such that the PDI approaches 1. 0 .
As previously stated, the crosslinker has a functionality which is reactive with active hydrogens such as the hydroxyl groups of the oligoester. The crosslinker may be a polyisocyanate which generally is not blocked because blocking generally will raise the viscosity of the isocyanate such that it will not be functional or useful in the practice of the invention.
Liquid blocked isocyanates may be used if the viscosity of the crosslinker or blend of crosslinkers is less than 3 . O Pa. s as described herein. Two useful polyisocyanate crosslinking agents whic~ may be used in the invention include hexamethylene diisocyanate which has the 1 85~54 structure shown below (HDI and sold commercially as Desmodur N-3200) Desmodur N-3200 O
CNH- ( CH2 ) 6-NCO
OCN- ( CH2 ) 6-N
CNH- ( CH2 ) 6-NCO
o 15 and a blend of polyisocyanates (sold commercially as Luxate XHD 0700 by Olin Corporation) with the following structures:
Luxate~ XHD 0700 (CH2~NCO O

r~ OCNtCH2)6 --N N _ ~CH2)~NCO
OCN~CH2)~ ~ ~1/ (CH2)6NCo \ C /
2 0 (Mixture ) Amino resins (usually made from amidines, ureas or amides by reaction with formaldehyde and subsequently usually with an alcohol) also may be used as a crosslinker which will react with the hydroxyls of the linear oligoester.
25 Melamine resins are a subclass of amino resins and may also be referred to as "melamine-formaldehyde resin" or "alcoholated melamine-formaldehyde resin." Melamine resin amounts should be adjusted according to the molecular weight of the oligoester diol. As the 30 molecular weight of the oligoester diol increases the equivalent weight ratio of melamine resin to total diol Wo 96/23035 l'CrlUS96/01141 should be adjusted from about~l:l to about 1.5:1 to about 1.7:1 and possibly higher to achieve desired film properties.
Suitable amino crosslinkers include, but are 5 not limited to melamine formaldehyde types such as hexakis (methoxymethyl) melamine resin ~HMMM) (sold as "Cymel 303" and "Resimene-747") and other amino resins as described in Wicks, Jones and Pappas "Organic Coatings:
Science and Technology" PP 83-103, Wiley Interscience, lO 1992. Additionally, the crosslinker may be solid under certain conditions as long as it is soluble in the oligoester diol/crosslinker blend and does not increase the viscosity of the oligoester diol/crosslinker blend or formulated coating composltion above the rages described 15 herein. These crosslinkers include a hexakis ~methoxymethyl) melamine (~MM) resin which sometimes appears as a solid, is highly alkylated and has the general formula:
N(CH20CH3)2 N j~N
(CH,OCH2)2N N N(CH2OCH3)2 20 The latter XMMM resin appears as a waxy solid with a melting point in the range of about 30C and is sold by Cytec Chemical Company under the name Cymel 300. A
similar melamine resin which sometimes appears to be a solid at about 25C and which can be used in the 25 invention is a highly monomeric, highly methylolated hexamethylolated melamine fQrmaldehyde resin which is sold by Monsanto Chemical Company under the designation ~M-2612 .
Properties of the coating binders resulting 30 from the use o~ amino resin crosslinkers may be improved with hardeners additional to the aforedescribed .

21 ~5454 W0 9612303s ~ '01141 crosslinkers. These additional hardeners include polyurethane diols. These diols include the urethane - diols K-FLEX VE 320-lO0~ and K-FLEX VD 320 W@~. K-FLEX
UD320-lO0 is a 100% polyurethane-diol with hydroxyl - 5 equivalent weight 160, viscosity 7.0 Pa.s at 50C. Its structure is thought to be XO ~CX2) 60CONH (CX2) 6NHCOO ~CX2) 60X.
K-FLEX UD-320N has the same structure as K-FLEX UD320-lO0, is a polyurethane-diol contained about lO~ by weight of water with hydroxyl equivalent weight 178, viscosity 8.0 Pa.s at 25C. Both may be obtained from King Industries. These additional hardeners also include crystalline polyols such as O O
HO(CH2)n[~0~~~3~CO(CHz)n~~x~OH

where n = 2 through 12 and x = l through 20i C (CH2OH) ~ and RC (CH2OH) 3 where R is methyl, ethyl, propyl and butyli and XOCH2 (C~IOH) ~CH2011.
Useiul among these aromatic hardeners include O O
Ho-[(CH2)c~0l~3-CO-]2(CH7)b-OH
and lOGT
O O
Ho-[(cH2)1c-oce~-lo-]7(cH7)~c-oH
Yet another example of a crystalline polyol is _ _ _ _ . .... .... ...

W096/23035 2 1 85454 Pcr/USs6/0ll41 l, 3, 5-tri (hydroxyethyl) cyanuric acid (TH~CA), which has the structure O
HOCH2CHz~ J~ ~CH2CH20H
O J~ N ~0 CHlCH20H
Mesogenic polyols, diesters of neopentyi glycol and 5 parahydroxybenzoic acid which diesters are hereinafter referred to as AY-l, a preferred AY-1 diester having the structural formula O CH, O
H~)-C-O-CHI- I -CH,-O-C~)-OH
CH, and phenolic ester alcohols (PHEAs) such as those having 10 hydroxyl groups extending from the aromatic and aliphatic portion of the molecule also provide useful hardeners for the coating composition. Generally the Mn or number average molecular weight for a PHEA is in the range of about 250 to about 1200. For a more complete description 15 of mesogenic polyols see published PCT application no.
US95/01058. These additional hardeners are èspecially useful if small amounts of organic solvents are used in the formulated coating composition. A useful P~EA has two ester groups, a phenolic hydroxy (which extends from 20 the aromatic group), an aliphatic hydroxy and has the structural formula:
O O
~O'~~oJ~ ' E~O C~H,~
HO

~v0 96n303s 2 18 5 4 5 4 PCTIUS96/01141 Amino resins by themselves without additives such as hardeners may not give desired film properties.
- The above-identified additional hardeners, especially PHEAs, are particularly useful with polymeric vehicles - 5 which include amino resins where each of the components are in amounts effective for providing a polymeric vehicle with the aforedescribed viscosity range and effective for providing a coating binder with a pencil hardness of at least about B at a thickness of about 1 10 mil dry. Isocyanates provide excellent film properties but may shorten the pot life of the polymeric vehicle or formulated coating composition.
A particularly useful crosslinker blend in the invention is a m~ m; n~ sold as Cymel 1135 (a 50/50 15 methylated/butylated melamine with 70% monomeric;
content obtained from Cytec Company) and Luxate XHD 0700 in a ratio of about 2 . 0 parts melamine to about 0. 65 to about 0.22 parts Luxate. The crosslinker has an average functionality reactive with the hydroxyls of the 20 oligoester of greater than about 2. ~, a viscosity of less than about 3.0 Pa.s at about 25C, and in an important aspect, is liquid at about 10C and is miscible with the oligoester .
The reaction between the oligoester and the 25 crosslinker which provides the coating binder generally is a catalyzed reaction. Although a catalyst is not required f~ some isocyanate crosslinkers, typical catalysts for isocyanate crossl ;nk;ng reactions include soluble zinc or tin catalysts such as dibutyl tin 30 dilaurate, tertiary amines such as diazabicyclo[2.2.2]
octane and zinc salts of organic acids. Typical catalysts for the amino resin crosslinking reactions include para toluene sulfonic acid (p-TSA), dodecyl benzene sulfonic acid and dinonyl nathrh~l~ne disulfonic 35 acid. Typically the catalyst comprises from about 0. 03 to about 0.5 weight percent of the blend of oligoester W096123035 2l~5454 P ~ 10l,4l ~

and crosslinker, based upon the weight of the oligoester, crosslinker and catalyst.
The polymeric vehicle comprises at least ab~out a stoichiometrlc amount of crosslinker which will react 5 with the hydroxyl groups of the oligoester. In general the polymeric vehicle comprises an oligoester diol and a crosslinker in an equivalent ratio in the range of from about 1. 0: 0 . 93 to about 1: 2 . 5, diol to crosslinker . In an important aspect, the polymeric vehicle will have a 10 viscosity of not more than about 1.2 Pa.s at the temperature of application, which usually is not more than about 50C and is preferably about 25C. The polymeric vehicle and formulated coating composition provide a coating binder having a pencil hardness of at 15 least about B when applied to a substrate at a thickness of about 1 mil dry.
The method of controlling the viscosity of the polymeric vehicle and formulated coating composition is practiced by providing the coating composition with the 20 linear oligoester diol having the chain segments with the structures -CX2-, -O- and -C (=O) -, which oligoester diol is within the molecular range and viscosity range as aforesaid with the oligoester also having a polydispersity index of less than about 2. 6, preferably 25 less than 2.2, preferably in the range of from about 1.4 to about 1.8 and most preferably less than 1.4 and mixing the oligoester with a crosslinking agent with the functionality and viscosity as aforesaid. Maintaining the linearity of the oligoester substantially without 30 side chains, maintaining the polydispersity index and also providing a low viscosity liquid crosslinker which is miscible with the oligoester, and has the fllnrtit~n~l;ty and viscosity as aforesaid permits control of the viscosity of the coating composition without the 35 use of organic solvents heretofore not previously known.
The formulated coating compositions are made by mixing the polymeric vehicle with pigments, catalysts and .. . . .. , . ... . , ., . , . . _ _ _ . . , W096l23035 2 1 8 5 4 5 4 PCr/US96/01141 additives such as def oamers, pigme~t dispersants, anticratering agents and rheology modi~iers. The formulated coating compositio~s have a viscosity of not more than about 1.2 at about 50C or less at shear rates 5 which may range from about 1 sec,~~ to about 100, 000 sec.
rlPrPnrl;n~ upon the method of application. The fnrr~l1At coating composition may be applied to a substrate by spraying (which has very high shear rates ), dipping (which has a low shear rate such as about 1 sec.-l), roll 10 coating, brushing (which may have shear rates of from about 1000 to abut 20, 000 sec.-~) or using other known Arpli~ At;nn Pc~-l; ' and thereafter thP --etting the coating ~ ~ ~citinn by the Arp~ At; nn of heat in the temperature range of from about 20C to about 300C for 15 about 0.5 to about 60 minutes. ~ nPrAl1y the formulated coating compositions will have less than 140 g/~ VOCs under AST~ Test D- 3 9 6 0 - 93 .
The following examples set forth compositions according to the inve~tion and how to practice the method 20 of the invention.
~Y~`'PLE I
6ynthesis and Viscosit~r of Ql~ ~G ~ ~1 D~ ols Synthesis of 1,4-but-n~ ol ~ e~te (Al) throug_ tr~sesterification with a stoi-h~ LL1C ~mount of 1~ 4 L..~ ol .
Al is synth~c,;~7~d from dimethyl azeleate with 1,4-b~ltAn-~;ol at a starting ratio of 2:3. The reaction ir,volved is shown below.

W0 96/23035 2 18 ~ ~ 5 ~ r ~ '01141 O O
ZcH3o~ cH2l7c-ocH3 t 3HOlCH214OH

N2 ZnAc 2H2O
FLOW ~ ~ 10.2X by weigh~
O O -HO- lCH21jO-¦-lCH217C-O -lCH214 -OH t 4 CH30H

Al A 500-mL, 4-neck flask is equipped with a mechanical stirrer, Dean-Stark trap, condenser, th~ -ter and nitrogen inlet. Dimethyl a~eleate (86.4 g, 0 . 4 mol ), 1, 4-butanediol ~ 54 g, 0 . 6 mol ) and zinc acetate dihydrate (0.2% of total wt.) are placed into the flask and gradually heated by an electrothermal heating mantle with controller from 130C to 170C during 3 hours. Nitrogen is bubbled through the solution to facilitate methanol removal. The temperature is then raised to 200C and maintained for one hour, as methanol is collected in the Dean-Stark trap. 94% Of the theoretical amount of methanol is collected during the 4 hours. A transparent liquid with low viscosity is obtained. Yield of the product (Al ) is about 95% .
The NMR spectra indicate that the Mn is about 570. A 8i~n~fi~nt NMR signal at 3 85 ppm for residual methyl group r, -ining in the oligomer solution is observed. The results in Table 1 describe the viscosity of A1.

W096123035 -23- ~ 1141 Viscosity of A1.
Temp C 25 30 35 40 50 mPa.s * 386 305 259 169 132 4-diol azelea'ce (Al): x = 2 . 0, Mn = 550 * milli Pascal-sec.
Table 2 describes the formulation of Al and 10 coatings based on Al. As shown in Table 2, solvent tmethyl ethyl ketone) resistance of the coating film is bad for the formulation in which the ratio of A to Resimene 747 was 7 to 3 and was very good for the formulation in which the ratio of A to Resimene 747 was 6 15 to 4. Resimene 747 is a fully methylated monomeric melamine resin in which hexakis (methoxymethyl~ melamine is a representative structure (obtained from Monsanto Chemical Company). Other properties are shown in Table 2.
2 0 TA~3I E 2 Formulation ~nd properties of coatings b~ed on A 1.
A} 70 phr ~ 60 phr Resimene 747 30 phr 40 phr 25 p-TSA 0.5 phr 0.5 phr Cure temp/cure time 150C/30 min. 150C/30 min.
Direct impact lb-in 80 60 Pencil hardness B-HB HB
Adhesion ** OB OB
30 MEK resistance, 100 200 double rubs ***
* phr means parts per hundred.
35 *~ As per test ASTM D 3359-87. Unless otherwise stated, adhesion was measured using this test.
*** MEK=methyl ethyl ketone.

W096/2303S 21 85~54 pCTlUS96/01141 ~
Synthesis of 1, 4 b~L~.~e 1; ol azeleate ~A 1) through transesterification with e~ccess 1,4 L-ll.anediol.
In order to eliminate the remalning hlethyl groups noted in the above described method and to study 5 the relatinnch;p between viscosity and Mn~ the transesterification reaction is done in the following way:

2~ ~5454 - ~01141 O O
Il 11 CH3 0 -C -[CH217C-OCH3 t 2 HOICH2l40H

N2 ZnAc 2H20 FLOW ~ ~ [0.2%byweight O O
HO-ICH214-0-C-ICH217C-O-[CHZ¦4-OH t ZCH30H
N2 ¦ 210C
FLOW
O O
Il 11 HO- ICH2liO-C-[CH2l7C-O -[CHzl4 -OH t HO lCHzl40H
-- x x= 1 -5 4-diol azelate W0 96/23035 2 1 8 5 4 5 4 pcrlus96lo1141 For A2 when x = 1, Mn = 332, and when x - 5, Mn = 1300.
A 500-mL, 4-neck flask is equipped with a mechanical stirrer, Dean-Stark trap, condenser, thermometer and nitrogen inlet. Dimethyl azeleate (130 5 g, 0.6 mol), 1,4-butanediol ~108 g, 1.2 mol) and zinc acetate dihydrate ~1.2~ of total wt. ) are placed into the flask and are gradually heated by an electrothermal heating mantle with controller from 130C to 170C during 3 hours. The temperature then is raised to 200C and 10 maintained for one hour, as methanol is collected in the Dean-~tark trap. Nitrogen is fed slowly through the solution to help methanol removal, and 91~ of the theoretical amount of methanol is collected during 4 hours. 20 g of the product (x=1) is taken out from the 15 flask.
The temperature is raised to 210C and the flow rate of nitrogen is increased to help 1, 4-butanediol (presumably formed by transesterification) removal. Five portions of products ~each 20 g) with different molecuLar 20 weights were removed. The molecular weight is contrslled by the amount of collected l, 4-butanediol .
In a subsequent experiment A2 with M~ of 695 was made in a batch by collecting 36 mL of 1, 4-butanediol.
Properties of Fractions of A 2 with Different M "
Derived from Dimethyl Azele~te with 1,4 Butanediol through Trans-~sterification.
Six fractions of A2 with different M~ were investigated. The degree of polymerization and M~ were measured by NMR spectra. The average number of repeating units x in the oligoester can be calculated from the NMR
peak area ratio of the methylene connected with the ester group (-CH2-O-CO-) at 4 . 0 ppm to the methylene connected with the hydroxy group (-CH2-OH) at 3 . 5 ppm.
Area ( -CH2-O-CO- ) x ~ . .
Area (-CH2-OH) 096/23035 -27~ nll4l where x is the repeating unit in the oligomer. Mn for A
can be calculated by the following equation:
Mn = x [MW(diacid) + MW(diol) - 2(18)] + MW(diol) where MW(diacid) and MW(diol) are the molecular weights of the monomers, azelaic acid and 1, 4-butanediol, respectively. M~ of the fractions of A2 are listed in Table 3. ~he viscosities of the oligomers are listed in 10 Table 4. It was found that the viscosity of the oligomers was directly affected by their molecular weights and increased quickly as the molecular weight increased. Since some oligomers with increased molecular weights crystallize at room temperature (25C), all 15 oligomers were warmed first and cooled down to room temperature right before viscosity measurements.
According to the viscosity (Table 4), non-volatile weight (NVW) (Table 3) and the NMR spectra of these six oligomers (A2), it was found that the best candidate for 20 solventless coating resin was A2 of portion 4 with Mn of 695. The absence of a peak for the residual methyl groups in the NMR spectrum con f i rm~d that the transesterification was complete. Its NVW (97.8~) means that relatively small amounts of small molecules will 25 evaporate during baking. The viscosity of A2 (Mn = 695) was about 7 0 0 mPa . s .

Degree of polymerization ~, M n, and NVW of the sis portionS of .~ 5 -c--r~rl by NMR
-Portion 1 2 3 4 5 6 x 1 1.4 1.9 2.5 3.5 5.5 Mn332 428 550 695 937 1421 NVW% 93.8 95.3 97.1 97.8 98.: 98.5 Wo96/2303s 2 1 854~4 ~ l4l ~

Viscosities ~ . s) ~ of the si~c portions of A 2 nt different temperntures Portion 1 2 3 4 5 6 milli Pascal-sec.
The mechanical properties of coatings of 15 oligoeste~ A2 are shown in Table 5 for Formulation I and in Table 6 for Formulation II~ Comparing properties=of the two formulations, it can been seen that the film hardness and MEK solvent resistance of Formulation II
were better than that of Formulation I. In Formulation 20 II, the film of the oligomers with low Mn was harder than that with higher M~, because the oligomer of low molecular weight may give relatively high crosslinking densities in a crosslinked network. It was noted that all coating films had poor adhesion on untreated steel panels, but 25 they have generally good adhesion on primed or pretreated steel panels.

~ W096123035 2 ~ 8 5 4 5 4 .~ '01141 TAB~E 5 ~- ' .n; r-~l properties o~ the 8ir portion A 2 in solventless coating formulation I (A 2/R~; e 747 = 7/3) Portion l 2 3 4 5 6 5Pencil HB HB B B B-HB B
Hardness Direct 20 60 60 60 80 80 Impact *
Solvent 80 l00 80 80 80 l00 l0 Resist.
Adhesion OB OB OB OB OB OB
* Films appeared to pass higher impact levels at first, but failed two days after impact test was l 5 perf ormed .

~- ' ,n; r,s-l propertie8 of the gis portion A 2 in solventless 20coating formulation II ~A 2/R~; ~e 747 = 6/4) Portion l 2 3 4 5 6 Pencil Xardness 2H 2H HB HB F HB
Direct Impact 60 60 60 60 60 60 M~K Resistance 200 200 200 200 200 200 25 Adhesion on Steel OB OB OB OB OB OB
*

Adhesion on Primed 5B 5B 5B 5B 5B 5B
**
30 * Adhesion on untreated steel panel.
** Adhesion on primed steel panel. Pencil hardness and impact on untreated steel panel.

W09612303~ 21 85454 PCrlUS96/01141 COMPAR~rIVE E~aMPLE I
Non-linear oligoeqter diol derived from 2, 2-dimethyl-1, 3-prop~r^~; ol ~ith dimethyl azQleate .
The reaction to make the non-linear= oligoester diol, which will be labeled PA, is shown below.
O O CH
2 CH3O-C-(CH2)~-C-OCH3 + HOCH2-C-CH2OH
CHJ

FLOW ¦ ZnAc 2H2O
(0 2% by weight) HO-~CH2-l-CH2-O-C-(CH2),-C-O~-CH~-C CH -OH + 4 CH OH

PA
A 500-mL, 4-neck flask is equipped with a mechanical stirrer, Dean-Stark trap, condenser, thermometer and nitrogen inlet. Dimethyl azeleate (864 g, 0.4 mol), 2,2-dimethyl-1,3-propanediol (54 g, 0.6 mol) and zinc acetate dihydrate (0.2~ of total wt) are placed into the flask and gradually are heated by an electrothermal heating mantle with controller from 130C
to 170C for 5 hours. The temperature is then raised to 190C and maintained for two hours, as methanol is collected in the Dean-Stark trap. Nitrogen is fed slowly through the solution to help methanol removal and 90~ of theoretical amount of methanol is collected during the 7 hours. A transparent liquid is obtained. Yield of the product is about 95%. Molecular weight is determined by NMR; x=2.4, Mn=718. NMR indicates that a small level of methyl groups remained in the material.

~ W096l23035 2 1 85454 PCT/US96101141 Properties of the Oligoester Diol ~PA) aAd a C.~ -ri~on of PA with a Linear o~
In order to compare the viscosity of an 5 oligoester diol with methyl side chain such as PA with linear oligoester diol (A2) with Mn of 695, the Mn of the above non-linear diol was controlled at 718, close to 695. Degree of polymerization, Mnl and NVW of PA are shown in Table 7. Comparison of the viscosity of PA with 10 A2 (Mn = 695) at different temperatures is listed in Table 8. The results indicate that the viscosity of oligoester diol (PA) was about twice as high as that of linear oligoester diol A2 (M~ = 695) . This result provides evidence that unbranched, linear chains have the lowest 15 viscosity.

Degree of polymerization ~, M L~ and NVW of oligoester diol PA .
20 Degree of polymerization x 2 . 4 Mn 718 NVW % 9 9 . 1 C , ri ~0~ of viscosity of PA with A 2 (NL = 695) (mPa. B) .

Temperature 25 30 35 40 45 50 PA Mn = 718 1550 1180 822 627 492 350 A2 Mn = 695 700 648 529 420 305 197 W096123035 ~18 5 4 5 4 r~ 5~141 E~aMPIE II
Synthesis of oligo~Le~ from dimethyl azeleate and other linear diols; viscosity of oliyv~Lers.
These oligomers were synthesi~ed using a procedure essentially identical to that described above for synthesis of A2 (Example I). Molecular weights (M~) were measured by NMR. As shown in Table 9, most of the products proved to be low-melting solids at room temperature. Viscosities of the materials were measured as described above using supercooled liquids when possible, or when crystallization rates were fast, at temperatures just above the melting points. Oligomers were esaentially colorless except for the oligomer made from diethylene glycol.
Table 9 Compositions, melting points, M "'s and viscosities of m~de from dimethyl Azeleate and linear diols.
2 0 ~o (C~2) n [OOC (cE~2) 7COO (C~2) 1~] yOE~
Viscositv nmelting point, C Mn (NMR) ~a.s/rpm @ ~C
2 25-30== _ _620 0.23/6 @ 30 25 3 34-38 540 0 . 48/6 @ 40 4 <40 700 0.70/6 @ 25 5 39 670 0 . 62/6 @ 25 6 39 600 0.53/6 @ 4a 3 0 HO ( CH2 ) 2 ( CH2 ) 2 [ OOc (CH2 ) 7COO ( CH2 ) 2CH2 ) 2 ] ~OH
Viscosit n melting point, C Mn (NMR) Pa. s/rpm @ ~C
35 --- <25 540 0.42/6 @ 2~

Wo96l23035 2 1 8 5 4 5 4 J~ '0~141 EXAMPI,E III
Synthesis o~ ol;a from 1,4 ~ Lal-eliol and mi~ctures of linear A;r~rh^~ycylic methyl esters.
These oligomers were synthesized using a procedure essentially identical to that described above for synthesis of Az tExample 1). Except as noted, the linear diesters in the mixtures were used in a 1:1 mol ratio. Molecular weights (Mn) were measured by NMR. As 10 shown in Table 10, the products proved liquids at room temperature. Viscosities were measured at 25C.
The dimethyl azeleate used in these experiments was a redistilled, commercial (Aldrich) product having a composition, as determined by gas chromatography/mass 15 spectroscopy, of the dimethyl esters of heptanedioic (1.8%), octanedioic (4.1~), azeleic (83.6%), decanedioic (3.5%) and undecanedioic (7.1%) acids_ "DBE-3" and "DBE-5" are products of the duPont Company; they are said to be mixtures of the dimethyl esters of succinic (SA), 20 glutaric (GA) and adipic tA~) acids in the following proportions: DBE-3: SA, <1%; GA, 5-15%; A~, 85-95%.
DBE-5 is said to be >98 . 5~ pure dimethyl glutarate. The products are liquid at 25C and are solids at 0C.
25 TABI,E 10 Compositions ~nd viscosities of ol;~, made from mi~tures of dimethyl esters of linenr A; ~ rh~ycylic ~cids and 1, 4 },, L~ne~liol .
Viscosity 30Diesters, (mol ratio) Mn (NMR) Pa.s/rpm @ C
Azeleate + adipate (1:1) >490 0.72/6 @ 25 Azeleate + DBE-3 + DBE-5 (1:1:1) >570 0.65/6 @ 25 W096/23035 2 1 8 5 4 5 4 PCT/US96/~1141 EX~PLE IV
Properties o~ "nr; ~ ted coatings made from ~elected o~
Promising oligomers from Examples II-III were formulated into unpigmented coatings with a triisocyanate crosslinker, Desmodur N-3200, a product of Miles Chemical Company. The crosslinker is stated to have a viscosity of 1.3 to 2.2 Pa.s at 25C.
The three oligoesters used in these experiments and their Mnls and viscosities in Pa.s at 6 rpm with a Brookfield viscometer descri~ed above were:
MI, Pa . s IV-l Dimethyl azeleate/diethylene 15 glycol (Example II) 540 0.42 @ 25C
IV-2 Dimethyl azeleate/l 4-butanediol + l, 6-hexanediol (Examplé II) >608 0.65 @ 30C
20 IV-3 Dimethyl azeleate + dimethyl adipate/l, 4-butanediol (Example III) 920 0.72 @ 25C
The Mn of oligoester IV-2 is reported at >608 because the molecular weight cannot be exactly calculated from end group analysis without knowing the proportions of the two diols incorporated in the product. It is probably only slightly above 6p8.
In each case, an equivalent ratio of isocyanate/hydroxyl was l . 3/l . 0 . No catalyst was added, but it was considered that the crosslinking reaction was catalyzed by the zinc catalyst residues dissolved in the ester oligomer. Evidence for this was that the viscoslty of the formulated coating began to increase as soon as the formulation was made. For this reason, it was not possible to make reliable measurements of the formulation viscosity. The values shown are higher than the initial viscosities .

W096123035 2 1 ~ ~ 4 ~ 4 PCT/US96/01141 The formulated coatings were drawn down on iron phosphate pretreated steel test panels with a wire-wrapped bar and baked at a temperature of 120C for one hour. The coatings were tested using the procedures 5 described above.

Formulations ~nd properties of ~nri, ted coatings.

10Oligoerter, g (meq) 4 (14.8) 4 (13.2) 4 (8.7) Isocyarlate g (meq) 3.48 (19.3) 3.09 (17.1) 2.05 (11.3) Wt. 96 solids, measured 99.2 99.6 99.2 Viscosity, Pa.s/rpm ¢1 C 2.7/3 ~ 28 1.2/6 eD 27 3.4/6 e~ 23 Film thickness um 20-23 20-23 22-25 151mpact resistance D;,~t/R.,.~ . (in/lb) 160/160 160/160 160/160 Pencil Hnrdness IH-2H IH-2H IH-2H
MEK rub resist., rubs > 200 > 200 > 200 Adhesion Appearance trarlsparen~ transparerlt tr~mrparent E~AMPLE V
(a) Formulations of an Oligoester Diol based upon 1,4-Bui - ' ol ~'-0~8l ;nL~ l with Poly-i3~.y~n~e ~nd mi~ced with Tit~nium Dio~cide An oligoester was made by reacting 1, 4-butanediol with a mixture of dimethyl esters of 30 HOOC(CH2)~COOH diacids, n=3, 4 and 7 in a 1:1:1 molar ratio. The procedure followed was essentially like those used to make A2. The product was vacuum stripped at 30C
to provide a product with an Mn300~ The film properties of the oligoester diol crosslinked with isocyanate are 35 described in Table 12 below.

W096/23035 2 ~ ~ 5 4 5 ~ PCT/US96/01141 TABI.E 12 Ol ~v_`~ Llivl (M==300) M~300 Mn300 M"300 M~300 Wt/mmol/meg. wt 2.67/8.61117.22 as leht 2.0/6.45/12.9 ~ as leh Crosslrnlcer Luxllte XHD ' Luxnte XHD

5Wt/meg. wt. 4.19/22.39 ' 3.10/16.77 "
TiO2DuPont R 700 ' DrPorlt R 700 (percentage of bmders)% 19.39 " 58.41 BYK-077 (Defoamer)~ 0.5% ' 0.5% "
10Panel Q-PHOS R-36-1 Q-Pamd R-36 Q-PHOS R-36-1 Q-Panel R
Film thicxness (mil) 2-4 2-3 2.0-2.2 1.5-1.8 Direct Impact (Ib-in) 160 160 160 160 Reverselmpacl (Ib-in) 160 160 160 160 Pcncil Hardness >4H >4H 5H SH
15MEK Rub R_istance > 200 > 200 > 200 > 200 Adhesion 5B SB 5B 5B
Appearance white white white white * Percentage of the total weight 20 ** Q-PHOS is a mar~ under which phosphated steel ~anels are sold. These panels were used in the tests described liereir.
(b) Formul~tions of ~n Oligoester Diol based ~pon 1,4 l~ e.~iol cros~l;n~ with Mol:~m;r7 and mi~ed with Titanium Dioxide The oligoester diol described in Example V (a) was mixed with titanium dioxide and crosslinked with a mol~m;ne formaldehyde resin. The film properties were 30 studied as described in Table 13 below:

W0961~3035 21 ~ ~L54 ~ '.'01141 1 6~ ' ' V (a) V (n) wt1 3.0g 3.0g Crosslinker Cymel 1135 Cymcl 1135 5Wt/ 3.0g 3.0g TiO2 DuPont R 700 DuPont R 700 (percenta~e of binders) 50% 50%
DNN DSA i'' 1% 1%
BYK-077 (Defoamer)~ 0.5 % 0.5 %
10P~md Q-PHOS R-36-1 Q-Psn~l R-36 film thickness (mil) 1.5-1.8 1.3-1.5 Direct Impact (lb-in) <60 <60 Reverse Impa~t (Ib-in) < 60 < 60 Pencil Hardness 6H 6H
15MEK Rub Resist~nce > 2C0 > 200 Adhesion -2B B
Appeanmce wbite white ~ Percentage of the total weight ' Dinonylnaphthalene disulfonic acid 2 5 EXaMPI,E VI
(a) Formulation9 of ~!m Oligoester Diol Qq n520) ba9ed upon 1,4 D.-Lculediol rrg~l;nlrr~l with M~ nc.
and mised with Titanium Dio~cide An oligoester diol was made by reacting 1, 4-30 butanediol and a mixture of dimethyl esters of HOOC (CH2) nCOOH diacids, n=3, 4 and 7 in a 1:1:1 molar ratio. The number average weight (Mn) was 520, and the oligoester had a viscosity of 0 . 64 Pa . s at 25C and had 98.7% solids as measured under ASTM D-2369. The film 35 properties of the oligoester (Mn520) crosslinked with a melamine formaldehyde resin were studied as described in Table 14 below.

Ol;ov_t~,~ ;' ' (M~520) M~520 M,520 M~520 Wt/ 3.0g ~s leR as leR
Crosslinker Cymel 1135 5Wt/ 2.0g 2.5g TiO~ DuPont R 700 s IeR
~ercentage of bmders) 60% 54.54% ~
Solvent (MEK)* --- -- 10%
BYK-077 (De~oamer)q' 0.5% ns leR as leR
10DNNDSA ~ ~ 1%
Panel Q-PHOS R-36-1 ~ r Film tbickness (mil) 1.3-1.6 1.3-1.6 1.2-1.3 Direct Imp~lct (Ib-im) > 80 > 80 > 100 Reverse Imp~ct (Ib-m) < 40 < 40 < 60 15Pencil Hardness 3H 3H 3H
MEK Rub Resist~mce >200 >200 >200 Adhesion 2B 2B 3B
Appeluance white wbite wbite 2 0 ~ Percentage of the total weight ' Dinonylnaphthalene diYulfonic acid.
~b) ForlltLtlations ba9Qd upon the Oligoe9ter of ~cample VI (a) r-o~clinlro~l with a Mol~ ?
I5o~allate Blend and Tit~tniunt Dio~cide The oligoester diol described in Example VI (a) was mixed with TiO2 and crosslinked with a mixture of mF~ m;ne formaldehyde and polyisocyanate crosslinkers in weight ratios of 2.0/0.65 to 2.0/0.22 (melamine resin/isocyanate), the polyisocyanate blend being sold as :Luxat.e XHD 0700. The film properties were studied as described in Table 15 below.

W096123035 2 1 8 5 ~ 5 4 r~ .'01141 TABI.E 15 Oli6,~,_.t.,. ;" ' Vl (a) Vl (a) Wt/ 3.0g as lefl Crosslinker (Cvmd 1135 5Luxate XHD 0700) Wt/wt 2.0/0.65 2.010.22 TiO~ DuPont R 700 as left (percentage of binders) 53% 57.5%
Solvent (MEK)~ 0 0 10BYK-077 (Defoamer)~ 0.5~6 0.5 DNNDSA ~ ' 1% 1%
P~mel Q-PHOS R-36-1 ~Is left Film tbickness (mil) 1.0-1.1 1.0 Direct Irnpact (Ib-in) 120 120 15ReverseImpact(lb-in) -100, >60 >60 Pencil Hardrless 4H 3H
MEK Rub Resistance > 2C0 > 200 Adhesiorl 4B-SB 3B-4B
Appeamnce white wbite * Percentage of the total weight.
' Dinonylnaphthalene disulfonic acid.
E~5PLE VII
25 (a) Fonmllations of Oligoester Diol with M~ 'n~
Resin and Polyurethane-DiolJ
A series of linear oligoester-diols with different molecular weights (Mn) were synthesized using a procedure essentially identical to that described in 30 Example I. Molecular weights (Mn) were measured by NMR.
Viscosities were measured at 25C.
The following compounds were used in formulations of the oligoester-diol. K-FLEX UD320-l00, was a 100% polyurethane-diol with hydroxyl equivalent 35 weight 160 and viscosity 7.0 Pa.s at 50C_ Its structure is HO ~CH2) 6OCONH (CH2) 6NHCOO (CH2) 6OH. K-F~EX UD-320W, having W0 96/23035 2 1 8 5 4 5 4 r~ 141 the same structure as K-FLEX UD320-100, was a polyurethane-diol containing about 10~ by weight of water with hydroxyl equivalent weight 178, viscosity 8.0 Pa.s at 25C. Both were obtained from King Industries.
Cymel 1135, a 50/50 methylated/butylated ~
melamine, with 70% monomeric content, was obtained from Cytec Co. Resimene 797, a modified methylated melamine resin, and Resimene HM2612, 100% methylated melamine with > 90% monomeric content, were obtained from Monsanto Chemical Company.
Catalyst dinonyl naphthalene disulfonic acid ~DNNDSA) in isobutanol was obtained from King Industries "Nacure-155" ) .
Defoamers BYK-077 and leveling additi~Te BYE~-358 were obtained from BYK Chemie.
The formulations were prepared by blending oligoester-diol, crosslinker, catalyst, and additive together .
Films were prepared by casting the blended solution on a panel by a 26# wire - wound draw bar and baking in an oven at 150C for 30 minutes unless otherwise stated.
Pencil hardness was measured according to ASTM
D3364-74 standard test method for film hardness by pencil test. Impact resistance, either direct or reverse impact, was measured according to the ~STM D2794-84 standard test method for resistance of organic coatings to the effects of rapid ~deformation (Impact) . Resistance to methyl-ethyl-ketone (MEK) was measured by double rubbing with MEK saturated non-woven paper ("Kim-Wipe").
The non-woven paper was kept saturated by MEK during the measurement. Dry film thickness was measured by an Elcometer Model 300 thickness gauge. Adhesion was measured according to ASTM standard ~Designation: D3359-87, test method B-cross-cut tape test). VOC and NVW were measured according to ASTM standard test method for volatile content of coatings (Designation D2369-a7).

Film properties are described in Table 16.

Forllwlation of Ol;~:~ ter-diol (M ~ 735) and PolyuLeLl.an~
diol with r~ Resin 5o1;~ M= 735 M 735 Wt (g) /meq. wt. 2.015.43 2.0/5.43 ' ' UD320-100~ UD320W~
Wt (g)/m~q. wt. 1.0/6.~5 1.0/5.625 Cymel 1135 wt.(g)/
10meq. wt. 1.615/18.78 1.615/18.78 Wt. ratio of r'' ' '~' ' 3.5/6.5 3.5/6.5 Eq. wt. ratio of r'' ' '~"' 1.61 1.70 158YK-358~ 0.5% 0.5%
DNNDSA 1% 1%
Pamd Q-PHOS R-36-1 Q-PHOS R-36-1 film thicknws (mil) 0.8-1.0 0.8-1.0 Direct Impact (Ib-in) 60 ~ 80 2 0 Reverse Impact (Ib-m) ~ 20 ~ 20 Pencil Hardnws 4H 4H
MEK Rub Rwist~mce > 200 > 2C0 Adhesio~ 2B 2B-3B
Appearance Tr~msparent Transparent * Percentage of the total weight ** UD320-100, K-FLEX-UD320-100; ~D320W, F-FLEX-UD320W.
The affect of variations in the molecular weight of the oligoester-diol on the film properties provided by the formulations were as ollows:

W096l2303s 21 85454 ~ 4l Fornmlation of Oli~t~ ~ster-.liol of .li ~f~r~nt MW with Polyurethane-diol and t' l: n~ Resin 01'goester-diol N" 300 520 7 5 wt (g)/meq. wt. 2.0/13.33 2.0/7.69 3 Polyurethane-diol 0Wt (g) /meq. wt. 1. 0/5 . 625 1. 0/5 . 625 1. 0/5. 625 Cymel 1135 wt. (g)/meq. wt. 2.45/28.48 1.72/19.98 1.55/18.04 BYK-358`' 0.5~ 0.5~ 0.596 DNNDSA 1 ~
5Panel Q-PHOS R-36-1 Q-PHOS R-36-1 Q-PHOS R-36-1 l~ilm thickness 1. 0-1.2 1. 0-1.1 1 1 (mil ) Direct Imp2ct (lb- > 20 > 40 > 60 in) 20 Reverse Impact (lb-in) ~ 10 ~ 10 ~ 10 Pencil Hardness SH 4H 3H
MER Rub Resistance >200 >200 >200 Adhesion 2B-3B 2B-3B 2B-3B
25Arr~.7r~rG Tr_nsparent Transp2rent Transparent ~ Percentage of t total welght W096l23035 2 1 8 5 4 5 4 PCr/US96101141 TAsLE 18 Formulation of Oligo~i,L~aL l;ol of different MW with Polyurethane-diol and ~ Resin oligoester-diol Mn 840 1600 1600 wt (g)/meq. wt. 2.0/4.76 2.0/2.5 2.0/2.5 Polyurethane-diol 0Wt (g)/meq. wt. 1.0/5.625 1.5/58.44 1.5/8.44 Melamine cymel 1135 cymel 1135 Resimene 797 wt. (g)/meq. wt. 1.33/15.49 1.49/17.33 1.3/
BYK-358~ 0.596 0.5~ 0.5 DNNDSA 1% 1~
15Panel Q-PHOS R-36-1 Q-PHOS R-36-1 Q-PHOS R-36-1 Film thickness (mil) 1.0-1.1 1.0 1.0-1.1 Direct Impact (lb- > 80 60 > 80 in) 20Reverse Impact (lb-in) = 20 10 ~ 40 Pencil Hardness ~ 2H 2H 2H
MEK Rub Resistance >200 >200 >200 Adhesion 4B 3B-4B ~ 5B
25Appearance Transparent Transparent Transparent * Percentage of the total weight.
3 0 E~aMPLE VIII
Formulation~ of Linear Oligoe~ter Diol with and ~'~s5~l;n~
A series of linear oligoester-diols with different molecular weights (M~) were synthesized using a procedure essentially identical to that descri'oed in Example III. Molecular weights (Mn) were measured NMR.
Viscosities were measured at 25C.
Hardeners used in the formulations were as follows: Aromatic oligoester diol 6GT and lOGT were synthesized with the following structure.

W096123035 2' a5454 PCT/US96/01141 O O
HO-[(CA2)6-OC-~-CO-]z(CHz)D-OH
lOGT
O O
Ho-[(CH2)~D-oc-~3-co-]~(cHz)~c-oH
5 ' 1,3,5-Tri (hydroxyethyl) cyanuric acid (THECA) 97%, was obtained from Aldrich Chemical Company. AY-l, a diester of neopentyl glycol ~NPG) esterified by parahydroxybenzoic acid (PHPA), having the- structures below .

HOCH2CH2~ J~ ~CHzCH20H
OJ~N O

HO~-C4-CH,- I -CH2-O-C~4H
CH, Wo 96/2303s 2 1 8 5 4 5 4 PCT/US96/~1141 Dispersant Solsperse 24000, a polyester/polyamine copolymer, with m.p. of 47.5C, was obtained from United Color Technology, Inc.
All other adhesives are described in Example 5 VII. ~
Hardeners were dissolved in the oligoester-diol - melamine resln blend at 150C along with a "E~yperdispersant" stabilizer, Solsperse 24000, and then cooled with stirring to give a dispersion of fine 10 particles. After cooling, catalyst was added and the dispersions were cast as a film and baked at 150C for 30 :
minutes .
All other procedures used for preparing the formulations and test film properties are described in 15 Example VII.
~a) Forlmllations of an Oligoester Diol with u- - s, Polyurethane Diol and MQl~mi Resins Tables 19-20 describe formulation of the oligoester-diols of Example III with varying molecular weights with hardeners, polyurethane diol and melamine.

Wo96/23035 2 1 8 5454 .~ 1141 Formulation of OligoesL~L- l;ol of l)iff~-ont MW with l~r~l nQr~ Polyurethane-diol lmd ~ n~ Resin 5Oligo-diol wt (g)/meq. wt 2.0/13.33 2.0/7.69 2.0/5.44 2.0/4.76 Polyurethane diol UD320 W
0wt (g) /meq. wt 0 . 5/2. 813 0 . 5/2 . 813 0. 5/2 . 813 0 . 5/2. 813 Hardene~ (I) THECA
wt (g)/meq. wt 0.25/2.87 0.25/2.87 0.25/2.87 0.25/2.87 Hardener (II) wt (g)/meq. wt 0.25/0.81 0.25/0.81 0.25/0.81 0.25/0.81 Cymel 1135 wt (g)/meq. 1.62/18.77 1.62/18.77 1.62/18.77 1.62/18.77 wt. ratio ** 3.5/6.5 3.5/6.5 3.5/6.5 3.5/6.5 20eq. wt. ratio~* 0.947 1.323 1.57 1.67 Solsper~e -24000* 19~ 196 196 1 BYK-358* 0 . 596 0 . 5~ 0 . 5~ 0. 5 DNNDSA* 1% 1~ 1~ 1 ii Panel R-36-1 R-36-1 R-36-1 R-36-1 Film-thick (mil) 1.0 09-1.0 1.0-1.1 1.0-1.1 Direct Impact 30(lb-inch) > 40 > 60 > 80 > 80, rl20 Revers e Impa ct (lb-inch) < 20 > 20 < 40 ~ 40 Pencil-hard ~ 6H SH-6H 3H-4H 2H
~iEK Rub Resist. > 200 > 200 > 200 > 200 35Adhesion 4B 2B 3B-4B ~ 6B
Trans-Drp~ n~ p2rent as left a~ left as left * Percentage of total weight.
** The ratio of melamine/total-diol.

Formulation of Ol; 7C - Ldr-diol of Different MW with Elardener, PolyuL~sthai.~ diol ~nd Mc~l: 'nl~ Resin 5Oligo-diol MW 300 520 735 840 wt (g) /meq. wt 2 . 0/13 . 33 2 . 0/7 . 69 2 . 0/5 . 44 2 . 0/4 . 76 Polyurethane diol UD320 W
wt (g) /meq. wt 0 . 5/2 . 813 0 . 5/2 . 813 0 . 5/2 . 813 0 . 5/2 . 813 0Hardener ~I) THECA
wt (g)/meq. wt 0.25/2.87 0.25/2.87 0.25/2.87 0.25/2.87 H~ rdener ( I I ) 15wt (g)/meq. wt 0.25/0.81 0.25/0.81 0.25/0.81 0.25/0.81 Cymel 1135 wt (g)/meq. 2.56/29.75 1.83/21.27 1.55/18.06 1.27/14.69 wt. ratio ~* 4.60/5.40 3.79/6.21 3.41/6.591 2.96/7.04 eq. wt. ratio~ 1.5 1.5 .5 1.36 20Solsperse -24000* 1% 1% 1% 1%
BYK-358~ 0 . 5% 0 . 5% 0 . 5% 0 . 5%
DNNDSA* 1% 1% 1% 1%
Q-PIIOS Q-PHOS Q-PHOS Q-PHOS
25Panel R-36-1 R-36-1 R-36-1 R-36-1 Film-thick (mil) 1.0 1.0 0.8-1.1 1.0-1.1 Direct Impact (lb-inch) > 40 - 80 > 80 - 120 30Reverse Impact (lb-inch) < 20 < 40 < 40 ~ 40 Pencil-hard 6H SH 3H-4H 2H
MEK Rub Resist. > 200 > 200 > 200 > 200 Adhesion 4B 3B-4B ~ 4B 4B
35 Trans-Appearance parent as left as left as left * Percentage of total weight.
40 ** The ratio of mel_ine/total-diol.

Wo 96n3035 ~ 1 8 5 4 5 4 PCT/US96/0114 ~b) Formulations of an Oligoester Diol and r~ n~r~ with mixed Croscl i n~ r.5 Tables 21-23 describe formulation Of 5 oligoester-diols in combination with hardeners and mixtures oi' crosslinkers.

Formulation of Oligoester-diol with Ni~ced c-oscl i nlr~r.c 0 MC.l: ' n-- Resin, Polyisocyanate and TiO 2 .
Oligo-diol 3 . 0/ 3 . 0/ 3 3 / 3 /
wt (g)/meq. wt 11.54 11.54 11.54 11.54 11.54 Mn 520 520 520 520 520 5Luxate 0.65/ 0.65/ 0.65/ 0.65/ 0.65/
XHD0700 3.48 3.48 3.48 3.48 3.48 Cymel 1135 2 . 0/ 2 . 0/ 2 . 0/ 2 . 0/ 2 . 0/
wt (g) /meq. wt. 23.26 23.26 23.26 23.26 23.26 Tio 20DuPont R700 % of binders 53~ 53% 57.5% 57.5% 57.5%
Solsper~e -24000~ 1% 1% 1% 1% 1%
BYR-077 0.5% 0.5~ 0.5% 0-5~ 0-5%
25(defo~mer) ~
DNNDSA~ 1% 1% 1% 1~ 1%
Solvent (MER) ~ - 10% - 5~ 5~
Q-PHOS Q-PHOS Q-PHOS Q-PHOS QPanel Panel R-36-1 R-36-1 R-36-1 R-36-1 R-36 3 0Film-thick (mil) 1.0-1.1 0.9-1.0 1.0 0.8-1.0 0.8 Direct Impact (lb-inch) 120 160 120 120 80 Reverse Impact 35(lb-inch) ~ 100 ~ 100 60 60 < 60 Pencil-hard 3H 3H-4H 2H 2H-3H 2H-3H
M~R Rub Resist. > 200 > 200 > 200 > 200 > 200 Adhesion 4B-5B 4B 3B-4B 4B 0-lB
~rrGA'Anre White White White White White * Percentage of total weight.

W096l23035 2 1 ~ 5 4 5 4 PCr/USs6/0ll4l Formulation of Oli~ve..~er-diols with mised ~'ros~
of Mol: ' no Resin, Polyisocyanate and P~rrl~nor TIIECA.

Oligoester-diol Mn 300 520 wt (g)/meq. wt. 10.1/66.67 14.4/55.38 Luxate XXD 0700 wt (g)/meq. wt 2.36/lZ.62 3.6/19.25 10Cymel 1135 wt . ~g) /meq. wt . 8 . 84/102 . 79 12 . 0/139 . 53 TE~ECA wt (g) /meq. wt 1. 8/20 . 69 3 . 63/41. 72 Solsperse 24000 1% 1%
BYK-077 (defoamer) * 0.5% 0.5%
15DNNDSA* 1% 1%
Panel Q-P~IOS R-36-1 Q-PHOS R-36-1 Fi lm thi cknes s (mil) 1.0-1.1 1.1 Direct Impact lb/in < 120 < 120 20Reverse Impact lb/in < 60 < 60 Pencil ~Iardness 5~ 5~I
MEK Rub Resistance > 200 > 200 Adhesion 4B-5B 3B-4B
25Appearance Transparent Transparent * Percentage of the total weight.

W096t23035 2~ 8545~ PCTtUS96tO1141 Fon~lation of Oligoester-diols with mised t'ro8~l; nlrQr~
of M.~ Resin, Polyisocyan~te and ~rr3Qn~r AY-l.

Oligoester-diol Mn 3 0 52 0 wt (g)/meq. wt. 10.1/66.67 14.4/55.38 Luxate X~D 0700 wt (g) /meq. wt 2.63/14.33 4.0/21.39 10Cymel 1135 wt. (g)/meq. wt. 10.0/116.28 14.4/167.44 AY-l wt (g) /meq. wt . 3 . 44/20 . 0 4 . 8/27 . 91 Solsperse 2 4 0 0 0 1% 1%
BYK-077 (defoamer) * 0 . 5% 0 . 5%
15DNNDSA* 1% 1%
Panel Q-PHOS R-36-1 Q-PHOS R-36-1 Film thickness (mil) 1.0-1.3 1.0-1.3 :
Direct~Impact lb/in ~ 80 > 120 Reverse Impact 20lb/in < 20 ~- 60 Pencil Xardness 6H 6H
~EK Rub Resistance > 200 > 200 Adhesion 4B-5B ~ 4B
Appearance Transparent Transparent * Percentage of the total weight.

Wo 96/23035 2 1 8 5 4 5 4 pcrNs96loll4l Formulation of mi~ced Oligve~Lel l:ols with mi~ced CroQI2l inlrcr.~ ~nd ~r~c~n~r Oligoester-diol ( 1 ) Mn 520 520 wt (g)/meq. wt. 1.0/3.85 1.0/3.85 Oligoester-diol (2) F931013-4 F931013-4 wt (g) /meq. wt. 1.0/1.41 1.0/1.41 Luxate XHD C700 wt (g) /meq. wt 0.25/1.34 0.25/1.34 Cymel 1135 15wt. (g)/meq. wt. 1.07/13.39 0.95/12.24 Hardener AY- 1 THECA
wt (g)/meq. wt. 0.5/2.91 0.5/5,75 Solsperse 24000 1% 1%
BYK-077 (defoamer) ~ 0.5% 0.5%
2 0 DNNDSA~ 1% 1%
Panel Q-PHOS R-36-l Q-PXOS R-36-1 Film thickness (mil) 1.0 1.0-1.2 Direct Impact lb/in 100 100 Reverse Impact 25lb/in 60 ~ 60 Pencil Hardness 5H 3H-4H
MEK Rub Resistance > 200 > 200 Adhesion 5B 4B-5B
Appearance Transparent Transparent ~ Percentage of the total weight.

Claims (34)

WHAT IS CLAIMED IS

1. A polymeric vehicle which is effective for providing a formulated coating composition which formulated coating composition does not require an organic solvent for application to a substrate and is liquid at not more than about 50°C, the polymeric vehicle comprising:
at least one linear oligoester diol having a number average molecular weight in the range of from about 275 to about 1200, a polydispersity index of less than about 2.6 and a viscosity of not more than about 1.2 Pa.s at from about 20°C to about 50°C; and a crosslinker which has a functionality which is greater than about 2.4 and which functionality is reactive with the hydroxyl groups of the oligoester diol, the crosslinker and oligoester diol forming a blend having a viscosity in the range of from about 0.1 to about 20 Pa.s at about 20 to about 60°C at a shear of about 1000 sec.-1, and being soluble in the linear oligoester diol, the polymeric vehicle comprising at least about a stoichiometric amount of crosslinker to react with the hydroxyl groups of the linear oligoester diol.

2. A polymeric vehicle as recited in claim 1 wherein the oligoester diol has a polydispersity index of less than about 2.2, and the crosslinker is liquid at about 10°C.

3. A polymeric vehicle as recited in claims 1 or 2 wherein the crosslinker is selected from the group consisting of an amino resin, a polyisocyanate, and mixtures thereof.

4. A polymeric vehicle as recited in claim 3 wherein the crosslinker is an amino resin and wherein the polymeric vehicle has at least about 92 weight percent solids.

5. A polymeric vehicle as recited in claim 3 wherein the crosslinker is a polyisocyanate and wherein the polymeric vehicle has at least about 97 weight percent solids.

6. A polymeric vehicle as recited in claim 2 wherein the crosslinker is an amino resin and wherein the polymeric vehicle has at least about 92 weight percent solids.

7. A polymeric vehicle as recited in claim 2 wherein the crosslinker is a polyisocyanate and wherein the polymeric vehicle has at least about 97 weight percent solids.

8. A polymeric vehicle as recited in claims 1, 2, 6 or 7 wherein the linear oligoester diol has a structure which is a longitudinal chain which is substantially without side chains, the longitudinal chain having the structures -CH2-, -O- and -C(=O)-, the longitudinal chain being terminated with hydroxyl groups.

9. A polymeric vehicle as recited in claims 1, 2, 6 or 7 wherein the oligoester has a viscosity in the range of from about 0.1 to about 1.2 Pa.s at a temperature in the range of from about 20°C to about 50°C
and a polydispersity index of less than about 1.8.

10. A polymeric vehicle as recited in claim 8 wherein the viscosity of the polymeric vehicle is less than 1.2 Pa.s at a temperature in the range of from about 25°C to about 50°C.

11. A polymeric vehicle as recited in claim 9 wherein the viscosity of the polymeric vehicle is less than 1.2 Pa.s at a temperature in the range of from about 25°C to about 50°C.

12. A liquid formulated coating composition which does not require an organic solvent for application to a substrate at not more than 50°C, the formulated coating composition comprising:
a polymeric vehicle, the polymeric vehicle comprising at least one linear oligoester diol and a crosslinker, the polymeric vehicle comprising at least about a stoichiometric amount of the crosslinker to react with the hydroxyl groups of the linear oligoester diol, the linear oligoester diol having a number average molecular weight in the range of from about 275 to about 1200, a polydispersity index of less than about 2.6 and a viscosity of not more than about 1.2 Pa.s at from about 20°C to about 50°C, the crosslinker having a functionality which is greater than about 2.4 and which functionality is reactive with the hydroxyl groups of the oligoester diol, the crosslinker and oligoester diol forming a blend in the range of from about 0.1 to about 20 Pa.s at about 20 to about 60°C at a shear of about 1000-1, and being soluble with the linear oligoester diol.

13. A formulated coating composition as recited in claim 12 wherein the composition further includes a catalyst.

14. A formulated coating composition as recited in claim 12 wherein the catalyst is selected from the group consisting of dibutyl tin dilaurate, diazabicyclo [2.2.2] octane, para toluene sulfonic acid, dodecyl benzene sulfonic acid and dinonyl nathphalene disulfonic acid.

15. A formulated coating composition as recited in claim 12 wherein the crosslinker is selected from the group consisting of an amino resin, a polyisocyanate, and mixtures thereof.

16. A formulated coating composition as recited in claim 12 wherein the crosslinker is an amino resin and wherein the polymeric vehicle has at least about 92 weight percent solids.

17. A formulated coating composition as recited in claim 12 wherein the crosslinker is a polyisocyanate and wherein the polymeric vehicle has at least about 97 weight percent solids.

18. A formulated coating composition as recited in claim 12 wherein the coating composition has less than 140 g/L volatile organic compounds.

19. A polymeric vehicle comprising:
at least one linear oligoester diol and a liquid crosslinker, wherein the linear oligoester diol is the reaction product of a linear dicarboxycylic acid or ester thereof which has not more than about 16 carbon atoms and a linear diol which has at least two carbon atoms and not more than 16 carbon atoms, the linear oligoester diol having a number average molecular weight in the rarlge of from about 275 to about 1200, a polydispersity index of less than about 2.2 and a viscosity of not more than about 1.2 Pa.s at from about 20°C to about 50°C, and wherein the liquid crosslinker has a functionality which is greater than about 2.4 and which functionality is reactive with the hydroxyl groups of the oligoester diol, the crosslinker having a viscosity of less than about 3.0 Pa.s at about 25°C, being liquid at about 10°C and being miscible with the linear oligoester diol, the polymeric vehicle comprising at least about a stoichiometric amount of crosslinker to react with the hydroxyl groups of the linear oligoester diol.

20. A polymeric vehicle as recited in claim 19 wherein the crosslinker is selected from the group consisting of an amino resin, a polyisocyanate, and mixtures thereof.

21. A polymeric vehicle as recited in claim 19 wherein the crosslinker is an amino resin and wherein the polymeric vehicle has at least about 92 weight percent solids.

22. A polymeric vehicle as recited in claim 19 wherein the crosslinker is a polyisocyanate and wherein the polymeric vehicle has at least about 97 weight percent solids.

23. A polymeric vehicle as recited in claims 19, 20, 21 or 22 wherein the dicarboxycylic acid or ester thereof is selected from the group consisting of azelaic acid, glutaric acid, adipic acid, decaneodioic acid, dodecandioic acid, dimethyl azeleate, dimethyl glutarate, dimethyl adipate, dimethyl decanedioate and dimethyl dodecandioate and wherein the diol is selected form the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, triethylene glycol and tetraethylene glycol.

24. A polymeric vehicle as recited in claim 19 wherein the diacid has an odd number of carbon atoms.

25. A polymeric vehicle as recited in claims 19, 20 or 21 wherein the oligoester has a viscosity in the range of from about 0.1 to about 1.2 Pa.s at a temperature in the range of from about 20°C to about 50°C
and a polydispersity index of less than about 1.8.

26. A method of controlling the viscosity of a coating composition such that the coating composition has a viscosity of not more than about 1.2 Pa.s at not more than about 50°C, the method comprising:
mixing a linear oligoester diol and a crosslinker to provide a coating composition, wherein the linear oligoester diol has a number average molecular weight in the range of from about 275 to about 1200, a polydispersity index of less than about 2.6 and a viscosity of not more than about 1.2 Pa.s at from about 20°C to about 50°C and wherein the crosslinker has a functionality which is greater than about 2.4 and which functionality is reactive with the hydroxyl groups of the oligoester, the crosslinker and oligoester diol forming a blend having a viscosity in the range of from about 0.1 to about 20 Pa.s at about 20 to about 60°C at a shear of about 1000 sec.-1, and the crosslinker being soluble in the linear oligoester diol, the blend comprising at least about a stoichiometric amount of crosslinker to react with the hydroxyl groups of the linear oligoester diol.

27. A polymeric vehicle comprising:
at least one linear oligoester diol having a number average molecular weight in the range of from about 275 to about 1200, a polydispersity index of less than about 2.6 and a viscosity of not more than about 1.2 Pa.s at from about 20°C to about 50°C and which oligoester diol is effective for crosslinking with a crosslinker which has a functionality which is greater than about 2.4 and which functionality is reactive with the hydroxyl groups of the oligoester diol, crosslinker and oligoester diol forming a blend having a viscosity in the range of from about 0.1 to about 20 Pa.s at about 20 to about 60°C at a shear of about 1000 sec.-1, and being soluble with the linear oligoester diol when mixed therewith.

28. A polymeric vehicle as recited in claim 27 wherein the oligomer has a polydispersity index of less than about 2.2 and the polymeric vehicle has a viscosity of not more than about 1.2 Pa.s at not more than 50°C.

29. A polymeric vehicle as recited in claims 27 or 28 wherein the polymeric vehicle is effective for providing a coating binder having a pencil hardness of at least about B when applied to a substrate at a thickness of about 1 mil dry.

30. A polymeric vehicle as recited in claims 27 or 28 wherein the linear oligoester diol has a structure which is a longitudinal chain which is substantially without side chains, the longitudinal chain having the structures -CH2-, -O- and -C(=O)-, the longitudinal chain being terminated with hydroxyl groups.

31. A polymeric vehicle as recited in claim 27 wherein the oligoester has a viscosity in the range of from about 0.1 to about 1.2 Pa.s at a temperature in the range of from about 20°C to about 50°C and a polydispersity index of less than about 1.8.

32. A polymeric vehicle as recited in claim 31 wherein the polymeric vehicle is effective for providing a coating binder having a pencil hardness of at least about B when applied to a substrate at a thickness of about 1 mil dry.

33. A polymeric vehicle which is effective for providing a formulated coating composition which formulated coating composition does not require an organic solvent for application to a substrate and is liquid at not more than about 50°C, the polymeric vehicle comprising:
at least one linear oligoester diol having a number average molecular weight in the range of from about 275 to about 1200, a polydispersity index of less than about 1.8, having at least 93 weight percent solids, and a viscosity of not more than about 1.2 Pa.s at from about 20°C to about 50°C, the linear oligoester diol having a structure which is a longitudinal chain which is substantially without side chains, the longitudinal chain having the structures -CH2-, -O- and -C(=O)-, the longitudinal chain being terminated with hydroxyl groups;
and a crosslinker which has a functionality which is greater than about 2.4 and which functionality is reactive with the hydroxyl groups of the oligoester diol, the polymeric vehicle comprising at least about a stoichiometric amount of crosslinker to react with the hydroxyl groups of the linear oligoester diol, the polymeric vehicle having a viscosity of not more than 1.2 Pa.s at a temperature in the range of from about 25°C to about 50°C, the polymeric vehicle having at least about 92 weight percent solids and is effective for providing a coating binder having a hardness of at least about B when applied to a substrate at a thickness of about 1 mil dry.

34. A polymeric vehicle as recited in claim 33 wherein the polymeric vehicle is effective in providing a formulated coating composition having less than about 140 g/L volatile organic compounds.