AU749637B2 - Compositions containing polyols, phenolic esters and isocyanates - Google Patents

Description

S&FRef: 359534D1

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

*5 Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: Exxon Chemical Company 4500 Bayway Drive Baytown Texas 77522 United States of America Vijay Swarup, Frank N. Jones, Albert I. Yezrielev and Ramachandran P. Subrayan Spruson Ferguson St Martins Tower 31 Market Street Sydney NSW 2000 Compositions Containing Polyols, Phenolic Esters and Isocyanates

C

S

The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845c COMPOSITIONS CONTAINING POLYOLS, PHENOLIC ESTERS AND ISOCYANATES FIELD OF THE INVENTION The present invention relates to polymeric vehicles for coating films or binders where the polymeric vehicles are thermosetting and include at least one phenolic ester alcohol, at least one polyol and at least one isocyanate compound with multi-isocyanate functionality. In an important aspect, the invention is directed to polymeric vehicles which include at least one phenolic ester alcohol, at least one isocyanate compound with multi-isocyanate functionality, at least 10 one polyol and at least one amino resin.

BACKGROUND OF THE INVENTION AND DESCRIPTION OF THE PRIOR

ART

One of the primary components in paint is the "film 15 former" that provides a film for the protective function of a substrate coated with paint. Film forming components of liquid paints include resins which have required organic solvents to provide the resins with suitable viscosities such that the paint can be applied 20 by existing commercial application equipment. Use of solvents, however, raises at least two problems. First, in the past and potentially in the future, petrochemical shortages mitigate against the use of organic solvent in great volumes. Second, environmental concern mitigates against the use of organic solvents and requires such use be minimized.

Thermosetting coating compositions, particularly coating compositions which include polyester, alkyd, acrylic and epoxy polymers are often materials of choice for making film formers for various substrates to which the coating composition is applied. Coating compositions provide a protective function for the substrate. Hence, coating compositions are generally -2formulated to provide a balance of properties which will maximize hardness, flexibility, hydrolytic stability, solvent resistance, corrosion resistance, weatherability, acid resistance and gloss, with emphasis on certain properties depending upon the purpose for which the coating is intended.

It has been a continuing challenge to provide coating compositions which upon thermosetting provide films with desired film properties such as hardness, flexibility, solvent resistance, acid resistance, corrosion resistance, hydrolytic stability, weatherability and gloss, reduce VOCs and still retain the ability to have the viscosities of the polymeric vehicle and formulated coating composition made 15 therefrom such that the formulated coating composition can be applied with existing commercial application equipment.

United States Patent No. 4,331,782 to Linden, United States Patent Nos. 3,836,491 and 3,789,044 to Taft et 20 al. and U.S. Patent No. 3,409,579 to Robbins describe phenol capped polymers which are crosslinked with polyisocyanates. They do not involve the use of a phenolic ester alcohol which includes a phenolic hydroxyl group and an aliphatic hydroxyl group in combination with an isocyanate compound with multiisocyanate functionality and/or polyol as described herein.

OBJECTS OF THE INVENTION It is an object of the invention to provide a coating composition which will maximize film properties such as hardness, hydrolytic stability, weatherability, flexibility, solvent resistance, corrosion resistance, acid resistance and gloss.

It is an object of the invention to provide a coating composition which will not sag or minimize sagging during the curing process to provide a coating binder.

It is another object of the invention to provide a coating composition which will be low in VOCs.

It is an object of this invention to provide formulated compositions which are s solventless or which are thinned by organic solvents and/or water.

Further objects and advantages of the invention will be found by reference to the following description.

SUMMARY OF THE INVENTION The present invention is directed to a polymeric vehicle, a formulated coating composition and a coating binder made from the polymeric vehicle and a method for making the polymeric vehicle where the polymeric vehicle includes at least one phenolic ester alcohol having at least one phenolic hydroxyl group and at least one aliphatic hydroxyl group; at least one polyol having a polydispersity index (PDI) of greater than 15 one; and at least one isocyanate compound having a average of more than one reactive isocyanate per molecule. The latter combination enhances film properties such as hardness, hydrolytic stability, corrosion resistance and weatherability.

Accordingly, in a first embodiment the invention provides a polymeric vehicle comprising: 20 at least about 5 weight percent, based upon the weight of the polymeric vehicle, of an isocyanate compound having an average isocyanate functionality of from about 1.9 S'to about 20 isocyanate groups per molecule; at least about 15 weight percent, based upon the weight of the polymeric vehicle, of a polyol having a polydispersity index greater than one; and 25 at least about 5 weight percent, based upon the weight of the polymeric vehicle, of a phenolic ester alcohol having at least one phenolic hydroxyl group and at least one aliphatic hydroxyl group, the isocyanate compound being reactive with the phenolic ester alcohol and polyol.

In a second embodiment, the invention provides a polymeric vehicle comprising: at least about 5 weight percent, based upon the weight of the polymeric vehicle, of an isocyanate compound having an average isocyanate functionality of from about 1.9 to about 20 isocyanate groups per molecule; at least about 15 weight percent, based upon the weight of the polymeric vehicle, J of a polyol having a polydispersity index greater than one and the polyol being selected [I:\DAYLB\Iibz]05606.doc:n from the group consisting of a polyester polymer, an acrylic polymer, an alkyd polymer, an epoxy polymer and mixtures thereof; and at least about 5 weight percent, based upon the weight of the polymeric vehicle, of a phenolic ester alcohol having at least one phenolic hydroxyl group, and at least one aliphatic hydroxyl group, the isocyanate compound being reactive with the phenolic ester alcohol and polyol, and wherein the phenolic ester alcohol has at least two ester groups and has the general formula HO O R 6 II I R Rs 5

-COCH-CH-R

7

OH

wherein R4 is selected from the group consisting of hydrogen, halogen, hydroxyl, C to C 8 alkyl and Ci to C 8 alkoxy, is selected from the group consisting of a direct bond, C 1 to C 20 organic 15 radical having only carbon and hydrogen atoms, and a Ci to C 20 organic radical which includes in its structure a substitution group selected from the group consisting of phenol, aliphatic hydroxyl, ester, ether, carbonate and combinations thereof, wherein R 6 is selected from the group consisting of hydrogen, a CI to C 2 0 organic *radical, a Ci to C 20 organic radical which includes in its structure at least one ester linkage 20 or a direct bond which forms with R 7 part of a 5 or 6 carbon atom cyclic ring structure, wherein R 7 is CH 2

R

8 wherein R 8 is selected from the group consisting of "hydroxy, OR 9 OC(O)Ro 0 and R 11 wherein R 9 is selected from the group consisting of a primary or secondary aliphatic group containing 3 to 20 carbon atoms, an aromatic group containing 6 to carbon atoms, a primary aliphatic group containing 3 to 20 carbon atoms which includes at least one ester linkage and a secondary aliphatic group containing 3 to 20 carbon atoms which includes at least one ester linkage, wherein Rio is selected from the group consisting of a primary aliphatic group containing 4 to 20 carbon atoms, a secondary aliphatic group containing 4 to 20 carbon atoms, a tertiary aliphatic group containing 4 to 20 carbon atoms, an aromatic group containing 6 to 20 carbon atoms, and combinations thereof, wherein the primary, secondary and tertiary aliphatic groups include at least one ester linkage; and [I:\DAYLIB\libz]05606.doc:lam wherein R, is selected from the group consisting of a C 2 to C 20 organic radical, a

C

2 to C 2 0 organic radical which includes in its structure at least one ester linkage, a C 2 to

C

20 organic radical which forms with R 6 part of a 5 or 6 carbon atom cyclic ring structure, and combinations thereof.

In the polymeric vehicle, the polyol preferably has an average hydroxyl functionality of from about 2 to about 100 hydroxyls per molecule, a PDI of greater than 1 and a molecular weight of at least 200. In an important aspect the polyol is a polyester, alkyd or acrylic polymer. The isocyanate compound has an isocyanate functionality of from about 1.9 to about 20 isocyanate groups per molecule. The isocyanate serves to o0 crosslink and interconnect the polyol and the phenolic ester alcohol as follows: PHEAisocyanate-polyol. The isocyanate functionality is reactive with the hydroxyls of the phenolic ester alcohol and polyols. When the phenolic ester alcohol, polyol and isocyanate compound are at low molecular weights, they may be blended in amounts effective for the blend providing a -4polymeric vehicle and/or formulated coating composition having less than about 3.5 pounds per gallons of composition.

In another important aspect, the polymeric vehicle includes an amino resin having a crosslinking functionality of from about 3 to about 30 crosslinking groups per molecule blended with the phenolic ester alcohol, isocyanate compound and polyol. It is preferred that the isocyanate compound has an average isocyanate functionality of about 2 or 3. In this aspect of the invention, when the number of equivalents of the isocyanate functionality of the isocyanate compound is about 100 percent or less of the number of equivalents of aliphatic hydroxyls in the blend, the 15 isocyanate group generally reacts with the aliphatic hydroxyl group of the PHEA and polyol and the phenolic hydroxyl group reacts with the amino resin to provide a crosslinked structure with the following components which are connected to provide predominantly the following linkages: Polyol residue/isocyanate residue/aliphatVc end of PHEA residue;phenolic end of PHEA residue/amino resin. It is believed that the aliphatic hydrpxyl of the PHEA'reacts first with the isocyanate-compound to build viscosity to reduce or eliminate sagging. Thereafter, the phenolic hydroxyl group of the PHEA reacts with the melamine resin to provide exceptional hardness properties to the resulting coating binder.

In an important aspect, the phenolic ester alcohol has the general formula which includes at least two ester linkages and at least one aliphatic hydroxyl group which is a secondary or primary hydroxyl group and which is described in the following general formula COCH-CH-

R,

R

OH

OH

A

wherein R 4 is selected from the group consisting of hydrogen, halogen, hydroxyl, Ci to C 8 alkyl and C 1 to C 8 alkoxy, R 5 is a direct bond or a C 1 to C 20 organic radical which may incorporate another phenol, aliphatic hydroxyl, ester, ether and/or carbonate group in its structure, R 6 is hydrogen or a C 1 to C 20 organic radical which may include an ester group, or a direct bond which may form with R, part of a 5 or 6 carbon atom cyclic ring structure, R, is CH 2 Re wherein Re is selected from the group consisting of hydroxy, OR 9 OOCRIo and R 1 wherein R, is a primary or secondary aliphatic group containing 3 to 20 carbon atoms which may include one or more ester 15 linkages or an aromatic group containing 6 to 20 carbon atoms, R 10 is a primary, secondary or tertiary aliphatic group containing 4 to 20 carbon atoms which may include one or more ester linkages or an aromatic group containing 6 to 20 carbon atoms, and R1 is a C 2 to C 20 organic radical which may include one or more ester linkages and where the organic radical may form with RI part of a 5 or 6 carbon atom cyclic ring structure. In a particularly important aspect R 5 or R 8 has the ester groups. The -OH expressly shown in formula A is illustrative of an aliphatic hydroxyl group.

In another important aspect of the invention, the phenolic ester alcohol is the reaction product of hydroxybenzoic acid, such as para hydroxybenzoic acid, and a monoglycidyl compound having a molecular weight in the range of from about 110 to 1000 such as the monoglycidyl compound with the formula 0\ 0

CH

2

CHCH

2

-OCC(R)

3

"B"

where R represents a mixture of aliphatic groups, most preferably the three R groups in the glycidyl compound having a total of 8 carbon atoms.

Such a glycidyl compound is commercially available from Exxon Chemical Company under the trademark Glydexx® An important phenolic ester alcohol for use in the invention has the general formula 0 o HO H HO

CH.

"C"

In making the polymeric vehicle, each component is in relative amounts effective for providing an acceptable coating binder which generally will have a pencil hardness of at least about HB and preferably F, an impact resistance of at least about 2.25J 10o pounds) direct, preferably 3.38J and at least about 2.25J (20-inch pounds) reverse, preferably 3.38 at a film thickness of about 12.7pm dry. The crosslinker may be a solid, but generally is a liquid. The viscosity of the blend which forms the polymeric vehicle, such as the phenolic ester alcohol, isocyanate and polyol, is in the range of from about 0.1 to about 20Pa.s at about 20 to about 60°C at a shear rate of at least 1000 sec.- 1 5 without organic solvent and/or water.

Generally the polymeric vehicle may have from about 5 to about 70 weight percent, based upon the weight of the polymeric vehicle, phenolic ester alcohol, from about 5 to about 40 weight percent, based upon the weight of the polymeric vehicle, isocyanate compound and at least about 15 weight percent and preferably from about 15 to about weight percent, based upon the weight of the polymeric vehicle, polyol. In the aspect of S the invention which includes the amino resin, the polymeric vehicle includes from about to about 55 weight percent of an amino resin. When the amino resin [n:\libc]01629:MEF -7is present in the blend of the polymeric vehicle, the polymeric vehicle will generally comprise from about 3 to about 45 weight percent amino resin.

DESCRIPTION OF THE PREFERRED EMBODIMENTS "Polyester" means a polymer which has linkages in the main chain of the polymer.

"Acrylic polymer" means a homo or copolymer of hydroxy substituted acrylic acid or acrylate, and/or hydroxy and alkyl substituted acrylic acid or acrylate as further described below.

"Isocyanate compound" means a compound which as isocyanate functionality or groups which compound has an average isocyanate functionality of from 15 about 1.9 to about 20 isocyanate groups per molecule which isocyanate functionality is reactive with the hydroxyls of the phenolic ester alcohol. The isocyanate compound may be a biuret, an isocyanurate and/or a blocked or unblocked isocyanate.

20 "Polyisocyanate" can mean compounds with two or more isocyanate groups which are reactive with hydroxyl groups and which compounds may be biurets and isocyanurates.

"Biuret" means an isocyanate reacted with water in a ratio of three equivalents of isocyanate to one equivalent of water, such as the biuret of HDI shown below.

An "isocyanurate" is a six-membered ring having nitrogens at the 1, 3 and 5 positions and keto groups at the 2, 4 and 6 positions, the nitrogens being substituted with an isocyanate group, such as shown below in the isocyanurate of HDI.

"Amino resin" means amino resins usually made from amidines, ureas or amides by reaction with formaldehyde and subsequently usually with an alcohol. Melamine resins are a subclass of amino resins and may also be referred to as "melamine-formaldehyde resin" or -8- "alcoholated melamine-formaldehyde resin." Amino resin amounts may be adjusted in amounts effective to obtain the properties desired and to control the viscosity of the polymeric vehicle which viscosity will also be a function of the molecular weights of the phenolic ester alcohol, isocyanate and polyol in the blend which form the polymeric vehicle.

"Crosslinking agent" means a compound having di- or polyfunctional isocyanate groups or a polyfunctional amino resin. The isocyanate compound or amino resin contains isocyanate or crosslinking functional groups that are capable of forming covalent bonds with hydroxyl groups that are present on the phenolic ester alcohol and/or polyol in the polymeric vehicle. The 15 crosslinking agent may be a blend; hence, there may be more than one substance which forms a blend of substances which form covalent bonds with the hydroxyl groups of the polyol. Amino reins and polyisocyanates are such crosslinking agents.

20 "Polymeric vehicle" means polymeric and resinous components in the formulated coating, before film formation, including but not limited to the phenolic ester alcohol, the polyol and additional hardeners which may be added.

25 "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 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.

"Residue" means that portion of a molecule that is left after a reaction which in general eliminates some atoms from the reactant or moves the atom to different positions among the reactants. By way of an example, a -9urethane linkage (H O I II forms by way of reaction of an alcohol and isocyanate. The residue of the alcohol and isocyanate forming the urethane linkage. An amine may react with an alcohol with the loss of water. The new molecule is a residue of the alcohol and amine.

"VOC" means volatile organic compounds.

"Diol" is a compound, oligomer or polymer with two hydroxyl groups. "Polyol" is a compound, oligomer or polymer with two or more hydroxyl groups.

"Solvent" means an organic solvent.

"Organic solvent" means a liquid which includes but is not limited to carbon and hydrogen and has a boiling 15 point in the range of from about 30*C to about 300'C at about one atmosphere pressure.

"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 United States of America 20 as any compound of carbon, excluding carbon monoxide, S. 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: acetone; methane; ethane; methylene chloride (dichloromethane); 1,1,1trichloroethane (methyl chloroform); 1,1,1-trichloro- 2,2,2-trifluoroethane (CFC-113); trichlorofluoromethane (CFC-11); dichlorodifluoromethane (CFC-12); chlorodifluoromethane (CFC-22); trifluoromethane (FC- 23); 1,2-dichloro-l,1,2,2-tetrafluoroethane (CFC-114); chloropentafluoroethane (CFC-115); 1,1,1-trifluoro 2,2dichloroethane (HCFC-123); 1,1,1,2-tetrafluoroethane (HF-134a); l,l-dichloro 1-fluoroethane (HCFC-141b); 1chloro 1,1-difluoroethane (HCFC-142b); 2-chloro- 1,1,1,2-tetrafluoroethane (HCFC-124); pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1trifluoroethane (HFC-143a); 1,1-difluoroethane

(HFC-

152a); and perfluorocarbon compounds which fall into these classes: Cyclic, branched, or linear, completely fluorinated alkanes; (ii) Cyclic, branched, or linear, completely fluorinated ethers with no unsaturations; (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.

S. A "film" is formed by application of the formulated coating composition to a base or substrate, evaporation 15 of solvent, if present, and crosslinking.

The invention includes a polymeric vehicle comprising at least one phenolic ester alcohol having at least one phenolic hydroxyl group and at least one aliphatic hydroxyl group; at least one polyol; and at 20 least one isocyanate compound having an average isocyanate functionality of from about 1.9 to about isocyanate groups per molecule which isocyanate functionality is reactive with the hydroxyls of the phenolic ester alcohol and polyol. In an important 25 aspect, the phenolic ester alcohol has about one aliphatic hydroxyl group. In the aspect of the invention, which includes the phenolic ester alcohol, isocyanate compound and polyol, each of these components in the polymeric vehicle are present in an amount effective to provide a coating binder with a hardness of at least about HB at a thickness of about 1 2 .7pm (0.5mil) dry.

In an important aspect of the invention which provides a high solids or solventless polymeric vehicle and/or formulated coating composition, the viscosity of the blend which constitutes the polymeric vehicle (which includes the phenolic ester alcohol, polyol and isocyanate compound) will be in the range of from about -11- 0.1 to about 20 Pa.s at about 20 to about 60"C at a shear rate of at least about 1,000 and preferably in the range of about 1,000 to about 1 X 106 sec.

1 in the absence of organic solvent and/or water.

The blend of the phenolic ester alcohol, polyol and isocyanate compound provides the polymeric vehicle with improved coating properties such as hardness, flexibility, hydrolytic stability, solvent resistance, corrosion resistance, weatherability, acid resistance and gloss. The polymeric vehicle and formulated coating compositions which include the polymeric vehicle of the invention may include organic solvents, water, or may not require water or organic solvents to provide a formulated coating composition with a viscosity such 15 that the formulated coating composition may be applied by existing application equipment. When the phenolic ester alcohol, polyol and isocyanate compound are at low molecular weights, such as when the phenolic ester alcohol has a number average molecular weight in the 20 range of from about 110 to about 1,000, the blend of the phenolic ester alcohol and isocyanate not only improves film properties, it does so while maintaining or lowering the VOCs in the polymeric vehicle and formulated coating composition. Frequently, the need is 25 reduced for organic solvents and/or water to lower the viscosity of the polymeric vehicle or formulated coating composition to permit the application of the formulated coating composition to a substrate.

The phenolic ester alcohol and isocyanate compound may be used as a reactive diluent in conjunction with the polyol. When the phenolic ester alcohol and isccyanate compound have low molecular weights as described above, they may be used as a blend which is a reactive diluent in the polymeric vehicle which includes the polyol. Moreover, by controlling the molecular weights of the phenolic ester alcohol, isocyanate and polyol, the blend may be used as a 12 reactive diluent which controls VOC and may be added to a polymeric vehicle to lower VOCs to levels of at least about 5 weight percent.

In high solids formulated coating compositions which include organic solvents (such as about 75 weight percent solids), one aspect of the invention contemplates the phenolic ester alcohol, isocyanate compound, amino resin, if any, and polyol being in amounts effective for maintaining VOCs in the formulated coating composition (which includes the polymeric vehicle) to less than about 0.42kg of VOC per litre of formulated coating composition while at least maintaining the pencil hardness of the coating binder, to at least about HB and maintaining an impact resistance of the coating binder to at least about 20-inch pounds direct and at least about 2.25J (20-inch pounds) indirect at a film thickness of about 12.7ipm dry. Indeed in the high solids aspect of the invention, the invention is effective for providing formulated coating compositions having less than 0.3kg of VOC per litre of formulated coating composition and in some cases less than 0.24kg of VOC per litre of formulated coating composition.

1 5 In yet another important aspect, the invention is effective for providing solventless liquid formulated coating compositions (not more than about 3 weight percent organic solvent) where the polymeric vehicle in the formulated coating composition comprises the phenolic ester alcohol and isocyanate compound, each at low molecular weight, a polyol having a molecular weight of at least 200, an average hydroxyl functionality of from about 2 to about 100 hydroxyls per molecule and an amino resin.

Further the blend of the phenolic ester alcohol, polyol and isocyanate compound is compatible with and permits the use of other diphenolic hardeners to improve coating properties, but yet also permits the use of the 0 4 0 [n:\libc]01629:MEF -13additional hardeners in a formulated coating composition which may include solvents. By way of example, a diphenolic polyol ester reaction product of hydroquinone and parahydroxy benzoic acid (known as SK101) has low solvent dispersibility or solubility, requires high-cure temperatures and often makes coatings intractable. The use of the blend of the invention permits the use of other diphenolic hardeners such as SK101 which has the structure to improve hardness yet reduces the other problems attendant with the use of such hardeners.

The Phenolic Ester Alcohol The phenolic ester alcohol has at least one phenolic hydroxyl group, and at least one aliphatic 15 hydroxyl group. In an important aspect, it has two ester groups and about one aliphatic hydroxyl group.

Generally, it is the reaction product of a phenol carboxylic acid and an epoxy compound. In an important aspect, the phenolic ester alcohol is represented by the general formula "A" O R R- COCH-CH- R

RHO

1

I

OH

S: n"A" wherein R4 is selected from the group consisting of hydrogen, halogen, hydroxyl, C 1 to C 8 alkyl and C, to C, alkoxy, R 5 is a direct bond or a Ci to C 20 organic radical which may incorporate another phenol, aliphatic hydroxyl, ester, ether and/or carbonate group in its structure, R is hydrogen or a C 1 to C 20 organic radical which may include an ester group, or a direct bond which may form with R 7 part of a 5 or 6 carbon atom cyclic ring structure, R, is CH 2

R

8 wherein Re is selected from the group consisting of hydroxy, OR 9

OOCR

0 and R 11 wherein R 9 is a primary or secondary aliphatic group containing 3 -14to 20 carbon atoms which may include one or more ester linkages or an aromatic group containing 6 to 20 carbon atoms, R 10 is a primary, secondary or tertiary aliphatic group containing 4 to 20 carbon atoms which may include one or more ester linkages or an aromatic group containing 6 to 20 carbon atoms, and R 1 is a C 2 to C 20 organic radical which may include one or more ester linkages and where the organic radical may form with R 6 part of a 5 or 6 carbon atom cyclic ring structure. In a particularly important aspect R 5 or Re has the ester groups. The -OH expressly shown in formula A is illustrative of an aliphatic hydroxyl group. A phenolic ester alcohol which is particularly important to the invention is represented by general formula C above. As used herein, an ester group means 0 0 :i II II -CO- or -OC- A phenol carboxylic acid reactant which may be reacted with the epoxy compound has the general formula: HO II S: wherein R 4 and R are as described above. Examples of suitable phenol carboxylic acids include hydroxybenzoic acids, acids where R 5 is alkylene such as phenyl acetic acid, hydroxy phenyl propionic acid, hydroxyphenyl stearic acid, and acids where in R 5 encompasses additional phenol functionality such as 4,4-bis hydroxyphenyl pentanoic acid and the like. In a preferred embodiment of the invention, R 4 in formula A is hydrogen, R 5 is a direct bond, R 6 is hydrogen and R, is

CH

2 OH, a hydrocarbon moiety or an organic moiety containing ester or ether groups and containing from 1 to about 20 carbon atoms, more preferably from about 3 to 20 carbon atoms.

In an important aspect of the invention, the phenolic ester alcohol is the ester reaction product of a hydroxybenzoic acid and an epoxy compound. Suitable hydroxybenzoic acids include ortho-hydroxybenzoic acid (salicylic acid), meta-hydroxybenzoic acid and parahydroxybenzoic acid (PHBA), with para-hydroxybenzoic acid being most preferred.

The epoxy compound may be selected from the group consisting of glycidyl esters, glycidyl alcohols, glycidyl ethers, linear epoxies and aromatic epoxies.

These include glycidol, glycidyl ethers of the structure: CH2- CHCH2OR, glycidyl esters of the structure: o\

CH

2 CHCHCH-OCCR, glycidyl or oxirane compounds having the structure: 20

O

*:R

6

CH-CHCHCOR

and cycloaliphatic epoxy compounds having the structures: 0 o R O1 O fR glycdylor xirne cmpondshavng te srucure -16wherein R 12 is an organic radical having 1-12 carbon atoms which can include ether, ester, hydroxyl or epoxy groups.

Other epoxy materials include epoxidized alphaolefins and bis aromatic epoxies such as the reaction product of bisphenol A or F with epichlorohydrin.

Suitable epoxy compounds particularly include monoepoxides containing a terminal glycidyl group or polyepoxides containing internal oxirane or glycidyl groups or terminal glycidyl groups. Suitable epoxy compounds include glycidyl acrylate or methacrylate monomers, alkyl glycidyl ether monomers, and low molecular weight copolymers of one or more of these 15 monomers with one or more ethylenically unsaturated monomers such as acrylates, methacrylates, vinyl aromatic monomers and the like.

Other suitable epoxy compounds include the ester reaction products of epichlorohydrin with mono- or 20 dibasic aliphatic or aromatic carboxylic acids or anhydrides containing from about 1 to 20 carbon atoms.

Inclusive of such acids are aliphatic acids such as acetic, butyric, isobutyric, lauric, stearic, maleic and myristic acids and aromatic acids such as benzoic, 25 phthalic, isophthalic and terephthalic acids as well as O *the corresponding anhydrides of such acids. Preferred such acids are primary, secondary or tertiary aliphatic carboxylic acids containing from 5 to 13 carbon atoms.

As described above, a very important aspect of the invention is when the epoxy compound is the glycidyl ester of a mixed aliphatic, mostly tertiary, mono carboxylic acid with an average of 9 to 11 carbon atoms such glycidyl ester being available from Exxon Chemical Co., under the trade name GLYDEXX* or from Shell Chemical Co., under the trade name CARDURA® E ester.

These may be represented by the general formula (Glydexx* general formula).

Still other epoxy compounds include glycidyl ether -17reaction products of epichlorohydrin with aliphatic or aromatic alcohols or polyols containing from about 1 to carbon atoms. Suitable alcohols include aromatic alcohols such as bisphenol, bisphenol A, bisphenol F, phenolphthalein and novolac resins; aliphatic alcohols such as ethanol, isopropanol, isobutyl alcohol, hexanol, stearyl alcohol and the like; and aliphatic polyols such as ethylene glycol, propylene glycol and butylene glycol.

Other epoxy compounds which may be used include the mono-epoxides of C9 to C 20 alpha mono-olefins.

The epoxy compound may also comprise epoxidized fatty compounds. Such epoxidized fatty compounds include epoxidized fatty oils, epoxidized fatty acid esters of monohydric alcohols, epoxidized fatty acid esters of polyhydric alcohols, epoxidized fatty nitriles, epoxidized fatty amides, epoxidized fatty amines and epoxidized fatty alcohols. Suitable alicyclic epoxide and polyepoxide materials include dicyclopentadiene diepoxide, limonene diepoxide, and the like. Additional useful epoxides include for example, vinyl cyclohexane dioxide, bis (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane carboxylate and 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4- 25 epoxy) cyclohexane-metadioxane.

In a very important aspect of making the phenolic ester alcohol, the hydroxybenzoic acid/epoxy reaction product may be formed by reacting the hydroxybenzoic acid and the epoxy compound to provide a phenolic ester alcohol with one aliphatic hydroxyl group, optionally in a solvent therefor, at a temperature ranging from about to about 120*C to initiate such reaction. Once the reaction, by heating, it is exothermic, and the reaction temperature can rise to a temperature of about 150* to 175*C usually without application of external heat. The reaction temperature then is maintained at about 150*C to 170*C (and preferably less than about 200*C) until -18the reaction has been determined to be substantially complete.

Reaction products of reduced discoloration can be produced by control of the maximum temperature of the exothermic reaction. This can be achieved by a staged and/or incremental addition of one of the reactants, e.g. the epoxy reactant, so that the reaction temperature is maintained at a temperature of about 150'C or below. The remainder of that reactant may then be added in stages or continuously while maintaining the reaction temperature below about 150*C. This process modification gives rise to reaction products having lower Color Index values.

Approximately stoichiometric quantities of the epoxy 15 compound and the phenol carboxylic acid are used in the reaction, although a slight molar excess of epoxy may be necessary to drive the reaction to completion.

4 The Isocvanate Compound Diisocyanates which may be used as isocyanate compounds in the invention additional to HDI include isophorone diisocyanate (IPDI), tetramethylxylene diisocyanate (TMXDI), and other aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene 25 diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate; cycloalkylene diisocyanates such as 1,3cyclopentane-diisocyanate, 1,4-cyclohexane-diisocyanate and 1,3-cyclohexane-diisocyanate; and aromatic diisocyanates such as m-phenylene diisocyanate, pphenylene diisocyanate, 4,4'-diphenyldiisocyanate, naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-toluene diisocyanate.

The isocyanate compound may have blocked isocyanate groups. Agents which block the isocyanate groups and "deblock" at elevated temperature are known and are used 19 in the invention. These include oxines, lactams, imines, carbamnates such as acetone oxime, methyl ethyl ketoxime, and r--caprolactam.

The polyisocyanates may be dimerized or trimerized diisocyanates such as trimerized HDI or IPDI and triisocyanates such as triphenylmethane-4,4' 4 '-triisocyanate, 1,3 ,5-triisocyanatobenzene, 1,3 ,5-triisocyanatocyclohexane, 2,4 6 -triisocyanatotoluene and o -isocyanatoethyl-2 ,6-diisocyanatocaproate; and tetraisocyanates, such as 4,4 d iphenyldimethylmethane-2 ,5,5 -tetraisocyanate.

They' also may be polymers or copolymers with vinyl monomers of isocyanate functional monomers such as In another aspect of the invention, unblocked or blocked biurets such as the biuret *of hexamethylene diisocyanate (HDI) which biuret has the structure 0 I HH 9- 157

'N=C=

In:\IibcO 1629: MEF and is a trimerized product of hexamethylene diisocyanate and water may be used as polyisocyanates.

In a particularly important aspect of the invention, the polymeric vehicle comprises an isocyanate, biuret, isocyanurate or blends thereof with an -NC=0 functionality of about 3, a phenolic ester alcohol shown in formula C above and a polyester polyol.

The Polvols In The Polymeric Vehicle The polyols which are used in the invention are selected from the group consisting of polyesters, alkyd 15 polymers, acrylic polymers and epoxy polymers. The polyols have a PDI of greater than one and an number average molecular weight of at least about 200, and may generally range from about 200 up to about 30,000, •c more preferably from about 280 up to about 15,000, and most preferably from about 300 up to about 3,000 to 6,000. Glass transition temperatures (Tg) of these e materials may generally range from as low as -90C up to +100'C or higher.

The diester and polyester polyols may be prepared by well known condensation processes using a molar excess of diol. Preferably the molar ratio of diol to dicarboxylic acid is p l:p wherein p represents the number of moles of dicarboxylic acid. The reaction may be conducted in the absence of or presence of a suitable polycondensation catalyst as is known in the art.

Polyesters also can be made from carboxylic acids and oxiranes, such as -21-

RCOOH

0

R

R

RCOOO

OH

R=H, alkyl, aryl Some preferred examples of the diols used to make the polyester polyols are one or more of the following: neopentyl glycol; ethylene glycol; hexamethylenediol; 1,2-cyclohexanedimethanol; 1,3-cyclohexanedimethanol; 1,4-cyclohexanedimethanol; diethylene glycol; triethylene glycol; tetraethylene glycol; dipropylene glycol; polypropylene glycol; hexylene glycol; 2-methyl-2-ethyl-1,3-propanediol; 2ethyl-1,3-hexandediol; 1,5-pentanediol; thiodiglycol; 1,3-propanediol; 1,2-propanediol; 1,2-butanediol; 1,3butanediol; 2,3-butanediol; 1,4-butanediol; 2,2,4trimethyl-1,3-pentanediol; 1,2-cyclohexanediol; 1,3cyclohexanediol; 1,4-cyclohexanediol; neopentyl diol hydroxy methyl isobutyrate, and mixtures thereof.

Examples of polyols include triols such as glycerine, timethylol ethane, trimethylol propane, pentaerythritol and the like.

The diols are reacted with carboxyl groups to make the polyesters. The carboxyl groups may be present in the form of anhydride groups, lactone groups, or equivalent ester forming derivatives such as the acid halide or methyl ester. The dicarboxylic acids or derivatives are preferably one or more of the following: phthalic anhydride, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, adipic acid, succinic -22acid, glutaric acid, fumaric acid, maleic acid, cyclohexane dicarboxylic acid, azelaic acid, sebasic acid, dimer acid, caprolactone, propiolactone, pyromellitic dianhydride, substituted maleic and fumaric acids such as citraconic, chloromaleic, mesaconic, and substituted succinic acids such as aconitic and itaconic, and mixtures thereof. Many commercially available polyesters are produced using a combination of aromatic and aliphatic dicarboxylic acids or a combination of cycloaliphatic and aliphatic dicarboxylic acids or combinations of all three types. However, where polyesters having low viscosity and low solvent content are desired, the most preferred acids used for the purposes of this invention are linear saturated or *15 unsaturated aliphatic dicarboxylic acids having from 2 to 10 carbon atoms such as succinic, glutaric, adipic, and similar materials.

The acrylic polymers which may be used as the polyol component in the present invention are acrylic copolymer resins. The acrylic copolymer resin is prepared from at least one hydroxy-substituted alkyl (meth) acrylate and at least one non-hydroxy-substituted alkyl (meth) acrylate. The hydroxy-substituted alkyl (meth) acrylates which can be employed as monomers 25 comprise members selected from the group consisting of the following esters of acrylic or methacrylic acid and aliphatic glycols: 2-hydroxyethyl acrylate, 3-chloro-2hydroxypropyl acrylate; l-hydroxy-2-acryloxy propane; 2hydroxypropyl acrylate; 3-hydroxy- propylacrylate; 2,3dihydroxypropylacrylate; 3-hydroxybutyl acrylate; 2hydroxybutyl acrylate; 4-hydroxybuty. acrylate; diethyleneglycol acrylate; 5-hydroxypentyl acrylate; 6hydroxyhexyl acrylate; triethyleneglycol acrylate; 7hydroxyheptyl acrylate; l-hydroxy-2-methacryloxy propane; 2-hydroxypropyl methacrylate; 2,2dihydroxypropyl methacrylate; 2-hydroxybutyl methacrylate; 3-hydroxybutyl methacrylate; 2- -23hydroxyethyl methacrylate; 4-hydroxybutylmeth-acrylate; 3,4-dihydroxybutyl methacrylate; methacrylate; and 7-hydroxyheptyl methacrylate. The preferred hydroxy functional monomers for use in preparing the acrylic resins are hydroxy-substituted alkyl (meth) acrylates having a total of 5 to 7 carbon atoms, esters of C 2 to C 3 dihydric alcohols and acrylic or methacrylic acids. Illustrative of particularly suitable hydroxy-substituted alkyl (meth) acrylate monomers are 2-hydroxyethyl methacrylate, 2hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2- 'hydroxypropyl methacrylate, and 2-hydroxypropyl **acrylate.

Among the non-hydroxy-substituted alkyl (meth) 15 acrylate monomers which may be employed are alkyl (meth) acrylates. Preferred nonhydroxy unsaturated monomers are esters of Ci to C 12 monohydric alcohols and acrylic or methacrylic acids, methyl methacrylate, hexyl oo acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, glycidyl methacrylate, etc. Examples of particularly suitable monomers are butyl acrylate, butyl methacrylate o and methyl methacrylate.

Additionally, the acrylic copolymer polyol resins used in the present invention may include in their composition other monomers such as acrylic acid and methacrylic acid, monovinyl aromatic hydrocarbons containing from 8 to 12 carbon atoms (including styrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene and the like), vinyl chloride, vinylidene chloride, acrylonitrile, epoxy-modified acrylics and methacrylonitrile.

The acrylic copolymer polyol preferably has a number average molecular weight not greater than 30,000, more preferably between about 280 and 15,000, and most preferably between about 300 and 5000.

Alkyd polymers may be used as the polyol component of this invention. These alkyd resins -24usually have a number average molecular weight in the range of from about 500 to about 20,000, are oil modified polyester resins and are broadly the product of the reaction of a dihydric alcohol and.a dicarboxylic acid or acid derivative and an oil, fat or carboxylic acid derived from such oil or fat which acts as a modifier. Such modifiers are drying oils, semi-drying oils or non-drying oils. The polyhydric alcohol employed is suitably an aliphatic alcohol, and mixtures of the alcohols also may be employed. The dicarboxylic acid, or corresponding anhydrides, may be selected from a variety of aliphatic carboxylic acids or mixtures of aliphatic and aromatic dicarboxylic acids. Suitable acids and acid anhydrides include, by way of example, 15 succinic acid, adipic acid, phthalic anhydride, isophthalic acid, trimellitic acid (anhydride) and bis 4,4'-benzophenone tetracarboxylic anhydride.

Mixtures of these acids and anhydrides may be employed to produce a balance of properties. As the drying oil 20 or fatty acid there is suitably employed a saturated or Sunsaturated fatty acid of 12 to 22 carbon atoms or a corresponding triglyceride, that is, a corresponding fat or oil, such as those contained in animal or vegetable fats or oils. Suitable fats and oils include tall oil, 25 castor oil, coconut oil, lard, linseed oil, palm oil, peanut oil, rapeseed oil, soybean oil and beef tallow.

Such fats and oils comprise mixed triglycerides of such fatty acids as caprylic, capric, lauric, myristic, palmitic, and stearic and such unsaturated fatty acids as oleic, eracic, ricinoleic, linoleic and linolenic.

Chemically, these fats and oils are usually mixtures of two or more members of the class. Alkyd resins made with saturated monocarboxylic acids and fats are preferable where improved weather resistance is of prime concern.

Epoxy polymers having a number average molecular weight in the range of from about 500 to about 6,000 may be used as the polyol component of this invention.

A well-known epoxy resin which may be used in the invention is made by condensing epichlorohydrin with bisphenol A, diphenylol propane. An excess of epichlorohydrin is used, to leave epoxy groups on each end of the low-molecular weight polymer: CH c- cHo *o OH 0 c- C--CHCH -0 OCCHCH,--- OCHCH-CH, The viscosity of the polymer is a function of molecular weight, the higher the molecular weight the w.el". more viscous the polymer.

Other hydroxyl-containing compounds, including resorcinol, hydroquinone, glycols, and glycerol may be used in lieu of bisphenol A.

The Amino Resins Methylol (alkoxymethyl) amino crosslinking agents are suitable for use in the present invention and are well known commercial products, and are generally made by the reaction of di (poly) amide (amine) compounds with formaldehyde and, optionally, a lower alcohol. The amino resins have from about 3 to about 30 crosslinking groups per molecule.

Examples of suitable amino-crosslinking resins include one or a mixture of the following materials.

-26- Melamine based resins

(ROCH

2 2 N -C N(CH 2 0R) 2 N(CH 2

OR)

2 wherein R is the following: R CH 3 (Cymel)O 300, 301, 303); R CH 3 CAH (Cymels 1116) R CH 3 CAH (CymelO 1130, 1133); .R C 4

H

9 (CymelO 1156) or R CH 3 H (CymelO 370, 373, 380, 385).

4.The preferred melamiine is hexamethoxymethyl melamine.

Benzoquanamine based resins

N

(ROCH 2 2 N CN

(CH

2

OR)

2 .440 wherein R4 HH(etem6,Bel~ CA CH 3 80H) .C l 12) Gycoluryl based resins -27-

ROCH

2

CH

2

OR

I I o c c= N N

ROCH

2 CH 2

OR

wherein: R CH 3

C

2

H

5 (Cymel 1171); or R C 4

H

9 (Cymel e 1170).

The amino resin may be a liquid or solid. In the :aspect the invention where VOCs are being minimized, if the amino resin is a solid, that solid is soluble in such blend of the polymeric vehicle and the viscosity of the formulated coating composition and polymeric vehicle should not exceed the ranges described herein. When the amino resin is a liquid, it preferably has a viscosity of less than about 3.0 Pa.s at about 25'C. A highly alkylated hexamethoxy-methylmelamine (HMMM) resin with following general formula is a very suitable crosslinker:

N(CHOCH)

2

(CHCH

2 2 N N N(CH 2

OCH

The latter HMMM resin appears to be a waxy solid under most conditions with a melting point in the range of about 30"C and is sold by Cytec Chemical Company under the name Cymel 300. A similar crosslinker which is a melamine resin which can be used in the invention is a highly monomeric, highly methylolated hexamethylolated -28melamine formaldehyde resin which appears to be a solid under most conditions at 25*C and is sold by Monsanto Chemical Company under the designation HM-2612.

Solvents And Optional Ingredients In the Polymeric Vehicle There are different aspects of the invention which include a polymeric vehicle effective for providing a formulated coating composition which is without any added organic solvent or at least does not have more than about 3 weight percent organic solvent, a polymeric vehicle which is effective for providing a high solids, low VOC formulated coating composition and a waterthinned formulated coating composition. Suitable optional solvents which may be included in the curable compositions of the invention comprise toluene, xylene, ethylbenzene, tetralin, naphthalene, and solvents which are narrow cut aromatic solvents comprising C, to C 13 aromatics such as those marketed by Exxon Chemical 20 Company under the name Aromatic 100, Aromatic 150, and Aromatic 200.

Other suitable solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl heptyl ketone, isophorone, isopropanol, n-butanol, sec.-butanol, isobutanol, amyl alcohol, isoamyl alcohol, hexanols, and heptanols.

Additional suitable oxygenated solvents include propylene glycol monomethyl ether acetate, propylene 3Q glycol propyl ether acetate, ethyl ethoxypropionate, dipropylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and like materials. Other such solvents include alkyl esters such as ethyl acetate, npropyl acetate, butyl acetate, amyl acetate, mixtures of hexyl acetates such as sold by Exxon Chemical Company under the name EXXATE9 600 and mixtures of heptyl acetates sold under the name EXXATE® 700. The list -29should not be considered as limiting, but rather as examples of solvents which are useful in the present invention. The type and concentration of solvents are generally selected to obtain formulation viscosities and evaporation rates suitable for the application and baking of the coatings.

Suitable pigments which may be included in the compositions of this invention are those opacifying pigments normally used in paint and coating formulations and include titanium dioxide, zirconium oxide, zircon, zinc oxide, iron oxides, antimony oxide, carbon black, as well as chrome yellows, greens, oranges, mixed metal oxides, ceramic pigments and the like. Preferred pigments include rutile Ti02 and particularly weather- 15 resistant coated types of TiO 2 The pigments may also be blended with a suitable extender material which does not contribute significantly to hiding power. Suitable extenders include silica, barytes, calcium sulfate, magnesium silicate (talc), aluminum oxide, aluminum 20 hydroxide, aluminum silicate, calcium silicate, calcium carbonate (mica), potassium aluminum silicate and other clays or clay-like materials.

Satisfactory baking schedules such as 38°C to 150*C for formulations of the present invention vary widely including, but not limited to, low temperature bakes of about 20 to 30 minutes at temperatures between 90°C and 105"C for large equipment applications and high temperature bakes of about 5 to 10 seconds in 300*C to 375"C air for coil coating applications. In an important aspect, the polymeric vehicles may be cured at about 25*C when the crosslinker is an isocyanate and the melamine is not relied upon to crosslink. In general, the substrate and coating should be baked at a sufficiently high temperature for a sufficiently long time so that essentially all solvents are evaporated from the film and chemical reactions between the polymer and the crosslinking agent proceed to the desired degree of completion. The desired degree of completion also varies widely and depends on the particular combination of cured film properties required for a given application. Further, catalyzed crosslinking also may be effected at ambient temperatures using many isocyanate-type crosslinkers.

Acid catalysts may be used to cure systems containing hexamethoxymethyl melamine and other amino crosslinking agents, and a variety of suitable acid catalysts are known to one skilled in the art for this purpose. These include, for example, p-toluene sulfonic acid, methane sulfonic acid, nonylbenzene sulfonic acid, dinonylnapthalene disulfonic acid, dodecylbenzene sulfonic acid, phosphoric acid, phosphorous acid, phenyl acid phosphate, butyl phosphate, butyl maleate, and the S"like or a compatible mixture of them. These acid catalysts may be used in their neat, unblocked form or combined with suitable blocking agents such as amines.

Typical examples of unblocked catalysts are the King Industries, Inc., products with the tradename K-CURE®.

Examples of blocked catalysts are the King Industries, Inc., products with the tradename NACURE®.

Catalysts for isocyanates include soluble tin salts such as dibutyltin dilaurate and dibutyltin diacetate, divalent zinc salts such as zinc diacetate, and tertiary bases including tertiary amines, such as diazabicyclooctane.

The amount of catalyst employed typically varies inversely with the severity of the baking schedule. In particular, smaller concentrations of catalysts are usually required for higher baking temperatures or longer baking times. Typical catalyst concentrations for moderate baking conditions (15 to 30 minutes at 150*C) would be about 0.01 to 0.2 wt% catalyst solids per polymer plus crosslinking agent solids. Higher concentrations of catalyst up to about 5 wt% may be employed for cures at lower temperature or shorter -31times. Formulations containing sufficient residual esterification catalyst, such as phosphorous acid, may not require the inclusion of any additional crosslinking catalyst to effect a proper cure at lower curing temperatures.

The following examples set forth compositions according to the invention and how to practice the invention.

EXAMPLE I Synthesis of the Phenolic Ester Alcohol from a Glycidyl Ester and PHBA Into a 1 liter flask equipped with agitation, nitrogen, heating and temperature probe, 326.6g Glydexx* 15 N-10 glycidyl ester and 173.4g parahydroxy benzoic (PHBA) were charged. The mixture was heated at 110C.

At that point, an exothermic reaction takes place. The maximum temperature reached was 160*C. The solution was then cooled and discharged. Physical properties are 20 given below.

oo o*oo o oooo Acid Number

NVM

Color 0 mg KOH/gram 99% <3 Gardner EXAMPLE II a. Ingredients BYK*301 302 Desmodur N3300 Flow control agent from Byk- Chemie.

From Miles Corporation is a cyclo-trimer of 1,6hexamethylene diisocyanate (isocyanurate of 1,6hexamethylene diisocyanate, HDI). Its viscosity is 1.8 4 mPa.s at 25'C, and its equivalent weight is 194.

-32- DNNDSA Catalyst Dinonyl naphthalene disulfonic acid in isobutanol is obtained from King Industries ("Nacure-155").

Cymel 300 An HMMM resin sold by Cytec Chemical Company having the formula:

N

S(CHOCH2 N( N(CHCH *.9 10 S: The latter HMMM resin appears to be a waxy solid under most conditions with a melting point 15 in the range of about DBTL Dibutyltin dilaurate catalyst b. Coatings 20 An oligoester diol was made from 1,4-butanediol and a 50/50 (mol/mol) mixture of dimethyl glutarate and dimethyl adipate. The following formulations using the latter oligoesterdiol (Mn 329), hardener, a phenolic ester alcohol as described in Example I (PHEA), the isocyanate Desmodur N3300 and melamine-formaldehyde resin, Cymel 300 were prepared in order to prepare formulations that have little or no sagging. The aliphatic-OH groups of the PHEA appear to react with the isocyanate groups at ambient or mildly elevated temperatures in the presence of the tin catalyst DBTDL, whereas the phenolic -OH group of the PHEA will condense with Cymel 300, the melamine resin at higher temperatures.

The PHEA was dissolved in the oligoesterdiol 0 .0 0.

.0.

o.* 33 followed by Cymel 300 at room temperature. To this solution, DNNDSA, melam-ine catalyst, and BYK-302 were added and the formulation was uniformly mixed. After this, Desmodur N3300 was added and mixed the formulation uniformly. Finally, a solution of dibutyltin dilaurate (DBTDL) in oligoesterdiol (9.O7wt. was added. Low amounts of DBTDL catalyst was added to allow the urethane formulation at slow enough rate for the coating applications. The acid catalyst DNNDSA allows the phenol to condense with the melamine resin.

These formulations were coated on phosphated steel panels using drawdown bar #26 and the coated panels were baked at the specified temperature. In Table 1, the effect of io varying amounts of the tin catalyst towards formulation was studied.

Table 1 Experiment 1 11 111 K V Oligoesterdiol 1.02g 1.0lg 1.02g 1.0og 1.05g (Mn 329) PHEA 1.05g 1.Olg 1.03g 1.04g 1.06g Desmodur N3300 2.02g 1.72g 1.73g 1.74g 1.73g Cymel 300 0.37g 0.37g 0.40g 0.38g O0.38g DBTDL soln. 0.2g O.Olg 0.02g 0.08g 0.02g DNNDSA 0.Olg O.Olg O.Oig O.Oig 0.03g BYK-302 0.03g 0.02g 0.02g 0.02g 0.02g Baking Formulation 300 0 F/ 300 0 F/ Formulation 300 0

F/

Conditions gelled right 30 min. 30 min. gelled right 30 min.

away away Appearance of Clear, less Clear, less Clear, less the panels uniform uniform uniform NVW (149-C, 95.96 95.74 96.11 1 Adhesion 5B 5B Pencil F F-H F-H Impact Resist. 160 160 160 Eiirect (1 b/in)[J] [181] [1 []Li8J] jn:\Iibcj01629:MEF Experiment I II III IV V Impact Resist. 160 160 -160 Reverse (lb-in)[J] [18J] [18J] [18J] MEK dbl. rub 200 200 -200 Resistance Desmodur N3300 was used to completely react with the aliphatic -OH groups of the diol and also that of PHEA. The amount of Cymel 300 used is 2X the phenol -OH equivalent.

Two sets of panels were baked for each formulation: one with the panels upright to study the effect of sagging and the other horizontal for comparison.

The data in Table 1 suggest a DBTDL catalyst solution concentration of -0.02wt. lo or less gives sufficient time for coating panels.

i" The thicknesses of these panels were measured at the top, middle and bottom at the left, center and right sides of the panels to determine whether any sagging has occurred.

The data are listed in Tables 2 and 3.

[n:\libc]01629:MEF of Films(um for Panels Bakdrl Vert+ic-ll Table 2. Thickness .o o Experiment II III

IV

L M R L M R L M R Top 25.4 35.6 25.4 25.4 25.4 20.3 33.0 25.4 27.9 Middle 30.5 25.4 22.9 30.5 15.2 25.4 30.5 25.4 25.4 Bottom 20.3 27.9 35.6 30.5 22.9 30.5 27.9 17.8 20.3 L= Left; M Middle; R Right Table 3. Thickness of Films (um)for Panels Baked Horizontally Experiment II III

IV

L M R L M R L M R Top 20.3 30.5 30.5 30.5 25.4 27.9 25.4 53.3 76.2 Middle 25.4 25.4 22.9 30.5 20.3 25.4 33.0 40.6 48.3 Bottom 27.9 30.5 30.5 0.8 15.2 30.5 20.3 33.0 45.7 The film thickness data suggests that little or no sagging has occurred.

c. Acetone Thinned Coating Compositions The formulations of II-b were quite viscous for coating applications. In the following formulations, acetone was added to decrease the viscosity of the formulations and thereby improve the flow characteristics.

PHEA was dissolved in the oligoesterdiol followed by Cymel 300 at room o1 temperature. To this solution, DNNDSA, BYK-302 and acetone were added and the formulation was uniformly mixed. After this, Desmodur N3300 was added and mixed the formulation uniformly. Finally, a solution of dibutyltin dilaurate (DBTDL) in oligoesterdiol RS93 (9.07wt.%) was added. The acid catalyst DNNDSA allows the phenol to condense with the melamine resin.

In:\libc]01629:MEF These formulations were coated on phosphated steel panels using drawdown bar #26 and the coated panels were baked at the specified temperature. In Table 4, varying amounts of the acetone was added in the formulations.

Experiment VI VII Vill Ix X Oligoesterdiol 1.02g 1.03g 1.03g 1.03g 1.02g (Mn 329 PHEA 1.03g 1.03g 1.03g 1.03g 1.02g Desmodur N3300 1. 74g 1.72g 1.75g 1.76g 1.78g Cymel 300 0.37g 0.38g 0.40g 0.36g 0.38g DBTDL soln. 0.02g 0.Olg 0.02g O.Olg 0.02g DNNDSA 0.Olg 0.Olg O.Olg 0.Olg O.Olg BYK-302 0.02g 0.Olg 0.Olg 0.Olg 0.05g Acetone 0.21g 0.42g 0.30 g 0.50 g 0.21 (9.l3wt. (6.58wt. (10.64wt. (4.66wt. Baking 149 0 C/ 149 0 C/ 149 0 C/ 149 0 C/ 149 0

C/

Conditionst 30mmn. 30min. 30mmn. 30mmn. Appearance of Clear, less Clear, less Clear, less Clear, less Clear, less the panels uniform uniform uniform uniform uniform NVW t 95.93 98.40 97.31 99.9 99.31 (149-C, lh, Adhesion 5B 5B SB 5B SB Pencil F F F F F Impact Resist. 160 160 160 160 160 Direct (lb/in) [18] [181 [18] [18] [18] Impact Resist. 160 160 160 160 160 Reverse (lb-in) [18] [18] [18] [18] [18] [.11 1 MEK db 1. rub 200 200 200 200 200 Resistance Desmodur N3300 was taken to completely react with the aliphatic -OH groups of 300 taken is 2X the phenol the diol and also that of PHEA.

OH equivalent.

The amount of Cymel Two sets of panels were baked for each formulation: one with the panels upright to study the effect of sagging and the other horizontal for [n:\Iibc]01629:MEF comparison.

The NVW was calculated without considering the acetone content. Some acetone might have already evaporated during the formulation thereby causing higher NVW values.

The thicknesses of these panels were measured at the top, middle and bottom at the left, center and right sides of the panels to determine whether any sagging has occurred.

The data is listed in Tables 5 and 6.

Table 5. Thickness of Films (im)for Panels Baked Vertically Experiment VI VII VIII L M R L M R L M R Top 15.2 30.5 35.6 22.9 25.4 25.4 22.9 27.9 25.4 Middle 15.2 25.4 30.5 20.3 22.9 27.9 15.2 27.9 27.9 Bottom 20.3 30.5 27.9 12.7 22.9 30.5 12.7 22.9 30.5 Experiment IX X L M R L M R Top 15.2 30.5 25.4 25.4 25.4 15.2 Middle 15.2 25.4 20.3 25.4 25.4 15.2 Bottom 17.8 30.5 40.6 45.7 27.9 15.2 o Table 6. Thickness of Films(tm)for Panels Baked Horizontally Experiment VI VII VIII L M R L M R L M R Top 25.4 25.4 25.4 25.4 25.4 27.9 25.4 27.9 30.5 Middle 25.4 20.3 25.4 25.4 27.9 27.9 22.9 27.9 25.4 Bottom 17.8 25.4 30.5 30.5 30.5 22.9 25.4 25.4 30.5 Experiment IX X L M R L M R Top 15.2 35.6 30.5 15.2 17.8 27.9 Middle 17.8 20.3 30.5 15.2 27.9 27.9 Bottorn 20.3 35.6 25.4 27.9 25.4 27.9 [n:\libc]01629:MEF a.

a.

The flow pattern of these formulations were similar to the previous set of experiments suggesting that some acetone might have evaporated during the formulation and coating process.

The viscosity of the formulation VI (with 4.75% acetone) was studied and the results are shown below.

Table 7. Formulation Data Oligoesterdiol 3.05 g (Mn 329) PHEA 3.01g Desmodur N3300 5.13 g Cymel 300 1.11 g Acetone 0.63 g This formulation had limited stability at 25 0 C even without the catalysts and therefore no catalysts were added. The viscosity vs. Time data is listed in Table 8.

Table 8. Viscosity vs. Time Data, Time (min) Viscosity Time (min) Viscosity (mPa.s) (mPa.s) 2 875 26 1285 4 890 28 1325 6 908 30 1375 7 920 32 1420 8 935 34 1455 9 950 36 1510 10 970 38 1545 a a. In:\libc]01629:MEF -39- Time (min) Viscosity Time (min) Viscosity (mPa.s) (mPa.s) 11 990 40 1600 12 1010 44 1685 13 1030 46 1730 14 1040 47 1765 1060 48 1790 16 1075 50 1825 17 1090 52 1870 18 1110 54 1915 19 1135 56 1965 20 1160 58 2010 22 1195 60 2080 24 1250 62 2115 These data indicate a pot life of about minutes for this coating composition using the criterion that the pot life is the time in which viscosity will double.

a..

go o oo *ooo oo o a. a.

a a a a

Claims (25)

1. A polymeric vehicle comprising: at least about 5 weight percent, based upon the weight of the polymeric vehicle, of an isocyanate compound having an average isocyanate functionality of from about 1.9 to about 20 isocyanate groups per molecule; at least about 15 weight percent, based upon the weight of the polymeric vehicle, of a polyol having a polydispersity index greater than one; and at least about 5 weight percent, based upon the weight of the polymeric vehicle, of a phenolic ester alcohol having at least one phenolic hydroxyl group and at least one aliphatic hydroxyl group, the isocyanate compound being reactive with the phenolic ester alcohol and polyol.

2. The polymeric vehicle according to claim 1, wherein the phenolic ester alcohol has at least two ester groups and has the general formula R67 R4 0 R 6 -R 7 15 OH wherein R 4 is selected from the group consisting of hydrogen, halogen, hydroxyl, C 1 to C 8 alkyl and C 1 to C 8 alkoxy, R 5 is selected from the group consisting of a direct bond, CI to C 20 organic radical having only carbon and hydrogen atoms, and a C 1 to C 2 0 organic radical which includes in its structure a substitution group selected from the group S 20 consisting of phenol, aliphatic hydroxyl, ester, ether, carbonate and combinations thereof, wherein R 6 is selected from the group consisting of hydrogen, a C 1 to C 20 organic radical, a C 1 to C 20 organic radical which includes in its structure at least one ester linkage or a direct bond which forms with R 7 part of a 5 or 6 carbon atom cyclic ring structure, wherein R 7 is CH 2 R 8 wherein Rg is selected from the group consisting of hydroxy, OR 9 OC(O)Ro 0 and R 11 wherein R 9 is selected from the group consisting of a primary or secondary aliphatic group containing 3 to 20 carbon atoms, an aromatic group containing 6 to carbon atoms, a primary aliphatic group containing 3 to 20 carbon atoms which includes at least one ester linkage and a secondary aliphatic group containing 3 to 20 carbon atoms which includes at least one ester linkage, [I:\DAYLIB\libz]05606.doc:lam wherein Rio is selected from the group consisting of a primary aliphatic group containing 4 to 20 carbon atoms, a secondary aliphatic group containing 4 to 20 carbon atoms, a tertiary aliphatic group containing 4 to 20 carbon atoms, an aromatic group containing 6 to 20 carbon atoms, and combinations thereof, wherein the primary, secondary and tertiary aliphatic groups include at least one ester linkage; and wherein R 1 1 is selected from the group consisting of a C 2 to C 20 organic radical, a C 2 to C 20 organic radical which includes in its structure at least one ester linkage, a C 2 to C 2 0 organic radical which forms with R 6 part of a 5 or 6 carbon atom cyclic ring structure, and combinations thereof.

3. A polymeric vehicle according to claim 2, wherein R 5 includes an ester group.

4. A polymeric vehicle according to claim 2 or claim 3 wherein R 8 includes an ester group.

5. The polymeric vehicle according to any one of claims 1-4, wherein the 15 phenolic ester alcohol has a molecular weight in the range of from about 110 to about 1000 and is the reaction product of a hydroxybenzoic acid and a monoglycidyl compound having a terminal glycidyl group.

6. The polymeric vehicle according to claim 5 wherein the hydroxybenzoic acid is parahydroxybenzoic acid and the monoglycidyl compound has the 20 formula 0 II CH 2 -CHCH 2 -OCC(R) 3 where R represents a mixture of aliphatic groups, the three R groups having a total of 8 carbon atoms.

7. The polymeric vehicle according to claim 2 wherein the polymeric vehicle comprises from about 5 to about 40 weight percent isocyanate compound, based on the weight of the polymeric vehicle, from about 15 to about 75 weight percent polyol, based on the weight of the polymeric vehicle, and from about 5 to about 70 weight percent phenolic ester alcohol, based on the weight of the polymeric vehicle.

8. The polymeric vehicle according to any one of claims 1-7 wherein the phenolic ester alcohol has the general formula O R 6 HO -R 5 -COCH-CH-R 7 R4 OH 42

9. The polymeric vehicle according to claim 8, wherein the phenolic ester alcohol has the general formula: O O O)CH HO HO HC 6 H 1 3 A polymeric vehicle according to any one of claims 1-9, wherein the phenolic ester alcohol, isocyanate compound and polyol have molecular weights effective for providing the polymeric vehicle with a viscosity in the range of from about 0.1 to about 20 Pa.s at about 20'C to about 60'C at a shear rate of at least about 1000 sec 1 in the absence of organic solvent.

11. A polymeric vehicle according to claim 10, wherein the isocyanate icompound, polyol and phenolic ester alcohol each have molecular weights in an amount effective for and are each in relative amounts effective to provide a formulated coating composition having less than about 0.42Kg of VOC per litre of formulated coating 5 composition.

12. A polymeric vehicle according to any one of claims 1-11, wherein the polyol is selected from the group consisting of a polyester, alkyd polymer and mixtures thereof.

13. The polymeric vehicle according to any one of claims 1-12, wherein the isocyanate compound has an average isocyanate functionality of from about 2 to about 3.

14. The polymeric vehicle according to any one of claims 1-11, wherein the polyol is selected from the group consisting of a polyester polymer, an acrylic polymer, an alkyd polymer, and epoxy polymer and mixtures thereof. The polymeric vehicle according to claim 14, wherein the polyol is a polyester polymer having a number average molecular weight in the range of from about 280 to about 30,000.

16. The polymeric vehicle according to claim 14, wherein the polyol is an acrylic polymer having a number average molecular weight in the range of from about 300 to about 5,000.

17. The polymeric vehicle according to claim 14, wherein the polyol is an alkyd polymer having a number average molecular weight in the range of from about 500 to about 20,000. 43

18. A polymeric vehicle comprising: at least about 5 weight percent, based upon the weight of the polymeric vehicle, of an isocyanate compound having an average isocyanate functionality of from about 1.9 to about 20 isocyanate groups per molecule; at least about 15 weight percent, based upon the weight of the polymeric vehicle, s of a polyol having a polydispersity index greater than one and the polyol being selected from the group consisting of a polyester polymer, an acrylic polymer, an alkyd polymer, an epoxy polymer and mixtures thereof; and at least about 5 weight percent, based upon the weight of the polymeric vehicle, of a phenolic ester alcohol having at least one phenolic hydroxyl group, and at least one aliphatic hydroxyl group, the isocyanate compound being reactive with the phenolic ester alcohol and polyol, and wherein the phenolic ester alcohol has at least two ester groups and has the general formula HO R6 )/----RS-COCH-CH-R7 R4 I 15 OH *0 wherein R 4 is selected from the group consisting of hydrogen, halogen, hydroxyl, CI to C 8 alkyl and Ci to C 8 alkoxy, *eo0 R 5 is selected from the group consisting of a direct bond, C, to C 20 organic 20 radical having only carbon and hydrogen atoms, and a C 1 to C 20 organic radical which includes in its structure a substitution group selected from the group consisting of phenol, o" aliphatic hydroxyl, ester, ether, carbonate and combinations thereof, wherein R 6 is selected from the group consisting of hydrogen, a Ci to C 20 organic radical, a Ci to C 20 organic radical which includes in its structure at least one ester linkage or a direct bond which forms with R 7 part of a 5 or 6 carbon atom cyclic ring structure, wherein R 7 is CH 2 R 8 wherein R 8 is selected from the group consisting of hydroxy, OR 9 OC(O)Rio and RI 1 wherein R 9 is selected from the group consisting of a primary or secondary aliphatic group containing 3 to 20 carbon atoms, an aromatic group containing 6 to 20 carbon atoms, a primary aliphatic group containing 3 to 20 carbon atoms which includes at least one ester linkage and a secondary aliphatic group containing 3 to 20 carbon atoms which includes at least one ester linkage, wherein Rio is selected from the group consisting of a primary aliphatic group containing 4 to 20 carbon atoms, a secondary aliphatic group containing 4 to 20 carbon 44 atoms, a tertiary aliphatic group containing 4 to 20 carbon atoms, an aromatic group containing 6 to 20 carbon atoms, and combinations thereof, wherein the primary, secondary and tertiary aliphatic groups include at least one ester linkage; and wherein R, 1 is selected from the group consisting of a C 2 to C 20 organic radical, a C 2 to C 20 organic radical which includes in its structure at least one ester linkage, a C 2 to C 20 organic radical which forms with R 6 part of a 5 or 6 carbon atom cyclic ring structure, and combinations thereof.

19. A polymeric vehicle according to claim 18 wherein the phenolic ester alcohol has the general formula 0 R 6 I1 I HO R 5 -COCH-CH-R 7 SOH R4 The polymeric vehicle according to claim 19 wherein the polymeric vehicle comprises from about 5 to about 40 weight percent isocyanate compound, based on the weight of the polymeric vehicle, from about 15 to about 75 weight percent polyol, 5 based on the weight of the polymeric vehicle, and from about 5 to about 70 weight opercent phenolic ester alcohol, based on the weight of the polymeric vehicle.

21. The polymeric vehicle according to any one of claims 18, 19 or wherein the isocyanate compound has an average isocyanate functionality of from about 2 to about 3. 20

22. The polymeric vehicle according to any one of claims 18, 19 or wherein the polyol is a polyester polymer having a number average molecular weight in -the range of from about 280 to about 30,000.

23. The polymeric vehicle according to any one of claims 18, 19 or wherein the polyol is an acrylic polymer having a number average molecular weight in the range of from about 300 to about 5,000.

24. The polymeric vehicle according to any one of claims 18, 19 or wherein the polyol is an alkyd polymer having a number average molecular weight in the range of from about 500 to about 20,000. The polymeric vehicle according to claim 21, wherein the polyol is a polyester polymer having a number average molecular weight in the range of from about 280 to about 30,000. .doc:lam

26. The polymeric vehicle according to claim 21, wherein the polyol is an acrylic polymer having a number average molecular weight in the range of from about 300 to about 5,000.

27. The polymeric vehicle according to claim 21, wherein the polyol is an alkyd polymer having a number average molecular weight in the range of from about 500 to about 20,000.

28. A polymeric vehicle according to claim 1, substantially as hereinbefore described with reference to any one of the Examples.

29. A process for the preparation of a polymeric vehicle according to claim 1, which process is substantially as hereinbefore described with reference to any one of the Examples. Dated 29 November, 2001 Exxon Chemical Company Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON *4 i.doc:lam