AU736624B2 - Coating composition comprising aldimine and isocyanate and processes for their preparation - Google Patents

Description

P/00/0011 Regulation 3.2

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

Name of Applicant: Actual Inventor: Address for service in Australia: Invention Title: BASF CORPORATION See Attached List CARTER SMITH BEADLE 2 Railway Parade Camberwell Victoria 3124 Australia COATING COMPOSITIONS COMPRISING ALDIMINE AND ISOCYANATE AND PROCESSES FOR THEIR

PREPARATION

The following statement is a full description of this invention, including the best method of performing it known to us COATING COMPOSITIONS COMPRISING ALDIMINE AND ISOCYANATE AND PROCESSES FOR THEIR PREPARATION BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to new coating compositions based on aldimines and isocyanates. The invention also teaches the dispersion of pigments in aldimines and its utility in coatings. It also relates to a method for processing dispersions of pigments in aldimines to achieve improved coating properties. It further relates to coating compositions containing novel aldimines.

2. Description of the Prior Art Polyurethane coatings prepared from the reaction of isocyanate functional resins with hydroxyl functional polyol resins is well known in the art. These coatings are known for a number of outstanding properties including high durability and chemical resistance. Their high glamour properties make them particularly suitable for automotive and industrial applications. With these coatings however, the polyol component contributes the majority of the bulk viscosity of the coating due to hydrogen bonding and the molecular weight of the polymeric backbone, restricting the freedom of the formulator to incorporate other materials and meet application solids specifications. Decreasing the molecular weight of the polyol eventually leads to slow network building unless there is significant energy input.

The properties of higher solids polyol containing polyurethane coatings can be improved by using reactive diluents. The best use of this technology has been demonstrated by U.S. Patent No. 5,214,086 Mormile et al. (assigned to BASF Corp.). In it are disclosed the uses of dialdimines, diketimines and hindered diamines to modify polyol compositions, resulting in a reduction of the overall reaction viscosities of the mixtures while maintaining and most often improving on the network building and overall physical properties. In these compositions, there is a reduced but still present contribution to viscosity from the polyol.

SEfforts to further decrease viscosities of polyurethane coatings by totally replacing hydroxyl bearing resins has led to work in several areas. One area of activity has been with acetoacetate bearing resins. The acetoacetate group does lend itself to lower viscosities due to reduced hydrogen bonding, but reaction with isocyanates is sluggish and some hydroxyl functionality is usually required. Another area of activity has focused on active hydrogen, amino compounds. One class of these compounds are primary and secondary amines.

DVG:JMD:#29501 6 October 1998 'd C, -3- Because of their high reactivity with isocyanates, primary and most secondary amine compounds are not useful in applications such as automotive refinish and general industrial where the components are routinely mixed in bulk prior to film application. Additionally, ambient temperature cure is predominantly used and force cure temperatures seldom exceed 75 0 C when employed. This precludes the use of heat activated, blocked isocyanates.

Secondary amines have longer usable times than primary amines, but still have short pot times in relationship to set times. Advancements have been made to reduce the reactivity of secondary amines. The best example of this is described in U.S. Patent No. 5,243,012 whereby hindering groups on the amine and incorporation of organotin compounds are used.

These compositions, though fine for final properties, do not have the pot time/set time relationship one is accustomed to in the automotive refinish and general industrial field.

Another class of active hydrogen, amino compounds are masked primary amines such as aldimines, ketimines and oxazolidines. Oxazolidines have limited utility as sole reaction partners with isocyanates because of generally slow setting film properties. Ketimines, as sole reaction partners with isocyanates, have a relatively good pot time/set time relationship.

Aldimines are of great interest as reaction partners with isocyanates because they can be made to possess low viscosity and colour, they give high yields with isocyanates in nonvolatile stoving tests and they can have a very good pot time/set time relationship. However, unlike the other aforementioned compounds, many aldimine compounds have the drawback 20 of possessing limited compatibility with traditional aliphatic polyisocyanates such as biurets and isocyanurates. It has been well established in the moisture cure coatings field that isocyanate functional polyurethane prepolymers can be formulated to be compatible with aldimine compounds. U.S. Patents 4,469,831 Bueltjer et al., 4,720,535 Schleier et al., and 4,853,454 Merger et al. (all assigned to BASF AG), all describe compositions of aldimine 25 functional resins and isocyanate functional prepolymers where the rate of reaction can optionally be accelerated by incorporation of acid catalysts. However, the prepolymer now is a major contributor to viscosity and again formulation latitude is restricted.

It has now surprisingly been found, in combinations of aldimines and isocyanates where the isocyanate is composed of uretdione diisocyanates, that compatible mixtures of very low viscosity are formed permitting the coatings formulator full latitude in other compounds he may use. Furthermore, even more surprising, ambient-cured coatings made from aldimines with functionalities as low as two and uretdione diisocyanate containing isocyanate combinations are very fast for property development on application and provide DVG:JMD:#29501 6 October 1998 for very long pot times.

U.S. Patent No. 5,098,983 describes polyisocyanate mixtures having (cyclo)aliphatically bound isocyanate groups, (cyclo)aliphatically bound uretdione groups and chemically incorporated carboxyl groups, processes for the production of these isocyanates and their use, optionally after at least partial neutralization with tertiary amines, as binders for coating compositions which maybe crosslinked under the effect of moisture and/or heat and as reactants for compounds containing isocyanate and/or carboxyl reactive groups in the production of high molecular weight plastics. The utility of aldimines as reaction partners with the uretdione structure is not revealed.

U.S. Patent No. 4,522,975 describes NCO-terminated uretdione group-containing polyurethane prepolymers prepared by reacting a uretdione group containing organic polyisocyanate with an isocyanate reactive hydrogen atom-containing compound, employing a select equivalent ratio of NCO to OH ranging from about 1.5/1 to about 2/1. The polyurethane prepolymers are useful in the preparation of lignocellulosic composite materials, such as particle board, and in making coatings. The utility of aldimines as reaction partners with the uretdione structure is not revealed.

It has also surprisingly been found a method for processing dispersions of pigments in aldimines to achieve improved coating properties. U.S. Patents 4,720,535, 4,469,831 refers to non-hydroxyl containing coating compositions which includes aldimine or polyaldimine.

20 U.S. Patent No. 5,214,086 describes coating compositions comprising at least one hydroxy functional resin, at least one isocyanate functional resin and a aldimine or ketimine.

U.S. Patent No. 5,288,804 describes acetoacetate aromatic aldimine resin compositions. U.S. Patent No. 5,288,802 describes an automotive refinish primer surfaces containing acetoacetate functional polyesterpolyol, a polyacrylate, and an amine functional 25 epoxy resin. None of these patents, however, teaches or illustrates the dispersion of pigments in aldimines.

The process can yield low viscosity dispersions containing little or no organic solvent. These dispersions allow for higher solids coatings than other film forming dispersion vehicles and again permit the formulator full latitude in other compounds he may use according to this invention.

DVG:JMD:#29501 6 October 1998 SUMMARY OF THE INVENTION The present invention relates to a coating composition comprising: a) an aldimine compound having the structure Ri C= N R2 n wherein n averages greater than 1; RI is alkyl, aryl, cycloaliphatic or substituted alkyl, aryl, cycloaliphatic or heterocyclic group; and

R

2 is monomeric or polymeric aliphatic, aromatic, arylaliphatic or cycloaliphatic group which may contain 0, N, S, or Si; b) an isocyanate functional component wherein the isocyanate component comprises uretdione functionality; c) at least one pigment, filler or extender; and d) optionally, other active hydrogen compounds wherein the pigments, filler(s) or extenders are dispersed in the aldimine compound and optionally other co-dispersing vehicles or optionally pigment wetting agents or optionally solvents are used.

20 The present invention also relates to a dispersed pigment concentrate composition comprising: a) an aldimine having the structure: n *o wherein n averages greater than 1, Ri is alkyl, aryl, cycloaliphatic or substituted alkyl, aryl, cycloaliphatic or heterocyclic group; and

R

2 is monomeric or polymeric aliphatic, aromatic, arylaliphatic or cycloaliphatic group which O may contain 0, N, S, or Si; I VG:YJ:40193425 19 March 2001 -7 b) at least one pigment, filler or extender wherein the pigment(s), filler(s) or extenders are dispersed in the aldimine compound and optionally other co-dispersing vehicles or optionally pigment wetting agents or optionally solvents are used.

The present invention also relates to a process for preparing pigment, filler or extender containing aldimine and isocyanate compositions wherein the pigment, filler or extender is dispersed in the presence of the aldimine and optionally with other co-dispersing vehicles and optionally with pigment wetting agents and optionally with solvent. The process includes a method for regulating moisture content in the system allowing more flexibility in formulation to produce coatings with improved properties.

The coating compositions of the present invention can be ambient cured or baked to cure. The coatings are especially useful as automotive refinish and industrial paint compositions. The compositions can contain well known paint additives such as catalysts, flow and wetting agents, mar and slip agents, anti-settling and anti-sag agents, etc.

The coating compositions can be of low volatile organic content (VOC), and in fact zero VOC, but the invention is not limited to only low VOC compositions. A range of VOC's can be obtained in part by the choice of the aldimine and the isocyanate components and also by the choice of co-reactants.

"The invention also relates to the utility of the compatibility of the uretdione 20 isocyanates toward the aldimine compounds, which not only makes them mutually suitable co-reactants, but also by co-blending with the uretdione, aids in the compatibilizing of other isocyanate functional resins which are not normally in themselves compatible with the S: aldimine compounds.

The invention also describes the surprisingly fast set time and property development of the coating compositions comprising an aldimine and uretdione isocyanate. The behaviour described in the invention is indicative of the uretdione structure apparently entering into and supporting the reactive matrix.

•This invention also relates to improving the compatibility characteristics of aldimine compounds in the presence of isocyanate compounds by proper selection of the amines and aldehydes used to formulate the aldimine compound.

This invention also relates to optionally using catalysts to accelerate the reaction rate of the aldimine functional compounds and isocyanate functional compounds. The catalysts used according to this invention are aromatic or aliphatic carboxylic acids or arylsulfonic DVG:JMD:#29501 6 October 1998 acids.

In addition to acid catalysts, this invention also relates to optionally using compounds such as organotin compounds to further regulate the reaction of the described compositions.

This invention also describes a method in which the aldimine compound is used as the pigment dispersant in isocyanate cured coatings. The resultant dispersions have surprisingly lower viscosity and good anti-settling characteristics and optionally can be made solvent-free.

The invention also relates to the reaction behaviour of the coating compositions being moisture-tempered.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating composition comprising: a) an aldimine compound having the structure Ri C= N R 2

HJ

n wherein n averages greater than 1; 20 Ri is alkyl, aryl, cycloaliphatic or substituted alkyl, aryl, cycloaliphatic or heterocyclic group; and

R

2 is monomeric or polymeric aliphatic, aromatic, arylaliphatic or cycloaliphatic group which may contain 0, N, S, or Si; b) an isocyanate functional component wherein the isocyanate component comprises Suretdione functionality; 25 c) at least one pigment, filler or extender; and d) optionally, other active hydrogen compounds wherein the pigments, filler(s) or extenders are dispersed in the aldimine compound and optionally other co-dispersing vehicles or optionally pigment wetting agents or optionally solvents are used.

The resultant dispersions have surprisingly low viscosity and good anti-settling characteristics and optionally can be made solvent-free.

Useful isocyanate functional uretdione structures are derived from any aliphatic, cycloaliphatic, or aromatic isocyanate which is susceptible to dimerization. Typical examples R iclude hexamethylene diisocyanate, isophorone diisocyanate, ethylene D :YJ:40193425 19 March 2001 diisocyanate, propylene diisocyanate, naphthalene 1,5-diisocyanate, 1-methyl-2,4- ,disocyanatocyclohexane, xylene diisocyanate, 1-methyl-2,4-disocyanatobenzene, and the like. According to the preferred embodiment of this invention, hexamethylene diisocyanate is used. The free isocyanate content may be partially blocked with any suitable monofunctional active hydrogen compounds such as alcohols, primary or secondary amines, oximes, and the like.

The invention also describes the surprisingly fast set time and property development of the coating compositions comprising an aldimine and uretdione isocyanate. The behaviour described in the invention is indicative of the uretdione structure apparently entering into and supporting the reactive matrix. The aforementioned U.S. Patents 5,098,983 and 4,522,975 teach one known reaction mechanism of the uretdione structure with active hydrogen compounds proceeding via elevated temperature induced cleavage of the uretdione to provide free isocyanate groups. Another known mechanism for uretdione reaction is one at ambient temperature whereby primary amine reacts with the uretdione structure to yield biuret is described in a Chemische Werke Huels AG publication, Huels Information "IPDI-BF 1540 Cross-Linking Agent Free From Blocking Agent for Saturated Polyesters Containing OH Groups"- attachment, May 1983.

The invention also relates to the utility of the compatibility of the uretdione .isocyanates toward the aldimine compounds, which not only make them mutually suitable co-reactants, but also by co-blending with the uretdione, aids in the compatibilizing of other isocyanate functional resins which are not normally in themselves compatible with the aldimine compounds. Compatibility is desirable to ensure clear, non-turbid solutions in pigment free compositions and also haze- and defect-free coating films.

Useful isocyanates which may be blended with the isocyanate functional uretdione 25 structures are di- or polyisocyanates which are aliphatic, cycloaliphatic or aromatic. Such isocyanates include hexamethylene diisocyanate, 1-methyl-2,4-diisocyanato-cyclohexane, isophorone, diisocyanate, 4, 4'-diisocyanatodicyclohexyl methane, toluene-2,4-diisocyanate, o- m- and p-xylene diisocyanate, 1,5-naphthalene diisocyanate, masked isocyanates, or mixtures thereof. It is also possible to use polyisocyanates with isocyanurate, allophanate or oxadiazenetrione structures. The polyisocyanates may optionally be reacted with a deficit or polyhydroxy compounds, such as water, glycols, polyalkylene glycols, neopentyl glycols, glycerol, trimethylol propane, hexane triol or alkyd resins, before being used.

The other active hydrogen compounds of this invention are non-hydroxyl functional, DVG:JMD:#29501 6 October 1998 isocyanate reactive resins possessing at least one active hydrogen, thereby allowing them to become crosslinked into the coating matrix. Examples are amines, mercaptans and acetoacetates. Preferred are secondary amines containing at least two active amino hydrogens, allowing them to become part of the crosslink matrix in a continuous scheme.

This type of material would most likely be a reaction product via nucleophilic addition, of a di-, primary amine with two moles of a mono unsaturated reactant. A material of this type for example, is a reaction product of one mole of 4,4'-Methylenebis (2 Methyl) Cyclohexanamine with two moles of diethyl maleate.

Difunctional aldimines of the invention are obtained from the reaction between a diamine and one or more types of aldehyde. Examples of aliphatic diamines include, but are not limited to: Ethylene Diamine, Ethylene Glycol Diamine, Propylene Glycol Diamine, Hexamethylene Diamine, 1,3-Diaminopentane, 2-Methyl-1,5-Diaminopentane, 1,8- Diaminooctane and 1,10-Diaminodecane.

According to this invention, 1,3-Diaminopentane, Hexamethylene Diamine, 2are preferred. Examples of cycloaliphatic diamines include, but are not limited to compounds having the following structures:

*C

DVG:JMD:#29501 6 October 1998

NH,

NH,

NH,

NH.

H.N CH.

HC

:H.

H, C

CH,

HNCH,_aH

N,

CH,

NH.

NH,

S S

CH

H.N 0 -CH.

NH.

HC CH, C.H, H. C. H.

Preferred cycloaliphatic diamines include

HH.

H, C

H

1 C CH, H.N

NH.

and HC CH., H:NCH

H

Trifunctional aldimines of the invention are obtained from the reaction between a triprimary-amine and one or more types of aldehyde. Examples of preferred triamines are 4methylamino-l,8-diaminooctane and the polyoxyalkylamines available from Texaco Chemicals under the trademark Jeffamine® T-series.

It follows that a polyfunctional aldimine can be prepared from a polyfunctional primary amine.

Polymeric aldimines of the invention are obtained from the reaction product of a polymer with pendant primary amine functional groups and an equivalence of an aldehyde.

A variety of synthetic strategies can be employed to prepare these primary amine functional polymers, for example, an N-vinyl formamide copolymer to which the formamide groups are subsequently hydrolyzed to yield the free primary amine. Alternatively, aldimine functional groups can be grafted directly onto a reactive group on a polymer chain or other multifunctional molecule by imitating a primary amine which has an additional reactive group that is complementary to a reactive group on the polymer chain and is unaffected by the Schiff base formation.

Aldehydes suitable for use in accordance with the invention include, but are not limited to those preferably containing 1 to 8 carbons such as propionaldehyde, butyraldehyde, pivalaldehyde, isobutyraldehyde, 2-Methylbutanal, heptaldehyde, 2-Ethylbutyraldehyde, valeraldehyde, isovaleraldehyde, hexaldehyde, Octyl aldehyde, methoxyacetaldehyde, methyl 20 ester of 2-methyl-3-oxopropanoic acid, methyl ester of 2,2-dimethyl-3-oxopropanoic acid, benzaldehyde, Anisaldehyde, 2-Methylbenzaldehyde, nicotinaldehyde and cyclohexanecarboxaldehyde. Other aldehydes such as 4-t-butyl benzaldehyde, 4-ethoxy benzaldehyde, 3-Methyl-p-anisaldehyde, 4-Ethylebenzaldehyde, cyclopropanecarboxaldehyde, 9-Ethyl-3-carbazolecarboxaldehyde, Diphenylacetaldehyde, 10-Methyalantracene-9-carboxaldehyde and Pyrrenecarboxaldehyde may also be suitable.

This invention also relates to improving the compatibility characteristics of aldimine compounds in the presence of isocyanate compounds by proper selection of the amines and aldehydes used to formulate the aldimine compound.

The present invention also relates to a dispersed pigment concentrate composition comprising: DVG:JMD:#29501 6 October 1998 -12a) an aldimine compound having the structure

R,

SC= N R,

H

n wherein n averages greater than 1; R, is alkyl, aryl, cycloaliphatic or substituted alkyl, aryl, cycloaliphatic or heterocyclic group; and

R

2 is monomeric or polymeric aliphatic, aromatic, arylaliphatic or cycloaliphatic group which may contain 0, N, S, or Si; b) at least one pigment, filler or extender wherein the pigment(s), filler(s) or extenders are dispersed in the aldimine compound and optionally other co-dispersing vehicles or optionally pigment wetting agents or optionally solvents are used.

The present invention also relates to a process for preparing pigment, filler or extender containing aldimine and isocyanate compositions wherein the pigment, filler or extender is dispersed in the presence of the aldimine and optionally with other co-dispersing vehicles and optionally with pigment wetting agents and optionally with solvent. The 20 process includes a method for regulating moisture content in the system allowing more flexibility in formulation to produce coatings with improved properties.

In isocyanate cured systems, it was found that aldimines gave better pot life and *higher yields in non-volatile stoving tests than did ketimines. This indicates that aldimines are less susceptible to hydrolysis than ketimines, since the hydrolysis products are highly reactive primary amines and volatile ketone or aldehyde. This makes aldimines relatively better grinding vehicles for dispersing pigments which normally contain moisture.

It is known that in the presence of moisture the imine/isocyanate reaction is favoured. It is known in the art to use additives such as oxazolidines, etc to remove moisture from systems. According to the process of this invention, proper levels of moisture scavenger can be used to keep the desired amount of moisture in the dispersion to aid in achieving a proper balance of pot life and cure of the coating film. Additionally, acid can be used to catalyze the reaction as needed and organotin compounds can be used to extend the DVG:JMD:#29501 6 October 1998 pot life as desired. By using this process, coatings with improved properties can be produced.

The ability to use the aldimine as a grinding vehicle provides a truly flexible, multipurpose concentrate for isocyanate cured coatings, allowing for a range of VOC depending on the selection of the let-down resin. The use of the aldimine compound as the dispersant to make zero or near-zero VOC dispersions allows for the lowest potential VOC with any given compatible film-forming let-down resin for use with isocyanate crosslinked coatings.

Equipment suitable for dispersing the compositions of this invention are those known to the art as high speed dissolvers, ball mills, sand mills, horizontal mills, and the like.

Useful isocyanates of the isocyanate functional component are di- or polyisocyanates which are aliphatic, cycloaliphatic or aromatic. Such isocyanates include hexamethylene diisocyanate, 1-methyl-2,4-diisocyanato-cyclohexane, isophorone, diisocyanate, 4, 4'diisocyanatodicyclohexyl methane, toluene-2,4-diisocyanate, o- m- and p-xylene diisocyanate, 1,5-naphthalene diisocyanate, masked isocyanates, or mixtures thereof. It is also possible to use polyisocyanates with isocyanurate, allophanate, uretdione or oxadiazenetrione structures. The polyisocyanates may optionally be reacted with a deficit of polyhydroxy compounds, such as water, glycols, polyalkylene glycols, neopentyl glycols, glycerol, trimethoylol propane, hexane triol or alkyd resins, before being used.

The other active hydrogen compounds of the invention wherein the pigments are dispersed in the aldimine compound may include hydroxyl and non-hydroxyl functional, 20 isocyanate reactive resins possessing at least one active hydrogen, thereby allowing them to become crosslinked into the coating matrix.

Useful pigments according to this invention are various types common to the art which include but are not limited to titanium dioxide, graphite, carbon black, zinc oxide, cadmium sulfide, chromium oxide, zinc sulfide, zinc chromate, strontium chromate, barium chromate, lead chromate, lead cyanamide, lead silico chromate, chromium oxide, zinc sulfide, yellow nickel titanium, yellow chromium titanium, red iron oxide, oxide, yellow iron oxides, black iron oxide, naphthol reds and browns, anthraquinones, dioxazine violet, isoindoline yellows, arylide yellow and oranges, ultramarine blue, phthalocyanine complexes, amaranth, quinacridones, halogenated thioindigo pigments, extender pigments such as magnesium silicate, aluminium silicate, calcium silicate, calcium carbonate, fumed silica, barium sulfate, zinc phosphate.

Organic solvents common to the art may be used. Suitable solvents include aromatics DVG:JMD:#29501 6 October 1998 19/106 '01 TITE 10:42 FAX 61 3 9288 1567 FREEHILLS CARTER SMITH B PATENT OFFICE [1004 14 like toluene and xylene, esters like alkylacetates of C, to C2o alcohols, alcohols such as n-Butanol, ketones like 2-Butanone and Methyl Isobutyl Ketone and the like.

This invention also relates to optionally using catalysts to accelerate the reaction rate of the aldimine functional compounds and isocyanate functional compounds. The catalysts used according to this invention are aromatic or aliphatic carboxylic acids or arylsulfonic acids. Acids which are useful are formic acid, mono-, di-, and trichloroacetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, heptanoic acid, pelargonic acid, isononanoic acid, benzoic acid, 4-hydroxybenzoic acid, mono-, di- and trichlorobenzoic acid and salicylic acid. Preferred acids are benzoic acid and heptanoic acid.

This invention also relates to optionally using organotin compounds to regulate the reaction of the compositions of the invention. Useful organotin compounds include dibutyltin mercaptide, dibutyltin diacetate, dibutyltin sulfide and dibutyltin bis-mercaptide. Most preferred according to the present invention is dibutyltin dilaurate.

The invention also provides coating compositions that include the dispersed pigment concentrate described above together with a non-reactive film forming let down resin. The term "let down resin" is well known in the surface coating technology field. The let down resin is used to reduce the concentration of the 20 pigment in the concentrated dispersion to that suitable for a surface coating.

Examples of suitable let down resins are lacquers, cellulose acetate butyrate (CAB), polyesters and blends thereof.

The invention also relates to the behaviour of the coating compositions being moisture-tempered.

25 Coating compositions described by the present invention find utility in applications of ambient film forming and curing such as automotive refinish and industrial coatings. It is also suggested that the present invention applies to coatings to be force dried or baked. Forced dry conditions range from 38 degrees Celsius to 88 degrees Celsius. Baking conditions common to the art may range from 79 degrees Celsius to over 190 degrees Celsius, The coating cure process for the 19 June 2001 19/06 '01 TUE 10:42 FAX 61 3 9288 1567 FREEHILLS CARTER SMITH B PATENT OFFICE00 14a present invention may also be accelerated by the utilisation of radiant heating or Infra Red emitting devices known to the art, Coating compositions described by the present invention find utility as clearcoats, basecoats, topcoats and undlercoats.

The present inventiou relates to a coated substrate prepared by coating a substrate with a coating of the present invention. Any substrate material can be coated with the coating composition according to the present invention. These substrate materials include such things as glass, ceramics, paper, wood, and plastic.

The coating system of the present invention is particularly adapted for metal substrates, and specifically as an automotive re-finish system. The substrate may be uncoated material or can be primed. The substrate may also be coated with paint products applied at the time of manufacture or just prior to 19 June 2001 application of the compositions of the present invention. The coating composition can be applied using conventional spray equipment or high volume low pressure spray equipment resulting in a high quality finish. Other modes of application are roller coating, brushing, sprinkling, flow coating, dipping, electrostatic spraying, or electrophoresis. Exemplary metal substrates include such things as steel, aluminium, copper, zinc, magnesium and alloys thereof.

The following examples are intended to illustrate the invention.

All quantities are shown on a weight basis unless otherwise indicated. All nonvolatile tests are according to ASTM D-3960-90, all weight/gallon determinations are according to ASTM D-1475-90. All VOC determinations include the use of the above test methods. EXAMPLE 1 and COMPARATIVE EXAMPLES 2 and 3 Clearcoats made with dialdimine, diol, and secondary diamine, each reacted with uretdione diisocyanate were made by blending the following as indicated.

ALDIMINE #1 is the reaction product of one mole of Isophorone Diamine with two moles of Isobutyraldehyde.

SECONDARY AMINE #1 is the reaction product of one mole of 4,4'-Methylenebis Cyclohexanamine with two moles of Diethyl maleate POLYESTER DIOL K-Flex@ 148 supplied by King Industries.

20 ISOCYANATE #1 Hexamethylene Diisocyanate Uretdione.

CATALYST #1 Heptanoic Acid.

CATALYST #2 Solution of 1.0% Dibutyltin Dilaurate and 99.0% Xylene.

ADDITIVES Flow modifier and Photostabilizers.

ORGANIC SOLVENTS Common to the art.

DVG:JMD:#29501 6 October 1998 Example Comparative Comparative 1 Example 2 Example 3 Aldimine #1 Polyester Diol #1 Secondary Amine #1 Catalyst #1 Catalyst #2 Isocyanate #1 Additives Organic Solvents Properties: Spray viscosity, sec.

#4 Ford cup Viscosity increase, after 2 hours VOC, g/litre Dust free, min.

Tack free, min.

Gas resistance, days Koenig hardness, sec.

24 hrs., 50 on glass Ambient conditions, oC R.H.

72.56 0.82 90.88 5.74 16.6 <12 96 50 70 1 171 25/27 67.40 1.26 56.50 4.03 40.81 22.0 viscous fluid 95.3 68.70 5.51 0.41 could not spray very rapid viscosity rise 0 0 0* 0 0 00 0 0 0 *0 *0 @0 0 *0000.

0 0**0 0* 0 0 *000

S

000* *000 0 S. 00 00 0 >240 >240 The dust free time testing is intended to define the time that elapses between film application and the point when the film will not retain particulate material which may come 5 to rest on the film. The test method is as follows; the paint to be tested is spray applied to a 100 mm x 300 mm previously base coated test panel at a dry film thickness of 5.0 to 62 tt.

At the appropriate time interval, approximately 1.0 gram of clean dry sea sand is applied to the surface. The sand is allowed to rest on the surface for 15 seconds, then the panel is dropped a prescribed distance through a guide, striking sharply on its side in order 19 March 2001 -17to dislodge the sand. The paint is considered dust free if all or all but a few of the grains of sand are removed.

Koenig Pendulum Hardness tester comprises a steel bar capable of oscillating on two hardened steel hemispheres fixed to the underside of the bar. A panel is held level in a suitable clamp above bench level and the pendulum bar is placed upon the surface to be tested with the steel hemispheres in contact with the panel. The pendulum is allowed to swing, measuring a "damping effect" and the time taken (in seconds) for the decrease from full amplitude of the swing to a deflection of half amplitude (60 to 30), is taken as the pendulum hardness.

Gas Resistance is measured by saturating 1/8 of a 63 mm cotton cosmetic pad (cut radially into equal parts) with 1 ml of unleaded premium gasoline. This cotton pad is then covered with a metal cap. And a weight (500 grams) is placed on the cap to ensure a seal.

After 5 minutes, the weight is removed, along with the cap and cotton pad. The area is then checked for swelling, softening, or other defects.

The data of Example 1 illustrates the surprisingly good property development obtained when a dialdimine and a uretdione diisocyanate are combined in a coating. The fast dry and chemical resistance are not indicative of a coating where the two reactants are behaving in a difunctional manner. There is obviously a three dimensional network being built in the coating film. This indicates that the uretdione structure is somehow entering S 20 into the reactive matrix. The slow viscosity buildup in the closed pot is characteristic of a moisture tempered composition where the mixed fluid coating is low in water content.

Comparative Example 2 illustrates a di-hydroxyl functional resin reacted with the uretdione diisocyanate. As a result of the high reactivity between the hydroxyl and the free isocyanate, the viscosity climbs relatively quickly. As expected, simple chain extension of 25 the two reactants is the predominant reaction, resulting in slow drying and poor chemical resistance. The secondary diamine of Comparative Example 3 is so reactive toward the free isocyanate that the rapid viscosity rise after the reactants are mixed made it impossible to spray.

EXAMPLES 4 9 Clearcoats made with aldimines of varying composition and reacted with uretdione isocyanate were made by blending the following ingredients as indicated.

ALDIMvINE #1 (Examples 1-3).

DVG:YJ:40193425 19 March 2001 ALDIMINE #2 is the reaction product of one mole of Jeffamine® T-403 supplied by Texaco Chemicals, with three moles of Isobutyraldehyde: Under inert gas, an excess of Isobutyraldehyde was slowly added to Jeffamine® T- 403. The addition rate was controlled to maintain a batch temperature of 50 0 C. After the add was completed, the batch was heated to reflux and the water of reaction was removed. A reflux was maintained until no more water came off and the excess aldehyde was removed. Absence of amine was verified by IR spectroscopy.

ALDIMINE #3 is the reaction product of one mole of 4- Methylamino-1,8- Diaminooctane with three moles of Isobutyraldehyde: Under inert gas, an excess of Isobutyraldehyde was slowly added to 4- Methylamino-1,8-diaminooctane while cooling was being applied. The addition rate was controlled to maintain a batch temperature of_< 50 0 C. After the add was completed, the batch was heated to reflux. The water of reaction was removed. A reflux was maintained until no more water was evolved and all excess aldehyde was removed. Absence of residual amine groups was verified by IR spectroscopy.

ALDIMINE #4 is the reaction product of one mole of 4- Methylamino-1,8- Diaminooctane with three moles of Cyclohexanecarboxaldehyde: Under inert gas, an excess of Cyclohexanecarboxaldehyde was slowly added to 4- Methylamino-1,8-diaminooctane. The addition rate was regulated to prevent the batch 20 temperature from exceeding 100 0 C. When the add was completed, the batch was heated to reflux and the water of reaction was removed. A reflux was maintained until no more water was evolved.

ALDIMINE #5 is the reaction product of one mole of 1,3- Diaminopentane with two moles of Benzaldehyde: Under inert gas, Benzaldehyde was slowly added to a very slight excess of 1,3- Diaminopentane. The batch was heated to reflux, the water of reaction was removed, and a reflux was maintained until no more water was evolved. The batch was then cooled to 35 0 C. An excess of Isobutyraldehyde was added to scavenge the remaining amine groups.

The batch was again heated to reflux and held at reflux until all water and excess aldehyde was removed. Absence of amine was verified by IR spectroscopy.

ALDIMINE #6 is the reaction product of one mole of 4- Methylamino-1,8- Diaminooctane with one mole of Benzaldehyde and two moles of Isobutyraldehyde: DVG:JMD:#29501 6 October 1998 Under inert gas, the stoichiometric amount of Benzaldehyde is slowly added to 4- Methylamino-l,8-diaminooctane. The batch was heated and held at reflux until no more water of reaction could be removed. The batch was then cooled to 50°C. Keeping the batch temperature 50 0 C, an excess of Isobutyraldehyde was slowly added. When the add was completed, the batch was again heated to reflux. The water of reaction was removed and a reflux was maintained until all water was removed. Absence of amine groups was verified by IR spectroscopy.

ISOCYANATE #1 (Examples 1-3) CATALYST #3 Solution of 5.0% Benzoic Acid and 95.0% n-Butyl Acetate.

ADDITIVES Flow modifier and Photostabilizers.

ORGANIC SOLVENTS Common to the art.

Example 4 Example 5 Example 6 Aldimine #1 41.65 Aldimine #2 45.74 Aldimine #3 36.59 Catalyst #3 0.94 0.86 0.94 Isocyanate #1 52.16 40.02 57.22 .Additives 3.09 2.83 2.16 Organic Solvents 2.16 10.55 2.16 Properties: Spray viscosity, sec. 22.0 22.7 21.2 #4 Ford cup Viscosity increase, after 2 7 18 hours VOC, g/litre 96 158 68 Dust free, min. 60 40 Tack free, min. 85 65 °0 Ambient conditions, 24/29 24/29 24/29 oC R.H.

19 March 2001 Example 7 Example 8 Example 9 Aldimine #4 37.26 Aldimine #5 37.95 Aldimine #6 34.47 Catalyst #3 0.86 0.93 0.89 Isocyanate #1 48.91 54.51 55.86 Additives 2.50 2.72 3.00 Organic Solvents 10.47 3.89 5.78 Properties: Spray viscosity, sec. 20.3 21.5 22.0 #4 Ford cup Viscosity increase, after 2 5 10 38 hours VOC, g/litre 128 108 Dust free, min. 90 >300 76 Tack free, min. 110 >300 98 Ambient conditions, 23/24 23/24 °C R.H.

Examples 4-9 illustrate the utility of using various amines and aldehydes in formulating aldimines. The diverse cure responses and physical properties demonstrate the formulation latitude for coatings composition flexibility. Example 7 demonstrates the ability to make a mixed aldimine, whereby the triamine is reacted with a blend of aliphatic and aromatic aldehyde.

EXAMPLES 10-14 SMixtures of Hexamethylene Diisocyanate Isocyanurate :Uretdione/Hexamethylene Diisocyanate Isocyanurate with Aldimine #1 were made for compatibility tests by blending the following ingredients as indicated.

ISOCYANATE #1 (Examples 1-3).

ISOCYANATE #2 Hexamethylene Diisocyanate Isocyanurate.

ALDIMINE #1 (Examples 1-3).

193425 19 March 2001 Example Example Example 12 Example 13 Example 14 11 Isocyanate #1 8.0 (40) 10.0 (50) 12.0 (60) 14.0 Isocyanate #2 20.0 (100) 12.0 (60) 10.0 (50) 8.0 (40) 6.0 Aldimine #1 14.4 14.6 14.8 15.0 15.2 Properties: Compatibility, incompatible I I I compatible (I) Examples 10-14 demonstrate that in absence of solvent, Hexamethylene Diisocyanate Isocyanurate is not compatible with Aldimine #1 and that it can be incorporated with the aldimine by blending with Hexamethylene Diisocyanate Uretdione.

EXAMPLES 15-18 Mixtures of Hexamethylene Diisocyanate Isocyanurate with various aldimines were prepared for compatibility tests by blending the following ingredients as indicated.

ISOCYANATE #2 (Examples 10-14).

ALDIMINE #3 (Examples 4-9).

ALDIMINE #3 (Examples 4-9).

ALDIMINE #5 (Examples 4-9).

ALDIMINE #6 (Examples 4-9).

Example 15 Example 16 Example 17 Example 18 Isocyanate #2 30.0 30.0 30.0 30.0 0 Aldimine #3 18.5 Aldimine #4 22.9 Aldimine #5 20.9 Aldimine #6 18.5 Properties: Compatibility, I I C

C

compatible (C) incompatible (I) DVG:JMD:#29501 6 October 1998 -22- *e (9 9*

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9* Examples 10-14 illustrate the latitude for formulating aldimines to alter their compatibility characteristics.

EXAMPLE 19 and COMPARATIVE EXAMPLE An aldimine and ketimine were compared in a coating composition by blending the following ingredients as indicated.

ALDIMINE #1 (Examples 1-3).

KETIMINE #1 The reaction product between one mole of Isophorone Diamine with two moles of Methyl Isobutyl Ketone.

ISOCYANATE #1 (Examples 1-3).

CATALYST #3 (Examples 4-9).

ADDITIVES Flow modifier and Photostabilizers.

ORGANIC SOLVENTS Common to the art.

Example 19 Comparative Example Aldimine #1 72.60 Ketimine #1 86.60 Catalyst #3 1.64 1.78 Isocyanate #1 90.90 90.90 Additives 5.74 6.23 Organic Solvents 13.00 Properties Spray viscosity, sec 21.4 22.8 #4 Ford cup Viscosity increase, 2 96 after 2 hours Dust free, min. 100 165 Tack free, min. 140 180-240 Ambient conditions, 24/23 24/23 oC R.H.

Examples 19 and 20 compare an aliphatic aldimine and ketimine made from the same diamine. The aldimine dries faster with longer pot time than the ketimine when 3 0 reacted with uretdione.

DVG:JMD:#29501 6 October 1998 C -23- For Examples 21-29, the ingredients are defined as follows: ALDIMINE #1 (Examples 1-3).

ALDIMINE #7 is the reaction product of one mole of Methylenebis Cyclohexanamine with two moles of Isobutyraldehyde.

KETIMINE #1 (Examples 19 and PIGMENTS used are Calcium Metasilicate available as Wollastonite@ ES-10 from NYCO, Barium Sulfate available as Bartex®- 65 from Hitox, Titanium Dioxide available from Du Pont, Zinc Phosphate available as Phosguard® from Mineral Pigments, Silicon Dioxide available as Novacite® L-207 from Malvern Minerals and a mixture of Zinc Molybdate/Zinc Phosphate available as Molywhite® ZNP from Sherwin Williams.

MOISTURE SCAVENGER Purmol® 3ST- Molecular sieve is sodium potassium alumino silicate (available from Zeochem).

PIGMENT WETTING AGENTS Anti-Terra® U (available from Byk Chemie) and Soya Lecithin.

ANTI-SETTLING AGENTS and THIXOTROPES MPA®® 2000-X (available from Rheox).

CATALYST SOLUTION #1 is the 15% solution of Benzoic Acid by weight in methyl amyl ketone.

CATALYST SOLUTION #2 is the 1% solution of Dibutyltin Dilaurate by weight 20 in methyl amyl ketone.

ADDITIVE SOLUTION #1 is the 60 solution of Modaflow® (flow additive from Monsanto) by weight in xylene.

ISOCYANATE HARDENER #1 was prepared as follows. Under an inert, anhydrous atmosphere, 850.0 grams of an isocyanate resin consisting of an approximately 25 2 to 1 molar ratio mixture of Hexamethylene Diisocyanate Uretdione and Hexamethylene Diisocyanate Isocyanurate was mixed with 40.0 grams of Ektapro EEP, 40 grams of urethane grade Butyl Acetate and 70.0 grams of Isobutyl Acetate. This mixture was filled *o into closed containers under an inert anhydrous atmosphere.

ISOCYANATE HARDENER #2 DiamontTM HS Solo Hardener SH28 (available from BASF Corp.).

RED TINTING BASE DiamontTM HS Solo Base HS82, acrylic polyol functional (available from BASF Corp.).

DVG:JMD:#29501 6 October 1998 -24- ORGANIC SOLVENTS common to the art are used.

EXAMPLES 21 and 22 The following examples demonstrate that pigments can be ground in the aldimine.

It also illustrates that by using a method where moisture content in the dispersion is controlled, coatings with improved properties are produced. Sealers for Examples 21 and 22 were prepared by dispersing the following ingredients in Aldimine #1 using a high density polyethylene jar (shaker mill). The following components were charged to the plastic jar and milled on the shaker for about 1 hour until the desired grind was achieved.

The temperature of 55 0 C was reached. The sealer was made by adding let down and mixing it for another 10 minutes.

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Aldimine #1 Butyl Acetate Oxo-hexyl Acetate Bentone® 27 Anti Terra U P M Acetate MPA® 2000-X Wollastonite® ES-10 Bartex®-65 Titanium Dioxide Phosguard® Novacite® L-207 Purmol® 3ST Aldimine #1 Butyl Acetate Let Down Aldimine #1

TOTAL

Sealer Grind Example 21 normal process Grams 116.54 48.37 3.62 0.72 5.21 8.44 11.29 102.04 127.56 35.72 153.06 91.93 23.31 15.00 32.81 775.52 16 microns Example 22 improved process Grams 116.54 48.37 3.62 0.72 5.21 8.44 11.29 102.04 127.56 35.72 153.06 91.83 10.20 23.31 23.70 33.65 795.251 15 microns DVG:JMD:#29S01 6 October 1998 DVG:JMD:#29501 6 October 1998 The utility of the above sealers is shown below in an isocyanate cured system. The sealers were reacted with Isocyanate Hardener using Catalyst Solution The acid catalyst level of 1.7% by weight on aldimine solids was used. Both of the sealers were sprayed over Taupe primers (dry sanded with 320 grit and clean wiped with pre-cleaning solution). A commercial 2K urethane monocoat was sprayed after 20' flash of the sealers in the booth. The panels were Cured for 1 hour 60 0 C and post cured overnight at room temperature before testing. Pot life, dry time, initial adhesion, VOC's of the sealers, etc.

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Sealer of Example 21 Sealer of Example 22 Isocyanate Hardener #1 Catalyst Solution #1 Butyl Acetate Properties: Isocyanate Index Pigment/Binder Initial Viscosity (Ford #4 cup) Pot life (2 x visc.) Dry Time (Sealer) Temperature °C Relative humidity VOC, g/litre Determined Theoretical Loss of Theo. VOC Initial Adhesion Sealer/primer Top coat/sealer/primer 200 Gloss (Top coated) Example 21 236.356 90.929 5.964 1.1 1.2 22.0" 80 minutes 35' 24 26 243 196 23.78% GtO GtO 85-86 Example 22 236.356 89.135 5.840 6.500 1.1 1.2 20.0 110 minutes 25-30' 24 26 256 225 14.01% GtO GtO 85-86 fG:YJ:40193425 19 March 2001 -26- The dry time is determined by using a BK Drying Recorder. The BK Drying Recorder is a film integrity tester. A 25 jt to 33 t (dry) film of paint is spray applied to a mm x 300 mm glass slide. The slide is immediately placed into the tester and testing is started. The tester pulls a 1.5 mm round end rod (held vertically) across the surface of the paint film at a consistent rate so the mark left on the film can be analysed and the time that the nature of the mark changes can be recorded. The dry time as determined for these examples is the time when the film has set enough that the rod will ride on top of the paint film instead of being pulled through the film.

The adhesion test was performed as per ASTM method D3359, test method B using a cutter which spaces the cuts 2 mm apart and make 6 cuts. The percent adhesion loss is expressed according to a scale of Gt0to Gt5. The ratings along with the corresponding percent adhesion loss is as follows: Gt0 0% loss; Gtl= 1-5% loss; Gt2 6-15% loss; Gt3 16-35% loss; Gt4 36-65% loss; Gt5 66-100% loss. The same method was used for Examples 21-29.

From Example 21 and 22, it is seen that by controlling the level of moisture in the pigmented base, the pot life can be improved as well as the retention of VOC's (measured vs. theoretical). It also shows the potential of aldimine based dispersions to produce low :oS: VOC coatings.

The following Examples 23, 24 and 25 illustrate this clearly further in depth oo 20 wherein the pigments are dispersed in other aldimines using to achieve the desired level of ,moisture in the system to produce useful coatings. The examples further demonstrate that by using the dispersion made in aldimine, pigmented coating of lower VOC can be *°*achieved.

0* 0EXAMPLES 23,24 and 25 Here the utility of the dispersions made in aldimines is shown as a tintable sealer o.where the tinting base contains hydroxyl resin. Using aldimine based dispersions, coatings

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of lower VOC can be produced than those with a similar composition wherein the pigments o* are dispersed in other vehicles such as those described in U.S. Patent No.5,214,086.

In the following examples pigments were ground in Aldimines #1 and It is known that in the presence of moisture the imine/isocyanate reaction is favoured. Also this -reaction can be catalysed by using an acid component. Controlling the rate of reaction of 19 March 2001 aldimine/isocyanate becomes more complex in presence of moisture (from pigments) in the pigmented system together with a hydroxyl component (from the tinting bases) in various humidity and temperature conditions. In the following example this complex situation exists wherein the tinting base contains organotin catalyst which accelerates the hydroxyl/isocyanate reaction. Additionally, moisture is brought into the system with the pigments. By using a method, thereby keeping a desirable amount of moisture in the system and further using acid catalyst as needed, Coatings with improved pot life and VOC are obtained. In addition, higher tinting strength was achieved.

Sealers were prepared by dispersing the following ingredients in Aldimine #1 and Aldimine #7 using a high density polyethylene jar (shaker mill). The following components were charged to the plastic jar and were milled on the shaker for about 1 hour until the desired grind was achieved. The temperature of 55 0 C was reached. The sealer was made by adding let down and mixing for another 10 minutes.

a a S a d a Aldimine #1 Aldimine #7 Butyl Acetate Oxo-hexyl Acetate Benetone® 27 Anti Terra® U Soya Lecithin Additive Sol #1 MPA® 2000-X Wollastonite® ES-10 Titanium Dioxide Molywhite@ ZNP Novacite® L-207 Purmol® 3ST Butyl Acetate Sealer Grind Example 23 Grams 70.00 100.00 14.00 1.05 1.05 1.04 1.05 5.25 70.00 84.00 21.00 105.00 70.00 9.00 14.00 16 microns Example 24 Grams 70.00 100.00 14.00 1.05 1.05 1.04 1.05 5.25 70.00 84.00 21.00 105.00 70.00 9.00 14.00 15 microns Example Grams 70.00 100.00 14.00 1.05 1.05 1.04 1.05 5.25 70.00.

84.00 21.00 105.00 70.00 9.00 14.00 16 microns *e DVG:JMD:#29501 6 October 1998 DVG:JMD:#29501 6 October 1998 Sealers of Examples 23, 24 and 25 were tinted with Red Tinting Base HS82 and reacted with Isocyanate Hardener using Catalyst Solution A benzoic acid catalyst level of 0.85% by weight on aldimine solids was used. The sealers were sprayed over cold rolled steel (sanded with 180 grit sand paper and wiped with pre-cleaning solution). A commercial 2K urethane monocoat was sprayed after 20' flash of the sealers in the booth.

The panels were cured for 1 hour 140 0 F and post cured overnight at room temperature before testing. Pot life, dry time, initial adhesion, VOC's of the sealers, etc. were measured as follows.

Example 23 Grams 200.87 Example 24 Grams Example Grams a a a.

Sealer of Example 23 Sealer of Example 24 Sealer of Example 25 Red Tinting Base Hardener #2 Catalyst Solution #1 Catalyst Solution #2 Properties Isocyanate Index Pigment/Binder Initial Viscosity (Ford #4 cup) Pot life (2 x visc.) Dry Time (Sealer) Temperature °C Relative Humidity VOC, g/litre Determined Theoretical 40.17 57.35 1.40 1.1 1.4 17.5 150 minutes 45'- 50' 25 31 353 349 200.87 40.17 47.71 1.40 200.87 40.17 57.35 1.40 0.20 17.5 50 minutes 15' 25 31 16.09" 180 minutes 30 31 365 349 :YJ:40193425 19 March 2001 :YJ:40193425 19 March 2001 Example 23 Example 24 Example Grams Grams Grams loss of Theo. VOC 1.37% 4.81 Initial Adhesion Sealer/primer GtO GtO GtO Top coat/sealer/primer GtO Gt0 GtO Example 24 show the capability of dispersing pigments in another aldimine besides aldimine The tinting bases have higher VOC. To achieve better depth of the top coat colour together with sand scratch coverage for the coarser sand paper, a higher amount of the tinting base is necessary. Also, lower viscosity is preferred for better flow of the sealer.

In Examples 23, 24 and 25 the ratio of sealer to the tinting base is 3/1 by volume.

The results illustrates the potential of achieving lower VOC if the pigments are dispersed in aldimine. Also, the longer pot life in Example 23 demonstrates that by using cases, pot life, VOC, etc are compared. The sealers in Examples 26 and 27 were made using a normal process while Examples 28 and 29 were made using the process so as to lower the moisture content of the system.

EXAMPLE 26 and COMPARATIVE EXAMPLE 27 SEALERS for Examples 26 and 27 were prepared by dispersing the following ingredients in Aldimine #1 and Ketimine 1.

a a Aldimine #1 Ketimine #1 Butyl Acetate Oxo-hexyl Acetate Benetone® 27 Anti Terra® U P M Acetate MPA® 2000-X Wollastonite® ES-10 Titanium Dioxide Example 26 Grams 97.12 40.31 3.02 0.60 4.34 7.03 9.41 85.03 106.30 29.77 Example 27 Grams 97.12 40.31 3.02 0.60 4.34 7.03 9.41 85.03 106.30 29.77 DVG:JMD:#29501 6 October 1998 DVG:JMD:#29501 6 October 1998 Phosguard® Novacite® L-207 Aldimine #1 Ketimine #1 Butyl Acetate Let Down Aldimine #1 Ketimine #1

TOTAL

Sealer Grind Example 26 Grams 127.55 76.53 19.43 12.50 Example 27 Grams 127.55 76.53 19.43 12.50 27.34 646.29 16 microns 41.02 659.96 16 microns Sealers of Examples 26 and 27 were reacted with isocyanate Hardener using Catalyst Solution The acid catalyst level of 1.7% on aldimine and ketimine was used for their respective formulation. Both of the sealers were sprayed over Taupe primers (dry sanded with 320 grit and wiped with pre-cleaning solution). A commercial 2K urethane monocoat was sprayed after 20' flash of the sealers in the booth. The panels were cured for 1 hour 140°F and post cured overnight at room temperature before testing. Pot life, dry 20 time, initial adhesion, VOC's of the sealers, etc. were measured as follows.

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Sealer of Example 26 Sealer of Example 27 Isocyanate Hardener #1 Catalyst Solution #1 Butyl Acetate Properties: Isocyanate Index Pigment/Binder Initial Viscosity (Ford #4 cup) Pot life (2 x visc.) Dry time (sealer) Example 26 307.27 118.21 7.75 1.1 1.2 22.0 80 minutes 35' 313.76 108.55 8.49 20.80 1.1 1.2 22.5 30 minutes Comparative Example 27 DVG:JMD:#29501 6 October 1998 -31- Temperature °C Relative Humidity VOC g/litre Determined Theoretical loss of Theo. VOC Initial Adhesion Sealer/primer Top coat/sealer primer 200 Gloss (Top coated) Ketimine #1 Isocyanate Hardener #1 Catalyst Solution #1 Butyl Acetate Isocyanate Index Pigment/Binder Initial Viscosity (Ford #4 cup) Pot life (2 x visc.) Dry time (sealer) Temperature °C Relative Humidity VOC. g/litre Determined Theoretical loss of Theo. VOC Initial Adhesion Sealer/Primer Top coat/sealer/primer 0 Gloss (Top coated) Example 26 24 26 243 196 23.78% Comparative Example 27 24 26 322 246 31.22% GtO GtO 82-85 118.21 7.75 8.62 1.1 1.2 22.0" GtO GtO 83-85 6.50 108.55 8.49 32.84 1.1 1.2 22.5 110 minutes 25 30 24 26 256 225 14.01% <30 minutes 12-15' 24 26 344 276 31.22% GtO GtO 82-85 GtO GtO 83-85 DVG:YJ:40193425 19 March 2001 -32- Comparing Examples 26 and 28, it is clear that pot life and the retention of VOC's (measured vs theoretical) is improved by using process of keeping desirable moisture content in dispersion made in aldimines. Also in this regard aldimines do perform better than ketimines.

EXAMPLES 30 and 31 Aldimine pigment dispersions were made by blending the following ingredients as indicated.

ALDIMINE #1 (Examples 1-3).

RED MILL BASE 68.2% of Aldimine #1 and 31.8% of C.I. Pigment Red 254.

WHITE MILL BASE 43.5% of Aldimine #1 and 56.5% of Titanium Dioxide.

ISOCYANATE #3 An approximately 2 to 1 molar ratio mixture of Hexamethylene Diisocyanate Uretdione and Hexamethylene Diisocyanate Isocyanurate.

Example Red Mill Base 110.0 Aldimine #1 123.3 The Red Mill Base was charged into a nine ounce glass jar. To disperse the pigment, 300 grams of 1.6-2.0 mm zirconia/silica beads were added to the jar. The jar was sealed and put on a Cyclone air operated paint shaker for thirty minutes resulting in a grind of 8 Hegman. To convert the mill base, Aldimine #1 was added and then shaken for additional 5 minutes. The resulting paint recovered by filtration has a viscosity of 33 -seconds #4 Ford cup. 100 grams of this mixture was blended with 123 grams of a Isocyanate This mixture with a theoretical VOC of zero was sprayed on panels and cured at ambient room conditions. A hard, chemically resistant film was formed.

4 Example 31 25 White Mill Base 115.0 Aldimine #1 101.0 The White Mill Base was charged into a nine ounce glass jar. To disperse the pigment, 300 grams of 1.6-2.0 mm zirconia/silica beads were added to the jar. The jar was sealed and put on a Cyclone air operated paint shaker for thirty minutes resulting in a grind DVG:JMD:#29501 6 October 1998 of 8 Hegman. To convert the mill base, Aldimine #1 was added and then shaken for additional 5 minutes. The resulting paint recovered by filtration has a viscosity of 27 seconds #4 Ford cup. After three weeks Examples 30 and 31 were found to be fluid, stable, and completely free of any pigment settling.

Examples 30 and 31 illustrate that stable, low viscosity dispersions containing little or no organic solvents can be made using aldimine as the dispersant.

For Examples 32-34, the ingredients are defined as follows: ALDIMINE #1 (Examples 1-3).

SECONDARY AMINE #2 is the reaction product of one mole of 4,4' Methylenebis (2 Methyl) Cyclohexanamine with 2 moles of diethyl maleate KETIMINE #1 (Examples 19 and ISOCYANATE #3 (Examples 30 and 31).

ISOCYANATE #4 Hexamethylene Diisocyanate Biuret.

PIGMENT WETTING AGENT is a solution of a salt of unsaturated polyamine amides and high molecular weight acidic esters that is electroneutral. An example of a product of this type is Anti- Terra® U (BYK-Chemie USA, Wallingford, CT).

ANTISETTLING AGENT is an organic rheological additive of a proprietary composition. An example of a product of this type is M-P-A® 1078X (Rheox, Hightstown, NJ).

20 Example 32 describes a curable pigmented primer surfacer composition based upon ketimine/secondary amine/isocyanate reaction that is known to the art. Examples 33 and 34 illustrate curable pigmented primer surfacer compositions according to the claimed invention.

The 2.1 VOC undercoat compositions were formulated by blending the following constituents as indicated.

DVG:JMD:#29501 6 October 1998 Percent by Weight Example Example Example 32 33 34 Secondary Amine #2 4.61 7.95 Methyl Isobutyl Ketone 3.40- Methyl Amyl Ketone 2.51 Propylene Glycol Monomethyl Ether Acetate 3.43 n-Hexyl Acetate 2.28 n-Butyl Acetate 8.54 Trialkylaryl Ammonium Hectorite 0.14 0.14 0.15 High Speed Disperse for 15 minutes. Add following in order with agitation: Pigment Wetting Agent 0.54 0.54 0.79 Antisettling Agent 0.29 0.29 0.29 High speed disperse for 15 minutes at 40 0 C. Add following with agitation: Titanium Dioxide 6.80 6.86 6.91 Yellow Iron Oxide 0.29 0.29 0.29 Magnesium Silicate (Talc) 5.10 5.14 5.18 Barium Sulfate 19.57 19.72 19.88 Zinc Phosphate 11.90 11.99 12.09 Grind to 20 microns. Let down with: Methyl Propyl Ketone 252 n-Butyl Acetate 2.54 1.84 Ketimine #1 13.43 Aldimine #1 10.73 16.34 When ready to apply, premix following and add to above.

Isocyanate #4 5.30 5.17 Methyl Amyl Ketone 4.31 4.11 3.68 Isocyanate #3 15.91 15.51 21.72 Methyl Propyl Ketone 3.38 3.31 2.30 Totals: 100.00 100.00 100.00

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@9 4* 9 *9 .9 9 .9 9* '9 4 9 .9 DVG:JMD:#29501 6 October 1998 I/ *f The coatings were prepared by first combining the first seven ingredients in a suitable vessel with agitation. This mixture was then high speed dispersed with a Cowles blade for 15 minutes. The next two ingredients were then added in order and high speed dispersed for 15 minutes at a temperature of 40'C. The remaining pigments were then added with high speed dispersion. Agitation continued for 15 minutes, then the mixture was ground to 20 microns with 1.1 mm zirconium shot in a high density polyethylene shaker mill. The mill was drained, and the next four ingredients were added with agitation to create the primer base component.

To prepare the primer for application, the last four ingredients were blended together, then added to the primer base component and blended immediately prior to application.

Physical Properties Example 32 Example 33 Example 34 Spray Viscosity, #4 Ford cup 18 sec 16 sec 16 sec Pot Life (Time for viscosity to reach 35 sec 50 min 120 min 240 min VOC, g/litre (Theoretical) 239.8 243.1 239.7 VOC, g/litre, ASTM D-3960-90 298.3 262.4 249.2 Pigment/Binder Ratio 1.13:1.0 1.14:1.0 1.16:1.0 Weight/litre, g/litre, ASTM D-1475-90 1400 1436 1416 The resulting primers were sprayed and cured at ambient conditions (25 0 C, RH). All three Systems sanded well and possessed a proper level of desired properties 15 expected of primer-surfacers. As illustrated, the use of aldimine ensures consistency of theoretical versus determined VOC results, while maintaining sufficient properties.

EXAMPLE A pigmented thermoplastic lacquer coating composition was made using an aldimine dispersion by blending the following ingredients as indicated.

20 WHITE BASE 115.0 grams of White Mill Base and 101.0 grams of Aldimine #1 according to Example 31.

ACRYLIC LACQUER CLEAR Alpha-Cryl TM 827 Clear (available from BASF Corp.).

ACRYLIC LACQUER THINNER Alpha-Cryl T M PNT90 (available from BASF

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)193425 19 March 2001 -36- Example White Base 15.0 Acrylic Lacquer Clear 37.5 Acrylic Lacquer Thinner 15.0 The above ingredients were mixed until uniform and then cast on a glass plate using a draw down bar. A dry, hard film was formed within ten minutes.

The above example illustrates that an aldimine dispersion can be used as a multipurpose concentrate in preparing coating compositions. It can reasonably be anticipated that other types of non-reactive or reactive let down resins could be combined with an aldimine dispersed pigment concentrate to prepare coating compositions.

DO*

'l go** o* n **o *ioe DVG:JMD:#29501 6 October 1998

Claims (9)

1. A coating composition comprising: a) an aldimine compound having the structure Ri SC== N R2 n wherein n averages greater than 1; Ri is alkyl, aryl, cycloaliphatic or substituted alkyl, aryl, cycloaliphatic or heterocyclic group; and R 2 is monomeric or polymeric aliphatic, aromatic, arylaliphatic or cycloaliphatic group which may contain 0, N, S, or Si; b) an isocyanate functional component wherein the isocyanate component comprises uretdione functionality; S" c) at least one pigment, filler or extender; and d) optionally, other active hydrogen compounds wherein the pigments, filler(s) or 20 extenders are dispersed in the aldimine compound and optionally other co-dispersing vehicles o or optionally pigment wetting agents or optionally solvents are used. S. 2. The coating composition of claim I wherein the isocyanate functional component comprises a group chosen from aliphatic, aromatic, or cycloaliphatic isocyanurates, biurets, oxadiazenetriones or isocyanate functional prepolymers. 25 3. The coating composition of claim 1 wherein the isocyanate functional component comprises aliphatic, aromatic, or cycloaliphatic uretdione.

4. The coating composition of claim I wherein the isocyanate functional component comprises aliphatic, aromatic, or cycloaliphatic allophante. F 5. The coating composition of claim 1 wherein the other hydrogen compound is DVG:YJ:40193425 19 March 2001 19/06 '01 TLTE 10:42 FAX 61 3 9288 1567FREIL CATRSTHB PEN OFCE I10 FREEHILLS CARTER SMITH B 444 PATENT OFFICE [a 006 38 a secondary amnine functional reactive diluent.

6.

7. 8

9. an undercoat. a topcoat.

11. a basecoat.

12. a clearc-oat.

13. The coating composition of claim 1 which is cured at ambient temperature. The coating composition of claim I which is baked to cure. The cured coating Composition of claim 6 or claim 7 The coating composition of claim 8 wherein the cured coating composition is The coating composition of claim 8 wherein the cured coating composition is The coating composition of claim 8 wherein the cured coating composition is The coating composition of claim 8 wherein the cured coating composition is A coated substrate prepared by coating a substrate with the coating 999999 0 99 9 9 9 *999 99 99 99 9 990 9 .9. .9 9 99 9 99 9. 0 9. 9.. 999999 9 9 9 9 9 6

99.. 99 9 .9 9 9999 .99. 9 9 9 9999 9999 90 9. 999999 composition of claim 1 and curing said coating. 14. The coating composition of claim 1 wherein the volatile organic content (VOC) is less than 335g per litre. The coating composition of claim 1 wherein the volatile organic content (VOC) is less than 265& per litre. 16. The coating composition of claim I wherein the volatile organic content 20 (VOC) is less than 120g per litre. 17. A method for preparing a coating composition including an aldinine as defined in claim 1, an isocyanate functional component, and one or more of the group consisting of pigments, fillers and extenders wherein the pigments, fillers and/or extenders are dispersed in the presence of the aldimine and optionally other co-dispersing vehicles and 25 optionally with pigment wetting agents and optionally with solvents. 18. A method according to claim 17 wherein sufficient moisture is included in the dispersion to achieve a proper balance of pot life and cure together with optional pigment wetting agents or optional solvents. 19. A coating composition as prepared according to the method of claim 18 which 30 is cured at. ambient temperature. A coating composition including dispersion of claim '18 which is cured at elevated temperatures. 21 A coating composition as prepared according to the method of claim 17 or claim 18 wherein the coating composition is an undercoat 19 June 2001 19/06 '01 TUE 10:43 FAX 61 3 9288 1567 FREEHILLS CARTER SMITH B 444 PATENT OFFICE 01007 I, 39. 22. A coating composition as prepared according to the method of claim 17 or 18 wherein the coating composition is a basecoat. 23. A coating composition as prepared according to the method of claim 17 or claim 18 wherein the coating composition is a topcoat. 24. A coating composition as prepared according to the method of claim 17 or claim 18 wherein the coating composition is a clearcoat. A coated substrate prepared by coating a substrate with a coating composition defined in claims 17 or claim 18 and curing said coating. 26. A coating composition as defined in claims 17 or claim 18 wherein the VOC of the coating composition is less than 335g per litre. 27. A coating composition as defined in claims 17 or claim 18 wherein the VOC of the coating composition is less than 265g per litre. 28 A coating composition as defined in claims 17 or claim 18 wherein the VOC of the coating composition is less than 120g per litre. 29. A dispersed pigment concentrate composition comprising: a) an aldimine compound having the structure 9\ @9i 99@9 20 wherein[ C}n 0, N Rr wh veae reate tha int~) lrs retner r ipre nth li ecmon op2tR 1 isnakllylth cclphatincf or ubstitute aiy aryles y paiphat orweteoyng agroup;an 20 H0 0 9. .9 n averages greater than 1; R is alky, aryl, cycloaliphatic or substituted alky!, aryl cycloaliphatic or heteroyclic group; sovets 25 and R s mnmrcor poyei lphati armac aliticc or wylaipai gru ch aycoti o, N,s, or i b) at least one pigment, fller or extender o wherein the pigment(s), filler(s) or extenders are dispersed in the aldimine compound optionally in the presence of other co-dispersing vehicles, pigment wetting agents and solvents. VG;JIh'40l!93425-RES 19 June 2001 19/06 '01 TUE 10:43 FAX 61 3 9288 1567 FREEHILLS CARTER SMITH B 44 PATENT OFFICE []008 4 A coating composition comprising: a) the dispersed pigment concentrate of claim 29, b) a non-reactive film forming let down resin. 31. The coating composition of claim 30 wherein b) is lacquer or polyester/CAB. 32. A coating composition comprising: a) The dispersed pigment concentrate of claim 29 b) a non aldimine-reactive let down resin; c) optionally, a co-reacting hardener component. 33. The coating composition of claim 31 wherein b) comprises imine, amine, hydroxyl, carboxylic acid, anhydride, carbodiimide, epoxy, alkyd enamel, acrylic enamel or blocked isocyanate functional resins. 34. The coating composition of claim 31 wherein c) comprises epoxy, carboxylic acid, anhydride, carbodiimide, amine, hydroxyl or blocked isocyanate functional resins. A coating composition as defined in claim 1 and substantially as hereinbefore S 15 described with reference to any one of the Examples. 19 June 2001 0 :FREEHILLS CARTER SMITH BEADLE S. Patent Attorneys for the Applicant: SBASF CORPORATION S C a 9* e*S o0,*• *e 19 Ju 2001