VEHICULES POLYMERES RENFERMANT UN DILUANT REACTIF D'URETHANE PHENOLIQUE

POLYMERIC VEHICLES WHICH INCLUDE A PHENOLIC URETHANE REACTIVE DILUENT

Abrégé français

L'invention porte sur un véhicule polymère, la composition d'enduction formulée et un liant d'enduction fabriqué à partir de ce véhicule polymère, et sur un procédé permettant de fabriquer ce véhicule polymère où celui-ci renferme un diluant réactif d'uréthane phénolique. Le diluant réactif d'uréthane phénolique peut se fabriquer à partir d'un alcool à esters phénoliques comprenant au moins un groupe hydroxyle aliphatique.

Abrégé anglais

The present invention is directed to a polymeric vehicle, the 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 a
phenolic urethane reactive diluent. The phenolic urethane reactive diluent may
be made from a phenolic ester alcohol having at least one aliphatic hydroxyl
group.

Revendications

-52-
WHAT IS CLAIMED IS:
1. A polymeric vehicle comprising:
a phenolic urethane reactive diluent,
the phenolic urethane reactive diluent being the
reaction product of a compound having an average
isocyanate functionality of from about 1.9 to about 20
isocyanate groups per molecule and a phenolic ester
alcohol having at least one aliphatic hydroxyl group
wherein about one equivalent of isocyanate is reacted
with about every equivalent of aliphatic hydroxy group
which is a part of the phenolic ester alcohol and
wherein the phenolic ester alcohol is the reaction
product of a phenol carboxylic acid and an epoxy
functional compound.
2. A polymeric vehicle as recited in claim 1
wherein the phenolic ester alcohol has at least two
ester groups and has the general formula
<IMG>
wherein R4 is selected from the group consisting of
hydrogen, halogen, hydroxyl, C1 to C8 alkyl and C1 to C8
alkoxy, R5 is selected from the group consisting of a
direct bond, C1 to C20 organic radical having only carbon
and hydrogen atoms, a C1 to C20 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, R6 is selected from the group consisting of
hydrogen, a C1 to C20 organic radical, a C1 to C20 organic
radical which includes in its structure a substitution
group selected from the group consisting of phenol,

-53-
aliphatic hydroxyl, ester, ether, carbonate and
combinations thereof, a direct bond, and a direct bond
which forms with R7 part of a 5 or 6 carbon atom cyclic
ring structure, R7 is CH2R8 wherein R8 is selected from
the group consisting of hydroxy and a C1 to C20 aliphatic
which includes in it structure a substitution group
selected from the group consisting of aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof, OR9, OOCR10 and R11 wherein R9 is selected from
the group consisting of a primary or secondary
aliphatic group containing 3 to 20 carbon atoms or an
aromatic group containing 6 to 20 carbon atoms and a
primary or secondary aliphatic group containing 3 to 20
carbon atoms which includes in its structure aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof, R10 is selected from the group consisting of a
primary, secondary or tertiary aliphatic group
containing 4 to 20 carbon atoms, an aromatic group
containing 6 to 20 carbon atoms, a primary, secondary
or tertiary aliphatic group containing 4 to 20 carbon
atoms which includes in its structure aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof and R11 is selected from the group consisting of
a C2 to C20 organic radical, a C2 to C20 organic radical
which includes in its structure aliphatic hydroxyl,
ester, ether, carbonate and combinations thereof, and a
C2 to C20 organic radical which forms with R6 part of a 5
or 6 carbon atom cyclic ring structure.

-54-
3. A polymeric vehicle comprising a phenolic
urethane compound which has the general formula
<IMG>
wherein N is about 1 to about 4, and where R12 is
selected from the group consisting of an alkyl, alkyl
difunctional radical, alkenyl, alkenyl difunctional
radical, aromatic and an aromatic difuctional radical.
4. The polymeric vehicle as recited in claim 3,
where R12 is selected from the group consisting of
<IMG>,
-(CH2)n-,
<IMG>,
and

-55 -
<IMG> .
wherein n is greater than 1.
5. The polymeric vehicle as recited in claim 4,
wherein the phenolic urethane reactive diluent has the
formula
<IMG>

-56-
6. The polymeric vehicle as recited in claim 4,
wherein the phenolic urethane reactive diluent has the
formula
<IMG>
7. A polymeric vehicle as recited in claims 4, 5
or 6, wherein the polymeric vehicle further comprises a
compound having an isocyanate functionality of from
about 1.9 to about 20 isocyanate groups per molecule.
8. A polymeric vehicle comprising:
a crosslinker selected from the group consisting
of a polyfunctional amino resin having an average
crosslinking functionality of from about 3 to about 30
crosslinking groups per molecule, a compound having an
average isocyanate functionality of from about 1.9 to
about 20 isocyanate groups per molecule and mixtures of
the polyfunctional amino resin and the polyfunctional

-57-
isocyanate compound; and
a phenolic urethane reactive diluent,
the phenolic urethane reactive diluent being the
reaction product of a compound having an average
isocyanate functionality of from about 1.9 to about 20
isocyanate groups per molecule and a phenolic ester
alcohol having at least one aliphatic hydroxyl group
wherein about one equivalent of isocyanate is reacted
with about every equivalent of aliphatic hydroxy group
which is a part of the phenolic ester alcohol and
wherein the phenolic ester alcohol is the reaction
product of a phenol carboxylic acid and an epoxy
functional compound.
9. A polymeric vehicle as recited in claim 8,
wherein the crosslinker and the reactive diluent are
each in amounts effective for reducing VOCs in a
formulated coating composition which includes the
polymeric vehicle to less than about 3 pounds of VOC
per gallon of formulated coating composition, the
crosslinker and the reactive diluent each in amounts
effective for providing a coating binder made from the
cured polymeric vehicle with a pencil hardness of at
least about HB and an impact resistance of at least
about 20-inch pounds direct and at least about 20-inch
pounds indirect.
10. The polymeric vehicle as recited in claims 8
or 9, wherein the phenolic ester alcohol has the
general formula
<IMG>
wherein R4 is selected from the group consisting of
hydrogen, halogen, hydroxyl, C1 to C8 alkyl and C1 to C8

-58-
alkoxy, R5 is selected from the group consisting of a
direct bond, C1 to C20 organic radical having only carbon
and hydrogen atoms, a C1 to C20 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, R6 is selected from the group consisting of
hydrogen, a C1 to C20 organic radical, a C1 to C20 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, a direct bond, and a direct bond
which forms with R7 part of a 5 or 6 carbon atom cyclic
ring structure, R7 is CH2R8 wherein R8 is selected from
the group consisting of hydroxy and a C1 to C20 aliphatic
which includes in it structure a substitution group
selected from the group consisting of aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof, OR9, OOCR10 and R11 wherein R9 is selected from
the group consisting of a primary or secondary
aliphatic group containing 3 to 20 carbon atoms or an
aromatic group containing 6 to 20 carbon atoms and a
primary or secondary aliphatic group containing 3 to 20
carbon atoms which includes in its structure aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof, R10 is selected from the group consisting of a
primary, secondary or tertiary aliphatic group
containing 4 to 20 carbon atoms, an aromatic group
containing 6 to 20 carbon atoms, a primary, secondary
or tertiary aliphatic group containing 4 to 20 carbon
atoms which includes in its structure aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof and R11 is selected from the group consisting of
a C2 to C20 organic radical, a C2 to C20 organic radical
which includes in its structure aliphatic hydroxyl,
ester, ether, carbonate and combinations thereof, and a
C2 to C20 organic radical which forms with R6 part of a 5

-59-
or 6 carbon atom cyclic ring structure.
11. The polymeric vehicle as recited in claims 8
or 9, wherein the phenolic ester alcohol has a
molecular weight in the range of from abut 110 to about
1000 and is the reaction product of a hydroxybenzoic
acid and a monoglycidyl compound having a terminal
glycidyl group.
12. The polymeric vehicle as recited in claim 10
wherein the hydroxybenzoic acid is parahydroxybenzoic
acid and the monoglycidyl compound has the formula
<IMG>
where R represents a mixture of aliphatic groups, the
three R groups having a total of 8 carbon atoms.
13. A phenolic urethane compound which is the
reaction product of a compound having an isocyanate
functionality of from about 1.9 to about 20 isocyanate
groups per molecule and a phenolic ester alcohol having
at least one aliphatic hydroxyl group, about one
equivalent of isocyanate being reacted with about every
equivalent of aliphatic hydroxyl group which is a part
of the phenolic ester alcohol, and wherein the phenolic
ester alcohol is the reaction product of a phenolic
carboxylic acid and an epoxy functional compound.
14. The phenolic urethane compound as recited in
claim 13, wherein the isocyanate compound is selected
from the group consisting of an isocyanate, a biuret,
an isocyanurate and mixtures thereof.
15. The phenolic urethane compound as recited in
claims 13 or 14, wherein the phenolic ester alcohol has

-60-
the general formula
<IMG>
wherein R4 is selected from the group consisting of
hydrogen, halogen, hydroxyl, C1 to C8 alkyl and C1 to C8
alkoxy, R5 is selected from the group consisting of a
direct bond, C1 to C20 organic radical having only carbon
and hydrogen atoms, a C1 to C20 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, R6 is selected from the group consisting of
hydrogen, a C1 to C20 organic radical, a C1 to C20 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, a direct bond, and a direct bond
which forms with R7 part of a 5 or 6 carbon atom cyclic
ring structure, R7 is CH2R8 wherein R8 is selected from
the group consisting of hydroxy and a C1 to C20 aliphatic
which includes in it structure a substitution group
selected from the group consisting of aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof, OR9, OOCR10 and R11 wherein R9 is selected from
the group consisting of a primary or secondary
aliphatic group containing 3 to 20 carbon atoms or an
aromatic group containing 6 to 20 carbon atoms and a
primary or secondary aliphatic group containing 3 to 20
carbon atoms which includes in its structure aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof, R10 is selected from the group consisting of a
primary, secondary or tertiary aliphatic group
containing 4 to 20 carbon atoms, an aromatic group
containing 6 to 20 carbon atoms, a primary, secondary

-61-
or tertiary aliphatic group containing 4 to 20 carbon
atoms which includes in its structure aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof and R11 is selected from the group consisting of
a C2 to C20 organic radical, a C2 to C20 organic radical
which includes in its structure aliphatic hydroxyl,
ester, ether, carbonate and combinations thereof, and a
C2 to C20 organic radical which forms with R6 part of a 5
or 6 carbon atom cyclic ring structure.
16. The phenolic urethane compound as recited in
claim 15, wherein the hydroxybenzoic acid is
parahydroxybenzoic acid and the monoglycidyl compound
has the formula
<IMG>
where R represents a mixture of aliphatic groups, the
three R groups having a total of 8 carbon atoms.
17. A polymeric vehicle which comprises:
a phenolic urethane reactive diluent;
at least one polyol having an average hydroxyl
functionality of from about 1.9 to about 20 hydroxyls
per molecule and a molecular weight of at least 200;
and
at least one crosslinker selected from the group
consisting of a compound having an average isocyanate
functionality of from about 1.9 to about 20 isocyanate
groups per molecule, an amino resin having from about 3
to about 30 crosslinking groups per molecule and
mixtures of the isocyanate compound and amino resin,
the phenolic urethane reactive diluent having the
general formula

- 62 -
<IMG>
wherein R4 is selected from the group consisting of
hydrogen, halogen, hydroxyl, C1 to C8 alkyl and C1 to C8
alkoxy, R5 is selected from the group consisting of a
direct bond, C1 to C20 organic radical having only carbon
and hydrogen atoms, a C1 to C20 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, R6 is selected from the group consisting of
hydrogen, a C1 to C20 organic radical, a C1 to C20 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, a direct bond, and a direct bond
which forms with R7 part of a 5 or 6 carbon atom cyclic
ring structure, R7 is CH2R8 wherein R8 is selected from
the group consisting of hydroxy and a C1 to C20 aliphatic
which includes in it structure a substitution group
selected from the group consisting of aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof, OR9, OOCR10 and R11 wherein R9 is selected from
the group consisting of a primary or secondary
aliphatic group containing 3 to 20 carbon atoms or an
aromatic group containing 6 to 20 carbon atoms and a
primary or secondary aliphatic group containing 3 to 20
carbon atoms which includes in its structure aliphatic

-63-
hydroxyl, ester, ether, carbonate and combinations
thereof, R10 is selected from the group consisting of a
primary, secondary or tertiary aliphatic group
containing 4 to 20 carbon atoms, an aromatic group
containing 6 to 20 carbon atoms, a primary, secondary
or tertiary aliphatic group containing 4 to 20 carbon
atoms which includes in its structure aliphatic
hydroxyl, ester, ether, carbonate and combinations
thereof and R11 is selected from the group consisting of
a C2 to C20 organic radical, a C2 to C20 organic radical
which includes in its structure aliphatic hydroxyl,
ester, ether, carbonate and combinations thereof, and a
C2 to C20 organic radical which forms with R6 part of a 5
or 6 carbon atom cyclic ring structure, wherein N is
about 1 to about 4, and where R12 is selected from the
group consisting of alkyl, an alkyl difunctional
radical, alkenyl, alkenyl difunctional radical,
aromatic and an aromatic difunctional radical.
18. The polymeric vehicle as recited in claim 17,
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.
19. The polymeric vehicle as recited in claim 17,
wherein the polyol is a polyester polymer having a
number average molecular weight in the range of from
about 200 to about 20,000.
20. The polymeric vehicle as recited in claim 17,
wherein the polyol is an acrylic polymer having a
number average molecular weight in the range of from
about 300 to about 5,000.
21. The polymeric vehicle as recited in claim 17,
wherein the polyol is an alkyd polymer having a number

-64-
average molecular weight in the range of from about 500
to about 20,000.
22. The polymeric vehicle as recited in claim 17,
wherein the polyol is an epoxy polymer having a number
average molecular weight in the range of from about 500
to about 6,000.
23. The polymeric vehicle as recited in claim 17,
wherein a polyester having molecular weight of from
about 200 to about 20,000 and wherein the phenolic
urethane reactive diluent has a molecular weight in the
range of from about 240 to about 1140.
24. The polymeric vehicle as recited in claim 17,
wherein the polyol is an acrylic polymer having a
number average molecular weight of from about 300 to
about 5,000 and wherein the phenolic urethane reactive
diluent has a molecular weight in the range of from
about 240 to about 1140.
25. The polymeric vehicle as recited in claim 17,
wherein the polyol is an alkyd polymer having a number
average molecular weight of from about 500 to about
10,000 and wherein the phenolic urethane reactive
diluent has a molecular weight in the range of from
about 240 to about 1140.
26. The polymeric vehicle as recited in claim 17,
wherein the polyol is an epoxy polymer having a number
average molecular weight of from about 500 to about
6,000 and wherein the phenolic urethane reactive
diluent has a molecular weight in the range of from
about 240 to about 1140.
27. A polymeric vehicle as recited in claim 17,
wherein the crosslinker, the polyol and the phenolic

-65-
reactive diluent are each in respective amounts for
providing a coating binder made from the cured
polymeric vehicle with a pencil hardness of at least
about HB and an impact resistance of at least 30-inch
pounds direct and at least about 30-inch pounds
indirect.
28. The polymeric vehicle as recited in claim 27,
wherein the polyol is a polyester having a number
average molecular weight of from about 200 to about
20,000.
29. The polymeric vehicle as recited in claim 27,
wherein the polyol is an acrylic polymer having a
number average molecular weight of from about 300 to
about 5,000.
30. The polymeric vehicle as recited in claim 27,
wherein the polyol is an alkyd polymer having a number
average molecular weight of from about 500 to about
6,000.
31. The polymeric vehicle as recited in claim 27,
wherein the polyol is an epoxy polymer having a number
average molecular weight of from about 500 to about
6,000.
32. The polymeric vehicle as recited in claim 17,
wherein the polymeric vehicle has a second hardener
which is a diphenolic hardener.
33. The polymeric vehicle as recited in claim 4
wherein R12 is selected from the group consisting of

-66-
<IMG>
and
<IMG>
and R12 is a difunctional radical.
34. The polymeric vehicle as recited in claim 17,
wherein the difunctional radical is selected from the
group consisting of
<IMG> ,
-(CH2)n-,

-67-
<IMG>
and
<IMG>
35. The polymeric vehicle as recited in claim 17,
wherein R12 is selected from the group consisting of
<IMG>
and

-68 -
<IMG>
and R12 is a difunctional radical.

Description

WO97/06129 2 2 0 ~ ~ ~ 2 PCT~S96/129l5
~ - 1 -
~ PQ~YMERIC VEHICLES WHICX INCLUDE A
PHENOLIC URETHANE REACTIVE DILUENT
This application claims the benefit of U.S.
Provisional Application No. 60/002,063, filed August 9,
1995, and is a continuation-in-part application of U.S.
Serial No. 08/621,177, filed March 21, 1996.
FIE~D OF T~E lN v~NllON
The present invention relates to polymeric
vehicles for coating ~ilms or binders where the
polymeric vehicles are thermosetting and include a
phenolic urethane reactive diluent. More particularly
this invention is directed to polymeric vehicles which
include at least one polyol, the reactive diluent and a
polyisocyanate and/or amino resin crosslinking agent.
15 R~ O~ND OF TaE lNv~NllON AND DESCRIPTION OF THE
PRIOR ART
One of the primary components in paint is the
"film former" that provides a film for the protective
~unction 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 by existing commercial application
equipment. Use of solvents, however, raises at least
25 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 m; n~m~ zed.
Thermosetting coating compositions, particularly
coating compositions which include polyester, alkyd,
acrylic and epoxy polymers are o~ten materials of

WO97/06129 ~ ~ PCT~S96/1291
--2--
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
formulated to provide a balance of properties which
will maximize hardness, flexibility, solvent
resistance, corrosion resistance, weatherability, acid
resistance, hydrolytic stability and gloss with an
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, corrosion resistance,
weatherability, acid resistance, hydrolytic stability
and gloss, reduce VOCs and still retain the ability to
have the viscosities of the polymeric vehicle and
formulated coating composition made therefrom such that
the ~ormulated coating composition can be applied with
existing commercial applica~ion equipment.
United States Patent No. 4,331,782 to Linden,
United States Patent Nos. 3,836,491 and 3,789,044 to
Taft et 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 urethane reactive diluent which is cross
linked or the use of such a diluent in a system which
includes a polyol, diluent and crosslinking agent.
OBJECTS OF T~E lN V~!iN'l'lQN
It is an object of the invention to provide a
coating composition which will m~X;m; ze film properties
such as hardness, flexibility, solvent resistance,
corrosion resistance, weatherability, acid resistance,
hydrolytic stability and gloss.
It is another object of the invention to provide a
coating composition which will be low in VOCs.

~ ~ O ~ ~ 8 2
WO 97/06129 PCT/US96/12915
~ -- 3 --
It is an object of this invention to provide
~ormulated compositions which are solventless as well
as formulated coating compositions which are thinned by
organic solvents and/or water.
Another object of this invention is to control
viscosity of the polymeric vehicle through the use of a
phenolic urethane reactive diluent and the ability to
use commercial equipment ~or the application o~ the
formulated coating composition made with the polymeric
vehicle through such viscosity control.
Further objects and advantages of the invention
will be found by reference to the following
description.
S~MM~Y OF TEE lNv~NllON
The present invention is directed to a polymeric
vehicle, a formulated coating composition, a coating
binder made from the polymeric vehicle and a method for
making the polymeric vehicle where the polymeric
vehicle includes a phenolic urethane reactive diluent.
The latter reactive diluent improves film properties
such as hardness. When the components of the polymeric
vehicle are at low molecular weights and when the
phenolic reactive diluent is at low molecular weights
such as in the range of from about 240 to about 1140,
the reactive diluent hardens the coating binder often
without increasing the viscosity of the polymeric
vehicle and coating composition. In an important
aspect, the invention provides a high solids or
solventless polymeric vehicle and/or ~ormulated coating
composition where the viscosity of the blend which
~ constitutes the polymeric vehicle (which includes the
phenolic reactive diluent), will be in the range o~
from about 0.1 to about 20 Pa.s at about 20 to about
60~C at a shear rate o~ at least about 1,000 and
preferably in the range of about 1,000 to about 1 X lo6
sec.~~ in the absence of organic solvent and/or water.

WO 97/06129 PCT/US96/12915
-- 4 --
The coating composition is crosslinked with a
crosslinker selected from the group consisting of a
compound with isocyanate functionality and an amino
resin having an average crosslinking functionality of
from about 3 to about 30 crosslinking groups per
molecule. This amino crosslinking functionality is
reactive with the hydroxyls of the phenolic urethane
reactive diluent and the isocyanate crosslinker
compound which has an average isocyanate functionality
of from about 1.9 to about 20 isocyanate groups per
molecule. The isocyanate functionality is reactive
with the hydroxyls of the phenolic urethane reactive
diluent and the amino crosslinker.
In one important aspect, the phenolic urethane
reactive diluent may be represented by the following
general formula where Rl through R,2 is set forth below.
O R
H03~ R5 COlH--fH R7
1~
f=o
N-H
N
R.2
where N=l to 4, where Rl2 is an alkyl, difunctional
alkyl radical, alkenyl, difunctional alkenyl radical,
alkylene, such as methylene, aromatic or difunctional
aromatic radical and where R~ through R~ is set forth
below in connection with formula A. R,2 is further
described below. Generally, the reactive diluent has a
molecular weight of not more than about 50,000, and in
an important aspect, not more than about 2,000.
In a very important aspect, the phenolic reactive

WO 97/06129 2 2 ~ O o 8 2 PCT/US96/12915
diluent has the f ormula
O O
~\0~\0~
C6H13
HO O =(
NH
2)6
NH
~ ~ O
O O
or
O O
'O~oJ~
HO O =( C6H,3 HO~
NH
(CHj)6
~ =( ~ (CH2)6 ~
(CH2)6 H
NH ~
~/ OH ~= ~
C5H~
O O

2 ~ 8 ~ .
WO97/06129 PCT~S96/12915
-6-
The phenolic urethane reactive diluent is the
reaction product of a phenolic ester alcohol having at
least one aliphatic hydroxyl group and a compound
having an average isocyanate functionality of from
about l.9 to 20 isocyanate groups per molecule. The
phenolic ester alcohol is the reaction product of a
phenol carboxylic acid and a compound having an epoxy
functionality. In one important aspect, the phenolic
ester alcohol has at least two ester linkages, at least
one phenolic hydroxyl group and at least one aliphatic
hydroxyl group, and in a very important aspect, about
one aliphatic hydroxyl group which aliphatic hydroxyl
is primary or secondary. Included in this aspect, the
phenolic ester alcohol has the general formula
HO ~ Rs - COCH-CH - R,
"A"
wherein R4 is selected from the group consisting of
hydrogen, halogen, hydroxyl, C~ to C8 alkyl and Cl to C8
alkoxy, Rs is a direct bond or a C~ to C20 organic
radical which may incorporate another phenol or
aliphatic hydroxyl, ester, ether and/or carbonate group
in its structure, R6 is hydrogen or a C1 to C20 organic
radical which may include one or more ester linkages or
a direct bond which may form with R7 part of a 5 or 6
carbon atom cyclic ring structure, R7 is CH2R8 wherein R8
is selected from the group consisting of hydroxy, OR9,
OOCRIo and Rl1 wherein R~ is a primary or secondary
aliphatic group containing 3 to 20 carbon atoms which
may include one or more ester linkages or an aromatic
group containing 6 to 20 carbon atoms, Rlo 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" is a C~ to C~0 organic radical which may

8 ~
WO 97J06129 PCT/US96/12915
-- 7--
include one or more ester linkages and where the
organic radical may form with R6 part of a 5 or 6 carbon
atom cyclic ring structure. In a particularly
important aspect, R5 or R8 has the ester linkages or
groups. As used herein, an ester group or linkage
means
O O
Il 11
-CO- or -OC-.
The -OH expressly shown as bonded to the -CH- group 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 ("B")
o O
/ \ 11
CH2 - CHCH2-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 and which the glycidyl
compound is commercially available from Exxon Chemical
Company under the trademark Glydexx~.
In yet another important aspect of the invention,
the polymeric vehicle comprises the phenolic urethane
reactive diluent; at least one polyol having an average
hydroxyl functionality of from about 1.9 to about 20
hydroxyls per molecule and a molecular weight of at
~ 35 least 200; and at least one crosslinker selected from
the group consisting o~ a compound having an isocyanate
functionality of from about 1.9 to about 20 isocyanate
groups per molecule, an amino resin having a
crosslinking functionality of from about 3 to about 30
crosslinking groups per molecule and mixtures of the

2 2 ~ ~ o 8 2
- WO 97/06129 PCTIUS96/12915
-- 8 --
isocyanate compound and amino resin.
In a very important aspect of this invention, the
polymeric vehicle includes the polyol which is a
polyester, alkyd or acrylic polyol, the reactive
diluent made with the phenolic ester alcohol having one
aliphatic hydroxyl group, where the isocyanate compound
used to make the reactive diluent has an average
isocyanate functionality of about 3 and an amino resin
crosslinker. In the aspect of the invention which
includes polyol, phenolic urethane reactive diluent and
crosslinker, each is in relative amounts effective for
providing an acceptable coating binder which generally
will have a pencil hardness of at least about HB, an
impact resistance of at least about 20-inch pounds
direct and at least about 20-inch pounds reverse at a
film thickness of about 0.5 mil dry.
In an important aspect, the coating binder will
have a hardness of about F at a thickness of about 0.5
mil dry and an impact resistance of about 30-inch
pounds direct and 30-inch pounds reverse at such
thickness.
Generally the polymeric vehicle may have from
about 0 to about 80 weight percent polyol, from about
10 to about 80 weight percent reactive diluent and from
about 8 to about 50 weight percent crosslinker where
the crosslinker is an amino resin and from about 8 to
about 50 weight percent crosslinker where the
crosslinker has an isocyanate functionality. Where a
polyol is present in the blend of the polymeric
vehicle, the polymeric vehicle generally will comprise
at least about 15 weight percent polyol and preferably
will have from about 15 to about 60 weight percent
polyol.
DESCRIPTION OF T~E PREFERRED EMBODIMENTS
"Polyester" means a polymer which has
-C(=O)O- linkages in the main chain of the polymer.

8 ~
~ WO97/06129 PCT~S96tl2915
g
"Polyisocyanate" can mean compounds with two or
more isocyanate groups [-N=C=O] which compounds may be
biurets and isocyanurates.
"Biuret" means an isocyanate reacted with water in
a ratio of three equivalents of isocyanate to one mole
of water, such as the biuret of HDI shown below.
An "isocyanurate" is a six-membered ring having
nitrogens at the l, 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.
"Crosslinking agent~ means a compound having di-
or polyfunctional isocyanate groups or a polyfunctional
amino resin. The isocyanate compound or amino resin
con~ains isocyanate or other crosslinking functional
groups that are capable of forming covalent bonds with
hydro~yl groups that are present or. the polyol in the
polymeric vehicle. The 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.
"Polymeric vehicle" means polymeric and resinous
components in the formulated coating, i.e., before film
formation, including but not limited to the polyol and
phenolic urethane reactive diluent.
"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.
IIVOCII means volatile organic compounds.

8 2
WO97/06129 PCT~S96/129l5
- 10 -
"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.
- 5 "Organic solvent" means a liquid which includes
but is not limited to carbon and hydrogen and has a
boiling point in the range of ~rom 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 as any compound of carbon, excluding carbon
monoxide, carbon dioxide, carbonic acid, metallic
carbides or carbonates, and ~mmo~1um 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); 1,1,1-
trichloroethane ~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-1,1,2,2-tetrafluoroethane (CFC-114);
chloropentafluoroethane (CFC-115); 1,1,1-trifluoro 2,2-
dichloroethane (HCFC-123); 1,1,1,2-tetrafluoroethane
(HF-134a); 1,1-dichloro 1-fluoroethane (HCFC-141b); 1-
chloro 1,1-difluoroethane (HCFC-142b); 2-chloro-
1,1,1,2-tetrafluoroethane (HCFC-124); pentafluoroethane
(HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1-
trifluoroethane (HFC-143a); 1,1-difluoroethane (HFC-
152a); and perfluorocarbon compounds which fall into
these classes:
(i) Cyclic, branched, or linear, completely
fluorinated alkanes;
(ii) Cyclic, branched, or linear, completely
fluorinated ethers with no unsaturations;

WO 97/06129 - 11 PCT/US96/12915
(iii) Cyclic, branched, or linear, completely
~luorinated tertiary amines with no unsaturations; and
(iv) Sulfur containing perfluorocarbons with no
unsaturations and with sulfur bonds only to carbon and
fluorine. Water is not a VOC.
A "film" is formed by application of the
~ormulated coating composition to a base or substrate,
evaporation of solvent, if present, and crosslinking.
The invention is directed to a polymeric vehicle
which comprises a phenolic reactive diluent as herein
described. Generally, the polymeric vehicle also
comprises a polyol and/or a crosslinker selected from
the group consisting o~ a poly~unctional amino resin,
an isocyanate compound having polyfunctional isocyanate
functionality and mixtures of the polyfunctional amino
resin and polyfunctional isocyanate compound. The
polymeric vehicle and formulated coating compositions
which include the polymeric vehicle of the invention
may include organic solvents or may not require organic
solvents or water to provide a formulated coating
composition with a viscosity such that the formulated
coating composition may be applied by existing
application equipment. Alternatively, in another
aspect, the polymeric vehicle and/or ~ormulated coating
composition of the invention permit the use of water
for obt~n~ng such a viscosity while reducing or
mitigating VOCs. The phenolic urethane reactive
diluent of the invention at low molecular weights, such
as in the range of from about 240 to about 1140,
improves ~ilm properties such as hardness often without
increasing the viscosities of the polymeric vehicle and
~ormulated coating composition. Further the phenolic
urethane reactive diluent is compatible with and
~ permits the use of other diphenolic hardeners to
improve coating properties, but yet also permits the
use of the additional hardeners in a formulated coating
composition which may include solvents. By way of

~ 2 ~ ~ ~ 8 ~
WO 97/06129 PCT/US96/12915
- 12 -
example, a diphenolic polyol ester reaction product of
hydroquinone and parahydroxy benzoic acid has low
solvent dispersibility or solubility, requires high-
cure temperatures and often makes coatings intractable.
The use of the phenolic urethane reactive diluent of
the invention permits the use of such other diphenolic
hardeners to improve hardness yet reduces the other
problems attendant with the use of such hardeners. In
high solids formulated coating compositions which
include organic solvents (such as about 75 weight
percent solids), one aspect of the invention
contemplates the crosslinker, reactive diluent and
polyol, if any, being in amounts effective for
maint~n;ng VOCs in the formulated coating composition
(which includes the polymeric vehicle) to less than
about 3.5 pounds of VOC per gallon of formulated
coating composition while at least maintaining the
pencil hardness of the coating binder, to at least
about HB and maint~;n;ng an impact resistance of the
coating binder to at least about 20-inch pounds direct
and at least about 20-inch pounds indirect. Indeed in
the high solids aspect of the invention, the invention
is effective for providing formulated coating
compositions having less than 2.5 pounds of VOC per
gallon of formulated coating composition and in some
cases less than 2.0 pounds of VOC per gallon of
formulated coating composition.
In yet another important aspect, the invention is
effective for providing solventless li~uid formulated
coating compositions (not more than about 3 weight
percent organic solvent) where the polymeric vehicle in
the formulated coating composition comprises the
phenolic urethane reactive diluent at low molecular
weight, a polyol having a molecular weight of at least
200, an average hydroxyl functionality of from about
1.9 to about 20 hydroxyls per molecule and a
crosslinker selected from the group consisting of the

T
8 ~
WO97/06129 PCT~S96/1291S
-13-
polyfunctional amino resin, the compound with
poly~unctional isocyanate ~unctionality and mixtures of
the polyfunctional amino resin and polyfunctional
isocyanate.
The Phenolic Urethane Reactive Diluent
In one aspect, the phenolic urethane reactive
diluent may be described as the reaction product of a
phenolic ester alcohol having at least one aliphatic
hydroxyl group and a compound having an average
isocyanate functionality of at least l.9. In this
aspect, the ratio of an isocyanate to phenolic ester
alcohol in the reaction mixture is in the range o~ from
about l equivalent isocyanate group per equi~alent of
aliphatic hydroxyl phenolic ester alcohol. The
isocyanate reacts with the aliphatic hydroxyl, which
reaction is catalyzed by soluble tin salts such as
dibutyl tin dilaurate and dibutyl tin diacetate and
divalent zinc salts such as zince diacetate.
In another aspect, the phenolic reactive diluent
has the following general formula where R1 through R~1
are defined above in connection with formula A and Rl2
is defined as set forth below.
O R
HO3~_ R5 - COCH--CH--R,
O
C=O
I
N-H
N
R1z
where N=l to 4, where R12 is an alkyl, alkenyl, aromatic
or alkyl, alkenyl and aromatic difunctional radicai,
where the radical can include or be

~ 2 ~ ~ o 8 ~
WO97/06129 -14- PCT~S96/12915
~} CH
~(CH2)n~ ~
H3C ~ CH3
~ \
/~ <CH2
CH3
or
CH3~/CH s
,~,
~ CH3
CH3
and where n = more than l and preferrably 6. In an
important aspect of the invention, the R~2 radical is

WO97/061292 2 ~ ~ ~ 8 2 PCT~S96/12915
-15-
-R12-~C \
N-R12-
/
-R.2-~ 11
O or
11
R~2~ N ~ N - R12
O N O
I
R,2
where R12 i9 a difunctional radical as described above.
The phenolic ester alcohol 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~
HO3~ 11 1 6
OH
"A"
wherein R4 through R7 is defined above.
A phenol carboxylic acid reactant to make the
phenolic ester alcohol may be used to prepare the

8 2
WO97/06129 PCT~S96/12915
-16-
phenolic ester reaction product of formula A. The
phenol carboxylic acid has the general formula:
O
3~ Rs--COH
wherein R4 and R5 are as described above. Examples of
suitable phenol carboxylic acids include hydroxybenzoic
acids, acids where R5 is alkylene such as phenyl acetic
acid, hydroxy phenyl propionic acid, hydroxyphenyl
stearic acid, and acids where in R5 encompasses
additional phenol functionality such as 4,4-bis
hydroxyphenyl pentanoic acid and the like. In a
preferred embodiment of the invention, R4 in formula A
is hydrogen, R5 is a direct bond, R6 is hydrogen and R7
is CH2OH, a hydrocarbon moiety or an organic moiety
containing ester or ether groups and contA;n;ng from l
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 used to make the phenolic
urethane reactive diluent 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 para-hydroxybenzoic 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 o~ the
structure:
o
/ \
CH,-CH-CH,OR9

8 ~
g7/06129 PCT~S96/12915
-17-
glycidyl esters of the structure:
O O
- 5 / \ 11
CH2-CH-CH2-O-C-Rlo
glycidyl or oxirane compounds having the structure:
R6-CH-CH-R,
O . ,.
15 and cycloaliphatic epoxy compounds having the ..
structures:
~ ~ 11 o ~ 11 OR,2
wherein R~2 is an organic radical having 1-12 carbon
atoms which can include ether, ester, hydroxyl or epoxy
groups, as well as other cycloaliphatic compounds
having the structures:
o ~ CH20 1l R" o ~ CH20CR,2 ~-OCH
Other epoxy materials include epoxidized alpha-
olefins and bis aromatic epoxies such as the reaction
product of bisphenol A or F with epichlorohydrin.
Suitable epoxy compounds particularly include
monoepoxides containing a term1nA1 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
monomers with one or more ethylenically unsaturated
monomers such as acrylates, methacrylates, vinyl

WO 97/06129 ~ 8 2 PCT/US96/12915
-18 -
aromatic monomers and the like.
Other suitable epoxy compounds include the ester
reaction products o~ epichlorohydrin with mono- or
dibasic aliphatic or aromatic carboxylic acids or
anhydrides cont~n;ng 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,
phthalic, isophthalic and terephthalic acids as well as
the corresponding anhydrides of such acids. Preferred
such acids are primary, secondary or tertiary aliphatic
carboxylic acids containing from 5 to 13 carbon atoms.
In a very important aspect of the invention, an epoxy
compound of this type is the glycidyl ester of a mixed
aliphatic, mostly tertiary, mono carboxylic acid with
an average of 9 to 11 carbon atoms such as 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 ~B~. (Glydexx~ general formula).
Still other epoxy compounds include glycidyl ether
reaction products of epihalohydrin with aliphatic or
aromatic alcohols or polyols cont~;n;ng from about 1 to
20 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 C8 to C20 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

~ WOg7/~6l29 ~ 8 2 PCT~S96~12915
-19 -
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 ~or
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-epoxy) cyclohexane-
metadioxane.
In a very important aspect of making the phenolicester used to make the phenolic urethane reactive
diluent, the hydroxybenzoic acid/epoxy reaction product
of this invention 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 90~ to about 120~C to
initiate such reaction. Once the reaction is
initiated, such reaction 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 the reaction has been determined to be
substantially complete.
Reaction products of reduced discoloration can be
produced by control of the m~;mnm temperature of the
exothermic reaction. This can be achieved by a staged
and/or incremental addition of one of the reactants,
e.gO 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
maint~;n;ng the reaction temperature below about 150~C.
This process modification gives rise to reaction
products having lower Color Index values.

WO 97/06129 ~ I Q 8 2 PCT/US96/12915
-20-
Approximately stoichiometric quantities of the
epoxy 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.
The phenolic urethane reactive diluent is the
reaction product of the phenolic ester alcohol, such as
the one shown in formula A, and a composition having a
polyisocyanate functionality, such as a polyisocyanate,
biuret or isocyanurate. One equivalent isocyanate is
reacted for every equivalent of aliphatic hydroxyl
group in the phenolic ester alcohol. The reaction is
catalyzed by an organo metallic catalyst such as
dibutyl tin dilaurate and zinc acetate. In many
15 instances the reaction proceeds at room temperature,
and if not, the reaction mixture may be heated as is
known to drive the reaction such that the aliphatic
hydroxyl groups are reacted to provide the phenolic
urethane reactive diluent which has free hydroxyl
20 groups extending from the aromatic ends of the
molecule. The phenolic urethane reactive diluent may
be made with low molecular weight diisocyanates such as
hexamethlenediisocyanate (HDI) as well as
polyisocyanates which have molecular weights up to
25 about 20,000. Unblocked or blocked di- or
polyisocyanates, unblocked or blocked biurets and
blocked or unblocked isocyanurates all may be reacted
with the aliphatic hydroxyls of the phenolic ester to
form carbamate linkages [-OC(=O)N(-H)-] and the
phenolic urethane reactive diluent. This diluent
serves as a hardener to harden the coating binder
without increasing the viscosities of the formulated
coating composition and polymeric vehicle. In many
important instances, the phenolic urethane reactive
diluent keeps the viscosity of the polymeric vehicle
low to aid in the reduction of VOCs.
Diisocyanates which may be used in the invention

~ W097/06129 ~ 2 0 ~ ~ 8 2 PCT~S96/12915
additional to HDI include isophorone diisocyanate
(IPDI), tetramethylxylene diisocyanate (TMXDI), and
other aliphatic diisocyanates such as trimethylene
diisocyanate, tetramethylene diisocyanate,
pentamethylene diisocyanate, l,2-propylene
diisocyanate, 2,3-butylene diisocyanate, l,3-butylene
diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene
diisocyanate; cycloalkylene diisocyanates such as l,3-
cyclopentane-diisocyanate, l,4-cyclohexane-diisocyanate
and l,3-cycloh~ne-diisocyanate; and aromatic
diisocyanates such as m-phenylene diisocyanate, p-
phenylene diisocyanate, 4,4'-diphenyldiisocyanate, l,5-
naphthalene diisocyanate, 4,4'-diphenylmethane
diisocyanate, 2,4- or 2,6-tolulene diisocyanate.
The polyisocyanates may be dimerized or trimerized
diisocyanates such as trimerized HDI or IPDI and
triisocyanates such as triphenylmethane-4,4',4"-
triisocyanate, l,3,5-triisocyanatobenzene, l,3,5-
triisocyanatocyclohexane, 2,4,6-triisocyanatotoluene
and ~-isocyanatoethyl-2,6-diisocyanatocaproate; and
tetraisocyanates, such as 4,4'-diphenyldimethylmethane-
2,2',5,5'-tetraisocyanate.
They also may be polymers or copolymers with vinyl
monomers of isocyanate functional monomers such as
NCO
and

wo97lo6l2s r ~ 8 ~ PCT~S96/12915
-22-
CH3
CH2=CCOCH2CH2N=C=O
In another aspect of the invention, unblocked or
blocked biurets such as the biuret of hexamethylene
diisocyanate (HDI) which biuret has the structure
C-NH- (CH2) 6 - NCO
OCN - (CH2) 6 - N
C-NH - (CH2) 6 - NCO
O
and is a trimerized product of hexamethylene
diisocyanate and water may be used in lieu of
polyisocyanates.
In a particularly important aspect of the
invention an isocyanate, biuret, isocyanurate or blends
thereof with an -NC=O functionality of about 3 provides
a particularly useful phenolic urethane reactive
diluent when reacted with a phenolic ester alcohol
which is a reaction product of a hydroxybenzoic acid
such as PHBA and glycidyl ester of a mixed aliphatic
such as Glydexx~.
Agents which block the isocyanate groups and
"deblock" at elevated temperature are known and are
used in the invention. These include o~1mes, lactams,
imines, carbamates such as acetone oxime, methyl ethyl
ketoxime, ~-caprolactam and ethyleneimine.
The Crosslinkinq Agent
The crosslinking agent which is used with the

WO97/06129 ~ 2 ~ ~ ~ 8 2 PCT~S96/12915
-23-
reactive diluent may be one or more unblocked or
blocked polyisocyanates, one or more unblocked or
blocked biurets, one or more blocked or unblocked
isocyanurates, one or more amino resins and/or a blend
o~ crosslinkers at least one crosslinker in the blend
having the -NC=0 functionality and one crosslinker in
the blend being an amino resin crosslinker. Effective
amounts o~ crosslinker for permitting the polymeric
vehicle to crosslink into a coating binder with the
hardness and impact resistance as described above are
used. When the polymeric vehicle includes a polyol and
reactive diluent, the polymeric vehicle generally
comprises at least about 15 weight percent polyol and
generally from about 15 to about 60 weight percent
polyol, from about lO to about 80 weight percent
reactive diluent and from about 8 to about 50 weight
percent crosslinker where the crosslinker is an amino
resin and from about 8 to about 50 weight percent
crosslinker where the crosslinker has an isocyanate
functionality.
The same polyisocyanates, biurets and
isocyanurates may be used as crosslinkers that are used
to make the phenolic urethane reactive diluent. If,
however, a compound which is high in isocyanate
~unctionality (numerous isocyanate groups) is used to
make the reactive diluent, then a compound which is
lower in isocyanate ~unctionality should be used as a
crosslinker.
Methylol (alkoxymethyl) amino crosslinking agents
are suitable ~or 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.
- Examples of suitable amino-crosslinking
resins include one or a mixture o~ the following
materials:

~ ~2~ ~8 ~
WO 97/06129 PCT/US96/12915
-24 -
Melamine based resins
,N~
(ROCH2)2N 1I C--N(cH2oR)2
CO
I
N(CH20R)2
wherein R is the following:
R = CH3 (Cymel)~ 300, 301, 303);
R = CH3, C2H5 (Cymel~ 1116);
R = CH3, C4H9 (Cymel0 1130, 1133);
R = C4H9 (Cymel~ 1156); or
10 R = CH3, H (Cymel~ 370, 373, 380, 385).
The preferred melamine is hexamethoxymethyl melamine.
Benzoqll~n~m;ne based resins
,N~
(ROCH2)2N ICI C N(CH20R)2
C~
IJ
wherein R = CH3, C2Hs (Cymel~ 1123).
Urea based resins
( ROCH2) 2 N - F - N ( CH2OR ) 2
O
wherein:
R = CH3, H (BeetleTM 60, BeetleTM 65); or
R = C4H9 (BeetleTM 80).
Gycoluryl based resins

WO 97/06129 ~ 2 0 ~ ~ 8 2 PCT/US96/12915
-25-
ROCH2 CH20R
/ \C~ \
O C I C--O
\N CH
ROCH2 CH20R
wherein:
R = CH3, C2H5 (Cymel~ 1171); or
R = C4H9 (Cymel~ 1170).
The Polyols In The Polymeric Vehicle
The polyols which are used in the invention are
selected from the group consisting of polyesters, alkyd
polymers, acrylic polymers and epoxy polymers. The
polyols have an number average molecular weight (~) of
at least about 200, and may generally range from about
200 up to about 20,000, more preferably from about 280
up to about 10,000, and most preferably from about 300
up to about 3,000 to 6,000. Glass transition
temperatures (Tg) of these materials may generally
range from as low as -90~C up to +100~C or higher.
The diesters and polyesters 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 ~rom carboxylic acids
and oxiranes, such as

~oo os 2
WO97/06129 PCT~S96/12915
-26-
RCOOH
o
1 ~1
R
R
RCOO~J~
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; h~x~methylenediol;
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; 2-
ethyl-1,3-hexandediol; 1,5-pentanediol; thiodiglycol;
1,3-propanediol; 1,2-propanediol; 1,2-butanediol; 1,3-
butanediol; 2,3-butanediol; 1,4-butanediol; 2,2,4-
trimethyl-1,3-pentanediol; 1,2-cyclohexanediol; 1,3-
cyclohexanediol; 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 o~ anhydride groups, lactone
yroups, or e~uivalent ester forming derivatives such as
the acid halide or methyl ester. The dicarboxylic
acids or derivatives are pre~erably one or more of the
following: phthalic anhydride, terephthalic acid,
isophthalic acid, naphthalene dicarboxylic acids,
adipic acid, succinic acid, glutaric acld, fumaric

WO97/06129 ~ Q 8 2 PCT~S96112915
-27-
acid, maleic acid, cyclohexane dicarboxylic acid,
azeleic 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 thereo~.
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 unsaturated aliphatic
dicarboxylic acids having ~rom 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 ~rom 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 comprise members selected from the
group consisting o~ the following esters of acrylic or
methacrylic acid and aliphatic glycols: 2-hydroxyethyl
acrylate, 3-chloro-2-hydroxypropyl acrylate; 1-hydroxy-
2-acryloxy propane; 2-hydroxypropyl acrylate; 3-
hydroxy- propylacrylate; 2,3-dihydroxypropylacrylate;
3-hydroxybutyl acrylate; 2-hydroxybutyl acrylate; 4-
hydroxybutyl acrylate; diethyleneglycol acrylate; 5-
hydroxypentyl acrylate; 6-hydroxyhexyl acrylate;
triethyleneglycol acrylate; 7-hydroxyheptyl acrylate;
1-hydroxy-2-methacryloxy propane; 2-hydroxypropyl
methacrylate; 2,2-dihydroxypropyl methacrylate; 2-
hydroxybutyl methacrylate; 3-hydroxybutyl methacrylate;

~-~2~ Q~ ~ '
WO 97/06129 PCT/US96/1291
-28-
2-hydroxyethyl methacrylate; 4-hydroxybutylmeth-
acrylate; 3,4-dihydroxybutyl methacrylate; 5-hydroxy-
pentyl methacrylate; and 7-hydroxyheptyl methacrylate.
The preferred hydroxy ~unctional monomers for use in
preparing the acrylic resins are hydroxy-substituted
alkyl (meth) acrylates having a total of 5 to 7 carbon
atoms, i.e., esters of C2 to C3 dihydric alcohols and
acrylic or methacrylic acids. Illustrative of
particularly suitable hydroxy-substituted alkyl (meth)
acrylate monomers are 2-hydroxyethyl methacrylate, 2-
hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-
hydroxypropyl methacrylate, and 2-hydroxypropyl
acrylate.
Among the non-hydroxy-substituted alkyl
(meth) acrylate monomers which may be employed are
alkyl (meth) acrylates. Preferred nonhydroxy
unsaturated mo~m~rs are esters of C, to Cl2 monohydric
alcohols and acrylic or methacrylic acids, e.g., methyl
methacrylate, hexyl acrylate, 2-ethylhexyl acrylate,
lauryl methacrylate, glycidyl methacrylate, etc.
Examples of particularly suitable monomers are butyl
acrylate, butyl methacrylate 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 about
30,000, more preferably between about 280 and about
15,000, and most preferably between about 300 and about
5000.
Alkyd polymers may be used as the polyol

. . . = . = = -- =
~ 2 ~
WO97/06129 PCT~S96/1291
-29-
component of this invention. These alkyd resins 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 ~at which acts as a modi~ier. 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 o~ aliphatic carboxylic acids or mixtures of
aliphatic and aromatic dicarboxylic acids. Suitable
acids and acid anhydrides include, by way of example,
succinic acid, adipic acid, phthalic anhydride,
isophthalic acid, trimellitic acid (anhydride) and bis
3,3', 4,4'-benzophenone tetracar-boxylic anhydride.
Mixtures of these acids and anhydrides may be employed
to produce a balance of properties. As the drying oil
or fatty acid there is suitably employed a saturated or
unsaturated fatty acid of 12 to 22 carbon atoms or a
corresponding triglyceride, that is, a corresponding
fat or oil, such as those contained in ~n;m~l or
vegetable fats or oils. Suitable fats and oils include
tall oil, 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

8 2
W097/06129 PCT~S96/12915
-30-
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,- CHCH,CI ~ HO ~ CH, aq.NaOH
CH,
CH, - CHCH, O ~ CH, OCH,CHCH, o ~ CH, OCH,CH - CH,
_ CH, - x CH,
The viscosity of the polymer is a function of
molecular weight, the higher the molecular weight the
more viscous the polymer.
Other hydroxyl-cont~; n; ng compounds, including
resorcinol, hydroquinone, glycols, and glycerol may be
used in lieu of bisphenol A.
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
polymerlc vehicle which is effective for providing a
high solids, low VOC formulated coating composition and
a water-thinned formulated coating composition.
Suitable optional solvents which may be included in the
curable compositions of the invention comprise toluene,

~ 2 ~ ~ ~ 8 ~
WO 97/06129 PCT/US96/1291
- 3 1 -
xylene, ethylbenzene, tetralin, naphthalene, and
solvents which are narrow cut aromatic solvents
comprising C8 to C,3 aromatics such as those marketed by
Exxon Chemical 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.
Suitable oxygenerated solvents include propylene
glycol monomethyl ether acetate, propylene 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, n-propyl acetate, butyl acetate, amyl acetate,
mixtures of hexyl acetates such as sold by Exxon
Chemical Company under the name EXXATE~ 600 and
mixtures of heptyl acetates sold under the name EXXATE~
700. The list should 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 e~aporation 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 TiO2 and
particularly weather-resistant coated types of TiO~.
The pigments may also be blended with a suitable

~ ~ O O 0 8 ~
WO 97/06129 PCT/US96/12915
-32 -
extender material which does not contribute
significantly to hiding power. Suitable extenders
include silica, barytes, calcium sulfate, magnesium
silicate (talc), aluminum oxide, aluminum hydroxide,
5 alllm; nllm silicate, calcium silicate, calcium carbonate
(mica), potassium aluminum silicate and other clays or
clay-like materials.
Satisfactory baking schedules 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 general, the substrate and
15 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
cont~; n; ng 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
3 5 phosphate, butyl maleate, and the like or a compatible
mixture of them. These acid catalysts may be used in
their nea~, unblocked form or co-mbined with suitable

~ ~ ~ n ~ 8
WO 97/06129 PCT/US96/12915
-33 -
blocking agents such as amines. Typical examples of
unblocked catalysts are the King Industries, Inc.,
products with the tradename K- CURE~. Examples o~
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 0.2 to 0.5 wt~ catalyst solids
per polymer plus crosslinking agent solids. Higher
concentrations of catalyst up to about 2 wt~ may be
employed for cures at lower temperature or shorter
times. 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
a. Synthesis of the Phenolic Ester from a Glycidyl
- Ester and PHBA
Into a 1 liter ~lask equipped with agitation,
~ nitrogen, heating and temperature probe, 326.6g
Glydexx~ N-10 glycidyl ester and 173.4g parahydroxy
benzoic (PHBA) were charged. The mixture was heated at
110~C. At that point, an exothermic reaction takes

WO97/06129 2 2 0 ~ ~ 8 ~ PCT~S96/l2915 ~
place. The maximum temperature reached was 160~C. The
solution was then cooled and discharged. Physical
properties are given below.
Acid Number : 0 mg KOH/gram
N~ : > 99~
Color : c3 Gardner
b. Synthesis of a Phenolic ~rethane Reactive Diluent
by the Reaction of the Phenolic Ester with HDI (in
the molar ratio 2:1)
Into a 25 mL round-bottomed flask equipped with a
magnetic stirrer was added the phenolic ester of
Example I-a (1.90 g, 5.21 mmol, MW 365) dissolved in 5
mL acetonitrile. A solution of HDI (0.44 g, 2.62 mmol,
MW 168) in 5 mL acetonitrile was also added followed by
dibutyltin dilaurate (DBTD~, 0.06 g, 2.5 wt~ total) as
catalyst. The clear, transparent solution was stirred
at room temperature for 24 hours. The reaction mixture
remained clear and transparent. An infrared spectrum
of the reaction mixture showed a weak to no ~NCO band.
Acetonitrile was removed from the reaction mixture
using rotary evaporation under aspirator pressure to
give a sticky, resinous material which was further
dried at room temperature overnight in a stream of air.
The reaction is shown below.

F' ~ 2 ~D 10 6~ ~ ~
WO 97/06129 PCT/US96/12915
-35 -
O O
-----~ O ~ OJ ~ ~ ONC-(CH2)6-NCO
HO
--2wt.% DBTDL,
CH3CN, rt,
12-24 h
O O
~ 10 C,H,,
HO 2 ~ =~
NH
(CHz)~
NH
0~
HO ~
O O
Approximately 0.08 g of this sample was dissolved in 1
m~ CDCl3 for NMR analysis. 13C NMR assignments of the
product are listed in the following table. It may be
noticed that the chemical shift of carbon (7)
substituted with the secondary -OH group changed from
72.26 ppm to 69.69 ppm. The chemical shifts of the two
methylene carbons (6 and 8) appeared in the product
compared to that in the phenolic ester. There are also
slight changes in the chemical shifts of the ester
carbons (5 and 9). The urethane carbon (10) appeared
at 156.24 ppm. There was no significant chemical
shifts for the phenolic carbons suggesting that no
reaction took place at the phenol moiety.

1 2~0 ~8 2
WO97/06129 PCT~S96/1291s
-36-
l3C 1 2 3 4 5
ppm 161.42 115.40 131.99 121.06 166.13
13c 6 7 8 9 10
ppm 63.21 69.24 62.69 176.96 156.24
c. Synthesis of a Phenolic Urethane Reactive Diluent
by the Reaction of the Phenolic Ester with the
Isocyanurate of EDI
Into a 25 mL round-bottomed flask equipped
with a magnetic stirrer was added a solution of the
phenolic ester of Example I-a (2.01 g, 5.51 mmol, MW
365) in 5 mL acetonitrile. A solution of the
isocyanurate of HDI (Desmodur N3300, 0.96 g, 1.64 mmol,
MW 585) in 5 mL acetonitrile was added to the reaction
flask followed by dibutyltin dilaurate (DBTDL, 0.06 g,
2 wt.~ total) as catalyst. The reaction mixture was
stirred at room temperature for 24 hours. An oily,
transparent product was precipitated at the bottom of
the flask. Acetonitrile was removed from the reaction
mixture in vacuum using a rotary evaporator under
aspirator pressure. The product obtained was left
overnight in a stream of air to remove the remaining
solvent. Approximately 0.08 g of reactive diluent
(PETG1-N3300) was dissolved in 1 mL CDCl3 for NMR
studies.

~2~ ~8 2
WO 97/06129 PCT/US96/12915
-37-
~ O O
ocN-(cHz)6~ N J~ N ~ 3 ~ o ~ o ~,H,,
HO
(CHz)~
-2wt.% D8TDL,
NCO CH3CN, rt,
. 12-24 h
o O
0 2 ~ ~< C6H~, HO
(CH,), o
o ~( N--(CH2)~
(CH2)~ H
NT~ ~
~1/ ~3~ OH j~ ~
O O
PTEGl-N3300
The 13C NMR chemical shift data are listed
below. Comparing these chemical shifts with the
chemical shifts of the reaction products of HDI with
the phenolic ester discussed above, it may be assumed
that the phenyl moiety did not undergo any reaction.
The significant changes in the chemical shifts o~
carbons 6, 7 and 8 suggest that the secondary aliphatic
-OH group reacted with the isocyanate functionality.

2 2 Q ~ O
WO97/06129 PCT~S96/12915
-38-
~3C 1 2 3 4 5
ppm 161.48 115.36 131.96 121.05 166.05
'3C 6 7 8 910 11
ppm 62.68 69.28 62.67 176.86 156.15 149.0
EXAMPLE II
PROCEDURE FO~ T~E ~YN-L~SIS OF OLIGOESTERDIOL
FROM DBE-3, DBE-5 AND 1,4-B~TANEDIOL
H3CO2C CO CH, + H,C02C~ CO2CH 4 HO/\/\/
DBE-5 DBE-3
0.01 wt.% Zn(OAc)2
~, N2
~CH,OH
(CH2)m ~ o ~ O m = 3 - 4
O O
Into a 2000-mL 4-necked reaction kettle
equipped with a Dean-Stark condenser, a reflux
condenser, a nitrogen inlet, a thermometer inlet and a
motor driven stirrer, was added 432.5 g of DBE-3
(dimethyl adipate, 2.5 mol, MW 173), 400 g of DBE-5
(dimethyl glutarate, 2.5 mol, MW 160), 924.60 g of 1,4-
butanediol (10.26 mol, MW 90.12) and 0.18 g zincacetate (0.01~ of total weight). The reaction vessel
was purged with nitrogen for 30 minutes. The contents
of the reaction vessel were heated to 140~C for 12
hours, 160~C for 8 hours, 200~C for 2 hours and 225~C
for 1 hour. The color of the reaction mixture turned
light yellow upon heating to 180~C. About 390 mL of
methanol distilled out of the reaction mixture during
this heating process (theoretical amount of methanol to
be distilled out = 400 mL). The remaining methanol is
assumed to have escaped. The reaction temperature was

2 ~ 8 2
WO97/06129 PCT~S96/12915
-39-
raised to 240~C to distil the excess l,4-butanediol.
Meanwhile, Brookfield viscosity of the aliquots of the
reaction mixture were performed at regular intervals of
l0 minutes at 25~C using spindle #31 at 6 rpm. In the
meantime, nearly 20 mL of l,4-butanediol was distilled
out. Once the viscosity reached about 500-600 mPa.s,
the reaction mixture was cooled to room temperature.
EXAMPLE III
FORM~LATIONS ~SING T~E REACTIVE DIh~ENT OF
I-c, THE DIOL OF EXAMPLE II AND CYMEL 300
a. I~gredients and Tests
BYK030l & 302 - Flow control agent from Byk-Chemie.
Desmodur N3300 - From Miles Corporation is a cyclo-
trimer of l,6-hP~m~thylene
diisocyanate (isocyanurate of l,6-
h~x~methylene diisocyanate, HDI).
Its viscosity is l.8 - 4 mPa.s at
25~C, and its equivalent weight is
194.
DNNDSA - Catalyst Dinonyl naphthalene
disulfonic acid in isobutanol is
obtained from King Industries
("Nacure-155").
GLYDEXX~ N-l0 - Glycidal ester of a mixture o~
tertiary aliphatic acids having 9-
ll carbon atoms available from
Exxon Chemical Company.
GLYDEXX~ND-l0l - Same as N-l0, but less pure.
SK l0l - A diphenolic polyol e~ter which is
- the reaction product of
hydroquinone and parahydroxy
benzoic acid.
Films were prepared by casting the blended
solution on panel by a 26# wire-wound draw bar.

- 2~0~ ~8 2
WO97/06129 PCT~S96/12915
-40-
Pencil hardness was measured according to ASTM
D3364-74 standard test method for film hardness by
pencil test. Impact resistance, either direct or
reverse impact, was measured according to the ASTM
D2794-84 standard test method for resistance of organic
coatings to the effects of rapid deformation (Impact).
Resistance to methyl-ethyl-ketone (MEK) was measured by
double rubbing with MEK saturated nonwoven paper ("Kim-
Wipe"). The nonwoven paper was kept saturated by MEK
during the measurement. Dry film thickness was
measured by an Elcometer Model 300 thickness gauge.
Adhesion was measured according to ASTM standard
(Designation: D3359-87, test method B-cross-cut tape
test). VOC and NVW were measured according to ASTM
standard test method for volatile content of coatings
(Designation D2369-87). Viscosity was measured on a
Brookfield viscometer at 6 rpm except as noted.
b. Preparation and Evaluation of Films
Polymeric vehicles and coating binders were made
with the phenolic urethane reactive diluent of Example
I-d and the oligoester diol of Example II.

8 ~
WO 97/06129 PCTtUS96/12915
-41-
Table A
Oligoesterdiol* 1.02 g
PTEG1-N3300 0.56 g
Cymel 300 0.51 g
BYK-302 0.04 g
DNNDSA 0.02 g
Baking Conditions 300~F/30 min.
10 Appearance Clear, glossy
Film Thickness 1.0-1.2 mil
Adhesion 3B
Pencil Hardness** HB
MEK rub resistance ~200
15 Impact resistance-Direct 80
Impact resistance-Reverse40
*Oligoesterdiol was synthesized from DBE-3, DBE-5 and
1,4-butanediol as per Example II.
**In the instances where the hardness was only HB, it
is believed an insufficient crosslinker was used.

2 ~ ~ O Q 8 2
WO97/06129 PCT~S96/lZ915
-42-
Table B
Oligoesterdiol* 0.51 g
PTBG1-N3300 0.50 g
Cymel 300 0.75 g
BYK-302 0.04 g
DNNDSA 0.02 g
Baking Conditions 300~F/30 min.
Appearance Clear, glossy
Film Thickness 0.9-1.1 mil
10 Adhesion 4B
Pencil Hardness 2H
MEK rub resistance ~200
Impact resistance-Direct 100
Impact resistance-Reverse 60
*Oligoesterdiol was synthesized from DBE-3, DBE-5 and
1,4-butanediol as per Example II.
Table C
Oligoesterdiol* 1.03 g
PTEG1-N3300 0.51 g
Cymel 300 1.04 g
BYK-302 0.04 g
DNNDSA 0.02 g
Baking Conditions 300~F/30 min.
25 Appearance Clear, glossy
Film Thickness 1.0 mil
Adhesion 4B
Pencil Hardness H
MEK rub resistance ~200
30 Impact resistance-Direct 80
Impact resistance-Reverse 40
*Oligoesterdiol was synthesized from DBE-3, DBE-5 and
1,4-butanediol.

wos7~06129 PCT~S96/12915
~ -43-
Table D
Oligoesterdiol* 1.0 g
PTEG1-N3300 1. 5 g
Cymel 300 1.5 g
BYK-302 0.04 g
DNNDSA 0.02 g
Baking Conditions 300~F/30 min.
Appearance Clear, glossy
Film Thickness 1.0 mil
10 Adhesion 4B
Pencil Hardness H
ME~ rub resistance ~200
Impact resistance-Direct 160
Impact resistance-Reverse 160
*Oligoesterdiol was synthesized from DBE-3, DBE-5 and
1,4- butanediol as per Example II.

~ ~ 2~ 8 ~
wos7to612s PCT~S96/1291
-44-
Table E
Oligoesterdiol* 1.0 g (4.219 meq)
PTEGl-N3300 1.0 g (1.786 meq)
Desmodur N3300 1.27 g
BYK-302 0.04 g
Baking Conditions 300~F/30 min.
Appearance Clear, glossy
Film Thickness 0.9-1.0 mil
Adhesion 4B
10 Pencil Hardness HB
MEK rub resistance ~200
Impact resistance-Direct 160
Im~act resistance-Reverse160
~Oligoesterdiol was synthesized from DBE-3, DBE-5 and
1,4-butanediol as per Example II.
Table F
Oligoesterdiol* 1.0 g (4.219 meq)
PTEGl-N3300 1.0 g (5.48 meq)
Desmodur N3300 2.04 g
BYK-302 0.06 g
Baking Conditions 300~F/30 min.
NVW 98.11~
Appearance Clear, glossy
25 Film Thickness 0.9-1.0 mil
Adhesion 4B-5B
Pencil Hardness HB
MEK rub resistance >200
Impact resistance-Direct 160
30 Impact resistance-Reverse 160
~Oligoesterdiol was synthesized ~rom DBE-3, DBE-5 and
1,4-butanediol as per Example II.

~ 2 ~ O o 8 2
_ wos7/0612s PCT~S96/12915
-45-
EXAMP~E IV
Phenolic Ester Alcohol of Example I-b Reacted with
~DI
In a 250-m~ three-necked flat bottomed flask
e~uipped with magnetic stirrer, condenser, therm~m~ter
and nitrogen inlet, were placed HDI (1.68 g, O.Ol mol),
and a solution of the phenolic ester alcohol from
Example I (AY-3 in Table) (8.75 g, 0.025 mol) dissolved
in 50 m~ CH3CN by heating to 70~C. Another lO0 mL CH3CN
was added to the reaction mixture along with dibutyltin
diacetate (0.05 g, 0.5~ o~ total reactant weight). The
stirred mixture was heated on a stirrer-hotplate. The
reaction mixture was refluxed for 5 hours (83~C) and
cooled to room temperature when FTIR showed absence of
N=C=0 peak at 2300 cm-~. The contents of the reaction
mixture were transferred into a one-necked round-
bottomed flask and the solvent was removed using rotary
evaporation under aspirator pressure. The product
obtained was light brown viscous li~uid. This
aforedescribed procedure also was used in making a
series of diluents which included SKlOl and the
isocyanate Desmodur N3300.
The formulation using Hardener C-l, etc., 1,4-BD
oligoester-diol and melamine, and the properties o~
~ilms made therefrom are shown in Table l. C-l is the
same composition as C-2, but without SKlOl.

WO97/06129 ~ 2 ~ ~ ~ 8 ~ pcT~s96ll29ls
-46-
AY-3 and SK101 blocked HDI
Hardener C-2Hardener C-3
HDI content1.68g, 0.01 mol1.68g, 0.01 mol
AY-3: SK101 9:1 8:2
AY-3 content6.3g, 0.018 mol5.6g, 0.016 mol
SK101 content0.46g, 0.002 mol0.92g, 0.004 mol
dibutyltin0.5~, 0.04 g 0.5~, 0.04 g
diacetate
Hardener C-4 Eardener C-5
HDI content1.68g, 0.01 mol1.68g, 0.01 mol
AY-3; SK101 7:3 6:4
AY-3 content4.9g, 0.014 mol4.2g, 0.012 mol
SK101 content0.92g, 0.004 mol1.84g, 0.008 mol
dibutyltin0.5~, 0.04 g 0.5~, 0.04 g
diacetate
20 AY-3 or AY-3 and SK101 blocked Desmodur N-3300
Hardener D-l Hardener D-2
N-3300 2.9 g, 0.005 mol N-3300 2.9 g, 0.005 mol
AY-3 5.25 g, 0.015 mol AY-3 : SK101 8 : 2
AY-3 4.2 g, 0.012 mol
SK101 0.69 g, 0.0003 mol
25 dibutyltin diacetate dibutyltin diacetate
0.5~, 0.03 g 0.5~, 0.004 g

~ Z ~ ~ o ~ 2
WO97/06129 PCT~S96/12915
-47-
Table 1. Formulation of Oligoester-diol (1,4-BD)
with Cymel 300 and Different Hardeners C
- A B C
Oligoester-diol B-440 B-440 B-440
wt(g)/meq. wt1.0/4.581.0/4.58 l.0/4.58
Hardener C-1 C-2 C-3
wt(g)/~ of1.0/100~ l.0/100~ 1.0/100
total diol
M~l~m;n~ Cymel 300 Cymel 300 Cymel 300
wt(g) 1.45 1.45 1.45
Le~eling BYK-301 BYK-301 BYK-301
wt(g) 0.5~ 0.017 0 017 0.017
DNNDSA wt(g) 0.5~ 0.017 0.017 0.017
Film Thickness 0.9-1.0 0.7 0.7
(mil)
D-Impact Rest.140 140 140
R-Impact Rest lO0 120 120
Pencil Hardness lH 2H 2H
M~ Rub ~200 ~200 ~200
Adhesion 4B-sB 4B-sB 4B-5B
AppearanceTransparentTransparentTransparent
Ba}cing temp/time 170~C/30 min170~C/30 min 170~C/30 min

~ 2 ~ ~ Q 8 2
WO97/06129 PCTtUS96tl2915
-48-
Table 1 (continued)
D E
Oligoester-diolB-440 B-440
wt(g)/meq. wt1. 0/4.581.0/4.58
Hardener C- 4 C- 5
wt(g)/~ o~ 1.0/100~ 1.0/100
total diol
Melamine Cymel 300 Cymel 300
wt(g) 1.45 1.45
Leveling BYK- 301 BYK-301
wt(g) 0.5~ 0.017 0.017
DNNDSA wt(g) 0.017 0.017
0.5~
Film Thickness 0.7 0.7
(mil)
D-Impact Rest. 160 160
R-Impact Rest 160 160
20 Pencil Hardness 3H 3H
MEK Rub ~200 ~200
Adhesion 4B-5B 4B-5B
AppearanceTransparent Transparent
w/few slight
craters
Baking temp/time 170~C/30 min 170~C/30 min

WO97106129 2 2 ~ ~ o 8 2 PCT~S96/12915
-49-
Table 2. Formulation of Oligoester-diol (1,4-BD)
with Cymel 300 and Hardener C-4 (different amt of H.O)
5Oligoester-diol B-440 B-440
wt(g)/meq. wt10.0/4.58 10.0/4.58
Hardener C-4 C-5
wt(g)/~ o~ 10.0/100~ 10.0/100
total diol
Melamine Cymel 300 Cymel 300
wt(g) 10.0 + 45 1Ø0 + 45
Leveling BYK-301 BYK-301
wt(g) 0.5~ 0.17 0.17
DNNDSA wt(g) 0.17 0.17
0.5
H20 ~ 5~
Viscosity 3620 1395
2 sec~~ 25~C
NVW 110~C 92~ 88
170~C 84~ 79~
Film Thickness 0.6 0.5-0.6
(mil)
D-Impact Rest. 160 160
R-Impact Rest 140 140
25 Pencil Hardness 3H 3H
MEK Rub ~200 ~200
Adhesion 3B 4B
Appearance Transparent Transparent
Baking temp/time 170~C/30 min 170~C/30 min

WO 97/06129 ~ Q PCT/US96/12915
-50-
Table 2 (continued)
H
Oligoester-diol B-440
wt(g)/meq. wt 10.0/4.58
Hardener C-4
wt(g)/~ of 10.0/100
total diol
Melamine Cymel 300
wt(g) 10.0 + 45
~eveling BYK-301
wt(g) 0.5~ 0.17
15 DNNDSA wt(g) 0.17
0.5
H2O ~ 7~
Viscosity 1280
2 sec~~ 25~C
NVW 110~C 87
170~C 78~
Film Thickness 0.6
(mil)
D-Impact Rest. 160
25 R-Impact Rest 140
Pencil Hardness 3H
MEK Rub ~200
Adhesion 4B
Appearance Transparent
Baking temp/time170~C/30
min

~ 2 ~ 2
WO97/06129 PCT~S96/1291
-51-
Table 3. Formulation of Oligoester-diol (1,4-BD)
with Cymel 300 and Hardener D-1 and Hardener D-2
5 Oligoester-diol B-440
wt(g)/mea. wt1.0/4.58
Hardener wt(g)/~ D-1
of total diol1.0/100~
Melamine Cymel 300
wt(g) 0.45 + 1.0
~eveling BYK-301
wt(g) 0.5~ 0.017
DNNDSA wt(g) 0.017
0.5~
15 Film Thickness 0.6-0.7
(mil)
D-Impact Rest. 140
R-Impact Rest 80
Pencil Hardness2H
20 MEK Rub ~200
Adhesion 5B
Appearance Transparent
Baking temp/time 170~C/30 min