Note: Descriptions are shown in the official language in which they were submitted.
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iN-SlT~J Flv1uLslFlED REACTIVE EPOXY POLYMER COMPOSITIONS
The invention relates to reactive epoxy polymer compositions
emulsified in water comprising a polymeric epoxy emulsion and an emulsified reactive
polymer curing composition. In another aspect, the invention relates to a process for
preparing such water emulsified reactive polymer compositions. In yet another
aspect, the invention relates to cured coatings resulting from further reaction of the
water emulsified reactive polymer compositions on a suitable substrate.
Two-part epoxy resin based coating systems generally comprise a
curable epoxy resin and a curing agent for the epoxy resin, and are commonly
dispersed or dissolved in a solvent, primarily an organic solvent, to prepare coating
compositions, for example paints and floor sealants. The use of such organic
solvent-based coating compositions is discouraged on environmental grounds. On
the other hand, such cured epoxy resin based coatings provide hard and abrasion
resistant coatings which are resistant to, amon~ others, hydrocarbons and aqueous
media.
Water-based resin systems consisting of an epoxy resin and a curing
agent dissolved or emulsified in water have been developed, and create less
environmental and health concerns. The development of such systems is reviewed
by Chou (Polymers Paint Colour Journal, Vol.184,1994, pp 413-417). Water-based
resin systems are described in U.S. Patent 4,289,826, in GB-A-1,533,825, and in GB-
A-1,380,t 08. Known two part water-based epoxy resin emulsion coating
compositions have significant disadvantages as described by Chou. In particular, the
deficiencies of amidoamine adducts or modified polyamines which disperse liquid
epoxy resin at the point of application is clearly described: these curing agents are
normally made water dispersible by salt formation with volatile organic acids. These
acids often create odor, flash rusting and water sensitivity problems. The problems of
flash rusting and corrosion are dealt with in detail by M. A. Jackson, "Guidelines to
Formulation of Waterborne Epoxy Primers", Polymers Paint Colour Journal, Oct.
1990, Vol.180, No 4270, pp 608-621 and by H. Leidheiser, Jr., "Mechanism of
Corrosion Inhibition with Special Attention to Inhibitors in Organic Coatings", Journal
of Coatings Technology, Oct.1988, pp 97-106.
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In general, it is difficult to develop stable emulsions which l~ave hjgh
solids content and low viscosity, and therefore good flowability. Furthermore, many
of the known systems display poor coating properties, as they do not readily coalesce
without solvents when coated on a substrate, resulting in cured coatings with poor
5 mechanical flexibility and adhesion, high porosity and excessively high film formation
temperature for ambient cure applications. Such systems l~ave a limited balance
between hydrophobic and hydrophilic properties, resulting in limited flexibility in the
formulation of coatings. Such systems may also suffer from the inability to effectively
incorporate pigments into the coating composition. Therefore, pigments are often10 blended with the cu~ring agent by means of grinding or agitation.
U.S. Patent 5,118,729 describes improved aqueous epoxy dispersions
obtained by grafting an emulsifier containing polyoxyethylene residues by reaction on
to a terminal epoxy reactive group of the epoxy molecule prior to dispersion.
U.S. Patent 5,344,856 describes an emulsifiable epoxy resin
composition which forms a water stable emulsion comprising the reaction product of
a polyepoxide type compound with nominally difunctional C123~fatty acids, dispersed
by means of the addition of a surfactant wherein the surfactant comprises an alkyl
20 aryloxy poly (propyleneoxy) poly (ethyleneoxy) ethanol or a C12 36 hydrocarbyloxy poly
(propyleneoxy) poly (ethyleneoxy) ethanol wherein the hydrocarbyloxy moiety is the
residue of a C12 36 fatty alcohol or C12 36 fatty acid: standard chain terminating agents
may be employed.
2~; U.S. Patent 3,297,5t 9 describes epoxy resins which are self-
dispersible in water without further dispersing aids in a concentration up to 10 percent
by weight: the resins described are selected glycidyl ethers based on bisphenol-A
containing tailored blocks of polyoxyethylene bridging the two bisphenol-A residues in
the molecule. These products are used as components of paper finishes.
U.S. Patent 5,319,004 describes water dispersible hardeners for epoxy
resins produced from the reaction of specific polyamidoamides with specific
polyamines and specific adducts of polyepoxy compounds with polyalkylene
polyether polyols.
--2-
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W0-A-9501387 describes the preparation of self-dispersible curable
epoxy compositions prepared by the reaction of an epoxy resin with a polyhydric
phenol and an amine-epoxy adduct: the amine-epoxy adduct is a reaction product of
an aliphatic polyepoxide and a polyoxyalkyleneamine. The products described are
5 asserted to require a catalyst to promote the amine-epoxy adduct reaction with the
polyhydric phenol and epoxy resin, and the dispersion of the self dispersible, curable
~ epoxy resin is stated to require high shear in specially designed equipment. Specific
reaction sequencing is stated to be necessary in order to avoid post-addition of the
amine-epoxy adduct to the epoxy resin, with such addition ieading to unstable
10 aqueous dispersions.
D.--A-4405148 describes water dispersible epoxy compositions
derived from the reaction of aromatic epoxy resins, bisphenol-A and polyglycidylether polyepoxides, which resins may be cured with conventional amine curing
15 agents for aqueous systems. Dispersion of the water-dispersible epoxy compositions
are stated to require high shear.
JP-A-H6-179801 describes water-based curable epoxy resin
compositions prepared from an epoxy resin, a seif-emulsifiable active organic amine
20 curing agent and water. Ease of dispersion is obtained by choice of the curing agent.
The application of the technology described two epoxy resins with an epoxy
equivalent weight of less than 200 is asserted: good leveling and film forming
properties are asserted.
EP-A- EP 0617726 describes a water miscible or soluble a.mine-
terminated resin useful as a curing agent for water-dispersible epoxy resins which
amine-terminated resin is the reaction product of: 1 ) a polyamine component
comprising one or more hydrophilic amine-terminated polyalkylene glycols, and,
optionally, one or more hydrophobic polyamines; 2) a polyepoxide derived from a
30 polyalkylene glycol or cycloalkylene glycol, and optionally hydrophobic polyglycidyl
~ ethers, and, optionally, an amine extender having two active amine hydrogen atoms,
and reaction products therefrom; 3) optionally a reactive diluent; and 4) optionally a
catalyst for the reaction of an amine with an epoxy resin.
-3-
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Despite the improvements made to date, the formation of stable
aqueous dispersions of emulsified reactive polymer compositions derived from epoxy
resins with an epoxy equivalent weight greater than 350 and aqueous dispersed ordispersible curing agents is generally difficult. Dispersions of such compositions
5 containing no solvent, exhibit a viscosity higher than optimal. In particular, two-
component pre-dispersed compositions are desired which cure at low ambient
temperature to provide final coatings with good mechanical properties.
It is desirable to provide emulsified reactive epoxy polymer
10 compositions which can be produced in presently employed industrial reactors. It is
also desirable that such reactive epoxy polymer compositions should be stable
without the addition of acid or a significant quantity of organic solvent, in order to
optimize final coating properties. it is further desirable that such reactive epoxy
polymer compositions should also accept and disperse the commonly used
15 hydrophobic curing agents, which may be required in certain applications to allow
economically attractive low ambient temperature curing while still providing final
coatings with excellent mechanical properties.
The present invention provides a reactive polymer emulsion
20 preparable by:
~ i)reacting at least one polyepoxide (Il) with at least one
polyoxyalkylene glycol diglycidyl ether ~Ill), optionally a polyhydroxy hydrocarbon (IX),
and optionally an advancement catalyst~XI), to produce a first reaction product,
(ii)reacting the first reaction product with a polyoxyalkylenediamine
and optionally at least one further amine (V), to produce a second reaction product
(Vlll),
(iii)emulsifying the second reaction product (Vlll) in water to provide an
30 aqueous polymeric epoxy emulsion (Vll) and
.
(iv)dispersing or dissolving a curing agent (Xll) in the aqueous
polymeric epoxy emulsion (Vll) of the reaction product (Vlll) to provide an emulsified
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reactive polymer composition (I), wherein the organic solvent content, if any, of the of
the composition (I) is not more than 1.5 percent.
The said at least one further amine preferably includes a
monofunctional amine, a polyamine, or a mixture of two or more thereof
The invention also provides a process for preparing a reactive polymer
emulsion (I) comprising:
(i) reacting at least one polyepoxide (Il) with at least one
,10 polyoxyalkylene glycol diglycidyl ether (Ill), optionally a polyhydroxy hydrocarbon (IX),
and optionaily an advancement catalyst (Xl), to produce a first reaction product,
(ii) reacting the first reaction product with a polyoxyalkylenediamine
and optionally at least one further amine (V), to produce a second reaction product
1 5 (Vlll),
(iii) emulsifying the second reaction product (Vlll) in water to provide
an aqueous polymeric epoxy emulsion (Vll) and
(iv) dispersing or dissolving a curing agent (Xll) in the polymeric epoxy
20 emulsion (Vll) to provide an emulsified-reactive polymer composition (I~, wherein the
organic solvent content, if any, of the composition (I) is not more than 1.5 percent.
In a further aspect, the invention provides a coating composition
comprising the cured product derived by curing the emulsified reactive epoxy polymer
25 composition (I).
The emulsified reactive polymer composition (I) demonstrates good
stability, wettability and viscosity characteristics. Furthermore, the coatings prepared
from the emulsified reactive epoxy polymer composition (I) demonstrate good
30 adhesion coalescence, flexibility, resiliency and toughness.
.
The term "emulsion" is used herein to indicate a stable mixture,
- wherein in the polymeric epoxy emulsion (Vll) or the dispersion of curing agent (Xll)
the continuous phase is water and the dispersed phase is the emulsified reactive
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epoxy polymer composition or the curing agent (Xll). The term "emulsifiable" as used
herein describes matter which is capable of forming a stable oil in water emulsion.
The term "emulsified" as used herein indicates matter present in the dispersed
phase. The term "stable emulsion" as used herein refers to an emulsion in which the
dispersed components do not settle to the bottom and form a solid cake at ambient
temperature for a period of six months at 23~C. The term "stable emulsion" as used
herein does not exclude compositions in which some settling of particles with time to
form a soft deposit which is easily redispersible by agitation occurs. This six months
emulsion stability at 23~C may be simulated in a test where emulsion stability over a
four week period at 40~C is observed.
The term "reactive polymer" is used herein to indicate a polymeric
species capable of further chemical reaction by virtue of reactive functional groups
present within the polymer backbone, pendant to the polymer chain or terminal to the
polymer chain.
The term "polyepoxide" as used herein indicates a compound which
contains, on average, more than one epoxy moiety per molecule. Also included arepartially advanced epoxy resins, that is, the reaction product of a polyepoxide and a
polyhydroxy hydrocarbon compound wherein the reaction product has an average of
more than one unreacted epoxide unit per molecule. Polyepoxides (polyglycidyl
ethers of a polyhydroxy hydrocarbon) may be prepared by reacting an epihalohydrin
with a polyhydroxy hydrocarbon or a halogenated polyhydroxy hydrocarbon. Such
preparation is well known in the art. See Kirk-Othmer Encyclopedia of Chemical
Technology 3rd Ed. Vol. 9 pp. 267 - 289.
The epihalohydrins correspond to Formula 1 wherein:
CH2 C CH2 Y
\/
Y is a halogen, preferably chloro or bromo, and most preferably chloro;
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W O 97131962 PCT~US97/0~695
and R is hydrogen or C1 ,4 alkyl, and more preferably methyl.
Polyhydroxy hydrocarbon means herein a compound with a
hydrocarbon backbone and on average more than one primary or secondary hydroxy
moiety, preferably the average hydroxy moieties per hydrocarbon molecule is two or
5 more. Halogenated polyhydroxy hydrocarbon means herein a polyhydroxy
hydrocarbon which is substituted with one or more halogens. The hydroxyl moieties
may be bound to aromatic aliphatic or cycloaliphatic mo;eties. Among preferred
classes of polyhydroxy hydrocarbons and halogenated polyhydroxy hydrocarbons arethe bisphenols; halogenated bisphenols; hydrogenated bisphenols; and novolac
10 resins, that is, the reaction product of phenols and simple aldehydes, preferably
formaldehyde. The reaction product of phenol and an aldehyde, preferably
formaldehyde, is a well-known product, as is the process for its production. Such a
product is commonly referred to as a novolac resin.
t 5 Preferred polyhydroxy compounds (IX) useful in this invention
correspond to Formula 2
A--EOH~l 2
wherein:
A is an aryl moiety; aryl moiety substituted with an alkyl or halo moiety;
a polyaryl moiety wherein the aryl moieties are connected by direct bonds, alkylene,
haloalkylene, cycloalkylene, carbonyl, sulfonyl, sulfinyl, oxygen, or sulfur, such poly
aryl moieties being optionally substituted with one or more alkyl or halo moieties; or
the oligomeric reaction product of an aldehyde and phenol;
and u is greater than 1. Preferably u is from greater than 1 to 10, even
more preferably from greater than 1 to 3, and most preferably, from 1.9 to 2.1.
More preferred polyhydroxy hydrocarbons and halogenated
polyhydroxy hydrocarbons include those corresponding to Formulas 3 to 6:
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HO ~ Rl ~ ox 3
HO~ 0X ~L
HO ~ R3~ R 3 ~O' )m 5
(R2 )m'
HO ~_ CH ~ OH 6
wherein R' is separately in each occurrence Cl 10 alkylene, C"O haloalkylene, C4,,3
cycloalkylene, carbonyl, sulfonyl, sulfinyl, oxygen, sulfur, a direct bond or a moiety
corresponding to Formula 7
Q - 7
1 5 ~
R2 is separately in each occurrence C, 3 alkyl or a halogen;
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R3 is separately in each occurrence Cl 10 alkylene or Cs 5p cycloalkylene;
Q is separately in each occurrence a tetravalent C, 10 hydrocarbyl
moiety;
Q is separately in each occurrence hydrogen, cyano, or a C, l4 alkyl
group;
a is in each occurrence 0 or 1;
m is independently in each occurrence from 0 to 4;
m' is separately in each occurrence from 0 to 3; s is from 0 to 4; and
tisfrom 1 to5.
Even more preferable polyhydroxy hydrocarbons are tllose
represented by Formulas 3 and 4 and 5.
Rl is preferably C, 3 alkylene, C, l haloalkylene, carbonyl, sulfur, or a
direct bond; rnore preferably a direct bond, propylene, or fluorinated propylene20 (-C(CF~)2-); and most preferably propylene. R2 is preferably methyl, bromo or chloro;
and most preferably methyl or bromo. R3 is preferably C, 3 alkylene or a polycyclic
moiety corresponding to Formula 8
~ 8
wherein:
t is from 1 to 5 inclusively, preferably from 1 to 3, and most preferably
1. Preferably, m' is from 0 to 2. Preferably, m is from 0 to 2. Preferably, s is from 0
to 8; and more preferably from 0 to 4.
.
Among preferred polyhydroxy hydrocarbons are the dihydroxy
30 phenols. Preferable dihydroxy phenols include those which contain substituents that
are non-reactive with the phenolic groups. Illustrative of such phenols are
g
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2,2-bis(3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis(4-hydroxyphenyl) propane;
2,2-bis(3,5-dichloro-4-hydroxyphenyl~ propane; bis(4-hydroxyphenyl) methane;
1,1-bis(4-hydroxyphenyl)-1-phenylethane; 1,1'-bis(2,6-dibromo-3,5-dimethyl-4
hydroxyphenyl) propane; bis(4-hydroxyphenyl) sulfone; bis(4-hydroxyphenyl) sulfide;
5 resorcinol and hydroquinone. The preferred dihydroxy phenolic compounds are
2,2-bis(4-hydroxyphenyl) propane (bisphenol A), 2,2 bis(4-hydroxyphenyl) methane(bisphenol F) and 2,2-bis(4-hydroxy-3,~-dibromophenyl) propane.
Cycloalkylene as used herein refers to monocyclic and polycyclic
10 hydrocarbon moieties. As used herein haloalkyl refers to a compound with a carbon
chain and one or more of the hydrogens replaced with a halogen. Haloalkyl also
means compounds wherein all of the hydrogen atoms have been replaced by
halogen atoms. Alkylene as used herein refers to a divalent alkyl moiety.
The polyepoxides useful in the invention preferably correspond to
Formula 9
\ o/ U
wherein A, u and R are previously defined.
Preferably the polyepoxides are chosen such that the reaction product
(Vlll) is not significantly crosslinked. Such highly crosslinked reaction products form
gels and do not form good coatings. Some branching may be present as long as thereaction product does not form a gel.
The polyepoxides more preferably correspond to one of Formulas 10
to 13
-10-
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tR2)m (R2)m IR (R2)m (R2)m 10
CHz -/CCH~O ~ Rl ~ OCH2fcH2O ~ Rl ~ r~CH~I\O/CH~
IR (R2)m (R ~ ~ (R ~ (R ~ lO
CH2 ~CCH20~Rl~OCH2fCH20~Rl~ocH2c~ ~CH2
OH r ~
CH2--CCH2o~R1~30CH2ClCH2o~Rl~ \ /
OH r
1 12
C~--CCH 2~
C\2 /ICH 20 ~ R ~ ~ ~ 2) R
~0
- - - - - - 13
RR2 R2 R
CH2 /CCH2O - CH ~ CH2 - ~CH2C - CH2
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W O 97131962 PCT~US97tO2695
wherein ~, Rl, R2, R3, a, m, m', s and t are as defined previously; r is from 0 to 40.
Preferably, r is from 0 to 10, and most preferably 1 to 5. Preferably, s is from 0 to 8;
and most preferably 0 to 4. The symbols, a, m, m', r, s, and t may represent an
average number, as the compounds to which they refer are generally found as a
5 mixture of compounds with a distribution of the units to which they refer.
If a polyepoxide corresponding to Formula 12 is used in the
preparation of reaction product (Vlll), then s should be chosen such that the reaction
product is not crosslinked to a stage that gel formation occurs. Preferably, s is from 0
10 to3.
Polyoxyalkylene glycol diglycidyl ether (Ill) as used herein refers to a
compound or a mixture of compounds which contains, on average, more than one
epoxy moiety per molecule, and which may be prepared by reacting an epihalohydrin
corresponding to Formula (1) with one or more polyhydroxy compounds or
15 halogenated polyhydroxy compounds corresponding to Formula (14)
R R4
l l 14
HO - CH - CH O - H
where R4 is separately in each occurrence hydrogen, methyl, halomethyl, or ethyl,
with a proviso that if one R4 on an alkoxy unit is ethyi the other must be hydrogen;
and q is from 1 to 400. Preferably, q is from 20 to 350, more preferably
from 40 to 300. The symbol q represents an average number, as the compounds to
which it refers are generally found as a mixture of compounds with a distribution of
units to which q refers.
The polyoxyalkylene glycol diglycidyl ethers (Ill) correspond to
Formula 15
-12-
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. R R4 R4 R
CH2 -~CCH2O - CH CH ~ - CH2C CH2
wherein R, R4 and q are as defined previously.
In reaction product (Vlll) the polyepoxide (Il) used preferably
corresponds to Formulas 10, 11, or 12, and the polyoxyalkylene glycol diglycidylether (Ill) corresponds to the Formula 15. In another preferred embodiment, the
polyepoxide (Il) used in reaction product (Vlll) is from 85 to 99.5 percent by weight of
polyepoxides corresponding to Formulas 10, 11, and 12, and 0 to 1~ percent by
1~ weight of the polyoxyalkylene glycol diglycidyl ether (Ill) corresponding to Formula 15.
In a more preferred embodiment 85 to 99.5 percent of the polyepoxide used in
reaction product (Vlll) corresponds to Formula 10 and 0.5 to 15 percent of the
poiyoxyalkylene glycol diglycidyl ethers (Ill) corresponds to Formula 15.
The amine composition (V) is present in sufficlent quantity such that in
combination with the polyoxyalkylene glycol diglycidyl ether (Ill) the polymeric epoxy
reaction product (I) has sufficient hydrophilic-lipophilic balance that the polymeric
epoxy reaction product (I) is water dispersible. Hydrophilic ~poly)amines or
hydrophobic (poly)amines may be present in the amine composition. The
20 polyoxyalkylene diamine (V) is a polyalkylene glycol terminated with primary or
secondary amine moieties. The polyalkylene glycol chains useful herein can comprise
units derived from C28 oxides, or C2 a glycol ethylene oxide, propylene oxide, butylene
oxide, ethylene glycol, propylene glycol, butylene glycol, a butane diol (such as
1,4-butane diol), tetrahydrofuran, a propane diol (such as 1,2- or 1,3-propane diol) or
2~i a mixture thereof. Preferably the polyoxyalkylene giycol chain is comprised of units
derived from ethylene oxide, propylene oxide, a mixture of ethylene oxide and
propylene oxide, or tetrahydrofuran and more preferably of units derived from
ethylene oxide or a mixture of units derived from ethylene oxide and propylene oxide.
In those embodiments where the polyoxyalkylene glycol chain contains a mixture of
30 units from different alkylene oxides, the arrangement of the different alkylene oxide
units may be random or in blocks of the same alkylene oxide. The polyoxyalkylene
-13-
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diamine require sufficient alkylene oxide derived units so that polyoxyalkylene
diamine and hydrophilic polyepoxides present render the final amine-terminated resin
water soluble or miscible. Preferably, the polyoxyalkylene diamine has an average
molecular weight of from 200 to 4000, and more preferably of from 300 to 3000, most
preferably. Preferably the polyoxyalkylene diamine useful in the invention correspond
to the Formula 16
-- R10 (Rl3 )
Z ~CH ~ o _ R NH2-h
t 0 wherein:
R'~ is independently in each occurrence hydrogen, methyl or ethyl;
R" is independently in each occurrence a C, ,0 straight- or branched-
chain alkylene, C, ,0 straight- or branched-chain alkenylene, or a Cs.,2 divalent
cycloaliphatic moiety;
R'3 is independently in each occurrence a Cl ,0 straight- or branched-
chain alkyl moiety or hydrogen;
Z is independently in each occurrence oxygen or
x~o3~
X is independently in each occurrence a straight- or branched-chain
Cl 6 alkyl moiety;
c is independently in each occurrence 1 or greater;
b is independently in each occurrence 2 or 3;
f is independently in each occurrence from 2 to 4; and
h is independently in each occurrence 0 or 1;
with the proviso that for each
CA 0224471~ 1998-07-28
W O 97/31962 PCT~US97102695
R10
CH O--
unit if f is 2 and one R'~ is ethyl, then the other R'~ must be hydrogen,
and if f is 3 or 4, R'~ is hydrogen.
Preferably Z is oxygen. Preferably X is a (~2-4 alkylene moiety.
Preferably R'~ is hydrogen or methyl and more preferably hydrogen. Preferably R" is
a C, ,0 straight- or branched-chain alkylene moiety and more preferably a C24 alkylene
moiety. Preferably c is from 2 to ~ and more preferably from 2.6 to 3. Preferably b is
2. Preferably h is 0.
Such polyoxyalkylene diamines are well known in the art. Examples of
preferred polyoxyalkylene diamines are the polyamines available from Texaco
Chemicals Company (Houston, Tx, USA) under the trade name JEFFAMINE, for
example, JEFFAI\AINE D 400, JEFFAMINE D 2000.
The additional amines which may optionally or alternatively be present
include amines containing at least one primary or secondary amine moiety which are
capable of reacting with an epoxy resin; preferably such compounds are sterically
hindered. The term "sterically hindered" in reference to a polyamine means that the
20 amine group is located on a secondary or tertiary carbon which is in a sterically
hindered position. Preferably such polyamines correspond to Formulas 17 or 18
R 13 Rl3
R12_ 1 17
Rl~ ~H 2 18
wherein R'3 is previously defined, R12 is independently in each occurrence cyclohexyl,
substituted cyclohexyl, or a C, so hydrocarbylene moiety, which may be substituted
with a non-interfering substituent and which may contain one or more secondary
amines, ether, amine or thioether moieties in the backbone. R12 is preferably
30 cyclohexyl, or a C2 8 hydrocarbylene moiety, optionally containing amide or secondary
-15-
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amino moieties in the backbone. R'3 is preferably hydrogen or a Cl 4 straight- or
branched-chain alkylene moiety. In Formula 16, R'3 is most preferably hydrogen. In
Formula 18, Rl4 is preferably a Ct,2s linear, branched, alicyclic or polyalicyclic moiety.
I~xamples of preferred amines include t-octylamine, N,N'-di-tertiarybutyl ethylene
5 diamine and 2,6-dimethylcyclohexylamine.
These polyamines are included in the composition in sufficient
amounts to enhance the final mechanical properties of the coatings prepared uponcure. If too much of certain polyamines are used the final resin may not be
10 sufficiently emulsifiable in water.
Polymeric epoxy emulsion (Vll) as used herein refers to a dispersion of
epoxy-terminated molecules as particles in water in the size range typified as an
emulsion prepared as described in this invention. In general, it is preferable to
15 produce resin emulsions with small droplet diameters of a median value of about 1.5
micrometers. Usually a distribution of droplet diameters is obtained for the poiymeric
epoxy emulsion particles of from 0.8 to 7.0 micrometers. Some settlement may occur
on prolonged standing or when the emulsions are highly dilute: this settlement is
easily reversible by thorough stirring at low shear, for example, hand stirring is
20 sufficient for up to 20 liters.
The polyhydroxy hydrocarbon (IX) means herein a compound with a
hydrocarbon backbone and on average more than one primary or secondary hydroxy
moiety, preferably two or more. Halogenated polyhydroxy hydrocarbon means herein25 a polyhydroxy hydrocarbon which is substituted with one or more halogens. Thehydroxyl moieties may be bound to aromatic aiiphatic or cycloaliphatic moieties.Among preferred classes of polyhydroxy hydrocarbons and halogenated polyhydroxy
hydrocarbons are the bisphenols; halogenated bisphenols; hydrogenated bisphenols;
novolac resins, that is, the reaction product of phenols and simple aldehydes,
30 preferably formaldehyde; and polyalkylene glycols. The reaction product of phenol
and an aldehyde, preferably formaldehyde, is a well-known product, as is the process
for its production. Such a product is commonly referred to as a novolac resin.
-16-
,
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Optionally, the emulsifiable composition comprising reaction product
(Vlll) may further comprise an organic solvent (X), present in sufficient amounts to
stabilize the epoxy emulsion in water. Optionally, such solvent is present in amounts
of up to 10 weight parts, more preferably 0 to 5 weight, and most preferably from 0 to
- 5 1.5 weight parts of solvent per 100 weight parts of reaction product (Vlll). Preferred
solvents include glycols based on alkylene glycols, and ethers thereof, alkyl orhydroxyalkyl-substituted benzenes, lower alkanols, ~-butyrolactone, 7~-caprolactone
and n-methyl pyrrolidone. The preferred alkylene glycols are those based on
ethylene, propylene, and butylene oxide. The glycol ethers are alkyl ethers of such
1~ glycols. Preferred glycols are those based on propylene oxide and butylene oxide,
with preferred glycol ethers being C1 4 alkyl ethers of propylene and butylene glycols.
The most preferred glycol ethers are the C,,4 alkyl ethers of propylene glycol.
Examples of the preferred solvents are methyl ether of propylene glycol, benzyl
alcohol, isopropyl alcohol, butyrolactone, ~caprolactone, n-methyl pyrrolidone, and
1 5 xylene.
Catalysts (Xl) which may be employed to facilitate the preparation of
reaction product tVIII) of the polyepoxide compound with the one or more
polyhydroxy hydrocarbons are those known to those skilled in the art for the reaction
of epoxy moieties with active hydrogen containing compounds. Examples of useful
catalysts include zinc carboxylate, organozinc chelate compound, trialkyl aluminum,
quaternary phosphonium and ammonium salts, tertiary amines and imidazole
compounds. The catalyst is generally employed in an amount of from 0.01 to 2;
preferably 0.02 to 1, most preferably 0.02 to 0.1, weight percent based on the
2~ combined weight of the polyepoxide compound (Il) and the optional polyhydroxy
hydrocarbons (IX) used.
Preferable curing agents (Xll) which may be used in this invention are
those which are soluble or dispersible in the polymeric epoxy emulsion reaction
product (Vlll) and which contain more than 2 active hydrogen atoms per molecule.Included as curing agents (Xll) are diamines and polyamines or adducts of such
polyamines with epoxy resin, such as for example a reaction product of an excess of
- equivalents of isophorone diamine with a diglycidyl ether of bisphenol A wherein such
reaction product preferably has an amine equivalent weight of 115; modified
-17-
-
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W O 97/31962 PCT~US97/02695
polyamides and amidoamines, and arylic anhydrides. Preferred are the polyamines.Also useful as curing agents are aminoalkylated interpolymers of vinyl carboxylic
acids, and salts thereof, as described in U.S. Patent 4,227,621 and the self-
dispersing curing agents described in the copending application GB 9604297.3 filed
29 February 1996. Preferred curing agents include aliphatic polyamines,
polyglycoldiamines, polyoxypropylene diamines, polyoxypropylene-triamines,
amidoamines, imidazolines, reactive polyamides, polycyclic polyamines, ketimines,
arylaliphatic)polyamines (that is, xylylene-diamine), cycloaliphatic amines (that is,
isophoronediamine or diamino-cyclohexane) methane diamine, 3,3-dimethyl-4,4-
diaminodicyclohexyl-methane, heterocyclic amines (aminoethyl piperazine), aromatic
polyamines, (methylene dianiline), diamino diphenyl sulfone, mannich base,
phenalkamines and N,N',N"-tris(6-aminohexyl) melamine. Example of more preferredcuring agents include modified polyamide curing agents like CasamidTM 360 (Anchor
Chemicals Ltd., Manchester, United Kingdom), or EpilinkrM DP 660 (Akzo, Deventer,
The Netherlands~ which is an amine-epoxy adduct. Other useful hardeners may be
of the Mannich base class which are reaction products between nonyl phenol,
formaldehyde and a polyamine for example, xylylenediamine. Such a product is sold
by Akzo under the trade name EpilinkTM DP 500.
The epoxy resin composition of this invention is contacted with
sufficient curing agents to cure the resin. Preferably the ratio of (epoxy glycidyl ether)
equivalents to equivalents of curing agent is from 0.5:1 and 2:1; more preferably
0.6:1.4 to 1.4:0.6; even more preferably 0.8:1.2 to 1.2:0.8 and most preferably 0.9:1.1
to 1.1:0.9.
The emulsions of this invention may include pigments, dyes,
stabilizers, plasticizers and other conventional additives. Preferably the formulation
dispersion or emulsion in water has a solids level of from 40 to 80 percent, and most
preferably from 50 to 70.
When used to form a coating, the emulsified reactive polymer
compositions of this invention are contacted with a substrate. Water and any
cosolvents used are then evaporated off to leave a coating. The coating will cure at
ambient conditions in several days. Elevated temperatures may be used to speed up
the cure of the coating composition. Such curing conditions are well known to those
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PCTrUS97/02695
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skilled in the art. The coating composition may be contacted with the substrate by
any means known in the art including spraying, pouring or roller-coating the
formulation.
Insofar as epoxy advancement reactions are carried out in order to
produce an advanced polyepoxide, procedures for performing such reactions well
known In the art are used: see "The Handbook of Epoxy Resins", H. Lee and K.
Neville (1g67), McGraw Hill, New York and U.S. Patents 2,633,458; 3,477,990;
3,821,243; 3,907,719; 3,975,397; and 4,071,477. Common catalysts for epoxy
1 0 advancement reactions, and co~ r~on chain regulators and chain terminators well
known in the art may be employed.
In producing coatin~ formulations, the use of pigments, slip additives,
fillers, dispersing aids, defoamers, léveling agents, air release agents and other
1 5 additi~es commoniy applied in the industry have been applied.
Epoxy Fmulsion n~ ty
The quality of an applied and cured emulsified two-component epoxy
binder system depends greatly on the quality of the emulsion, particularly on the
droplet size and distribution. Emulsion quality particularly influences the filmformation, drying time, water resistance, gloss, pigment binding capacity, yield,
flexibility, adhesion and hardness.
Compared with conventional solvent systems, water dispersed resins
tend to foam more when they are produced and when they are applied. This
undesirable build-up of foam may result from the impact of mechanical energy during
emulsification procedures particularly when the process is not run under vacuum.Foam can lead to blemishes in appearance such as pitting, bubbles, and fish-eyes.
The non-ionic emulsifiers in the experimental epoxy resins were selected also for
their ability to furnish low foam emulsions. However, additives such as BYK 023 (Byk
Chemie, Wesel, Germany~ antifoaming agent, may be added to the epoxy-terminated
species before they are emulsified. Defoamer should be added in a concentration of
0.04 to 0.5 percent.
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Flocculation or aggregation of resin droplets can cause uneven and
matted surfaces. The droplet size of the emulsion has a variable influence on
different properties of the fiim.
Properties like gloss, water-resistance, stability and pigment-binding,
seem to suffer with increased droplet particle size while drying time, hold-out and
brush ability improves with increased droplet particle size. Clearly a balance of
properties is sought.
In general it is preferable to produce resin emulsions with small droplet
diameters of a medium value of about 1.5 micrometers. Usually a distribution of
droplet diameter is obtained for the experimental epoxy resins of 0.8 and 7
micrometers. However, some settlement might occur upon prolonged standing and
when the emulsions are highly diluted. Therefore thorough stirring of the emulsion is
necessary before taking fractional amounts out of the container to avoid
inconsistencies due to concentration differences.
In one embodiment, this invention provides, as an aqueous dispersion,
a blend of an aqueous epoxy-terminated polymeric amino-epoxy adduct emulsion
(Vll) and a curing agent (Xll), the aqueous epoxy-terminated polymeric amino-epoxy
adduct (Vll) comprising the reaction product of from 30 to 90 parts by weight,
preferably 50 to 85 parts by weight, more preferably 60 to 80 parts by weight of one
or more aromatic polyepoxides (Il) of average molecular weight greater than 300,from 2 to 50 parts by weight, preferably ~ to 30 parts by weight, most preferably 10 to
20 parts by weight of a polyoxypropylene diglycidyl ether (Ill) having an average
molecular weight of 250 to 12,000 and from 2 to 50 parts by weight, preferably from 5
to 30 parts by weight, most preferably from 10 to 20 parts by weight of an
compound (V), the aqueous epoxy-terminated polymeric amino-epoxy adduct (Vll)
having an epoxy equivalent weight (EEW) based on solids of from 178 to 1000,
preferably from 250 to 750, most preferably from 400 to 650. The aqueous epoxy-
terminated polymeric amino-epoxy adduct emulsion is blended with a curing agent,the curing agent (Xll) being present as an aqueous solution or dispersion, or the
curing agent being dispersible in the aqueous epoxy-terminated polymeric amino-
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epoxy adduct emulsion, to produce an aqueous emulsified reactive polymer
composition (I).
In a further embodiment, the aromatic polyepoxides and
5 polyoxypropylene diglycidyl ethers may be (co)-advanced with each other or with a
polyhydric phenol or with an alcohol by standard means known to those skilled in the
art to provide higher molecular weight epoxy-terminated species prior to reaction with
the amine compound.
A further embodiment is a process by which the aqueous emulsified
reactive polymer composition is prepared. In this process, the polyepoxides and
amines are mixed in the liquid phase at a temperature of between 70~C and t 35~C,
more preferably between 80~C and 130 ~C, most preferably between 85~C and
125~C. The reaction of the polyepoxides with the amines takes place at a
temperature of between 80~C and 200 ~C, more preferably between 80~C and 180~C,
and most preferably between 80~C and 160 ~C. The emulsification of the resultingproduct in water takes place at a temperature between 50 and 110 ~C, more
preferably between 50~C and t 00~C, most preferably between 50~C and 90~C. To
produce an aqueous epoxy-terminated polymeric amino-epoxy adduct emulsion, the
2~ aqueous epoxy-terminated polymeric amino-epoxy adduct emulsion and the curingagent is mixed at ambient temperature under conditions of low shear agitation.
Generally, hand agitation or mixing in conventional equipment used in the art at less
than 100 rpm (revolutions per minute) is sufficient to emulsify the amino-epoxy
adduct and curing agent in water. Higher agitation speeds may be used, but are not
25 required.
Further embodiments are cured coatings derived from the ambient
cure of the aqueous emulsified reactive polymer compositions. The stable epoxy-
terminated emulsion as described above provides a stable emulsified reactive
3() polymer composition, which, upon cure at a temperature between 5~C and 35 ~C,
preferably between 1 0~C and 30~C, for a period of between 5 and 75 hours,
preferably between 10 and 50 hours, at a relative humidity of between 10 and 100percent, preferably of between 25 and 60 percent, provides a glossy cured film
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exhibiting good cure properties, good Pendulum Hardness resistance and good
chemical resistance.
Clear coating formulations and pigmented formulated formulations
5 were produced using methods common in the industry and well known to those
skilled in the art.
The test methods used in evaluating cure characteristics and coating
properties are also common in the industry and well known to those skilled in the art.
10 The specific test methods used are now referred to or described.
Further embodiments are cured coatings derived from the ambient
cure of the aqueous emulsified reactive polymer compositions. The stable epoxy-
terminated emulsion as described above provides a stable emulsified reactive
15 polymer composition, which, upon cure at a temperature between 5~C and 35 oc,preferably between 1 0~C and 30~C, for a period of between 5 and 75 hours,
preferably between 10 and 50 hours, at a relative humidity of between 10 and 100percent, preferably of between 25 and 60 percent, provides a glossy cured film
exhibiting good cure properties, good Pendulum Hardness resistance and good
20 chemical resistance.
Clear coating formulations and pigmented formulated formulations
were produced using methods common in the industry and well known to those
skilled in the art.
The test methods used in evaluating cure characteristics and coating
properties are also common in the industry and well known to those skilled in the art.
The specific test methods used are now referred to or described.
30 Pi~mented Formulations
For the pigmented coating studies described in this invention a variety
of paint was produced.
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-
First the curing agent and pigments were mixed at 2500 rpm in a
Dispermat Fr (VMA Getzmann, Reichshof, Germany)for 5 minutes. To the pigment
paste, glass beads of 2 mm diameter had been added so that the pigment paste to
glass bead weight ratio was 1:1. Then milling was carried out under water cooling for
5 2~ minutes at 2500 rpm. After the milling water and defoamer had been added to the
mill base, the pigmented mixture was allowed to be stirred for another 5 minutes at
1000 rpm. Grindometer readings were taken from the pigment paste both after
milling, and also on the following day in order to reconfirm the values. In some cases
air bubbles contained in the paste prevented an immediate measurement. The
10 average particle size of the pigment paste was ca. 10 micrometers.
Coating Application
Coatings were either drawn down with an Erichsen ~pplic~tor
15 (Erichsen, Hemer-Sundwig, Germany) or air-sprayed to a predetermined film
thickness of 50 to 60 micrometers in a one-coat application for physical tests (curing
rate, and gloss, flexibility,). All chemical resistance tests were conducted on one coat
applications of ca. 90 micrometers dry film thickness.
20 Bubstrates
Three substrates were employed in the testing.
1. Sand blasted cold-rolled steel with a ~0 micrometer peak to
25 valley profile for salt-spray resistance. This was conducted on two-coat
applications. Buildup on each coat was approximately 50 to 60 micrometer
thickness and 1 day was allowed between coats for curing at ambient conditions.
2. Bonder steel 26 - 60 - OC (190 mm x 105 mm x 0.7~ mm) for
30 physical tests.
3. Glass plates to follow gloss and transparency during pot life and
film formation.
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Curing C;onditions Used for the Studies
Test panels were allowed to cure at ambient conditions (23~C/45 to 55
percent RH) on the following schedule prior to testing:
1. Physical properties - 7 days
Z. Resistance properties - three weeks (minimum) exceptions to
these conditions and schedules are obvious and noted in the data tables.
tO
3. Cure under adverse conditions examines curing characteristics at
10~C and at very high humidity of ca. 80 percent RH (relative humidity). In thiscase panels are examined after removal from the test environment to determine
any lasting adverse effects like flash rusting.
Physical Tests
Throu~h Film Drying Time (TFDT)
Through film drying time is a measure of the various stages and rates
of film formation in the drying or curing of organic coatings for the purpose ofcomparing types of coatings or ingredient changes, or both. The procedure followed
is, in principle, covered by ASTM D1640-83, however here an Erichsen drying timerecorder (Model 509, Erichsen, Hemer-Sundwig, Germany) is used. This is a
recorder which pulls a needle with a constant speed over a glass bar on which a
coating has been drawn.
Methyl Ethyl Ketone (MEK) Resistance/Double Rubs
This test monitors the resistance of a coating against MEK in the initial
phase of cure as a function of the time elapsed after application. Coatings are
prepared on steel and after the coating is tack-free, the dry film thickness of the
system to be tested and a reference system is determined. The dry film thicknessshould differ by not more than 10 percent. The actual test is then performed as
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WO 97/31962 PCT/US97t~}269',
follows: the flat end of a 500 g hammer is covered with a piece of cotton-wool. The
cotton-wool is soaked with MEK and a hammer is brought to one side of the panel.The hammer is moved forth-and-back over the whole coating, being one double rub.Care has to be taken not to put any additional pressure on the hammer. After every
5 20 double rubs the cotton-wool is re-soaked with MEK. The procedure is repeated
until the coating is rubbed off to such an extent that the panel becomes visible or
other defects occur. This test is repeated daily until the application withstands 100
double rubs without visible effect. The difference in MEK double rub developmentgives an indication of the rate at which cross-linking is achieved.
Gloss
Readings are made using a gloss meter (Type L, Dr. Lange, Berlin,
Germany) and measured at 20~, 60~ and 80~ angles of reflection.
Pendulum Hardness Development
This test method uses a pendulum damping tester as a measure of the
rate of cure by means of hardness development of organic coatings that have been20 applied to acceptable plane rigid surfaces. The test follows the proposal by ASTM
D4366-84 method B: "Hardness of organic coatings by pendulum (Persoz) damping
test".
Sudden Impact Resistance
Impact tests were conducted using a Gardner Heavy Duty Variable
Impact Tester. Reverse (substrate between the impacter and the test coating) anddirect (impacter applied to coating) impact tests were conducted. Results are
reported as the force (Joules) necessary to cause failure (cracking) of the film;
30 therefore, the higher the reading - the more flexiole the film.
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,
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Film Thickness
This test is performed following the guide-lines by ASTM D1186-81;
"Non-destructive measurement of dry film thickness of non-magnetic coatings applied
to ferrous base" (11).
Adhesion
The cross-cut test is a simple empirical test to determine the adhesion
of a one or more coat system on its substrate as well as the intercoat adhesion. This
test was performed in accordance with ASTM D335g-83: "Measuring adhesion by
tape test", method B. This method covers a procedure for ~ssessing the adhesion of
coating films to metaliic substrates by applying and removing tape over cuts made in
the film. In the examples described in this report TESAPACK 4124 tape is used.
Resistance Against Slow Deformation/Erichsen Indentation
This empirical test gives an indication about the resistance of a coating
system against cracking and/or loss of adhesion due to deformation of the substrate.
The test is performed in accordance with DIN/ISO 1520 of February 1982:
"Tiefungspruefung".
Chemical Resistance
2~ This test gives a quick indication about the chemical resistance and is
to be used on a relative basis only.
A piece of cotton-wool of approximately 1 cm diameter is saturated
with the chemical against which the coating has to be tested. The chemicals for this
purpose were:
Deionized water, ethanol, xylene, toluene, gasoline, aqueous sodium
hydroxide solution ~10 percent by weight.), aqueous acetic acid solution (10 percent
by weight.), aqueous hydrochloric acid solution (10 percent by weight.) and aqueous
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W O 97/31962 PCT~US97/02695 .
sulfuric acid soiution (10 percent by weight.). The cotton-wool is covered with a glass
lid of 50 mm diameter and a height of 30 mm which is sealed with silicon grease to
the coating. Hourly or daily the appearance of the coating is Judged by means ofdetermining the degree of blistering, and discoloration. The test is performed for one
~i week. The results of blistering and visual surface test like color changes or softening
have been monitored and rated on a scale of 0 (poorest) to 10 (best).
Salt S,cray
Tests were conducted in a salt-fog cabinet saturated with a fog from a
~ percent salt solution. Test temperature was 55~C. The panel was inscribed withthe Greek letter lambda through to the substrate. Panels were examined after 50û,
750 and 1000 hours exposure. Failure to protect the substrate is indicated by severe
blistering or creepage from the scribe in excess of 6 mm.
Humidity Resistance
Tests were conducted in a 40~C and 100 percent humidity cabinet.
Examinations occurred after 550, 750 and 1000 hours exposure. Failure to protect20 the substrate, was indicated by blistering.
The following examples are included for illustrative purposes and are
not intended to limit the scope of claims herein. All parts and percentages stated
herein are by weight, unless otherwise indicated.
2~
FY~rnple 1
A one liter, five-neck round-bottom glass reactor equipped with a
nitrogen inlet, water cooled condenser and metal anchor design agitator driven by an
30 electric motor was used. A 250 mL dropping funnel was employed. Temperature
- control was provided by a thermocouple, heating mantle and temperature controller.
Diglycidyl ether of Bisphenol-A having an epoxy equivalent weight
(EFW) of 180 (A, 360 g) and a polyoxyalkylene diglycidyl ether having an epoxy
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W O 97131962 PCT~US97/02695
equivalent weight of 5450 and an ethylene oxide/propylene oxide mole ratio of 5:1 (B,
60 g) were charged into the reactor and heated within 30 minutes to 100~C under a
nitrogen blanket. Agitation was applied after B was molten, and 2,6-dimethyl
cyclohexylamine (C, 80 g) added under agitation. The reaction mixture was heated to
120~C whereupon an exothermic reaction ensued which peaked at ca.160~ C. The
reaction mixture was allowed to react for two hours. The resultant epoxy resin was a
non-tacky semi solid, exhibiting good solubility in acetone. The resin was cooled to
100~C, and water (500 g) added continuously over 90 minutes while maintaining a
temperature of 85~C to 95~C during addition of the first 250 mL and 70~C to 75~Cduring addition of the second 250 mL of water. The resulting emulsion was kept at
60~C for a further two hours, cooled to below 30~C and bottled. The epoxy emulsion
had a solids content of 50 percent, a viscosity of ca.7,500 mPa.s at 23~C and anEEW of ca.1250.
Poly(methylenecyclohexanamine) in benzyl alcohol with an amino
hydrogen e~uivalent weight (AHEW) of 108 (Ancamine 2280, Anchor Chemicals UK,
8.4 g) was emulsified into the epoxy emulsion prepared above (100 g) by hand
stirring. Water (15 mL) was then added for dilution. Films were cast from this blend
on Bonder 26 60 OC steel panels using a 200 micrometer draw down bar. The
coatings became tack free after one hour, and withstood 100 MEK double rubs after
24 hours cure at 23~C, and 200 MEK double rubs after 7 days cure at ~3~C. A dropof water placed on this coating after 7 hours did not attack or dissolve the film: the
adhesion of the coating was excellent. After 7 days cure at room temperature, the
coating formed developed an impact of 17 Joules and an Erichsen indentation value
of 9.
Ex~mple 2
A reaction sequence, reactants and equipment similar to those used in
Example 1 were employed. Diglycidyl ether of bisphenol-A having an epoxy
equivalent weight (EEW) of 180 (A, 387 g) and a polyoxyalkylene diglycidyl etherhaving an epoxy equivalent weight of 5450 and an ethylene oxide/propylene oxide
mole ratio of 5:1 (B, 63 g) were charged into the reactor and heated within 30
minutes to 100~C under a nitrogen blanket. Agitation was applied after B was molten,
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W O 9713~962 PCTnUS97/02695'
and tert-octylamine (C, 80 g) added under agitation. The reaction mixture was
heated to 120~C, whereupon an exothermic reaction ensued which peaked at ca.
145~C. The reaction mixture was allowed to react for two hours. The resin was
cooled to 70~C, and water (47~) g) added over one hour while maintaining a
temperature of 50~C to 70~C. The resulting emulsion had a solids content of 52.5percent, a viscosity of 10,000 to 15,000 mPa.s at 23~C and an EEW of ca. t 075.
This advanced epoxy emulsion was pigmented as shown in Table I
and cured with a 1:1 by weight blend of the relatively hydrophobic curing agents~(~ polyamidoamide Versamid 140 (AHEW 125, Cray Valley, Newport, Wales, UnitedKingdom) and polyoxypropylenediamine with a molecular weight of 400 (Jeffamine
400, Texaco Chemicals Company). The pigmented systems described in Table I
were further diluted with water, and sprayed on Bonder 26 60 OC panels. The paint
formulations dried within 30 minutes at 23~C: after 7 days cure at 23~C the coated
panels withstood more than 200 MEK double rubs and had excellent condensed
water resistance (7 days exposure to condensed humidity at 55~C).
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TABLE I
Pigmented Water Emulsified Reactive Epoxy Polymer Comparisons
PROCEI:~URE/INGREDIENTSPAINT l* PAINT 2**
Mix under Agitation Weight Weight
Epoxy Emulsion (EEW 1075, Non-Volatile Content 49.78 41.82
52,5%) - Example 2
Water, demineralized. 10.23 16.10
Iron oxide red (Bayferrox t30M/BayerAG, Leverkusen, - .81
Germany)
Pigment mixture of Fe2O3 and Mn2O3 (Bayferrox 1.14
303T/Bayer AG)
Ir~.n oxide yellow (Bayferrox 920/Bayer AC) - .81
~ itanium dioxide (Finntitan RR2/Kemira, 'ori, Finland)3.73 11.53
--alcum - contains magnesite MgCOs (Ta cum AT 1.82
Extra/Norwegian Talc Deutschland GmbH, Bad Soeden-
Salmuenster, Germany)
Calcium carbonate (Durcal 10/OMYA Gmbl~, Koeln,17.54
Germany)
Muscovite-mica (Micro Mica W 1/Norwegian Talc, 9.37
Deutschland GmbH)
Precipitated barium sulfate (Blanc Fix N/Sabed, Massa, - 11.53
Italy)
Zinc phosphate (Sicor ZNP/S/BASF AG, Ludwigshafen, - 11.53
Germany)
Emulsion of hydrophobic non-volatile, emulsifiers and 0.60 .59
anti-foaming polysiloxane
(BYK 203/Byk-Chemie GmbH, Wesel, Germany)
Disperse on a horizontal pearl mill under
coo ing '< 40~C) to < 10,um
Ad- un~er agitation
Po yam noamide (Versamid 140/Cray Valley) 54.40
Polyoxypropylene diamine (Ancamine 480/Anchor .79
Chemical)
Catalyst blend at AHEW ca.124 (Ancamine K 54/
Anchor Chemical)
Leveling agent (BYK S 715/Byk-Chemie
GmbH) 81
Polyether modified methylalkyl-
polysiloxane-copolymer (BYK A 525/Byk-Chemie GmbH) 81
TOTAL AMOUNT 1 100.00
00.00
*Paint I = grey paint**Paint 2 = rose red paint
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Example 3
Following the method of Example 1, diglycidyl ether of Bisphenol-A
having an epoxy equivalent weight tEEW) of 180 (A, 141.6 g), bisphenol-A (B, 44.5
5 g), a polyoxyalkylene diglycidyl ether having an epoxy equivalent weight of 5450 and
an ethylene oxide/propylene oxide mole ratio of 5:1 (C, 64.7 g), p-tert-butyl phenol (D,
7.6 g) and methoxypropanol (E, 4.2 g) were charged into the reactor and heated
within 30 minutes to 80~C under a nitrogen blanket. Agitation was applied, the
mixture was heated to 90~C, and ethyltriphenylphosphonium acid acetate 70 percent
10 active in methanol (F, 0.4 g) was added under agitation. The mixture was heated to
115~C whereupon an exothermic reaction ensued which peaked at ca. 140~C. The
reaction mixture was then further heated at 1 45~C for 2 hours to yield an advanced
epoxy resin with an epoxy equivalent weight of 760.
This resin was cooled to 90~C and the polyoxypropylenediamine with a
molecular weight of 400 (Jeffamine D400, G, 163.6 g) and isophorone diamine (H,
67.4 g) added under agitation. All heating was switched off, and the reaction
contents cooled to about 70~C before an exothermic reaction took place which
peaked out at 86~C. The reaction mixture was heated slowly to 1 20~C over 45
minutes, maintained at this temperature for 1.5 hours and cooled to 99~C over 15minutes. Water (404.0 g) was continuously added over 35 minutes with agitation
while maintaining a temperature of at least 65~C, and the resulting emulsion stirred at
60~C for 30 minutes before cooling to below 30~C and bottling.
The resulting emulsion had a solids content of 55 percent, a viscosity
of ca. 5,000 mPa.s at 23~C, an amino hydrogen equivalent weight (AHEW) of ca. 315
and a pH of 11.4
Example 4
Poly (methylenecyclohexamine) (Ancamine X2280/ Anchor Chemical,
85 g) was intimately mixed at room temperature with dispersing aid Disperbyk 182(Byk Chemie, 10.5 g) and tris-2,4,6-dimethylaminomethylphenol (Ancamine
K54/Anchor Chemicals, 4.5 g).
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Example 5
A reaction sequence, reactants and equipment similar to those used in
Example 1 were employed. Diglycidyl ether of bisphenol-A having an epoxy
equivalent weight (EEW) of 180 (A,235 g), a polyglycidyl ether of a bisphenol-F with
a functionality of 2.2 and an EEW of 168 (B,100 g), a polyoxyalkylene diglycidyl ether
having an epoxy equivalent weight of 5450 and an ethylene oxide/propylene oxide
mole ratio of 5:1 (C, 60 g) and bisphenol-A (D, 42.5 g) were charged into the reactor
and heated within 30 minutes to 80~C under a nitrogen blanket. Agitation was
applied, the mixture was heated to 90~C, and ethyltriphenylphosphonium acid
acetate 70 percent active in methanol (E, 0.6 g) was added under agitation. The
mixture was heated to 115~C whereupon an exothermic reaction ensued which
peaked at ca.1~5~C. The reaction mixture was then further heated at 145~C for 1.5
hours to yield an advanced epoxy resin with an epoxy equivalent weight of 288. This
1 ~ resin was cooled to 100~C and a polyoxypropylenediamine with a molecular weight of
2000 (Jeffamine D 2000, F, 62.5 g) added under agitation. The reaction mixture was
allowed to react at between 92 and 95~C for one hour.
Water (500.0 9) was continuously added over one hour with agitation
while maintaining a temperature of at least 70~C, and the resulting emulsion stirred at
60OC for one hour before cooling to below 30~C and bottling.
The resulting emulsion (Exampls 5) had a solids content of 50 percent,
a viscosity of 2,000 to 8,000 mPa.s at 23~C and an EEW of ca. 718 (based on
emulsion).
Formulations to produce clear coats containing the epoxy resin
emulsion prepared as described above separately with the three hardeners (Example
5.1) a polyamino epoxy adduct solution in water at 70 percent solids and AHEW 200
as solution (Anquamine 401/Anchor Chemical), (Example 5.2) the amine curing agent
the preparation of which was described in Example 3 and (Example 5.3) the amine
curing agent the preparation of which is described in Example 4, are described in
Table ll as Systems 1 to 3 respectively, and the clear coat properties obtained by
curing these systems at 23~C are described in Table lll. Pigmented paint
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formulations based on the resin and hardener components described in this Example
5 are described in Tables IV, V and Vl and a comparison of general properties of the
paints produced from these formulations by curing separately at 23~C and at 1 0~Care
shown in Table Vll. Corrosion resistance properties for the paints produced from5 these formulations by curing at 23~C are shown in Table Xlll.
TABLE ll
Clear Coat Formulations
INGREDIENTS IN PARTS BYWEIGHTSYSTEM SYSTEM SYSTEM
2 3
Mix under agitation for 15 minutes
Epoxy Emulsion - Example 5 721.7 618.1 716.0
Curing Agent 5 (1 ) 198.8 - -
Curing Agent 5 ~2~ - 267.7
Curing Agent 5 (3) - - 142.0
Tris-2,4,6-dimethylaminophenol (Catalyst - 13.9
Ancamine K54/Anchor Chemicals)
Dilute with demineralized water 79.5 100.3 142.0
Viscosity at 23~C lmPa.s] ca. 3000ca. 4500 ca. 2500
Application solids, % 50.0 50.0 50.0
Amine-H to epoxye~uivalentwt. ratio1~ 0.9
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CA 02244715 1998-07-28
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TABLE l l l
Clear Coat Performance Properties
FEATURE SYSTEM SYSTEM SYSTEM
2 3
I)Wet varnish
Percent benzyl alcohol atapplication zero zero ca. 7
Pot life [h] max. 3 1.5 max. 2.5
Through film drying time - 6 ~ 8 ~ 6
(TFDT) [h]
lI)Dry film (on Bonder 26-60-OC)
Film Thickness [~m] 43 57 45
Persoz hardness [s]
1 d RTcure 40 60 90
7 d RT cure 90 159 236
Film appearance Hazy Sl. Hazy High
clarity
Cross-hatch adhesion [% remain]
7 d RT cure 100 100 100
Erichsen indentation [mm] > 10 9 9
7 d RT cure
Resistance to water-spotting poor good excellent
1 d RT cure
Resistance to MEK rubs > 100 100 >150
1 d RT cure
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CA 022447l5 l998-07-28
W O 97/31962 PCT~US97/02695
TABLE IV
Paint Formulation 1
PROCEDIJRE/INGREDIENTS WEIGHT
Mix under agitation
Aqueous Comparative Example 5 312.70
Finntitan P~R2 (Titanium dioxide from Kemira) 101.72
SicorZNP/S (Zincphosphatefrom BASF) 101.72
Blanc fix N (barium sulfate from Solvay SA, B-1050 Brussels,
Belgium) 101.72
Bayferrox 130 M (Iron oxide, red from Bayer AG) 7.13
Bayferrox g20 (Iron oxide, yellow from Bayer AG) 7.13
Demineralized water 86.36
Byk 023 (Defoamer from Byk Chemie GmbH~ 4.81
Disperse on a horizontal pearl mill under cooling
(< 40~C) to < 10 ~m
Add under agitation a pre-solution containing:
Epoxy Curing Agent for Example 5 (1 ) 87.57
Demineralized Water 189.13
Add demineralized water for required application viscosity 1000.00
Parameters
Solids content: 53.7
PigmenVbinder ratio: 1:0.7 (solids)
Pigment Volume Concentration (PVC) 30.0%
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CA 02244715 1998-07-28
W O 97/31962 PCT~US97/~2695
TABLE V
Paint Formulation 2
PROCEDURE/INGREI[)IENTS WEIGHT
Mix under agitation
Curing Agent from Example 5 (2) 124.77
Catalyst Ancamine K54 ~Anchor Chemicals Ltd.) 8.76
Finntitan RR2 (Titanium dioxide) 112.77
Sicor ZNP/S (Zinc phosphate) 112.77
Blanc fix N (Barium sulphate) 112.77
Bayferrox 130 M (Iron oxide, red~ 7.90
Bayferrox 920 (Iron oxide, yellow) 7.90
Demineralized water 65.32
Byk 033 (Defoamer) 2.22
Disperse on a horizontal pearl mill under cooling
(< 40~C) to c 10 ~um
Add under agitation
Aqueous Epoxy comparative for Example 5 287.92
Demineralized Water 156.90
Add demineralized water for required application viscosity 1000.00
Parameters
Solids content: 57.6
PigmenVbinder ratio: 1 :0.7 (solids)
PVC 30%
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CA 02244715 1998-07-28
W O 97/31962 P~l/U~7/0269
TABLE Vl
Paint Formulation 3
PROCEDURE/INGREDIENTS WEIGHT
~ Mix under agitation
Aqueous Epoxy comparative from Example 5443.66
Finntitan RR2 (Titanium dioxide) 76.01
Sicor ZNP/S (Zinc phosphate) 76.01
Blanc fix N (Barium sulphate) 76.01
Bayferrox 130 M (Iron oxide, red) 5.32
Bayferrox 920 (Iron oxide, yellow) 5.32
Demineralized water 31.14
Byk 023 (Defoamer) 4.65
Disperse on a horizontal pearl mill under cooling
(< 40~C) to c 10 lum
Add under agitation
Curing Agent from Example 5.3 8
8.98
Then add demineralized water
92.90
Add demin. water for required application viscosity
000.00
Parameters
Solids conL~I ,l. 55.0
Pigment/binder ratio: 1 :1.3
PVC 20%
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CA 02244715 1998-07-28
W O 97131962 PCTnUS97/02695
TABLE Vll
Water-borne Paints 1, 2 and 3 - Comparison of
General Properties (Cure at 23~C)
GENERAL PROI~t~ l l~:~i PAINT 1 PAINT 2 PAINT 3
Contains epoxy hardener 5.1 5.2 5.3
Pigment volume concenl,2.tion of point [%]
Coating thickness [,um] ca. 55 ca.55 ca.55
Drying time, tack-free [h] 1.8 2.5 2.8
Gloss 20~/60~t80~ 1/2/33 1/6/27 9/50/86
MEK resistance lDR] 1. day cure > 100 80 > 100
Pendulum hardness 133 137 198
according to Persoz [s]
Cross-cut adhesion tape test remain [%} 100 100 100
Erichsen indentation [mm]
7.daycure 55 35 50
14.daycure 33 34 45
Water-borne Paints 1,2 and 3 - Comparison of General Properties
(Cure at 10~C/80% RH)
GENERAL PROlJt~ lltS PAINT 1 PAINT 2 PAINT 3
Contains epoxy hardener 5.1 5.2 5.3
PVC of paint[%] 30 30 20
Coating thickness Ll-m] ca. 55 ca.55 ca.55
Gioss 20~/60~/80~ 1/3/36 3/22/50 14/62/91
MEK resistance ~DR] 7 days cure ~ 100 > 100 > 100
Penduium hardness according to Persoz68 76 111
[s~
Cross cut adhesion tape test remain [%} 100 100 100
Erichsen indentation ~mm] 6.1 3.9 8.7
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TABLE Vlll
Corrosion Resistance Paint 1, 2 and 3
PROPt~ I ItS PAINT 1 PAINT 2 PAINT 3
Humidity ASTMD 4885-86A 0 5 7
7 days constant at 55~C blisters l10 = best]
Adhesion after24 h recoveryat23~C/50% RH 0 99 99
tape, remain [%]
Sal- spray - ASTM (B-1 17-730* [H~ 350 500 1000
Scr pe c eep [mm] ca. 2 C 0
Scr ~e b isters r10 = best] 4 ~ 9
Surace ~listers[10=best] 4 ~ 9
Surace corrosion none none none
ADetermine on 40 ~um Sand Biasted Steel with pea~ to valley ratio of maximum 40
5 IJm, with 50 ~um first coat and 60 ~m second coat
FY~mple 6
A reaction sequence, reactants and equipment similar to those used in
10 Example 1 were employed. A polyglycidyl ether of a phenolic novoiac with a
functionality of 3.6 and an EEW of 178 (A, 390 g), and a polyoxyalkylene diglycidyl
ether having an epoxy equivalent weight of 5450 and an ethylene oxide/propylene
oxide mole ratio of 5:1 (B, 60 g) were charged into the reactor and heated to 90-C
under a nitrogen blanket. Agitation was applied, the mixture was heated at 90~C for a
further 15 minutes and a polyoxypropylenediamine with a molecular weight of 2000(Jeffamine 2000, C, 50.0 g) added under agitation. The temperature dropped to
84~C and the mixture became turbid. The reaction mixture underwent an exothermicreaction to yield a clear solution at 90~C. The mixture was heated to 1 00~C andmaintained at this temperature for 15 minutes before water (250.0 g) was
20 continuously added over 30 minutes with agitation while maintaining a temperature of
85~C to 95~C. The mixture was maintained at 90~C for 15 minutes before water
(118.0 g) was continuously added over 15 minutes with agitation while maintaining a
temperature of 70~C to 80~C. The mixture was cooled to 50~C and maintained at this
temperature for 90 minutes before cooling to below 30~C and bottling.
The resulting emulsion had a solids content of 57.5 percent, a viscosity
of 2,500 mPa.s at 23~C and an EEW of ca. 415.
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A water-emulsified reactive polymer composition was produced by
dispersing the amine curing agent, the preparation of which is described in Example
4 (13 g) with the epoxy-functional emulsion prepared as described above (42 g).
Wet coatings were cast on glass plates, and on Bonder steel panels
26 60 OC at 200 micrometer wet thickness. The through film drying time of the film
was ca. 2 hours, when cured at 23~C. Water, acid and solvent resistance of the
cured coatings was much better than that normally obtained from water emulsl~iedreactive polymer compositions derived from water-dispersed epoxy resins and amine
curing agents. Specifically, these films exhibited faster cure time of ca. 3 hours than
the ca.12 hours of typical water dispersed bisphenol-A type liquid epoxy resin
systems: these films described in Example 8 also had a solvent resistance some two
to three times better and a water spotting resistance some four times better than
typical water-dispersed bisphenol-A type liquid epoxy resin systems.
Example 7
A diglycidyl ether of bisphenol-A having an epoxy equivalent weight
(EEW) of 510 (A,174 g), a diglycidyl ether of bisphenol-A having an epoxy equivalent
weight (EEW) of 182 (B,126 g), and a polyoxypropylene diglycidyl ether with EEW
328 (D.E.R.TM 732, trademark of The Dow Chemical Company, C, 300 g) were mixed
into a
1 litre vessel, held in an oven at 80~C for one hour and thoroughly mixed until a clear,
homogeneous mixture was formed.
F~rnple 8
A reaction sequence and equipment similar to those used in Example
1 were employed. A polyoxyalkyiene diglycidyl ether having an epoxy equivalent
weight of 5450 and an ethylene oxide/propylene oxide mole ratio of 5:1 (A, 71.5 g)
and isophoronediamine (B,187 g) were added to the reactor and heated over a
period of 20 minutes to
75~C. Agitation was started and the mixture heated to 90~C and maintained at this
temperature for 15 minutes. The polyepoxide blend produced in Example 7 (2g1.5 g)
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CA 0224471~ 1998-07-28
W O 97/31962 PCT~US97/02695.
was added at a temperature of 90 to 95~C over a period of 40 minutes, and the
mixture maintained at 90~C for a further 90 minutes. The contents were cooled to80~C and water (450 g) added over 45 minutes with agitation while maintaining the
temperature of the mixture above 50~C. After water addition was compiete, the
5 resultant emulsion was stirred for a further one hour while maintaining the
temperature between 4~~C and 50~C, before cooling to 30~C and bottling. The
polymeric aqueous dispersed curing agent exhibited an AHEW of 28~ to 315.
F~z~mple 9
A reaction sequence and equipment similar to those used in Example
1 were employed. A polyoxyalkylene diglycidyl ether having an epoxy equivalent
weight of 5450 and an ethylene oxide/propylene oxide mole ratio of 5:1 (A, 65 g) and
N,N'-di-tert-butylethylenediamine (B, 84 g) were charged into the reactor and heated
15 to 75~C under a nitrogen blanket. Agitation was applied, the mixture was heated at
135~C over 30 minutes and maintained at this temperature for an additional 15
minutes. A polyoxypropylene diglycidyl ether with an EEW of 328 (D.E.R.TM 732, C,
35 g) and a diglycidyl ether of bisphenol-A having an epoxy equivalent weight (EEW)
of 180 (D, 316 g) were added under agitation and the temperature raised to 1 45~C
20 and maintained at this temperature for 2 hours. The mixture was then cooled to 90~C
before water (500.0 g) was continuously added over a period of 45 to 60 minutes with
agitation while maintaining a temperature of at least 50~~C. The mixture was
maintained at 50~C for an additional 30 minutes before cooling to below 30~C andbottling.
The resulting emulsion had a solids content of 50 percent, a viscosity
of 500 to 1000 mPa.s at 23~~C and an EEW of ca. 1000 to 1200. The emulsion was
blended in a stoichiometric ratio of 1:1 with the polymeric epoxy-amino adduct
emulsion the preparation of which is described in Example 8 and cured at
30 temperatures of 1 0~C and higher to yield coatings exhibiting a Persoz hardness of 90
and an adhesion of 100 percent after 24 hours cure at 23~~C, and an Erichsen
indentation of 6 and a resistance to over 100 MEK double rubs after 7 days cure at
23~C. A rapid through film drying time is a feature of the systems prepared from the
epoxy emulsion described in Example 9.
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W O 97/31962 PCTAUS97/02695.
Gomparative Example 10
Polyethylene glycol with an average molecular weight (Mw) of 3000
(technical grade,150 g) and a bisphenol-A based polyglycidyl ether with an epoxyequivalent weight of 185 (18.5 g) were heated to 100~C and diluted under agitation
with boron trifluoride etherate (0.9 g~ diluted to 5 weight percent with dioxane. The
mixture was heated to 130~C, and maintained at this temperature until the ensuing
reaction had ceased, as witnessed by an increase in the epoxy equivalent weight.The epoxy equivalent weight of the product A was ca. 360,000. A bisphenol-A based
polyglycidyl ether with an epoxy equivalent weight of 183 (325 g), bisphenol-A
(98 g~, the adduct A (27 g) and triphenylphosphine (750 mg) were mixed in a two-liter
three-necked flask equipped with a thermometer, an agitator, a reflux condenser and
a dropping funnel and heated at between 150~C to 160~C until an epoxy equivalentweight of 490 to 500 was obtained. The rnixture was cooled and diluted with benzyl
alcohol (27 g) and methoxypropanol (60 g). The temperature was reduced to below
100~C and water (105 g) was added continuously over a period of 5 to 30 minutes
while maintaining an agitator speed of 800 rpm and allowing the temperature to fall to
between 70~C and 60~C. An aqueous dispersion was obtained which was further
diluted with water (173 g). The dispersion had a solids content of 55.7 percent and a
viscosity of 11,700 mPa.s. A water-emulsified reactive epoxy polymer compositioncan be prepared from this dispersion by the addition, under agitation, of any common
amine hardener suited for curing aqueous systems.
Comparative F~rnple 11
Isophorone diamine (26 g) was added to a three-necked glass flask
equipped with a thermometer, an agitator and a condenser, and the contents were
thoroughly agitated while maintaining a temperature of between 40~C to 50~C. A
polyglycidyl ether, having an epoxy equivalent weight of 1980 obtained from one mole
of propylene oxidelethylene oxide random polymer type polyether polyol PR-3009
(Asahi Denka Kogyo K.K.) having a molecular weight of 3,000 and an ethylene oxide
content of 85 percent by weight and 2.2 moles of epichlorohydrin, (13 g) and thehydrophobic epoxy compound EP-4901 (EEW 182, Asahi Denka Kogyo K.K., 12 g)
were added slowly while checking heat generation. The reaction was allowed to take
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CA 0224471~ 1998-07-28
W O 97/31g62 PCT~US97/02695.
place over two hours at 90~C, and water (13 g) was added to obtain the seif-
emulsifying activated curing agent (X). Adeka resin EP-4200 (Asahi Denka Kogyo
K.K., EEW 190, 10 g) the self-emulsifying activated curing agent X (7 g) and water
(10 g) were mixed and cured. The film performance was tested to give the following
results. Film condition after 24 hours was "good,"' pencil hardness was "H,"' water
resistance after 7 days of soaking was "good" and adhesion (mortar board
checkerboard test) was 100/100.
Comparative Example 12
Preparation of Amine-epoxide Adduct (66 Percent Capped)
Into a one-liter reaction flask equipped with a stirrer, heating mantle,
nitrogen line, cooling condenser, and thermometer was charged 485 grams (0.4
1~ equivalents) Jeffamine 2000 (Texaco Chemical Company, Houston, Texas) and
142.2 grams (0.61 equivalents) of polyepoxide of propoxylated (5PO) pentaerythritol
(Henkel Corporation, Ambler, PA). The reaction mixture was heated slowly to 125~C
to 1 30~C with stirring and held at this temperature for about 2.5 hours. The reaction
mixture was then cooled to 70~~:: and analyzed for epoxide and amine content. The
product amine polyepoxide adduct had 0.4 meq/gm of total amine and 0.33 meq/gm
of epoxide which indicated that about 66 percent of the initial free epoxide groups had
been reacted with the amine.
Preparation of Self-Dispersin~ Resin
Into a 250 mL reaction flask equipped with heating mantle, nitrogen
line, cooling condenser, thermometer and stirring means, was charged 66.4 grams
(0.348 equivalents) of the diglycidyl ether of bis-phenol A, and 19.6 grams (0.172
equivalents) of bis-phenol A. The reactants were heated to 95~C and then 12.0
grams (0.004 equivalents) of the amine-epoxide adduct prepared above was added
with 0.15 grams triphenyl phosphine. The reaction mixture was heated slowly to
1 50~C with stirring whereupon an exothermic reaction was observed. cooling was
immediately applied to maintain the reaction temperature between 1 50~C and 1 60~C.
After the exothermic reaction subsides, the reaction mixture was maintained at 160~C
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CA 0224471~ 1998-07-28
W O 97t31962 PCTrUS97/02695 -
for an additional hour followed by a 15 minute period at 190~C. The reaction mixture
was then cooled to 160~C and 14 grams of propyl CellosolveTM (trademark of UnionCarbide Corporation) was added which immediately began refluxing. The reaction
mixture was cooled to 100~C and analyzed. The resultant self-dispersing resin,
present at 87.5 percent solids in propyl CellosolveTM, has 0.07 meq/gm total amine
and an epoxide equivalent weight of 552 based on resin solids.
Preparation of Water-Borne Dispersion
Into a 500 mL reaction flask equipped with a stirrer, heating mantle,
nitrogen line, cooling condenser and thermometer was charged 112 grams of the
self-dispersing resin (SDR) prepared as above. The resin was heated to 100~C
whereupon 16.5 grams of water were added gradually with stirring over a thirty
minute period while the temperature dropped to about 55~C. Then an additional 48grams of water was added as the temperature was brought to 70~C over twenty
minutes. At 70~C, there was added 2 grams of water followed by stirring for twenty
minutes and then 3 grams of water was added. The resulting water in oil dispersion
was stirred for 45 minutes while it cooled to 45~C, and thereafter was in the form of
an oil in water dispersion. After the inversion was completed, 2.0 grams of C5 ~0
alcohol mono-glycidyl ether from CVC Specialty Chemicals Corp. was added as a
reactive diluent. Then 36.3 grams of water was added at 50~C over a one hour
period. The resulting water-borne dispersion contained 56 percent resin solids in
water/propyl CellosolveTM ~82/18) solvent.
Preparation of Coating Composition
Into a 25 mL plastic cup was charged 12.4 gm (56 percent solids) of the water-borne
dispersion prepared as above followed by an equal equivalent amount (2 gm) of
epoxy curing agent available as 8290 by HiTech (a modified diethylene triamine with
3û a hydrogen equivalent weight of 163). Sufficient water is then added to bring the
mixture to a spre~d~hle consistency. The epoxy dispersion/curing agent blend is
aged for 10 minutes then a film casting was produced by drawing the blend down on
a pre-sanded TRU COLD cold rolled steel panel (3 x 6 x 0.32 inches) using a #34
wire wound steel rod. The film was tack-free after 45 minutes. The physical
-44-
CA 02244715 1998-07-28
W O 97/31962 PCT~US97/02695
properties of the coating composition which were rated "PASS" were measured after
the film had air-dried at room temperature for 28 days.
-45-
