U.S. patent application number 12/122980 was filed with the patent office on 2012-02-16 for coating compositions comprising polyurea and a phosphorous-containing polyol.
This patent application is currently assigned to PPG INDUSTRIES OHIO, INC.. Invention is credited to Steven V. Barancyk, John M. Furar, Thomas R. Hockswender, Howard L. Senkfor, Debra L. Singer, Michael A. Zalich.
Application Number | 20120037034 12/122980 |
Document ID | / |
Family ID | 41203725 |
Filed Date | 2012-02-16 |
United States Patent
Application |
20120037034 |
Kind Code |
A1 |
Barancyk; Steven V. ; et
al. |
February 16, 2012 |
COATING COMPOSITIONS COMPRISING POLYUREA AND A
PHOSPHOROUS-CONTAINING POLYOL
Abstract
The present invention is directed to a coating composition
comprising polyurea formed from a reaction mixture comprising: (a)
a first component comprising isocyanate, wherein said isocyanate
comprises an isocyanate functional prepolymer formed from a
reaction mixture comprising isocyanate and a material comprising a
phosphorus-containing polyol; and (b) a second component comprising
an amine.
Inventors: |
Barancyk; Steven V.;
(Wexford, PA) ; Senkfor; Howard L.; (South Euclid,
OH) ; Singer; Debra L.; (Wexford, PA) ; Furar;
John M.; (Pittsburgh, PA) ; Zalich; Michael A.;
(Pittsburgh, PA) ; Hockswender; Thomas R.;
(Gibsonia, PA) |
Assignee: |
PPG INDUSTRIES OHIO, INC.
Cleveland
OH
|
Family ID: |
41203725 |
Appl. No.: |
12/122980 |
Filed: |
May 19, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11460439 |
Jul 27, 2006 |
7928160 |
|
|
12122980 |
|
|
|
|
Current U.S.
Class: |
106/18.19 ;
106/18.18 |
Current CPC
Class: |
C08G 18/10 20130101;
C08G 18/10 20130101; C08G 18/721 20130101; C09D 175/02 20130101;
C08G 18/5075 20130101; C08G 18/3225 20130101; C08G 18/3878
20130101 |
Class at
Publication: |
106/18.19 ;
106/18.18 |
International
Class: |
C09D 5/00 20060101
C09D005/00 |
Claims
1. A coating composition comprising polyurea formed from a reaction
mixture comprising: (a) a first component comprising isocyanate,
wherein said isocyanate comprises an isocyanate functional
prepolymer formed from a reaction mixture comprising an isocyanate
and a material comprising a phosphorus-containing polyol; and (b) a
second component comprising an amine, wherein the ratio of
equivalents of isocyanate groups to equivalents of amine groups is
greater than 1 and the isocyanate and the amine can be applied to a
substrate at a volume mixing ratio of 1:1.
2. The composition of claim 1, wherein the material is a flame
retardant material.
3. (canceled)
4. The composition of claim 1, wherein the phosphorus-containing
polyol comprises polyphosphate diol, phosphite diol and/or blends
thereof.
5. The composition of claim 1, wherein the first component further
comprises a non-prepolymer isocyanate.
6. The composition of claim 1, wherein the reaction mixture further
comprises one or more of polyol, polythiol and/or polyamine.
7. The composition of claim 6, wherein the polyol comprises
butanediol, polytetramethylene ether glycol, or mixtures
thereof.
8. The composition of claim 1, further comprising a flame retardant
material added to the first component, the second component, or
both.
9. The composition of claim 8, wherein the flame retardant material
comprises halogenated phosphate, halogen-free phosphate,
tris(2-chloropropyl) phosphate, 12/122,980 Page 2 of 5 Amendment
tris(2,3-dibromopropyl) phosphate, tris(1,3-dichloropropyl)
phosphate, diammonium phosphate, powdered or fumed silica, layered
silicate, aluminum hydroxide, brominated fire retardant,
halogenated aromatic compound, antimony oxide, alumina trihydrate,
metal borates, zinc borate, barium metaborate pentahydrate,
phosphate esters, polyvinyl chloride, melamine cyanurate, melamine
phosphates, polymelamine phosphates, melamine pyrophosphates,
polymelamine pyrophosphates, melamine borate, other melamine
derivatives, and combinations thereof.
10. The composition of claim 8, wherein the flame retardant
material comprises graphite.
11. The composition of claim 1, wherein the ratio of equivalents of
isocyanate groups to equivalents of hydroxyl groups is greater than
1.
12. The composition of claim 1, wherein the phosphorus-containing
polyol is the reaction product of an initial phosphorus-containing
polyol and an epoxy functional compound.
13. The composition of claim 12, wherein the epoxy functional
compound comprises ethylene oxide, propylene oxide,
1,2-epoxybutane, butyl glycidyl ether, neodecanoic acid glycidyl
ester, or combinations thereof.
14. The composition of claim 1, wherein the phosphorus-containing
polyol is the reaction product of a phosphorus-containing acid, an
epoxy functional compound, and, optionally, an initial
phosphorus-containing polyol.
15-32. (canceled)
33. A coating composition comprising polyurea formed from a
reaction mixture comprising: (a) a first component comprising an
isocyanate functional prepolymer and a non-prepolymer isocyanate,
wherein said isocyanate functional prepolymer is substantially
compatible with said non-prepolymer isocyanate, and wherein said
isocyanate functional prepolymer is formed from a reaction mixture
comprising an isocyanate and a material comprising a
phosphorus-containing polyol; and (b) a second component comprising
an amine, wherein the ratio of equivalents of isocyanate groups to
equivalents of amine groups is greater than 1 and the isocyanate
and the amine can be applied to a substrate at a volume mixing
ratio of 1:1.
34. The coating composition of claim 33, further comprising a flame
retardant material is added to the first component, the second
component, or both.
35. The coating composition of claim 33, wherein the
phosphorus-containing polyol is the reaction product of an initial
phosphorus-containing polyol and an epoxy functional compound.
36. The composition of claim 35, wherein the epoxy functional
compound comprises ethylene oxide, propylene oxide,
1,2-epoxybutane, butyl glycidyl ether, neodecanoic acid glycidyl
ester, or combinations thereof.
37. The composition of claim 33, wherein the phosphorus-containing
polyol is the reaction product of a phosphorus-containing acid, an
epoxy functional compound, and, optionally, an initial
phosphorus-containing polyol.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This patent application is a Continuation-In-Part (CIP) of
patent application Ser. No. 11/460,439 filed on Jul. 27, 2006,
hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention is directed to a coating composition
comprising polyurea or polyurea and polyurethane.
BACKGROUND
[0003] Coating compositions are used in a wide variety of
industries. Such industries may include but are not limited to
landcraft such as cars, trucks, sport utility vehicles,
motorcycles; watercraft such as boats, ships and submarines;
aircraft such as airplanes and helicopters, industrial such as
commercial equipment and structures including walls and roofs;
construction such as construction vehicles and structures including
walls and roofs, military such as military vehicles, for example
tanks and humvees, and military structures including walls and
roofs, for example, ammunition cases and battery enclosures; and
the like. In these industries, coatings serve a variety of purposes
such as protecting various components against damage due to
corrosion, abrasion, impact, chemicals, ultraviolet light, flame
and heat, and other environmental exposure as well imparting
ballistic and blast mitigation properties to the components onto
which they are deposited. Accordingly, considerable efforts have
been expended to develop coating compositions with improved
properties.
SUMMARY OF THE INVENTION
[0004] The present invention is directed to a coating composition
comprising polyurea formed from a reaction mixture comprising: (a)
a first component comprising isocyanate, wherein said isocyanate
comprises an isocyanate functional prepolymer formed from a
reaction mixture comprising isocyanate and a material comprising a
phosphorus-containing polyol; and (b) a second component comprising
an amine. The present invention is also directed to an article
partially coated with such a coating composition as well as a
method of applying such a coating composition onto the article.
[0005] The present invention is also directed to a coating
composition comprising: (a) a polyurea formed from a reaction
mixture comprising: (i) a first component comprising isocyanate,
wherein the isocyanate comprises an isocyanate functional
prepolymer formed from a reaction comprising isocyanate and a
material comprising a phosphorus-containing polyol; and (ii) a
second component comprising an amine; and (b) a polyurethane. The
present invention is also directed to an article partially coated
with such a coating composition as well as a method of applying
such a coating composition onto the article.
[0006] The present invention is also directed to a coating
composition comprising polyurea formed from a reaction mixture
comprising: (a) a first component comprising an isocyanate
functional prepolymer and an isocyanate, wherein the isocyanate
functional prepolymer is substantially compatible with the
isocyanate, and wherein the isocyanate functional prepolymer is
formed from a reaction mixture comprising isocyanate and a material
comprising a phosphorus-containing polyol; and (b) a second
component comprising an amine.
DETAILED DESCRIPTION OF THE INVENTION
[0007] As used herein, unless otherwise expressly specified, all
numbers such as those expressing values, ranges, amounts or
percentages may be read as if prefaced by the word "about", even if
the term does not expressly appear. Any numerical range recited
herein is intended to include all sub-ranges contained therein.
Plural encompasses singular and vice versa. "Including" and like
terms are open ended; that is, they mean "including but not limited
to". For example, while the invention has been described herein
including the claims in terms of "a" polyurea, "a" polyurethane,
"an" isocyanate, "an" amine, "a" polyol, "a" polythiol, "a"
prepolymer, "a" catalyst, and the like, mixtures of all of such
things can be used. Also, as used herein, the term "polymer" is
meant to refer to prepolymers, oligomers and both homopolymers and
copolymers; the prefix "poly" refers to two or more.
[0008] The present invention is directed to a coating composition
comprising polyurea formed from a reaction mixture comprising a
first component comprising an isocyanate ("isocyanate component"),
and a second component comprising an amine ("amine component"); and
optionally polyurethane.
[0009] The isocyanate component comprises an isocyanate functional
prepolymer formed from a reaction mixture comprising isocyanate and
a material, such as a flame retardant material, comprising a
phosphorus-containing polyol. In certain embodiments, the
isocyanate component also comprises an isocyanate (non-prepolymer
isocyanate or additional isocyanate) that is not used to form the
isocyanate functional prepolymer. It should be noted that the
non-prepolymer isocyanate can be the same or different from the
isocyanate used to form the isocyanate functional prepolymer. It
should also be noted that in certain embodiments, the isocyanate
functional prepolymers can be substantially compatible with the
non-prepolymer isocyanate. As used herein, "substantially
compatible" means the ability of a material to form a blend with
other materials that is and will remain substantially homogeneous
over time.
[0010] The amine component may be referred to herein as a
"curative" because it will react or cure with the isocyanate to
form a polyurea. In certain embodiments, the ratio of equivalents
of isocyanate groups to equivalents of amine groups is greater than
1 and the isocyanate component and the amine component can be
applied to a substrate at a volume mixing ratio of 1:1.
[0011] As used herein, the term "isocyanate" includes unblocked
compounds capable of forming a covalent bond with a reactive group
such as a hydroxyl, thiol or amine functional group. Thus,
isocyanate can refer to "free isocyanate", which will be understood
to those skilled in the art. In certain embodiments, the isocyanate
of the present invention can be monofunctional (containing one
isocyanate functional group (NCO)) or the isocyanate used in the
present invention can be polyfunctional (containing two or more
isocyanate functional groups (NCOs)).
[0012] Suitable isocyanates for use in the present invention are
numerous and can vary widely. Such isocyanates can include those
that are known in the art. Non-limiting examples of suitable
isocyanates can include monomeric and/or polymeric isocyanates. The
isocyanates can be selected from monomers, prepolymers, oligomers,
or blends thereof. In an embodiment, the isocyanate can be
C.sub.2-C.sub.20 linear, branched, cyclic, aromatic, or blends
thereof.
[0013] Suitable isocyanates for use in the present invention may
include but are not limited to isophorone diisocyanate (IPDI),
which is 3,3,5-trimethyl-5-isocyanato-methyl-cyclohexyl isocyanate;
hydrogenated materials such as cyclohexylene diisocyanate,
4,4'-methylenedicyclohexyl diisocyanate (H.sub.12MDI); mixed
aralkyl diisocyanates such as tetramethylxylyl diisocyanates,
OCN--C(CH.sub.3).sub.2--C.sub.6H.sub.4C(CH.sub.3).sub.2--NCO;
polymethylene isocyanates such as 1,4-tetramethylene diisocyanate,
1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate
(HMDI), 1,7-heptamethylene diisocyanate, 2,2,4- and
2,4,4-trimethylhexamethylene diisocyanate, 1,10-decamethylene
diisocyanate and 2-methyl-1,5-pentamethylene diisocyanate; and
mixtures thereof.
[0014] Non-limiting examples of aromatic isocyanates for use in the
present invention may include but are not limited to phenylene
diisocyanate, toluene diisocyanate (TDI), xylene diisocyanate,
1,5-naphthalene diisocyanate, chlorophenylene 2,4-diisocyanate,
bitoluene diisocyanate, dianisidine diisocyanate, tolidine
diisocyanate, alkylated benzene diisocyanates,
methylene-interrupted aromatic diisocyanates such as
methylenediphenyl diisocyanate, 4,4'-isomer (MDI) including
alkylated analogs such as 3,3'-dimethyl-4,4'-diphenylmethane
diisocyanate, polymeric methylenediphenyl diisocyanate; and
mixtures thereof.
[0015] In certain embodiments, isocyanate monomer may be used. It
is believed that the use of an isocyanate monomer (i.e.,
residual-free monomer from the preparation of prepolymer) may
decrease the viscosity of the polyurea composition thereby
improving its flowability, and may provide improved adhesion of the
polyurea coating to a previously applied coating and/or to an
uncoated substrate. In alternate embodiments of the present
invention, at least 1 percent by weight, or at least 2 percent by
weight, or at least 4 percent by weight of the isocyanate component
comprises at least one isocyanate monomer.
[0016] In certain embodiments of the present invention, the
isocyanate can include oligomeric isocyanate such as but not
limited to dimers such as the uretdione of 1,6-hexamethylene
diisocyanate, trimers such as the biuret and isocyanurate of
1,6-hexanediisocyanate and the isocyanurate of isophorone
diisocyanate, allophonates and polymeric oligomers. Modified
isocyanates can also be used, including but not limited to
carbodiimides and uretone-imines, and mixtures thereof. Suitable
materials include, without limitation, those available under the
designation DESMODUR from Bayer Corporation of Pittsburgh, Pa. and
include DESMODUR N 3200, DESMODUR N 3300, DESMODUR N 3400, DESMODUR
XP 2410 and DESMODUR XP 2580.
[0017] As used herein, "prepolymer" means isocyanate which is
pre-reacted with polyamine or other isocyanate reactive group such
as polyol. As used herein, "isocyanate functional prepolymer" means
prepolymer having at least one isocyanate functional group (NCO).
In certain embodiments of the present invention, an isocyanate
functional prepolymer comprises isocyanate that is pre-reacted with
a material comprising a phosphorus-containing polyol wherein the
ratio of equivalents of isocyanate groups (NCOs) to equivalents of
hydroxyl groups (OHs) is greater than 1. Suitable isocyanates
include those previously disclosed herein. Any
phosphorus-containing polyols known in the art can be used in the
present invention. Suitable phosphorus-containing polyols include,
but are not limited to, phosphate and polyphosphate polyols,
phosphite and polyphosphite polyols, phosphonate, polyphosphonate
polyols, or combinations thereof. In certain embodiments, the
phosphorus-containing polyols are EXOLIT OP 550 (LV) (available
from Clariant Corporation), LEVAGARD 4090N (available from Lanxess
Corporation), and blends thereof. In certain embodiments, the
phosphorus-containing polyols may comprise two or more hydroxyl
groups.
[0018] In certain embodiments, the phosphorus-containing polyol can
be the reaction product of an initial phosphorus-containing polyol
with an epoxy functional compound. It will be recognized by those
skilled in the art that the reaction product of a polyol with an
epoxy functional compound will also be a polyol. The initial
phosphorus-containing polyol can include those
phosphorus-containing polyols known in the art, such those
described in the preceding paragraph. It should be noted that the
phosphorus (i.e. inorganic) content of many polyols can render them
or the reaction products comprising them substantially incompatible
with organic materials, such as the non-prepolymer isocyanates,
useful in the "first component" in this invention. As used herein,
the term "substantially incompatible" means the inability of a
material to form a blend with other materials. Accordingly, the
blend will remain substantially heterogeneous over time. Increasing
the organic content of the initial phosphorus polyol by
modification with another compound, such as an epoxy functional
compound, can improve the compatibility of the initial phosphorus
polyol with organic materials, such as the non-prepolymer
isocyanate, while maintaining the flame retardant properties of the
initial phosphorus polyol. Any epoxy functional compounds known in
the art may be utilized in the present invention. Suitable epoxy
functional compounds include, without limitation, ethylene oxide,
propylene oxide, 1,2-epoxybutane, butyl glycidyl ether, and CARDURA
E-10P (neodecanoic acid glycidyl ester available from Resolution
Performance Products LLC). In certain embodiments, the
phosphorus-containing polyol comprises the reaction product of
EXOLIT OP 550 (LV) and CARDURA E-10P.
[0019] In certain embodiments, the phosphorus-containing polyol can
be the reaction product of a phosphorus-containing acid and an
epoxy functional compound. Any phosphorus-containing acid known in
the art can be used in the present invention. Suitable
phosphorus-containing acids include, without limitation, phenyl
phosphonic acid, methyl phosphonic acid, ethyl phosphonic acid,
propyl phosphoric acid, butyl phosphonic acid, or combinations
thereof. In certain embodiments, the phosphorus-containing acid
comprises organic functionality, such as alkyl, aryl, alkylaryl
groups, for reasons of compatibility with organic materials as
described in the preceding paragraph. In certain embodiments, the
phosphorus-containing acid comprises phenyl phosphonic acid, and
the epoxy functional compound comprises propylene oxide. In certain
embodiments, the phosphorus-containing acid comprises phenyl
phosphonic acid and the epoxy comprises CARDURA E10-P.
[0020] In certain embodiments, the phosphorus-containing polyol can
be the reaction product of a phosphorus-containing acid and an
epoxy functional compound, and wherein the reaction is conducted in
the presence of an initial phosphorus-containing polyol. In certain
embodiments, the phosphorus-containing polyol can be the reaction
product of a phosphorus-containing acid, an epoxy functional
compound, and, optionally, an initial phosphorus-containing polyol.
For example, in certain embodiments, the phosphorus-containing acid
comprises phenyl phosphonic acid, the epoxy comprises propylene
oxide, and the phosphorus-containing polyol comprises EXOLIT OP 550
(LV). In another particular embodiment, the phosphorus-containing
acid comprises phenyl phosphonic acid, the epoxy comprises CARDURA
E-10P, and the first phosphorus-containing polyol comprises EXOLIT
OP 550 (LV).
[0021] A polyurea coating composition, which can exhibit improved
flame and/or heat resistance, can comprise the
phosphorus-containing isocyanate prepolymer. As used herein, the
term "flame retardant", "flame resistant", "heat retardant" and
"heat resistant" and the like refers to the ability to withstand
flame or heat without igniting. As used herein, the terms "improved
flame resistance" and "improved heat resistance" means any degree
of improved flame resistance or heat resistance, respectively that
is demonstrated by a coating composition with flame retardant
material as compared to a coating composition without flame
retardant material.
[0022] The isocyanate functional prepolymer may further comprise an
additional polyol, and/or polythiol, and/or polyamine. Suitable
polyols are numerous and can vary widely. Such polyols can include
those that are known in the art. Non-limiting examples of suitable
polyols can include but are not limited to polyether polyols,
polyester polyols, polyurea polyols (e.g., the Michael reaction
product of an amino functional polyurea with a hydroxyl functional
(meth)acrylate), polycaprolactone polyols, polycarbonate polyols,
polyurethane polyols, poly vinyl alcohols, addition polymers of
unsaturated monomers with pendant hydroxyl groups such as those
containing hydroxy functional (meth)acrylates, allyl alcohols and
mixtures thereof. Non-limiting examples can include but are not
limited to diols such as 1,2-butane diol, glycols such as neopentyl
glycol and mixtures thereof. Further examples include commercially
available materials such as TERATHANE 650 from Invista Corporation.
In certain embodiments, wherein the isocyanate functional
prepolymer comprises an additional polyol, the ratio of equivalents
of isocyanate groups (NCOs) to equivalents of hydroxyl groups (OHs)
is greater than 1.
[0023] A "polythiol" refers to such a compound having more than one
SH group, such as a dithiol or higher functionality thiol. Suitable
polythiols are numerous and can vary widely. Such polythiols can
include those that are known in the art. Non-limiting examples of
suitable polythiols can include, but not limited to,
trimethylolpropane tri mercaptoacetate, pentaerythritol
tetramercaptoacetate, trimethylolpropane
tris(.beta.-thiopropionate) and pentaerythritol
tetrakis(.beta.-thiopropionate), thioplast G4 and G44 (available
from Akzo Nobel), 3,6-dioxa-1,8-octanedithiol (available from
Sigma-Aldrich), or mixtures thereof. In certain embodiments,
wherein the isocyanate functional prepolymer comprises a polythiol,
the ratio of equivalents of isocyanate groups (NCOs) to equivalents
of thiol groups (SHs) is greater than 1.
[0024] Suitable polyamines are numerous and can vary widely. Such
polyamines can include those that are known in the art.
Non-limiting examples of suitable polyamines can include but are
not limited to primary and secondary amines, and mixtures thereof,
such as any of those listed herein. Amine terminated polyureas may
also be used. Amines comprising tertiary amine functionality can be
used provided that the amine further comprises at least two primary
and/or secondary amino groups. In certain embodiments, wherein the
isocyanate functional prepolymer comprises a polyamine, the ratio
of equivalents of isocyanate groups (NCOs) to equivalents of amine
groups (NHs) is greater than 1.
[0025] As noted above, the polyurea of the present compositions is
formed from a reaction mixture comprising an isocyanate component
and an amine component.
[0026] Suitable amines for use in the present invention are
numerous and can vary widely. Such amines can include those that
are known in the art such as primary and secondary amines, and
mixtures thereof. In certain embodiments, the amine may include
monoamines, or polyamines having at least two functional groups
such as di-, tri-, or higher functional amines; and mixtures
thereof. In further embodiments, the amine may be aromatic or
aliphatic such as cycloaliphatic, or mixtures thereof. Non-limiting
examples of suitable monoamines can include aliphatic polyamines
such as, but not limited to, ethylamine, isomeric propylamines,
butylamines, pentylamines, hexylamines, cyclohexylamine, and
benzylamine. Suitable primary polyamines include, but are not
limited to, ethylene diamine, 1,2-diaminopropane,
1,4-diaminobutane, 1,3-diaminopentane (DYTEK EP, Invista),
1,6-diaminohexane, 2-methyl-1,5-pentane diamine (DYTEK A, Invista),
2,5-diamino-2,5-dimethylhexane, 2,2,4- and/or
2,4,4-trimethyl-1,6-diamino-hexane, 1,11-diaminoundecane,
1,12-diaminododecane, 1,3- and/or 1,4-cyclohexane diamine,
1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 2,4- and/or
2,6-hexahydrotoluoylene diamine, 2,4'-diaminodicyclohexyl methane,
4,4'-diaminodicyclohexyl methane (PACM-20, Air Products) and
3,3'-dialkyl-4,4'-diaminodicyclohexyl methanes (such as
3,3'-dimethyl-4,4'-diaminodicyclohexyl methane (DIMETHYL DICYKAN or
LAROMIN C260, BASF; ANCAMINE 2049, Air Products) and
3,3'-diethyl-4,4'-diaminodicyclohexyl methane), 2,4- and/or
2,6-diaminotoluene, 3,5-diethyltoluene-2,4-diamine,
3,5-diethyltoluene-2,6-diamine,
3,5-dimethylthio-2,4-toluenediamine,
3,5-dimethylthio-2,4-toluenediamine, 2,4'- and/or
4,4'-diaminodiphenyl methane, dipropylene triamine, bis
hexamethylene triamine, or combinations thereof.
Polyoxyalkyleneamines are also suitable. Polyoxyalkyleneamines
comprise two of more primary or secondary amino groups attached to
a backbone, derived, for example, from propylene oxide, ethylene
oxide, butylene oxide or a mixture thereof. Examples of such amines
include those available under the designation JEFFAMINE, such as,
without limitation, JEFFAMINE D-230, D-400, D-2000, HK-511, ED-600,
ED-900, ED-2003, T-403, T-3000, T-5000, SD-231, SD-401, SD-2001,
and ST-404 (Huntsman Corporation). Such amines have an approximate
molecular weight ranging from 200 to 7500.
[0027] Secondary cycloaliphatic diamines may also be used in the
present invention. Suitable cycloaliphatic diamines include,
without limitation, JEFFLINK 754 (Huntsman Corporation), CLEARLINK
1000 (Dorf-Ketal Chemicals, LLC), and aspartic ester functional
amines, such as those available under the name DESMOPHEN such as
DESMOPHEN NH1220, DESMOPHEN NH 1420, and DESMOPHEN NH 1520 (Bayer
Materials Science LLC.). Other suitable secondary amines that can
be used in the present invention include the reaction products of
materials comprising primary amine functionality, such as those
described herein, with acrylonitrile. For example, the secondary
amine can be the reaction product of
4,4'-diaminodicyclohexylmethane and acrylonitrile. Alternatively,
the secondary amine can be the reaction product of isophorone
diamine and acrylonitrile, such as POLYCLEAR 136 (available from
Hansen Group LLC).
[0028] Other amines that can be used in the present invention
include adducts of primary polyamines with mono or polyepoxies such
as the reaction product of isophorone diamine with Cardura
E-10P.
[0029] The present polyurea compositions may also comprise one or
more amines such as those describe in U.S. patent application Ser.
Nos. 11/611,979, 11/611,984, 11/611,988, 11/611,982, and
11/611,986, all of which are incorporated in their entirety herein
by reference.
[0030] In certain embodiments, the amine component may be a mixture
of primary and secondary amines wherein the primary amine may be
present in an amount of from 20 to 80 percent by weight or from 20
to 50 percent by weight, with the balance being secondary amine. In
other embodiments, the primary amines present in the composition
may have a molecular weight greater than 200, and the secondary
amines present may include diamine having molecular weight of at
least 190, or from 210 to 230.
[0031] In certain embodiments, the second component of the
composition, and/or the composition itself, are substantially free
of primary amine functionality (unreacted primary amino groups).
"Substantially free of primary amine functionality" and like terms
means that theoretically there is no primary amine functionality
but there maybe some primary amine functionality present that is
purely incidental, i.e., impurities in amines that are otherwise
secondary amine functional and/or trace primary amine functionality
that did not react.
[0032] In another embodiment, the amine component may include at
least one secondary amine which may be present in an amount of from
20 to 80 percent by weight or 50 to 80 percent by weight.
[0033] In another embodiment, the amine component may include
aliphatic amine. It is believed that the presence of aliphatic
amine may provide enhanced durability. In this embodiment, the
amine typically is provided as a liquid having a relatively low
viscosity, for example, less than about 100 mPas at 25.degree.
C.
[0034] In certain embodiments, the coating composition may comprise
an additional flame and/or a heat resistant material, such as a
flame retardant material, in addition to the isocyanate functional
pre-polymer described herein. The additional flame retardant
material can be added to the isocyanate and/or the amine component
of the present invention. Any flame retardant material known in the
art can be used as the additional flame retardant material in the
present invention.
[0035] In certain embodiments, a flame retardant material
comprising graphite can be added to the isocyanate and/or the amine
component of the coating compositions of the present invention.
Suitable graphites are known in the art and can include natural and
synthetic graphites. Non-limiting examples of suitable graphites
can include expandable graphite and/or exfoliated graphite. In
certain embodiments, expandable graphite in the form of a solid or
powder is intercalated with an acid such as, but not limited to,
organic acids (e.g. acetic acid) and inorganic acids (e.g.
H.sub.2SO.sub.4 and HNO.sub.3). Non-limiting examples of such
graphites include commercially available graphites under the
tradenames NORD-MIN from Nano Technologies, Incorporated and
NYAGRAPH including but not limited to NYAGRAPH 35, 251 and 351,
from Nyacol, Incorporated. In certain embodiments, if the graphite
is added to the first component, the graphite can be substantially
compatible with the isocyanate functional prepolymers and the
additional isocyanate.
[0036] Other suitable flame retardant materials include, without
limitation, the flame retardant polymers disclosed in U.S. Pat.
Nos. 6,015,510 (column 4, line 31 thru column 5, line 41) and
5,998,503 (column 4, line 31 thru column 5, line 41), halogenated
phosphates or halogen free phosphates, powdered or fumed silica,
layered silicates, aluminum hydroxide, brominated fire retardants,
tris(2-chloropropyl) phosphate, tris(2,3-dibromopropyl)phosphate,
tris(1,3-dichloropropyl)phosphate, diammonium phosphate, various
halogenated aromatic compounds, antimony oxide, alumina trihydrate,
polyvinyl chloride and the like, and mixtures thereof. In certain
embodiments, the flame retardant material is tris(2-chloropropyl)
phosphate, which is available from Supresta under the designation
FYROL PCF. When the flame retardant is a low viscosity liquid, it
also can reduce the viscosity of the isocyanate and/or amine
component, enhancing sprayability.
[0037] In certain embodiments, the flame retardant material may
include at least one phosphinic salt of the formula (I), and/or one
diphosphinic salt of the formula (II), and/or polymers of
these,
##STR00001##
wherein R.sup.1 and R.sup.2 are identical or different and are
C.sub.1-C.sub.6-alkyl, linear or branched, and/or aryl; R.sup.3 is
C.sub.1-C.sub.10-alkylene, linear or branched,
C.sub.6-C.sub.10-arylene, -alkylarylene, or -arylalkylene; M is Mg,
Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K
and/or a protonated nitrogen base; m is from 1 to 4; n is from 1 to
4; x is from 1 to 4, and also may include at least one synergistic
halogen-containing component. The flame retardant component of this
embodiment is further described in United States Patent Publication
Nos. 2005/0004277A1 and 2005/0004278A1, from paragraph [0025] to
paragraph [0070] in both applications.
[0038] In certain embodiments, the additional flame retardant may
optionally contain mineral oxides such as but not limited to zinc
borate, barium metaborates, calcium borate and/or melamine
derivatives such as, but not limited to, melamine cyanurate,
melamine phosphates, polymelamine phosphates, melamine
pyrophosphates, polymelamine pyrophosphates, melamine borate, other
melamine derivatives and the like, and mixtures thereof.
[0039] The amount of the additional flame retardant material in
addition to the isocyanate functional pre-polymer present in the
coating composition of the present invention can vary widely. In
certain embodiments, the additional flame retardant material and
the isocyanate functional pre-polymer comprise up to 35 percent by
weight based on the total weight of reactants in the coating
composition.
[0040] In certain embodiments, the coating compositions used
according to the present invention may include a blend of polyurea
and polyurethane. As used herein, "polyurea" includes both polyurea
and blends of polyurea and polyurethane. It will be appreciated by
those skilled in the art that polyurethane can be formed as a
by-product in the reactions according to the present invention. In
alternate embodiments, the polyurethane can be formed in-situ
and/or it can be added to the reaction mixture; a non-limiting
example is an isocyanate functional prepolymer formed by the
reaction of a polyol and a isocyanate as disclosed herein. A
non-limiting example of polyurethane formed in-situ may include the
reaction product of isocyanate and hydroxyl-functional material.
Non-limiting examples of suitable isocyanates may include those
described herein. Non-limiting examples of suitable
hydroxyl-functional material may include polyols such as those
described herein. Another example of polyurethane formed in-situ
may include the reaction product of a hydroxyl functional
prepolymer and isocyanate-functional material. Suitable examples of
these reactants may include those described herein. The coating
composition of the present invention may be formulated and applied
using various techniques known in the art.
[0041] The polyurea coating compositions of the present invention
may optionally include materials standard in the art such as but
not limited to fillers, fiberglass, stabilizers, thickeners,
adhesion promoters, catalysts, colorants, antioxidants, UV
absorbers, hindered amine light stabilizers, rheology modifiers,
flow additives, anti-static agents and other performance or
property modifiers which are well known in the art of surface
coatings, and mixtures thereof. In alternate embodiments, such
materials may be combined with the isocyanate, the amine, or both.
In a further embodiment, at least one of these materials is added
to the amine prior to reaction with isocyanate.
[0042] In another embodiment, the composition further comprises a
filler such as but not limited to clay, silica or mixtures thereof.
In a further embodiment, the filler is added to the amine. Such a
coating composition has been found to have better adhesion to a
metal substrate than a similar coating composition without clay or
silica (as determined in accordance with the test method in ASTM D
1876, without use of a fixturing device).
[0043] The clay may be selected from any of a variety of clays
known in the art including montmorillonite clays such as bentonite,
kaolin clays, attapulgite clays, sepiolite clay, and mixtures
thereof. Additionally, the clay may be surface treated as is known
in the art. Any suitable surface treatment may be used. In a
non-limiting embodiment, the clay is treated with one or more of
the following amines:
R.sup.1--NR.sup.2R.sup.3
R.sup.1--N.sup.+R.sup.2R.sup.3R.sup.7
R.sup.4--C(O)--NR.sup.5--R.sup.6--NR.sup.2R.sup.3
R.sup.4--C(O)--NR.sup.5--R.sup.6--N.sup.+R.sup.2R.sup.3R.sup.7
wherein R.sup.1 and R.sup.4 are independently C.sub.4-C.sub.24
linear, branched, or cyclic alkyl, aryl, alkenyl, aralkyl or
aralkyl, R.sup.2, R.sup.3, R.sup.5 and R.sup.7 are independently H
or C.sub.1-C.sub.20 linear, branched, or cyclic alkyl, aryl,
alkenyl, aralkyl or aralkyl, and R.sup.6 is C.sub.1-C.sub.24
linear, branched, or cyclic alkylene, arylene, alkenylene,
aralkylene or aralkylene.
[0044] In a non-limiting embodiment, surface treated bentonite as
described in U.S. Pat. No. 3,974,125 may be used.
[0045] In an embodiment, the clay may be present in the coating
composition of the present invention in an amount of at least 0.5
percent by weight, or at least 1 percent by weight, or at least 1.5
percent by weight. In other embodiments, the clay can be present in
an amount of up to 6 percent by weight, or up to 5 percent by
weight, or up to 4 percent by weight of the composition. The amount
of clay in the coating composition can be any value or range
between any values recited above, with the proviso that the
adhesion properties and application viscosity of the coating
composition are not adversely affected.
[0046] In another embodiment, the coating composition of the
present invention may include silica. Any suitable silica can be
used, provided that application and coating performance properties
are not adversely impacted. The silica may be selected from
surface-treated/surface-modified silica, untreated/unmodified
silica and mixtures thereof. Non-limiting examples of suitable
silica may include but are not limited to precipitated, fumed,
colloidal and mixtures thereof. In alternate non-limiting
embodiments, the silica may be present in an amount such that it
constitutes at least 0.5 percent by weight, or at least 1 percent
by weight, or at least 1.5 percent by weight of the coating
composition. In other embodiments, the silica can be present such
that it constitutes up to 6 percent by weight, or up to 5 percent
by weight, or up to 4 percent by weight of the composition. The
amount of silica in the two-component coating composition can be
any value or range between any values recited above, provided that
the adhesion properties and application viscosity of the coating
composition are not adversely affected.
[0047] In another embodiment, the coating composition of the
present invention may include an adhesion promoter which may
enhance adhesion of the coating composition to a substrate. When
the coating composition of the present invention is applied over a
first coating, an adhesion promoter may be present in the first
coating composition, or it may be added to the isocyanate and/or
amine of the second coating composition, or it may be applied as a
separate layer directly to the substrate or first coating prior to
application of the second coating thereto. When applied as a
separate layer, the adhesion promoter may be applied using a
variety of conventional techniques such as but not limited to
wiping, dipping, roll coating, curtain coating, spraying or the
like.
[0048] Non-limiting examples of suitable adhesion promoters for use
in the present invention may include amine-functional materials
such as 1,3,4,6,7,8-hexahydro-2H-pyrimido-(1,2-A)-pyrimidine,
hydroxyethyl piperazine, N-aminoethyl piperizine, dimethylamine
ethylether, tetramethyliminopropoylamine (commercially available as
POLYCAT 15 from Air Products and Chemicals, Inc.), blocked amines
such as an adduct of IPDI and dimethylamine, tertiary amines, such
as 1,5-diazabicyclo[4.3.0]non-5-ene,
1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane,
1,5,7-triazabicyclo[4.4.0]dec-5-ene, and
7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, amino silanes such as
.gamma.-aminopropyltriethoxysilane (commercially available as
Silquest A1100 from Momentive Performance Mateirals, Inc.),
melamine or amino melamine resin (e.g. Cymel 220 or Cymel 303,
available from Cytec Industries Inc.), metal complexes including
metal chelate complexes such as an aluminum chelate complex (e.g.
K-KAT 5218 available from King Industries) or tin-containing
compositions such as stannous octoate and organotin compounds such
as dibutyltin dilaurate and dibutyltin diacetate, urethane acrylate
compositions, salts such as chlorine phosphate, butadiene resins
such as an epoxidized, hydroxyl terminated polybutadiene resin
(e.g. POLY BD 605E available from Atofina Chemicals, Inc.),
polyester polyols (e.g. CAPA 3091, a polyester triol available from
Solvay America, Inc., and urethane acrylate compositions such as an
aromatic urethane acrylate oligomer (e.g. CN999 available from
Sartomer Company, Inc.); and mixtures thereof. For example, the
adhesion promoter disclosed in U.S. patent application Ser. No.
11/591,312, which is incorporated in its entirety herein by
reference, may be used in the present invention.
[0049] It is believed that the underlying mechanism which enhances
adhesion may involve one or more phenomena such as but not limited
to catalysis of a reaction between reactive groups on the substrate
or previously applied coating (e.g. hydroxyl groups) and functional
groups of the coating composition, reaction with the substrate or
bonding with the substrate such as via hydrogen bonding, although
the inventors do not wish to be bound by any mechanism.
[0050] In an embodiment, the adhesion promoter comprises at least
one component selected from melamine, urethane acrylate, metal
chelate complex, salt, tin-containing compound and polyhydric
polymer.
[0051] In certain embodiments, the coating may further comprise
small amounts of solvent and in certain embodiments the coating may
be substantially solvent-free. "Substantially solvent-free" means
that the coating may contain a small amount of solvent, such as 5%,
2%, 1% or less.
[0052] In another embodiment, the coating composition of the
present invention may include a colorant. As used herein, the term
"colorant" means any substance that imparts color and/or other
opacity and/or other visual effect to the composition. The colorant
can be added to the coating in any suitable form, such as discrete
particles, dispersions, solutions and/or flakes. A single colorant
or a mixture of two or more colorants can be used in the coatings
of the present invention.
[0053] Example colorants include pigments, dyes and tints, such as
those used in the paint industry and/or listed in the Dry Color
Manufacturers Association (DCMA), as well as special effect
compositions. A colorant may include, for example, a finely divided
solid powder that is insoluble but wettable under the conditions of
use. A colorant can be organic or inorganic and can be agglomerated
or non-agglomerated. Colorants can be incorporated into the
coatings by grinding or simple mixing. Colorants can be
incorporated by grinding into the coating by use of a grind
vehicle, such as an acrylic grind vehicle, the use of which will be
familiar to one skilled in the art.
[0054] Example pigments and/or pigment compositions include, but
are not limited to, carbazole dioxazine crude pigment, azo,
monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone,
condensation, metal complex, isoindolinone, isoindoline and
polycyclic phthalocyanine, quinacridone, perylene, perinone,
diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone,
anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone,
dioxazine, triarylcarbonium, quinophthalone pigments, diketo
pyrrolo pyrrole red ("DPPBO red"), titanium dioxide, carbon black,
carbon fiber, graphite, other conductive pigments and/or fillers
and mixtures thereof. The terms "pigment" and "colored filler" can
be used interchangeably.
[0055] Example dyes include, but are not limited to, those that are
solvent and/or aqueous based such as acid dyes, azoic dyes, basic
dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes,
sulfur dyes, mordant dyes, for example, bismuth vanadate,
anthraquinone, perylene, aluminum, quinacridone, thiazole,
thiazine, azo, indigoid, nitro, nitroso, oxazine, phthalocyanine,
quinoline, stilbene, and triphenyl methane.
[0056] Example tints include, but are not limited to, pigments
dispersed in water-based or water miscible carriers such as
AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA
COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available
from Accurate Dispersions division of Eastman Chemical, Inc.
[0057] As noted above, the colorant can be in the form of a
dispersion including, but not limited to, a nanoparticle
dispersion. Nanoparticle dispersions can include one or more highly
dispersed nanoparticle colorants and/or colorant particles that
produce a desired visible color and/or opacity and/or visual
effect. Nanoparticle dispersions can include colorants such as
pigments or dyes having a particle size of less than 150 nm, such
as less than 70 nm, or less than 30 nm. Nanoparticles can be
produced by milling stock organic or inorganic pigments with
grinding media having a particle size of less than 0.5 mm. Example
nanoparticle dispersions and methods for making them are identified
in U.S. Pat. No. 6,875,800 B2, which is incorporated herein by
reference. Nanoparticle dispersions can also be produced by
crystallization, precipitation, gas phase condensation, and
chemical attrition (i.e., partial dissolution). In order to
minimize re-agglomeration of nanoparticles within the coating, a
dispersion of resin-coated nanoparticles can be used. As used
herein, a "dispersion of resin-coated nanoparticles" refers to a
continuous phase in which is dispersed discreet "composite
microparticles" that comprise a nanoparticle and a resin coating on
the nanoparticle. Example dispersions of resin-coated nanoparticles
and methods for making them are identified in U.S. application Ser.
No. 10/876,031 filed Jun. 24, 2004, which is incorporated herein by
reference, and U.S. Provisional Application No. 60/482,167 filed
Jun. 24, 2003, which is also incorporated herein by reference.
[0058] Example special effect compositions that may be used in the
coating of the present invention include pigments and/or
compositions that produce one or more appearance effects such as
reflectance, pearlescence, metallic sheen, phosphorescence,
fluorescence, photochromism, photosensitivity, thermochromism,
goniochromism and/or color-change. Additional special effect
compositions can provide other perceptible properties, such as
reflectivity, opacity or texture. In a non-limiting embodiment,
special effect compositions can produce a color shift, such that
the color of the coating changes when the coating is viewed at
different angles. Example color effect compositions are identified
in U.S. Pat. No. 6,894,086, incorporated herein by reference.
Additional color effect compositions can include transparent coated
mica and/or synthetic mica, coated silica, coated alumina, a
transparent liquid crystal pigment, a liquid crystal coating,
and/or any composition wherein interference results from a
refractive index differential within the material and not because
of the refractive index differential between the surface of the
material and the air.
[0059] In certain embodiments, a photosensitive composition and/or
photochromic composition, which reversibly alters its color when
exposed to one or more light sources, can be used in the coating of
the present invention. Photochromic and/or photosensitive
compositions can be activated by exposure to radiation of a
specified wavelength. When the composition becomes excited, the
molecular structure is changed and the altered structure exhibits a
new color that is different from the original color of the
composition. When the exposure to radiation is removed, the
photochromic and/or photosensitive composition can return to a
state of rest, in which the original color of the composition
returns. In one non-limiting embodiment, the photochromic and/or
photosensitive composition can be colorless in a non-excited state
and exhibit a color in an excited state. Full color-change can
appear within milliseconds to several minutes, such as from 20
seconds to 60 seconds. Example photochromic and/or photosensitive
compositions include photochromic dyes.
[0060] In an embodiment, the photosensitive composition and/or
photochromic composition can be associated with and/or at least
partially bound to, such as by covalent bonding, a polymer and/or
polymeric materials of a polymerizable component. In contrast to
some coatings in which the photosensitive composition may migrate
out of the coating and crystallize into the substrate, the
photosensitive composition and/or photochromic composition
associated with and/or at least partially bound to a polymer and/or
polymerizable component in accordance with a non-limiting
embodiment of the present invention, have minimal migration out of
the coating. Example photosensitive compositions and/or
photochromic compositions and methods for making them are
identified in U.S. application Ser. No. 10/892,919 filed Jul. 16,
2004 and incorporated herein by reference.
[0061] In general, the colorant can be present in the coating
composition in any amount sufficient to impart the desired
property, visual and/or color effect. The colorant may comprise
from 1 to 65 weight percent of the present compositions, such as
from 3 to 40 weight percent or 5 to 35 weight percent, with weight
percent based on the total weight of the compositions.
[0062] In another embodiment, the coating composition of the
present invention when applied to a substrate possesses color that
matches the color of an associated substrate. As used herein and in
the claims, the term "matches" or like terms when referring to
color matching means that the color of the coating composition of
the present invention substantially corresponds to a desired color
or the color of an associated substrate. This can be visually
observed, or confirmed using spectroscopy equipment.
[0063] The coatings of the present invention may be part of a
multi-layer coating composite comprising a substrate with various
coating layers such as a pretreatment layer, electocoat, primer,
base coat and clear coat. At least one of the base coat and clear
coat may contain colorant and/or the clear coat may contain an
adhesion promoter. It is believed that the addition of adhesion
promoter to the clear coat may improve the adhesion between the
clear coat and the coating composition applied thereover, although
the inventors do not wish to be bound by any mechanism. In this
embodiment, the coating composition of the present invention may be
the reaction product of isocyanate and amine with a colorant
additive. The coating composition of the present invention
containing colorant may be applied to at least a portion of the
article or structure. The color of the coated article or structure
may match the color of an associated substrate. An "associated
substrate" may refer to a substrate which comprises the article or
structure but is not coated with the coating composition of the
present invention; or a substrate which is attached, connected or
in close proximity to the article or structure, but is not coated
with the coating composition of the present invention.
[0064] Accordingly, the present invention is further directed to
methods for coating a substrate comprising applying to at least a
portion of the substrate any of the coating compositions described
herein. In an embodiment, conventional spraying techniques may be
used. In this embodiment, the isocyanate and amine may be combined
such that the ratio of equivalents of isocyanate groups to
equivalents of amine groups is greater than 1 and the isocyanate
and amine can be applied to a substrate at a volume mixing ratio of
1:1; and the reaction mixture may be applied to an uncoated or
coated substrate to form a first coating on the uncoated substrate
or a subsequent coating on the coated substrate. When determining
the ratio of equivalents of isocyanate groups to equivalents of
reactive amine groups, the total amine groups are taken into
consideration; that is the amine groups from any amine or amines
used in the coating.
[0065] It will be appreciated that the present compositions are two
component or "2K" compositions, wherein the isocyanate component
and the amine component are kept separate until just prior to
application. Such compositions will be understood as curing under
ambient conditions, although a heated forced air or a heat cure can
be applied to accelerate final cure or to enhance coating
properties such as adhesion. In an embodiment, the sprayable
coating composition may be prepared using a two-component mixing
device. In this embodiment, isocyanate and amine are added to a
high pressure impingement mixing device. The isocyanate is added to
the "A-side" and amine is added to the "B-side". The A- and B-side
streams are impinged upon each other and immediately sprayed onto
at least a portion of an uncoated or coated substrate. The
isocyanate and the amine react to produce a coating composition
which is cured upon application to the uncoated or coated
substrate. The A- and/or B-side can also be heated prior to
application, such as to a temperature of 140.degree. F. Heating may
promote a better viscosity match between the two components and
thus better mixing, but is not necessary for the curing reaction to
occur.
[0066] The volume mixing ratio of the isocyanate and amine may be
such that the resulting isocyanate and amine reaction mixture can
be applied to a substrate at a volume mixing ratio of 1:1. As used
herein, "volume mixing ratio 1:1" means that the volume mixing
ratio varies by up to 20% for each component, or up to 10% or up to
5%.
[0067] It is believed that the ratio of equivalents of isocyanate
groups to amine groups may be selected to control the rate of cure
of the coating composition of the present invention. It has been
found that cure and adhesion advantages may result when the ratio
of the equivalents of isocyanate groups to amine groups (also known
as the reaction index) is greater than one, such as from 1.5:1 to
0.9:1 or from 1.3:1 to 1.05:1.
[0068] In a non-limiting embodiment, a commercially available
mixing device available commercially under the designation GUSMER
VR-H-3000 proportioner fitted with a GUSMER Model GX-7 spray gun
may be used. In this device, pressurized streams of the A- and
B-side components are delivered from two separate chambers, are
impacted or impinged upon each other at high velocity, to mix the
two components and form a coating composition, which may be applied
to an uncoated or coated substrate using the spray gun. The mixing
forces experienced by the component streams may depend upon the
volume of each stream entering the mixing chamber per unit time and
the pressure at which the component streams are delivered. A 1:1
volume ratio of the isocyanate and amine per unit time may equalize
these forces.
[0069] Another suitable application device known in the industry
includes a "static mix tube" applicator. In this device, the
isocyanate and amine are each stored in a separate chamber. As
pressure is applied, each of the components is brought into a
mixing tube in a 1:1 ratio by volume. Mixing of the components is
effected by way of a torturous or cork screw pathway within the
tube. The exit end of the tube may have atomization capability
useful in spray application of the reaction mixture. Alternatively,
the fluid reaction mixture may be applied to a substrate as a bead.
A static mix tube applicator is commercially available from Cammda
Corporation or Plas-Pak Industries, Inc.
[0070] The coating composition of the present invention may be
applied to a wide variety of substrates. Non-limiting examples of
suitable substrates can include, but are not limited to, metal,
natural and/or synthetic stone, ceramic, glass, brick, cement,
concrete, cinderblock, wood and composites and laminates thereof;
wallboard, drywall, sheetrock, cement board, plastic, paper, PVC,
roofing materials such as shingles, roofing composites and
laminates, and roofing drywall, styrofoam, plastic composites,
acrylic composites, ballistic composites, asphalt, fiberglass,
soil, gravel and the like. Metals can include but are not limited
to aluminum, cold rolled steel, electrogalvanized steel, hot dipped
galvanized steel, titanium and alloys; plastics can include but are
not limited to TPO, SMC, TPU, polypropylene, polycarbonate,
polyethylene, and polyamides (Nylon). The substrates can be primed
metal and/or plastic; that is, an organic or inorganic layer is
applied thereto. Further, the coating composition of the present
invention can be applied to said substrates to impart one or more
of a wide variety of properties such as but not limited to
corrosion resistance, abrasion resistance, impact damage, flame
and/or heat resistance, chemical resistance, UV light resistance,
structural integrity, ballistic mitigation, blast mitigation, sound
dampening, decoration and the like. As used herein, "ballistic
mitigation" refers to reducing or alleviating the effects of a
bullet or other type of firearm ammunition. As used herein, "blast
mitigation" refers to reducing or alleviating the secondary effects
of a blast. In non-limiting examples, the coating composition of
the present invention can be applied to at least a portion of a
building structure or an article of manufacture such as but not
limited to a vehicle. "Vehicle" includes but is not limited to
civilian, commercial, and military land-, water-, and air-vehicles,
for example, cars, trucks, boats, ships, submarines, airplanes,
helicopters, humvees and tanks. The article of manufacture can be a
building structure. "Building structure" includes but is not
limited to at least a portion of a structure including residential,
commercial and military structures, for example, roofs, floors,
support beams, walls and the like. "Building structure" also
includes structures, including those that define apertures,
associated with mining. Typical mine structures include mains,
submains, gate road entries, production panels, bleeders, and other
active working areas associated with underground mining.
Accordingly, the present compositions can also be used to coat mine
supports, beams, seals, stoppings, ribs, exposed strata, and the
like and can be further used, alone or in conjunction with other
layers, to seal and/or reinforce mine structures. As used herein,
the term "substrate" may refer to a surface, either external or
internal, on at least a portion of an article of manufacture or the
article of manufacture itself. In an embodiment, the substrate is a
truck bed.
[0071] In an embodiment, the coating composition of the present
invention may be applied to a carrier film. The carrier film can be
selected from a wide variety of such materials known in the art.
Non-limiting examples of suitable carrier films may include, but
are not limited to thermoplastic materials, thermosetting
materials, metal foils, cellulosic paper, synthetic papers, and
mixtures thereof. As used herein, the term "thermoplastic material"
refers to any material that is capable of softening or fusing when
heated and of solidifying (hardening) again when cooled.
Non-limiting examples of suitable thermoplastic materials may
include polyolefins, polyurethanes, polyesters, polyamides,
polyureas, acrylics, and mixtures thereof. As used herein, the term
"thermosetting material" refers to any material that becomes
permanently rigid after being heated and/or cured. Non-limiting
examples may include polyurethane polymers, polyester polymers,
polyamide polymers, polyurea polymers, polycarbonate polymers,
acrylic polymers, resins, copolymers thereof, and mixtures thereof.
As used herein, the term "foil" refers to a thin and flexible sheet
of metal. Non-limiting examples may include aluminum, iron, copper,
manganese, nickel, combinations thereof, and alloys thereof. As
used herein, the term "synthetic paper" refers to synthetic plain
or calendered sheets that can be coated or uncoated and are made
from films containing polypropylene, polyethylene, polystyrene,
cellulose esters, polyethylene terephthalate, polyethylene
naphthalate, poly 1,4-cyclohexanedimethylene terephthalate,
polyvinyl acetate, polyimide, polycarbonate, and combinations and
mixtures thereof. A non-limiting example of suitable synthetic
paper is available under the tradename TESLIN from PPG Industries,
Inc., Pittsburgh, Pa.
[0072] In an embodiment, a carrier film having a first and second
major surface may serve as a substrate and the coating composition
of the present invention may be applied to the first surface of the
film to form a coating layer.
[0073] In other embodiments, the carrier film may have a film
thickness of at least 0.5 .mu.m, or at least 1 .mu.m, or at least 2
.mu.m, or at least 3 .mu.m or at least 5 .mu.m. In other
embodiments, the carrier film may have a thickness of up to 100
.mu.m, or up to 90 .mu.m, or up to 75 .mu.m, or up to 50 .mu.m, or
up to 40 .mu.m. The carrier film can vary and range between any
thickness recited above provided that the carrier film can
adequately support the coating layer and is sufficiently flexible
for a desired end use application.
[0074] In another embodiment, the carrier film may include an
adhesive layer superimposed on the second surface of the film. Any
suitable adhesive composition known in the art can be used to form
the adhesive layer. Suitable adhesive compositions include those
that contain at least one acrylic latex polymer prepared from a
monomer composition that includes C.sub.1-C.sub.5 linear, branched,
or cyclic alkyl (meth)acrylate monomers.
[0075] In a further embodiment, a temporary protective cover may be
superimposed over the adhesive layer. Any suitable material can be
used as the protective cover. Suitable materials include, but are
not limited to, paper and polymeric materials. In these
embodiments, the temporary protective cover can be removed and the
second side of the carrier film may be applied or adhered to a
desired substrate.
[0076] In certain embodiments, the coating composition of the
present invention may be applied to a bare (e.g., untreated,
uncoated) substrate, a pretreated substrate and/or coated substrate
having at least one other coating. In an embodiment, the coating
composition of the present invention may be applied to a
multi-layer coating composite. The first coating applied to a
substrate may be selected from a variety of coating compositions
known in the art for surface coating substrates. Non-limiting
examples may include but are not limited to electrodepositable
film-forming compositions, primer compositions, pigmented or
non-pigmented monocoat compositions, pigmented or non-pigmented
base coat compositions, transparent topcoat compositions,
industrial coating compositions, and the like. In another
non-limiting embodiment, the coating composition of the present
invention may be applied to a multi-layer coating composite
comprising a pretreated substrate and coating layers such as but
not limited to electrocoat, primer, base coat, clear coat, and
combinations thereof.
[0077] In another embodiment, the coating composition of the
present invention can be used in a two-coat application resulting
in a textured surface. A first coat is applied to an uncoated or
coated substrate to produce a smooth, substantially tack-free
layer. The Tack-Free Method is used to determine if the layer is
substantially tack-free. The Tack-Free Method includes spraying the
coating composition in one coat onto a non-adhering plastic sheet
to a thickness of from 10 to 15 mil (254-381 microns). When
spraying is complete, an operator, using a loose fitting,
disposable vinyl glove, such as one commercially available under
the trade name Ambidex Disposable Vinyl Glove by Marigold
Industrial, Norcross Ga., gently touches the surface of the
coating. The coating may be touched more than one time by using a
different fingertip. When the glove tip no longer sticks to, or
must be pulled from, the surface of the layer, the layer is said to
be substantially tack-free. The time beginning from the completion
of spraying until when the coating is substantially tack-free is
said to be the tack-free time. In an embodiment, the tack-free time
and the cure time may be controlled by balancing levels of various
composition components such as the ratio of primary amine to
secondary amine.
[0078] A second coat may then be applied to the first coating layer
as a texturizing layer or "dust coating". The second coating layer
can be applied by increasing the distance between the
application/mixing device and the coated substrate to form discrete
droplets of the coating composition prior to contacting the coated
substrate thereby forming controlled non-uniformity in the surface
of the second layer. The substantially tack-free first layer of the
coating is at least partially resistant to the second layer; i.e.,
at least partially resistant to coalescence of the droplets of
coating composition sprayed thereon as the second layer or dust
coating such that the droplets adhere to but do not coalesce with
the previous layer(s) to create surface texture. The final coating
layer typically exhibits more surface texture than the first or
previous coating layers. An overall thickness of the coating layers
may range from 20 to 1000 mils, or from 40 to 150 mils, or from 60
to 100 mils (1524-2540 microns), or from 500 to 750 mils. In a
non-limiting embodiment, the first layer may be the majority of the
total thickness and the dust coating may be from 15-50 mils
(381-1270 microns). In various embodiments of the present
invention, the "first" coating layer may comprise one, two, three
or more layers; and the "second" coating layer may be one or more
subsequent layers applied thereover. For example, four polyurea
layers may be applied, with the fourth layer being the dust coating
and each layer having a thickness of from 15 to 25 mil (381-635
microns). It will be appreciated that these coating layers are
relatively "thick". The coating compositions of the present
invention can also be applied as much thinner layers as well, such
as 0.1 to less than 15 mils, such as 0.1 to 10, 0.5 to 3, or 1 to 2
mils. Any of the endpoints within these ranges can also be
combined. Such layers can be used alone or in conjunction with
other coating layers, such as any of those known in the art or
otherwise described herein. When applied at a sufficient thickness
(e.g., 10 to 1000 mils, such as 100 to 200 mils, or 125 mils+/-10
mils), the present polyurea layer(s) can provide blast and/or
ballistic mitigation.
[0079] In other embodiments, the coating layers may comprise the
same or different polyurea or polyurea/polyurethane coating
compositions. For example, the first layer may be a polyurea
composition comprising aliphatic and/or aromatic amine components
and/or aliphatic and/or aromatic isocyanate; and the second layer
may comprise the same or different combination of aliphatic and/or
aromatic amine components and/or aliphatic and/or aromatic
isocyanate. "Amine component" in this context means any amine used
in the present coatings. In another embodiment, the outermost
coating layer may comprise a coating composition that provides a
desired durability. The desired durability may depend upon the use
of the coating composition of the present invention and/or the
substrate to which it may be applied. In an embodiment, a
combination of aliphatic and/or aromatic amine and/or isocyanate
may be selected such that the composition of the outermost layer
has substantial durability. For example, the outermost coating
layer may have a durability of from 1000 kJ to 6000 kJ, or from 800
hours to 4000 hours, when tested using a Weatherometer (Atlas
Material Testing Solutions) in accordance with method SAE J1960. In
this embodiment, the first layer may be a polyurea composition
comprising isocyanate and amine, wherein at least one of the amine
and/or polyisocyante may be aromatic, and the second layer may be a
polyurea composition comprising aliphatic amine and aliphatic
isocyanate.
[0080] While specific embodiments of the invention have been
described in detail, it will be appreciated by those skilled in the
art that various modifications and alternatives to those details
could be developed in light of the overall teachings of the
disclosure. Accordingly, the particular arrangements disclosed are
meant to be illustrative only and not limiting as to the scope of
the invention which is to be given the full breadth of the claims
appended and any and all equivalents thereof.
Example A
[0081] A modified polyphosphate diol was prepared from the
following ingredients:
TABLE-US-00001 Ingredient Amt in g Exolit OP 550 (LV).sup.1 233.4
p-toluene sulfonic acid 3.6 Cardura E-10P.sup.2 130.1
.sup.1Polyphosphate diol available from Clariant Corporation.
.sup.2Neodecanoic acid glycidyl ester available from Resolution
Performance Products LLC.
[0082] The above ingredients were charged to a suitable reactor
equipped with a heating mantle, reflux condenser, overhead stirrer,
thermocouple, and N.sub.2 inlet. A N.sub.2 blanket was applied to
the reactor and the mixture heated in 10.degree. C. increments over
two hours to 140.degree. C. The reaction mixture was held at this
temperature and sampled for epoxy equivalent weight approximately
every 4 hours. After 13.25 hours, the epoxy equivalent weight was
determined to be infinite (no end point in titration) and the
reaction was judged to be complete. The resulting resin was a
clear, viscous fluid and was found to have a measured solids
(110.degree. C., 1 hr) of 88.4 percent, a viscosity of Z2- on the
Gardner-Holt scale, an acid value of 2.7 mg KOH/g, a hydroxyl value
of 82.2 mg KOH/g, and a M.sub.w of 1126, a M.sub.n of 553, a
M.sub.z of 1866, and a peak molecular weight of 620 as determined
by gel permeation chromatography versus a polystyrene standard.
Example B
[0083] A compatible isocyanate component comprising a
phosphorus-containing isocyanate-functional prepolymer was prepared
from the following ingredients as described below:
TABLE-US-00002 Ingredients Parts by Weight (grams) DESMODUR
XP2580.sup.3 82 RESIN FROM EXAMPLE A 88 Dibutyltin dilaurate 0.02
FYROL PCF.sup.4 77 DESMODUR XP2580 390 DESMODUR XP2410.sup.5 210
.sup.3Polyisocyanate available from Bayer Material Science
Corporation. .sup.4tris (2-chloroisopropyl) phosphate flame
retardant available from Supresta. .sup.5Polyisocyanate available
from Bayer Material Science Corporation.
[0084] A total of 82 grams of DESMODUR XP2580 was placed in a
suitable reaction vessel equipped with a stirrer, temperature
probe, a condenser and a nitrogen inlet tube and blanketed with
nitrogen gas. A total of 88 grams of RESIN FROM EXAMPLE A was then
added and mixed for 15 minutes at ambient temperature. Then, 0.02
grams of dibutyltin dilaurate was added and the mixture was heated
slowly to 50.degree. C., then to 80.degree. C. and finally to
100.degree. C. At this point the isocyanate equivalent weight was
measured and found to be 656 grams per equivalent. The reaction
mixture was then cooled to 80.degree. C. and 77 grams of FYROL PCF,
390 grams of DESMODUR XP2580 and 210 grams of DESMODUR XP2410 were
then added to the reaction mixture. The contents of the reactor
were cooled and poured out. The final material was a clear,
compatible resin with a measured solids of 98% and an isocyanate
equivalent weight of 266 grams per equivalent.
Example C
[0085] A blended polyphosphate diol/phosphonate diol was prepared
from the following ingredients:
TABLE-US-00003 Ingredients Amt in g Charge 1 Exolit OP 550
(LV).sup.1 175.1 Phenylphosphonic acid 35.6 Charge 2 Cardura
E-10P.sup.2 162.7 Charge 3 Cardura E-10P.sup.2 37.5
[0086] The ingredients of Charge 1 were charged to a suitable
reactor equipped with a heating mantle, reflux condenser, overhead
stirrer, thermocouple, and N.sub.2 inlet. A N.sub.2 blanket was
applied to the reactor and the mixture heated over 1 hour to
140.degree. C. Charge 2 was then added to the reaction mixture over
a period of 3 hours. After a two hour hold, the acid value of the
reaction mixture was found to have stabilized at 7.8 mg KOH/g.
Charge 3 was added to the reactor over 0.5 hr, and the reaction
mixture was held at temperature for an additional 2.3 hours, at
which time no acid could be detected. After an additional 5.1 hours
hold, the reaction mixture was sampled and found to have an epoxy
equivalent weight of 9002 g/equiv. After an additional hold of 11.5
hours, the epoxy equivalent weight was found to be 29005 g/equiv.
At this point the reaction mixture was poured out. The resulting
resin was a clear viscous fluid and was found to have a measured
solids (110.degree. C., 1 hr) of 93.1 percent, a viscosity of Z3+on
the Gardner-Holt scale, an acid value of 0.1 mg KOH/g, an epoxy
equivalent weight of 35687, a hydroxyl value of 90.3 mg KOH/g, and
a M.sub.w of 1247, a M.sub.n of 584, a M.sub.Z of 2231, and a peak
molecular weight of 644 as determined by gel permeation
chromatography versus a polystyrene standard.
Example D
[0087] A compatible isocyanate component comprising a
phosphorus-containing isocyanate-functional prepolymer was prepared
from the following ingredients as described below:
TABLE-US-00004 Ingredients Parts by Weight (grams) ISOPHORONE
DIISOCYANATE 34 RESIN FROM EXAMPLE C 92 Dibutyltin dilaurate 0.02
FYROL PCF.sup.4 61 DESMODUR XP2580.sup.3 275 DESMODUR XP2410.sup.5
149
[0088] A total of 34 grams of ISOPHORONE DIISOCYANATE was placed in
a suitable reaction vessel equipped with a stirrer, temperature
probe, a condenser and a nitrogen inlet tube and blanketed with
nitrogen gas. A total of 92 grams of RESIN FROM EXAMPLE C was then
added and mixed for 15 minutes at ambient temperature. Then, 0.02
grams of dibutyltin dilaurate was added and the mixture was heated
slowly to 50.degree. C., then to 80.degree. C. and finally to
100.degree. C. At this point the isocyanate equivalent weight was
measured and found to be 797 grams per equivalent. The reaction
mixture was then cooled to 80.degree. C. and 61 grams of FYROL PCF
and 275 grams of DESMODUR XP2580 and 149 grams of DESMODUR XP2410
were then added to the reaction mixture. The contents of the
reactor were cooled and poured out. The final material was a clear,
compatible resin with a measured solids of 97% and an isocyanate
equivalent weight of 267 grams per equivalent.
Example E
[0089] A blended polyphosphate diol/phosphonate diol was prepared
from the following ingredients:
TABLE-US-00005 Ingredients Amt in g Charge 1 Exolit OP 550
(LV).sup.1 136.2 Phenylphosphonic acid 110.6 Charge 2 Propylene
oxide 121.8 Charge 3 Propylene oxide 30.4 Charge 4 Propylene oxide
10.0
[0090] The ingredients of Charge 1 were charged to a suitable
reactor equipped with a heating mantle, reflux condenser, overhead
stirrer, thermocouple, and N.sub.2 inlet. A N.sub.2 blanket was
applied to the reactor and the mixture heated over 1 hour to
100.degree. C. Charge 2 was then added to the reaction mixture over
a period of 3.25 hours. After a two hour hold, the acid value of
the reaction mixture was found to be 26.6 mg KOH/g. Charge 3 was
added to the reactor over 0.75 hr, and the reaction mixture was
held at temperature for an additional 2.1 hours. The reaction
mixture was resampled and found have an acid value of 8.2. Charge 4
was added and held for an additional 1 hour. At that time, the acid
value was determined to be 3.8 mg KOH/g resin. The reaction mixture
was then subjected to vacuum at 60 mm Hg for 1 hour at the reaction
temperature to remove any residual propylene oxide. The resulting
resin was a clear viscous fluid and was found to have a measured
solids (110.degree. C., 1 hr) of 87.9 percent, a viscosity of V+ on
the Gardner-Holt scale, an acid value of 4.3 mg KOH/g, an epoxy
equivalent weight of >100000, a hydroxyl value of 242.7 mg
KOH/g, and a M.sub.w of 532, a M.sub.n of 305, a M.sub.z of 808,
and a peak molecular weight of 485 as determined by gel permeation
chromatography versus a polystyrene standard.
Example F
[0091] A compatible isocyanate component comprising a
phosphorus-containing isocyanate-functional prepolymer was prepared
from the following ingredients as described below:
TABLE-US-00006 Ingredients Parts by Weight (grams) DESMODUR
XP2580.sup.3 141 RESIN FROM EXAMPLE E 51 Dibutyltin dilaurate 0.03
FYROL PCF.sup.4 68 DESMODUR XP2580.sup.3 274 DESMODUR XP2410.sup.5
148
[0092] A total of 141 grams of DESMODUR XP2580 was placed in a
suitable reaction vessel equipped with a stirrer, temperature
probe, a condenser and a nitrogen inlet tube and blanketed with
nitrogen gas. A total of 88 grams of RESIN FROM EXAMPLE E was then
added and mixed for 15 minutes at ambient temperature. Then, 0.03
grams of dibutyltin dilaurate was added and the mixture was heated
slowly to 50.degree. C., then to 80.degree. C. and finally to
100.degree. C. At this point the isocyanate equivalent weight was
measured and found to be 449 grams per equivalent. The reaction
mixture was then cooled to 80.degree. C. and 68 grams of FYROL PCF,
274 grams of DESMODUR XP2580 and 148 grams of DESMODUR XP2410 were
then added to the reaction mixture. The contents of the reactor
were cooled and poured out. The final material was a clear,
compatible resin with a measured solids of 99% and an isocyanate
equivalent weight of 264 grams per equivalent.
Example G
[0093] A phosphonate diol was prepared from the following
ingredients:
TABLE-US-00007 Ingredients Amt in g Charge 1 Phenylphosphonic acid
711.0 Butyl acetate 720.0 Charge 2 Propylene oxide 522.0 Charge 3
Propylene oxide 209.5 Charge 4 Propylene oxide 47.3
[0094] The ingredients of Charge 1 were charged to a suitable
reactor equipped with a heating mantle, reflux condenser, overhead
stirrer, thermocouple, and N.sub.2 inlet. A N.sub.2 blanket was
applied to the reactor and the mixture heated over 0.3 hour to
50.degree. C. The heating mantle was then removed from the reactor.
At this point the reaction mixture was a slurry. Charge 2 was then
added to the reaction mixture over a period of 3.6 hours. An
exotherm was observed; during the feed, the temperature of the
reaction mixture varied from 41 to 58.degree. C. Approximately 1
hour into the feed the reaction mixture began to clear. After a 3.3
hour hold, the acid value of the reaction mixture was found to be
43.1 mg KOH/g. Charge 3 was then added to the reactor over 2.75 hr
over a temperature range of 52 to 63.degree. C.; afterward, the
reaction mixture was held at 52.degree. C. for 1.1 hours. The
reaction mixture was resampled and found have an acid value of 7.8
mg KOH/g. Charge 4 was then added at a temperature of 52.degree. C.
and then held for 1 hour. At that time, the acid value was
determined to be 5.1 mg KOH/g resin. The reaction mixture was then
subjected to vacuum at 50 mm Hg at 65.degree. C. for 1 hour at the
reaction temperature to remove butyl acetate. The temperature was
raised to 75.degree. C. at 60 mm Hg and held for 0.3 hour, then
raised to 85.degree. C. and held for 1 hour. The resulting resin
was a clear viscous fluid and was found to have a measured solids
(110.degree. C., 1 hr) of 77.2 percent, a viscosity of U- on the
Gardner-Holt scale, an acid value of 6.4 mg KOH, a hydroxyl value
of 326.6 mg KOH/g, and a M.sub.w of 371, a M.sub.n of 329, a
M.sub.z of 421, and a peak molecular weight of 272 as determined by
gel permeation chromatography versus a polystyrene standard.
Example H
[0095] A compatible isocyanate component comprising a
phosphorus-containing isocyanate-functional prepolymer was prepared
from the following ingredients as described below:
TABLE-US-00008 Ingredients Parts by Weight (grams) DESMODUR
XP2580.sup.3 398 RESIN FROM EXAMPLE G 108 Dibutyltin dilaurate 0.04
FYROL PCF.sup.4 121 DURANATE TLA-100.sup.6 556 .sup.6Polyisocyanate
available from Asahi Kasei Chemicals Corporation.
[0096] A total of 398 grams of DESMODUR XP2580 was placed in a
suitable reaction vessel equipped with a stirrer, temperature
probe, a condenser and a nitrogen inlet tube and blanketed with
nitrogen gas. A total of 108 grams of RESIN FROM EXAMPLE G was then
added and mixed for 15 minutes at ambient temperature. Then, 0.04
grams of dibutyltin dilaurate was added and the mixture was heated
slowly to 50.degree. C., then to 80.degree. C. and finally to
100.degree. C. At this point the isocyanate equivalent weight was
measured and found to be 413 grams per equivalent. The reaction
mixture was then cooled to 80.degree. C. and 121 grams of FYROL PCF
and 556 grams of DURANATE TLA-100 were then added to the reaction
mixture. The contents of the reactor were cooled and poured out.
The final material was a clear, compatible resin with a measured
solids of 98% and an isocyanate equivalent weight of 266 grams per
equivalent.
Example I
[0097] A phosphonate diol was prepared from the following
ingredients:
TABLE-US-00009 Ingredients Amt in g Charge 1 Phenylphosphonic acid
300.2 Butyl acetate 608.0 Charge 2 Cardura E-10P.sup.2 915.8 Charge
3 Cardura E10P.sup.2 81.3
[0098] The ingredients of Charge 1 were charged to a suitable
reactor equipped with a heating mantle, reflux condenser, overhead
stirrer, thermocouple, and N.sub.2 inlet. A N.sub.2 blanket was
applied to the reactor and the mixture heated over 0.7 hour to
80.degree.
[0099] C. At this point the reaction mixture was a slurry. Charge 2
was then added to the reaction mixture over a period of 2 hours. At
1 hour into the feed the reaction mixture was clear. After a 3 hour
hold, the acid value of the reaction mixture was found to be 7.6 mg
KOH/g. Charge 3 was then added to the reactor and held for 0.75
hour. The reaction mixture was resampled and found have an acid
value of 4.7 mg KOH/g. The reaction mixture was then subjected to
vacuum at 60 mm Hg at 80.degree. C. for 1 hour at the reaction
temperature to remove butyl acetate. The temperature was raised to
75.degree. C. at 60 mm Hg and held for 1.75 hour; vacuum was broken
and the flask and contents weighed. Vacuum at 60 mm Hg was
reapplied and the temperature raised to 90.degree. C. for 1 hour.
The strip was determined to still not be complete by weight. The
vacuum was reapplied again for 1 hour at 90.degree. C.; at this
time the strip was considered to be complete. The resulting resin
was a clear viscous fluid and was found to have a measured solids
(110.degree. C., 1 hr) of 90.1 percent, a viscosity of Z2- on the
Gardner-Holt scale, an acid value of 3.1 mg KOH, a hydroxyl value
of 158.6 mg KOH/g, and a M.sub.w of 643, a M.sub.n of 519, a
M.sub.z of 769, and a peak molecular weight of 668 as determined by
gel permeation chromatography versus a polystyrene standard.
Example J
[0100] A compatible isocyanate component comprising a
phosphorus-containing isocyanate-functional prepolymer was prepared
from the following ingredients as described below:
TABLE-US-00010 Ingredients Parts by Weight (grams) ISOPHORONE
DIISOCYANATE 86 RESIN FROM EXAMPLE I 130 Dibutyltin dilaurate 0.02
FYROL PCF.sup.4 118 DESMODUR XP2580.sup.3 911
[0101] A total of 86 grams of ISOPHORONE DIISOCYANATE was placed in
a suitable reaction vessel equipped with a stirrer, temperature
probe, a condenser and a nitrogen inlet tube and blanketed with
nitrogen gas. A total of 130 grams of RESIN FROM EXAMPLE I was then
added and mixed for 15 minutes at ambient temperature. Then, 0.02
grams of dibutyltin dilaurate was added and the mixture heated
slowly to 50.degree. C., then to 80.degree. C. and finally to
100.degree. C. At this point the isocyanate equivalent weight was
measured and found to be 540 grams per equivalent. The reaction
mixture was then cooled to 80.degree. C. and 124 grams of FYROL PCF
and 943 grams of DESMODUR XP2580 were then added to the reaction
mixture. The contents of the reactor were cooled and poured out.
The final material was a clear, compatible resin with a measured
solids of 96% and an isocyanate equivalent weight of 265 grams per
equivalent.
Example K
[0102] An isocyanate component comprising isocyanate-functional
prepolymer was prepared from the following ingredients as described
below:
TABLE-US-00011 Ingredients Parts by Weight (grams) DESMODUR
XP2580.sup.1 2264 EXOLIT OP550.sup.2 452 LEVAGARD 4090N.sup.3 279
Dibutyltin dilaurate 0.3 FYROL PCF.sup.4 840 DESMODUR XP2580.sup.1
2262 DESMODUR XP2410.sup.1 2262 .sup.1Available from Bayer Material
Science Corporation. .sup.2Available from Clariant Corporation.
.sup.3Available from Lanxess. .sup.4Flame retardant available from
Supresta.
[0103] A total of 2264 grams of DESMODUR XP2580 was placed in a
suitable reaction vessel equipped with a stirrer, temperature
probe, a condenser and a nitrogen inlet tube and blanketed with
nitrogen gas. A total of 452 grams of EXOLIT OP550 and 279 grams of
LEVAGARD 4090N were added and mixed for 15 minutes at ambient
temperature. Then, 0.3 grams of dibutyltin dilaurate was added and
the mixture heated slowly to 50.degree. C., then to 80.degree. C.
and finally to 100.degree. C. At this point the isocyanate
equivalent weight was measured and found to be 431 grams per
equivalent. The reaction mixture was then cooled to 80.degree. C.
and 840 grams of FYROL PCF, 2262 grams of DESMODUR XP2580 and 2262
grams of DESMODUR XP2410 were then added to the reaction mixture.
The contents of the reactor were cooled and poured out. The final
material had a measured solids of 96% and an isocyanate equivalent
weight of 274 grams per equivalent.
EXAMPLES 1-8
[0104] Polyurea coating compositions of the invention (Examples
1-6) were prepared from combining an isocyanate functional "A" side
component (materials comprising prepolymers comprising phosphorus
diols of Examples B, D, F, H, and J, and K) and an amine functional
"B" side component not containing phosphorus (BDL-1724S available
from PPG Industries, Inc.) in the following manner: The A and B
side components were charged to separate canisters and heated to
140.degree. F. in an oven for 1-3 hours prior to spraying. Polyurea
coating compositions were produced by mixing a 1:1 volume ratio of
each of the A-side components to each the B-side components in a
static mix tube applicator device available from Plas-Pak
Industries, Inc. The coating compositions were applied by spraying
to 6''.times.18'' panels of a calcium silicate fiber reinformced
autoclaved building sheet containing fibers of natural origin
(available under the designation Tunnel Board Z from Taylored
Industries, Indianola, Pa.) at a film thickness of 70 to 90 mils.
Tack times for the coatings were determined by periodically
touching the panel with a gloved hand and were judged to be tack
free when the glove no longer stuck to the coatings. In all cases
the coatings were tack free in <2 minutes. The ratio of
equivalents of isocyanate to amine were within the range of 1.0 to
1.1 Two comparative examples (Examples 7 and 8) were also applied
in the manner described above. In these examples, the isocyanate
"A" side component was CAT-128 (available from PPG Industries,
Inc.) which does not contain a phosphorus diol. In Example 8, the
"B" side component was furthermore a 95:5 blend by weight of
BDL-1724 and Fyrol PCF.
[0105] The polyurea coatings prepared as described above were
tested for flame resistance in accordance with ASTM E 162-02. In
this test method, the coated substrate to be tested is held near a
radiant heat source, where the top of the substrate is 13/4'' away
from the heat source and leaning at a 30.degree. angle. A pilot
flame is brought into contact with the top of the coated substrate
in an attempt to ignite the coating. The distance that the flame
travels down the coated substrate is monitored versus time. The
temperature of the exhaust stack above the burning coating is also
monitored. Per the test method a "flame spread index" (I.sub.S) is
calculated from flame spread factor (F.sub.S) and the heat
evolution factor (Q). In most of the examples (although not all),
the test was run in duplicate or triplicate. Table 1 shows the
results of this testing.
TABLE-US-00012 TABLE 1 "A" side Average Example component I.sub.s 1
I.sub.s 2 I.sub.s 3 I.sub.s 1 Isocyanate 71.4 84.0 77.7 77.6
component of Example B 2 Isocyanate 74.1 89.5 81.8 component of
Example D 3 Isocyanate 72.5 58.2 83.3 71.3 component of Example F 4
Isocyanate 68.0 77.5 78.9 75.0 component of Example H 5 Isocyanate
102.7 111.0 85.5 100.0 component of Example J 6 CAT-128 260 305 283
(comparative) 7 CAT-128 194 194 (comparative)
[0106] Examples 1-5 illustrate that the polyurea coating
compositions comprising isocyanate components comprising isocyanate
functional prepolymers comprising phosphorus diols have superior
flame resistance compared to comparable coating compositions
comprising an isocyanate component not made with phosphorus diols
(Examples 6 and 7). Furthermore, Example 7 demonstrates that a
composition with a non-reactive phosphorus flame retardant without
a phosphorus diol in the isocyanate component prepolymer does not
afford the same degree of flame resistance as compositions with
both the phosphorus flame retardant and the phosphorus diol in the
isocyanate component.
* * * * *