US007037958B1

(12) United States Patent (10) Patent No.: US 7,037,958 B1

Hansen et al. (45) Date of Patent: May 2, 2006
(54) EPOXY COATING 4,961,973 A 10/1990 Molnar ....................... 427/423
5,077,137 A 12/1991 Molnar ... ... 428,601
(75) Inventors: George P. Hansen, Austin, TX (US); 5,084,521 A 1/1992 White .............. ... 523,436
Rock A. Rushing, Spicewood, TX 5,094.902 A 3/1992 Haenggi et al. .. ... 428, 150
s s 5,110,657 A 5/1992 Ainslie ............. ... 428,141
Set osnia
Y, t R
Liguool, Austin,
5,124,178 A
5, 198,065 A *
6/1992 Haenggi et al. ............ 427/204
3/1993 Eadara ............. ... 156,315
TX (US); Brad A. Rix, Spicewood, TX 5,367,024. A 1 1/1994 Neckermann .. ... 525/123
(US) 5,395,673 A 3/1995 Hunt ... 428,148
5.431,960 A 7, 1995 Watts ..... ... 427,359
(73) Assignee: Texas Research International, Inc., 5,445,670 A 8, 1995 Each et al. .................... 106.3
Austin, TX (US) 5,494,729 A * 2/1996 Henry et al. ... ... 428,147
5,561,173 A 10/1996 Dry ............................ 523,218
(*) Notice: Subject to any disclaimer, the term of this 5,660,624 A 8/1997 Dry ............................ 106,677
patent is extended or adjusted under 35 5,686,507 A 11/1997 Hermele et al. .. ... 523,153
U.S.C. 154(b) by 76 days. 5,989,328 A 1 1/1999 Stahovic et al. .............. 106.36
5,989,334 A 11/1999 Dry .................. ... 106,677
5.990,234. A * 11/1999 Stahovic et al. ............ 524,839
(21) Appl. No.: 10/683,976 6,248,204 B1 6/2001 Schuft ........................ 156,305
(22) Filed: Oct. 10, 2003 FOREIGN PATENT DOCUMENTS
Related U.S. Application Data JP O6145630 A * 5, 1994
(63) Continuation-in-part of application No. 09/939,204. OTHER PUBLICATIONS
filed on Aug. 24, 2001, now Pat. No. 6,632,860. CAPLUS accession No. 1992:573461 for Chinese Patent
(51) Int. Cl No. 1,057,849, Zhan et al., Jan. 15, 1992.*
CSK 3/22 (2006.01) * cited by examiner
CSK 7/4 2006.O1
COSL 63/00 30: 8: Primary Examiner Robert Sellers
COSL 63/02 (2006.015 (74) Attorney, Agent, or Firm Robert M. O’Keefe;
(52) U.S. Cl. ....................................... s23428.523,434. O'Keefe, Egan & Peterman, LLP
(58) Field of Classification Search ................ 427/214, (57) ABSTRACT
427/257, 410; 523/435, 428
See application file for complete search history. This invention concerns an epoxy coating for use as a
non-skid Surface for applications such as the deck of an
(56) References Cited aircraft carrier. The epoxy coating can be formulated from
U.S. PATENT DOCUMENTS
(a) an amine curing agent, (b) an epoxide-containing tough
ening agent such as a polysulfide and/or a polythioether, (c)
3,962,168 A 6, 1976 Edwards .. ... 260/29.6 an epoxy resin, (d) a rubber toughening agent, and (e) an
4,172,063 A * 10/1979 O’Brill .......................... 524/5 optional fire retardant, a glass fiber thixotrope and impact
4,205,109 A 5/1980 France et al. ............... 428, 150 toughening agent, an optional pigment, an optional corro
4,292.213 A 9, 1981 Elliott et al. ................. 260/2.3 sion inhibitor, an optional moisture penetration inhibitor, an
4,708,978 A 11/1987 Rodgers ........................ 524/5 optional ultraviolet light stabilizer, an optional abrasive
4,744,725 A 5/1988 Matarese et al. ........... 415,172
4,760, 103 A * 7/1988 Kraft et al. ................. 523,150 aggregate, or a combination thereof.
4,774,278 A 9, 1988 Yoshioka et al. ........... 524,506
4,859,522 A 8, 1989 Cambon ..................... 428,215 31 Claims, No Drawings
 US 7,037,958 B1
1. 2
EPOXY COATING resin, a rubber toughening agent, a pigment, optionally, a
corrosion inhibitor, and optionally, a moisture penetration
This application is a continuation-in-part of application inhibitor.
Ser. No. 09/939,204, filed Aug. 24, 2001, now U.S. Pat. No. In another broad respect, this invention is a process useful
6,632,860, incorporated herein by reference. for providing a coating for a solid Surface, comprising:
Subject to rights of the assignee afforded under a Small applying a coating onto the Solid Surface, wherein the
Business Innovation Research program, the U.S. Govern coating is prepared from an amine side which comprises a
ment has a paid-up license in this invention and the right in mixture of an amine curing agent, a rubber toughening
limited circumstances to require the patent owner to license agent; and an epoxy side which comprises a mixture of an
others on reasonable terms as provided for by the terms of 10 epoxy resin, an epoxide-containing toughening agent, and
contract number N00024-00-C-4080 awarded by the wherein the coating is also prepared from an optional fire
Department of the Navy. retardant, optionally a glass fiber thixotrope and impact
toughening agent, a pigment, and an optional abrasive
BACKGROUND OF INVENTION aggregate, and wherein the Surface may be primed or
15 un-primed prior to application of the topcoat. In another
This invention pertains to an epoxy useful, for example, broad respect this invention is a method of manufacturing an
as a coating for aircraft carrier decks. epoxy side and an amine side for use in the formation of a
It is important that many surfaces are made of a non-skid coating, comprising: forming a mixture of an amine side
coating. For instance, it is desirable that the deck of an from an amine curing agent and a rubber toughening agent,
aircraft carrier be made of a non-skid surface. It is also forming a mixture of an epoxy side from an epoxy resin and
desirable that such surfaces be durable. This is particularly an epoxide-containing toughening agent, wherein the amine
true for the portion of the deck where the aircraft take off and side is also formed from an optional fire retardant, an
land, which is exposed to severe wear. Currently, the aircraft optional glass fiber thixotrope and impact toughening agent,
decks are made using solvent-based epoxy coatings, which a pigment, an optional abrasive aggregate, a moisture pen
are applied so as to form ridges. 25 etration inhibitor, an ultraviolet light stabilizer, or combina
The present inventors have recognized, however, that tion thereof, and wherein the epoxy side is also formed from
there exists a need for a more durable coating, and a coating an optional fire retardant, an optional glass fiber thixotrope
made without solvents. The present inventors have also and impact toughening agent, a pigment, an optional abra
recognized that a coating lacking Volatile solvents would be sive aggregate, a moisture penetration inhibitor, an ultravio
desirable so as to avoid use of solvents that can be hazard 30 let light stabilizer, or combination thereof. In another broad
ous, and which must be evaporated off to provide the final respect, this invention is an epoxy coating formulated from
coating. (a) an amine curing agent, (b) an epoxide-containing tough
ening agent, (c) an epoxy resin, (d) a rubber toughening
SUMMARY OF INVENTION agent, and (e) an optional fire retardant, an optional glass
35 fiber thixotrope and impact toughening agent, a pigment, a
This invention solves one or more of the problems and corrosion inhibitor, a moisture penetration inhibitor, an
disadvantages described above. ultraviolet light stabilizer, an optional abrasive aggregate, or
In one broad respect, this invention is a process useful for a combination thereof. In another broad respect, this inven
providing a coating for a solid Surface, comprising: applying tion is a process useful for providing a coating for a solid
a primer onto the Solid Surface to form a primer coating, 40 Surface, comprising: applying a coating onto the Solid Sur
wherein the primer is prepared from an amine curing agent, face, wherein the coating is prepared from (a) an amine
an epoxide-containing toughening agent, an epoxy resin, a curing agent, (b) an epoxide-containing toughening agent,
rubber toughening agent, an optional fire retardant, option (c) an epoxy resin, (d) a rubber toughening agent, and (e) an
ally a glass fiber thixotrope and impact toughening agent, optional fire retardant, an optional glass fiber thixotrope and
and a pigment; applying a topcoat onto the primer coating, 45 impact toughening agent, a pigment, a corrosion inhibitor, a
wherein the topcoat is prepared from an amine curing agent, moisture penetration inhibitor, an ultraviolet light stabilizer,
an epoxide-containing toughening agent, an epoxy resin, a an optional abrasive aggregate, or a combination thereof.
rubber toughening agent, an optional fire retardant, option In one broad respect, this invention is a process useful for
ally a glass fiber thixotrope and impact toughening agent, a providing a coating for a solid Surface, comprising: applying
pigment, and an optional abrasive aggregate. For spray 50 a primer onto the Solid Surface to form a primer coating,
applications, and especially for the primer, it may sometimes wherein the primer is prepared from an amine curing agent,
be desirable to omit the fiber and/or the aggregate. By a polysulfide and/or polythioether toughening agent, an
contrast, the glass fiber, while optional, is generally present epoxy resin, a rubber toughening agent, an optional fire
in a topcoat formulation. In one embodiment, the epoxide retardant, an optional glass fiber thixotrope and impact
containing toughening agent is a polysulfide, a polythioet 55 toughening agent, and a pigment; applying a topcoat onto
her, or a combination thereof. In another broad respect, this the primer coating, wherein the topcoat is prepared from an
invention is an epoxy topcoat comprising a cured mixture amine curing agent, a polysulfide toughening agent, an
that is formulated from an epoxy resin, an epoxide-contain epoxy resin, a rubber toughening agent, an optional fire
ing toughening agent, optionally, an ultraviolet light stabi retardant, an optional glass fiber thixotrope and impact
lizer, a pigment, optionally a glass fiber thixotrope and 60 toughening agent, a pigment, and an optional abrasive
impact toughening agent, an optional abrasive aggregate, an aggregate. As used herein, "coating may refer to either the
optional fire retardant, an amine curing agent, and a rubber primer, the topcoat, a generic mixture formed from the
toughening agent. In another broad respect, this invention is components described herein, or combinations thereof.
an epoxy primer comprising a cured mixture that is made In general, a coating of this invention may be prepared
from an amine curing agent, an epoxide-containing tough 65 from (formulated from), independently in each occurrence,
ening agent, an optional fire retardant, optionally a glass about 20 to about 60 percent of the amine curing agent;
fiber thixotrope and impact toughening agent, an epoxy about 0.01 to about 30 percent of the polysulfide and/or
 US 7,037,958 B1
3 4
polythioether toughening agent; about 0.01 to about 15 In another broad respect, this invention is an epoxy
percent based on the total weight of the coating of the topcoat comprising a cured mixture that is formulated from
corrosion inhibitor; about 0.01 to about 10 percent based on an epoxy resin, a polysulfide and/or polythioether toughen
the total weight of the coating of the glass fiber; about 0.01 ing agent, optionally, an ultraviolet light stabilizer, a pig
to about 3 percent based on the total weight of the coating ment, an optional glass fiber thixotrope and impact tough
of an moisture penetration inhibitor; about 0.01 to about 35 ening agent, an optional abrasive aggregate, an optional fire
percent based on the total weight of the coating of the fire retardant, an amine curing agent, and a rubber toughening
retardant; about 10 to about 90 percent based on the total agent.
weight of the coating of the epoxy resin; 4 to about 40 In another broad respect, this invention is an epoxy primer
percent based on the total weight of the coating of the rubber 10
toughening agent; about 0.01 to about 30 percent based on comprising a cured mixture that is made from an amine
the total weight of the coating of the pigment. about 0.01 to curing agent, a polysulfide and/or polythioether toughening
about 10 percent based on the total weight of the coating of agent, an optional fire retardant, an optional glass fiber
the ultraviolet light stabilizer; and/or about 0.01 to about 45 thixotrope and impact toughening agent, an epoxy resin, a
percent based on the total weight of the coating of the 15 rubber toughening agent, a pigment, optionally, a corrosion
abrasive aggregate. inhibitor, and optionally, a moisture penetration inhibitor.
In one broad respect, this invention is a process useful for In another broad respect, this invention is a process useful
providing a coating for a solid Surface, comprising: applying for providing a coating for a solid Surface, comprising:
a primer onto the Solid Surface to form a primer coating on applying a coating onto the Solid Surface, wherein the
the surface, wherein the primer is prepared from a first coating is prepared from an amine side which comprises a
amine side which comprises a mixture of an amine curing mixture of an amine curing agent, a rubber toughening
agent, a toughening agent, at least one corrosion inhibitor, a agent; and an epoxy side which comprises a mixture of an
moisture penetration inhibitor, an optional fire retardant, and epoxy resin, an epoxy-terminated polysulfide and/or poly
an optional glass fiber thixotrope and impact toughening thioether toughening agent, and wherein the coating is also
agent; a first epoxy side which comprises a mixture of an 25
prepared from an optional fire retardant, an optional glass
epoxy resin, a toughening agent, at least one corrosion fiber thixotrope and impact toughening agent, a pigment,
inhibitor, a moisture penetration inhibitor, a darkening pig and an abrasive aggregate, and wherein the Surface may be
ment, and an optional glass fiber thixotrope and impact primed or un-primed prior to application of the topcoat.
toughening agent, applying a topcoat onto the primer coat
ing, wherein the topcoat is prepared from a second amine 30 The primer is used to promote adhesion of the non-skid
side which comprises a mixture of an amine curing agent, topcoat and to inhibit corrosion of a metal substrate to which
a toughening agent, an ultraviolet light absorber and stabi the primer may be applied. Either or both of the primer sides
lizer, an optional fire retardant, an infrared light reflecting may include an ultraviolet light absorber and stabilizer. In
pigment, an optional glass fiber thixotrope and impact one embodiment, the second amine side or the second epoxy
toughening agent, and an optional abrasive aggregate, and a 35 side or both may include a pigment, Such as a darkening
second epoxy side which comprises a mixture of an epoxy pigment. In one embodiment the epoxy side and amine side
resin, a toughening agent, an optional glass fiber thixotrope include different pigments (e.g., one is white and one is
and impact toughening agent, an ultraviolet light absorber black) to assist the user in achieving adequate mixing of the
two sides.
and stabilizer, and an optional abrasive aggregate.
In one embodiment, the first amine side comprises about 40 In one embodiment, the topcoat is applied in a manner
40 to about 60 percent of the amine curing agent, about 10 Such that a plurality of ridges are formed by the topcoat Such
to about 30 percent of the toughening agent, about 0.01 to as by rolling, trowelling, raking or spraying. The rolling can
about 6 percent of at least one corrosion inhibitor, about 0.01 be through use of a phenolic napless roller of a design Such
to about 5 percent of the glass fiber, about 0.01 to about 3 that upon application, ridges and Valleys are formed to
percent of the moisture penetration inhibitor, and/or about 45 Supply additional slip resistance. For many applications, the
10 to about 35 percent of the fire retardant. topcoat may be applied using one gallon of topcoat for every
In one embodiment, the first epoxy side comprises about 20–30 square feet of surface to be coated. The topcoat may
50 to about 90 percent of the epoxy resin, about 10 to about be applied to the primer as soon as the primer is cured to a
40 percent of the toughening agent, about 0.01 to about 6 tack free state. Typically, the topcoat is tack free within 1 to
percent of the corrosion inhibitor, about 0.01 to about 15 50 48 hours after being applied, depending on temperature and
percent of the pigment, and/or about 0.01 to about 2 percent other conditions. In general, hotter ambient temperatures
of the glass fiber. lead to shorter tack free times. Alternatively, the topcoat is
In one embodiment, the second amine comprises about 25 applied prior to the primer reaching a tack free State and may
to about 50 percent of the amine curing agent, about 0.01 to be applied promptly after the primer is applied.
about 10 percent of the toughening agent, about 0.01 to 55 In another broad respect, this invention is a method of
about 6 percent of the corrosion inhibitor, about 15 to about manufacturing an epoxy side and an amine side for use in the
25 percent of the pigment, about 0.01 to about 45 percent of formation of a coating, comprising: forming a mixture of an
the abrasive aggregate, about 0.01 to about 5 percent of the amine side from an amine curing agent and a rubber tough
glass fiber, and/or about 5 to about 15 percent of the fire ening agent, forming a mixture of an epoxy side from an
retardant. 60 epoxy resin and a polysulfide and/or polythioether tough
In one embodiment, the second epoxy side comprises ening agent, wherein the amine side is also formed from an
about 20 to about 45 percent of the epoxy resin, about 8 to optional fire retardant, an optional glass fiber thixotrope and
about 20 percent of the toughening agent, about 0.01 to impact toughening agent, a pigment, an optional abrasive
about 6 percent of the corrosion inhibitor, about 0.01 to aggregate, a moisture penetration inhibitor, an ultraviolet
about 10 percent of the ultraviolet light stabilizer, about 0.01 65 light stabilizer, or combination thereof, and wherein the
to about 15 percent of the pigment, and/or about 0.01 to epoxy side is also formed from an optional fire retardant, an
about 5 percent of the glass fiber. optional glass fiber thixotrope and impact toughening agent,
 US 7,037,958 B1
5 6
a pigment, an optional abrasive aggregate, a moisture pen This invention thus provides a coating useful for appli
etration inhibitor, an ultraviolet light stabilizer, or combina cations such as but not limited to the deck of an aircraft
tion thereof. carrier. Advantageously, the coating may be made from
In another broad respect, this invention is a process useful 100% solids components obtained from a supplier without
for providing a coating for a solid Surface, comprising: further dilution, i.e., without the addition of volatile sol
applying a coating onto the Solid Surface, wherein the vents. As used herein, a solvent Such as water or an organic
coating is prepared from (a) an amine curing agent, (b) a compound refers to materials that dissolves the epoxy resin
polysulfide toughening agent, (c) an epoxy resin, (d) a and/or amine starting materials, and which evaporates from
rubber toughening agent, and (e) an optional fire retardant, 10 the coating upon application and/or exposure to an open
an optional glass fiber thixotrope and impact toughening environment (such as to air). Representative examples of
agent, a pigment, a corrosion inhibitor, a moisture penetra Such volatile organic solvents that may be advantageously
tion inhibitor, an ultraviolet light stabilizer, an optional absent from the components used to make the final coating
abrasive aggregate, or a combination thereof. include low molecular weight halogenated hydrocarbons
The Surfaces to be coated may include metal Surfaces such 15
Such as chloroform and carbon tetrachloride, hydrocarbons,
as but not limited to the deck of a ship, including the deck alcohols, ketones, ethers, glycol ethers, and so forth. In the
of an aircraft carrier, the surface of an oil well drilling practice of this invention, the starting materials and final
platform, an industrial walkway and other industrial or cured coating are Substantially free of solvents, containing at
utility thoroughfares. most only minor amounts of such solvents and no more than
The composition may include at least one moisture pen about 40 percent of the component weight. Advantageously,
etration inhibitor in the first amine side and at least one the coating has excellent durability and has improved dura
moisture penetration inhibitor in the first epoxy side. In one bility relative to the solvent-based coatings currently in use.
embodiment, the amine curing agent side is white and the The type of Substrates and Surfaces on which the coating
epoxy side is black (or vice versa) so that when mixed, a 25
of this invention may be used vary widely. For example, the
gray color is created. This is advantageous for purposes of type of surfaces that can be treated with the coating of this
handling, mixing, and application of the materials. invention includes glass, ceramics, metals, and plastics.
In one aspect, the toughening agent may be a polythio Typically, the Surface is metal.
ether toughening agent or a polysulfide toughening agent. 30
In one respect, the abrasive aggregate is comprised of a DETAILED DESCRIPTION OF THE
mixture of coarse aluminum powder and aluminum pellets. INVENTION
In another respect, this invention is a coating composite
formed by application of a topcoat layer to a primer layer. The final cured coating of this invention has a thickness
The topcoat and primer may be made from the epoxy and 35 which can vary widely depending on the end use. In general,
amine sides described herein. The laminate can thus be the coating has a thickness of from about 0.1 cm to about 2
described as a composition comprising a topcoat layer cm, though thicknesses above and below these thicknesses
adhered or bonded to a primer layer. In some instances are anticipated.
where corrosion of the substrate is not likely, the primer is 40
The epoxy resin used in the practice of this invention may
not necessary, since the topcoat adhesion is adequate; that is, vary and includes conventional, commercially available
it is self priming. epoxy resins. Two or more epoxy resins may be employed
In another broad respect, this invention is a process useful in combination. In general, the epoxy resins can be glyci
for making a non-skid coating kit, comprising a first amine dated resins, cycloaliphhatic resins, epoxidized oils, and so
side and first epoxy side of a primer and a second amine side 45 forth. The glycidated resins are frequently the reaction
and a second epoxy side of a topcoat, wherein the process product of a glycidyl ether, Such as epichlorohydrin, and a
comprises: (a) combining an amine curing agent, a tough bisphenol compound Such as bisphenol A. C. Cs alkyl
ening agent, a corrosion inhibitor, and an optional fire glycidyl ethers: C-C alkyl-and alkenyl-glycidyl esters:
retardant to form the first amine side; adding the first amine 50 C-C2s alkyl-, mono- and poly-phenol glycidyl ethers;
side to a first container and then sealing the container; (b) polyglycidyl ethers of pyrocatechol, resorcinol, hydro
combining an epoxy resin, a toughening agent, a corrosion quinone, 4,4'-dihydroxydiphenyl methane (or bisphenol F),
inhibitor, an ultraviolet light stabilizer, a pigment, and an 4,4'-dihydroxy-3,3'-dimethyldiphenyl methane, 4,4'-dihy
optional thixotrope glass fiber reinforcing agent to form the droxydiphenyl dimethyl methane (or bisphenol A), 4,4'-
first epoxy side; adding the first epoxy side to a second 55 dihydroxydiphenyl methyl methane, 4,4'-dihydroxydiphenyl
container and then sealing the container; (c) combining an cyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl pro
amine curing agent, a rubber toughening agent, a corrosion pane, 4,4'-dihydroxydiphenyl Suflone, and tris (4-hydroxy
inhibitor, an ultraviolet light absorber and stabilizer, an phynyl)methane; polyglycidyl ethers of the chlorination and
optional fire retardant, a thixotrope glass fiber reinforcing bromination products of the above-mentioned diphenols:
60
agent to form the second amine side to a container and then polyglycidyl ethers of novolacs; polyglycidyl ethers of
sealing the container, and (d) combining an epoxy resin, a diphenols obtained by esterifying ethers of diphenols
toughening agent, a pigment, an optional thixotrope glass obtained by esterifying salts of an aromatic hydrocarboxylic
fiber reinforcing agent, an ultraviolet light absorber and acid with a dihaloalkane or dihalogen dialkyl ether, polyg
stabilizer, and an optional aggregate to form the second 65 lycidyl ethers of polyphenols obtained by condensing phe
epoxy side; adding the second epoxy side to a second nols and long-chain halogen paraffins containing at least two
container and then sealing the container. halogen atoms: N,N'-diglycidyl-aniline; N.N'-dimethyl-N,
 US 7,037,958 B1
7 8
N'-diglycidyl-4,4'-diaminodiphenyl methane; N.N.N',N'-tet or more of an epoxide-containing toughening agent. In
raglycidyl-4,4'-diaminodiphenyl methane; N.N'-diglycidyl another embodiment, the toughening agent is one or more of
4-aminophenyl glycidyl ether; N.N.N',N'-tetraglycidyl-1,3- an epoxide-containing toughening agent that contains Sulfur.
propylene bis-4-aminobenzoate; phenol novolac epoxy In another embodiment, the toughening agent is a polysul
resin; cresol novolac epoxy resin; and combinations thereof. fide, a polythioether, or a combination thereof. The follow
Representative non-limiting examples of epoxy resins useful ing include additional toughening agents that do not contain
in this invention include bis-4,4'-(1-methylethylidene) phe Sulfur. These toughening agents contain ether linkages
nol diglycidyl ether and (chloromethyl) oxirane Bisphenol A between consecutive epoxy functional groups which provide
diglycidyl ether. Commercially available epoxy resins that 10
flexibility. The low viscosities of these toughening agents
can be used in the practice of this invention include but are improve the rheology. Another representative toughening
not limited to Aralydyte GY6010 and Epon 828. The epoxy agent is an aliphatic triglycidyl ether, such as a low viscosity
aliphatic triglycidyl ether sold commercially as HELOXY
resin can be used in any amount effective to form a coating Modifier 48, including aliphatic triglycidyl ether having an
of this invention. In general, the amount of epoxy resin used epoxy group content in the range from about 6400 to about
15
in the first epoxy side for the primer is from about 50 to 7500 mmol/kg and a viscosity at 25 C of from about 125 to
about 90 percent by weight, and from about 20 to about 45 about 250 mPas (ASTM D445). A representative formula
percent in the second epoxy side for topcoat. The epoxy for such trifunctional aliphatic triglycidyl ethers is:
resin is thinner (less viscous) than the type of resin used to
make solvent-based epoxy coatings. Typically, the epoxy
resin has a viscosity of from about 11,000 to about 14,000 R-C(CHOCH-CH-CH)
centipoise. S/
The toughening agent used in the practice of this inven
tion provides toughening and durability characteristics to the
coating. By toughening it is meant that the material has 25 where R is a lower alkyl, such a C-C alkyl, and in one
imparted to it a greater impact strength. The toughening embodiment ethyl.
agent may be selected from conventional toughening agents Another representative toughening agent is a polyepoxide
Such as rubber toughening agents and an epoxide-containing modifier, such as a low viscosity polyepoxide modifier sold
toughening agent such as polysulfide, polythioether poly commercially as HELOXY Modifier 505, including poly
mer, aliphatic triglycidyl ether, a polyepoxide, aliphatic
30 epoxide modifier having an epoxy group content in the range
monoglycidyl ether, and aliphatic epoxy resin toughening from about 1500 to about 1900 mmol/kg and a viscosity at
agents. The toughening agent can vary. The polysulfide 25 C of from about 300 to about 500 mPas (ASTM D445).
toughening agent may be an epoxy terminated polysulfide For example, the polyepoxide can be a polyglycidyl ether of
polymer. One representative formula for such materials is: 35 castor oil, including a trigycidyl ether of castor oil. Another
representative toughening agent is an aliphatic monogly
cidyl ether containing alkyl chains which are predominantly
O O C8 to C10 in length, such as an aliphatic monoglycidyl ether
/N MN containing alkyl chains which are predominantly C8 to C 10
CH-CH-CHS(CHOCHSS),CHOCH2OCH-CH-CH
40 in length sold commercially as HELOXY Modifier 7,
including an aliphatic monoglycidyl ether containing alkyl
where n may be from 1 to 1,000. It is believed that the chains which are predominantly C8 to C10 in length modi
polysulfide toughening agent reacts during the epoxy curing fier having an epoxy group content in the range from about
to the amine function of the curing agent. Such compounds 4200 to about 4600 mmol/kg and a viscosity at 25 C of from
are well known, and are currently available commercially 45
about 3 to about 5 mPa.s (ASTM D445). A representative
under the tradename ELP-3, sold by Rohm & Haas, or formula for Such an aliphatic monoglycidyl ether is:
EPS-25, sold by Akzo Nobel. The polysulfide toughening
agent is epoxy terminated and can react with the amine
curing agent, but is stable in the epoxy resin. Another
representative toughening agent is a polythioether toughen 50 R-O-CH-CH-CH
ing agent Such as an epoxy terminated difunctional poly Y/
thioether polymer, Such as an epoxy terminated difunctional
polythioether polymer sold commercially as PERMAPOL
L-5534, including an low viscosity epoxy terminated difunc where R' is an alkyl of from 4 to 14 carbons in one
tional polythioether polymer having an epoxy equivalent 55 embodiment is C, in one embodiment is Cs-Co. Another
weight in the range from about 515 to about 550, a flash representative toughening agent is a low viscosity aliphatic
point above 230 F, and a viscosity at 25 C of from about 5 epoxy resin, such as an low viscosity aliphatic epoxy resin
to about 6 mPa.s (ASTM D445). It should be appreciated sold commercially as EPIKOTE resin 877, including an low
that a polythioether has —S— linkage(s), as opposed to a Viscosity aliphatic epoxy resin having an epoxy group
polysulfide which has —S—S— linkage(s). Advanta 60 content in the range from about 2900 to about 3300 mmol/kg
geously, in contrast to the polysulfide, the polythioether has and a viscosity at 25 C of from about 40 to about 90 mPa.s
less viscosity which imparts the ability to use less of it to (ASTM D445). Another representative toughening agent is
achieve the same rheology in a given formulation, Such as a bispheonal A type epoxy resin, Such as an internally
60% of the amount needed relative to the polysulfide. The flexible bisphenol A epoxy resin sold commercially as
polythioether provides improved rheology, impact resis 65 ARALDITE PY 4122 US, including an bisphenol A epoxy
tance and wear resistance relative to the polysulfide tough resin having an epoxy equivalent amount of about 330 to
ening agent. In one embodiment, the toughening agent is one about 365 g/eq. and a viscosity at 25 C of from about 40 to
 US 7,037,958 B1
10
about 90 mPa.s (ASTM D445). A representative formula of For the primers, one or more corrosion inhibitors may be
such bisphenol A type epoxy resin toughening agents is as included. These serve to reduce the amount of corrosion of
follows: a metal substrate at the primer/surface interface. A wide
variety of such corrosion inhibitors may be used. Represen
HC-O-CH-CH-CH-O-Ar-O-CH-CH-CH2-O-C Ho
tative examples of such corrosion inhibitors include zinc
based inhibitors such as zinc phosphate, zinc-5-nitro-isoph
O
O
O
O
thalate, zinc molybdate, and Zinc oxide and hydrophobic,
/N
CH-CH-CH
/N
CH-CH-CH
moisture penetration inhibitors such as hydrophobic, amor
10 phous fumed silica. These may be used in any amount
effective to provide corrosion inhibition.
wherein Ar represents a —CH C(CH3)2 CH In the practice of this invention, a UV light stabilizer may
diradical group. be included. This serves to protect the cured coating from the
A toughening agent functions to improve impact resis harmful effects of UV light. Representative examples of
15
tance. Toughening agents function by forming a secondary such stabilizers include sterically hindered piperidine
phase within the polymer matrix. This secondary phase is derivatives including an alkyl substituted hydroxy pip
rubbery and hence is capable of crack growth arrestment. eridines such as dimethyl sebacate, methyl-1.2.2.6,6-pen
This crack arresting function provides improved impact tamethyl-4-piperidinyl sebacate, bis (1.2.2.6,6-pentamethyl
toughness. 4-piperidinyl) sebacate, and 1.2.2.6,6-pentamethyl-4-
Representative examples of a rubber toughening agents piperidinol. This may be used in any amount effective to
provide UV stabilization.
includes amine-terminated butadiene nitrile (ATBN) and The coating can include one or more pigments to provide
carboxy-terminated butadiene nitrite (CTBN). ATBN is any desired color. The pigments can vary, depending on the
amine terminated so that it can react with the epoxy func 25 desired color of the final coating. For example, if a gray
tionality and is stable upon mixture with an amine curing coating is desired, white and black pigments can be used. If
agent; as such the rubber toughening agent is generally a yellow coating is desired, then yellow pigments can be
present in the amine side of a formulation, if there are an employed, and so on. A representative example of a dark
amine side and epoxy side. Representative examples of an ening pigment is black iron oxide. Black iron oxide also has
epoxy-containing toughening agent are polysulfide tough 30 the desirable property of being infrared transparent and thus
ening agents, polythioether toughening agents, and combi may serve as an IR transparent darkening agent. This is
nations thereof. The epoxy-terminated toughening agents beneficial because infrared absorption by the coating causes
are normally present in the epoxy side of a formulation, if the surface temperature to rise, which is undesirable. Like
there are an amine side and an epoxy side. The ability of 35 wise, an IR reflector may be included in the coatings of this
ATBN or the polysulfide toughening agent to react with their invention. One such IR reflector is titanium dioxide, which
resin complements allows for good chemical bonding may also serve as a pigment. By reflecting IR light, the
between separate phases (rubber and resin). coating is less prone to becoming heated in sunlight.
The abrasive aggregate may be selected from a wide Various fire retardants may optionally be used in the
variety of materials. The abrasives are employed in amounts 40 practice of this invention. Common fire retardants include an
effective to provide additional anti-skid properties to the alumina such as alumina trihydrate, magnesium hydroxide,
coating. Representative examples of such abrasives include bismuth oxide, zinc borate, potassium tripolyphosphate, and
metals such as aluminum, pumice, garnet, sand, gravel, antimony oxide. Combinations of these fire retardants can be
silica, ceramic fibers or whiskers such as of magnesium 45 employed, such as magnesium hydroxide with alumna tri
oxide, aluminum nitride, boron nitride, Zinc oxide, alumi hydrate, and zinc borate with magnesium hydroxide and/or
num oxide, crushed glass, quartz, polymer, rubber, and alumna trihydrate. Fire retardants that are not a known
combinations thereof. The aggregate is employed in a wide carcinogens are preferred in the practice of this invention. In
range of amounts. In general, the aggregate is used in an general, the fire retardants may be employed in an amount
amount of from about 20 to about 50 percent by weight of 50 of from about 5 to about 40 percent by weight based on the
the second amine side, and from about 25 to about 60 total weight of a given formulation.
percent of second epoxy side. The aggregate serves to On the amine side of the primer and topcoat, an amine
provide filler material and an abrasive surface. curing agent is employed. Various polyamines can be used
The coating of this invention includes a glass fiber, which 55 for this purpose, including aliphatic and aromatic amines,
provides both thixotropic rheology modification as well as cycloaliphatic amines, a Lewis base or a Mannich base. For
an impact toughening agent. Such glass fibers include those example, the aliphatic amine and cycloaliphatic amines may
having an average fiber diameter of about 0.2 to about 5 be alkylene diamines such as ethylene diamine, propylene
microns and a surface area as measured by BET of about diamine, 1,4-diaminobutane, 1,3-diaminopentane, 1.6-di
0.01 to about 25 meters squared per gram (m/g). In one 60
aminohexane, 2,5-diamino-2,5-dimethylhexane, 2.2.4-trim
embodiment, the BET is about 0.3 to about 6.25 m/g. In the ethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-di
first amine side, the amount of glass fiber may be from about aminododecane, 1.3- or 1.4-cyclohexame diamine, 1-amino
0.01 to about 5 percent; from about 0.01 to about 2 percent 3,3,5-trimethyl-5-aminomethyl-cyclohexane, 2,4- or 2.6-
for the first epoxy side; from about 0.01 to about 5 percent 65 hexahydrotolxylene diamine, 2,4'- O 4,4'-
for the second amine side, and from about 0.01 to about 5 diaminodicyclohexyl methane, 3,3'-dialkyl-4,4'-diamino
percent for the second epoxy side. dicyclohexyl methane isophoronediamine,
 US 7,037,958 B1
11 12
trimethythexamethylene diamine, triethylene diamine, pip
erazine-n-ethylamine, polyoxyalkylene diamines made from TABLE 1a-continued
propylene oxide and/or ethylene oxide. Commercially avail Primer Composition
able amine curing agents may sometimes include residual
amounts of solvents such as benzyl alcohol used in the Weight
manufacture of the compounds. The aromatic polyamines Supplier/Tradename? Component Percent
may include 2,4- or 2,6-diaminotoluene and 2,4'- or 4,4'- Epoxy Side
diaminodiphenyl methane. Mixtures of amine curing agents 10
may be employed. The amount of amine curing agent may Vantico Epoxy Resin 69.4
vary depending on the amount of epoxy resin to be cured. In Araldyte GY6010 Phenol, 4,4'-(1-methylethylidene)bis-,
polymer with (chloromethyl)oxirane
general, the amount of amine curing agent employed is so Bisphenol A Diglycidyl Ether Polymer
that the Volumetric ratio of an amine side to an epoxy side Rohm & Haas Polysulfide Toughening Agent 23.5
15 ELP-3 Epoxy terminated polysulfide
is from about 30:70 to about 70:30, with a weight ratio of
Sherwin-Williams Corrosion Inhibitor O.6
from about 1:15 to 15:1 being most typical. Typically, the Moly White 101 Zinc Molybdate
mole ratio of amine curing agent to the epoxy resin is in the Zinc Oxide
range from about 0.25 to about 2.5, and in one embodiment Rockwood Industries Corrosion Inhibitor O.3
is about 1:1. PhOS Plus Zn(PO)-2,-4 H2O Mixture
Heucotech Corrosion Inhibitor O.O3
The following examples are illustrative of this invention Heucorin RZ Zinc-5-Nitro-Iso Phthalate
and are not intended to be limiting as to the scope of the Degussa Hydrophobic Moisture Penetration O.S
invention or claims hereto. Unless otherwise denoted all Aerosil 812 Inhibitor
percentages are by weight of the total part (i.e., the primer 25 Amorphous Fumed Silica
epoxy or topcoat amine and so forth). Ferro UV Light Stabilizer 2.0
UV 55-07051 Bis(1,2,2,6,6-Pentamethyl-4-
Piperidinyl)Sebacate
EXAMPLE 1.
LaPorte Darkening Pigment 1.2
30 Black Iron Oxide Fe3O4.
A primer and topcoat were prepared containing the com Lauscha Fiber Thixatrope 1.4
ponents and respective amounts shown in Tables 1a and 1b. internat. Glass Fiber Reinforcing Agent
B-1S-F
Each of the sides was thoroughly mixed prior to application
onto a metal Surface. The components were mixed using low 35 98.93
shear (1000 RPM), and when all the components have been
added, the speed was increased to 2000–2500 RPM. In the
table, the Lauscha Fiber International B-15-F (a thixatrope TABLE 1b.
glass fiber reinforcing agent) has a BET of 1.08 square 40
meters per gram, and a nominal diameter of 1.48 microns. Top-Coat Composition
Weight
TABLE 1 a Supplier/Tradename Component Percent
Primer Composition Amine Side
45
Weight Air Products Amine Curing Agent 39.5
Supplier/Tradename? Component Percent Ancamime 2074 Isophoronediamine
Trimethylhexamethylenediamine
Amine Side B. F. Goodrich Rubber Toughening Agent 3.9
Hycar 1300X16 ATBN
Vantico Hardener Amine Curing Agent 49.O 50 Aminoethyl piperazine
HY 2963 Cyclohexanemethanamine, 5 Ribelin Sales Corrosion Inhibitor: UV Reflector 7.9
amino-1,3,3-trimethyl Zinc Oxide (Grade ZnO
Isophoronediamine 210)
Bisphenol A Alcan Chemicals Fire Retardant 4.7
B. F. Goodrich Rubber Toughening Agent 17.0 Alumina Trihydrate Al2O3.3H2O
Hycar 1300X16 ATBN 55 H-10
Aminoethyl piperazine Laurel Industries Fire Retardant 4.7
Sherwin-Williams Corrosion Inhibitor 1.4 IlC. Sb2O3
MollyWhite 101 Zinc Molybdate Fireshield (R)
Zinc Oxide Kronos Pigment 11.8
Alcan Chemicals Fire Retardant 11.2 Titanium Dioxide
Alumina Trihydrate Al2O3.3H2O P25
60 Lauscha Fiber
H-10 Thixatrope 1.6
Laurel Industries Inc. Fire Retardant 20.6 internal. Glass Fiber Reinforcing Agent
Fireshield (R) Sb2O3 B-1S-F
Degussa Hydrophobic Moisture O.9 Atlantic Equipment Aggregate 26.1
Aerosil 812 Penetration Inhibitor Eng. Aluminum
Amorphous Fumed Silica Aluminum Powder
65
Total 100.1 Total 10O2
 US 7,037,958 B1
13 14
TABLE 1 b-continued TABLE 2a
Top-Coat Composition Primer Composition
Weight Weight
Supplier/Tradename Component Percent Supplier/Tradename Component Percent

Epoxy Side Amine Side

Vantico Epoxy Resin 48.4 Vantico Hardener Amine Curing Agent 49.0
Araldyte GY6010 Phenol, 4,4'-(1- 10 HY 2963 Cyclohexanemethanamine,
methylethylidene)bis-, polymer 5-amino-1,3,3-trimethyl
with (chloromethyl)oxirane Isophoronediamine
Bisphenol A Diglycidyl Ether Bisphenol A
Polymer B. F. Goodrich Rubber Toughening Agent 17.0
Rohm & Haas Polysulfide Toughening Agent 16.1 Hycar 1300X16 ATBN
ELP-3 Epoxy terminated polysulfide 15 Aminoethyl piperazine
LaPorte Darkening Pigment 4.8 Sherwin-Williams Corrosion Inhibitor 2.24
Black Iron Oxide Fe3O4. Moly White 101 Zinc Molybdate
Lauscha Fiber Internat. Thixatrope 1.9 Zinc Oxide
B-1S-F Glass Fiber Reinforcing Agent Alcan Chemicals Fire Retardant 31.8
Ferro UV Light Stabilizer 2.0 Alumina Trihydrate Al2O3.3H2O
UV 55-07051 Bis(1,2,2,6,6-Pentamethyl-4- H-10
Piperdinyl)Sebacate Degussa Hydrophobic Moisture
Atlantic Equipment Eng. Aggregate 25.8 Aerosi R812 Penetration Inhibitor
Aluminum Powder Aluminum Amorphous Fumed Silica
Lauscha Fiber Thixatrope 1.O
99 Internat. Glass Fiber Reinforcing
B-1S-F Agent
25
Total
Thus, the first amine side and first epoxy side were Epoxy Side
combined and mixed, then applied to a metal Surface using
a phenolic napless roller (or can be sprayed) to thereby form Vantico Epoxy Resin 694
a primed surface. After the primer has cured to a tack free Araldyte GY6010 Phenol, 4,4'-(1-
30 methylethylidene)bis-, polymer with
state, the second amine side and the second epoxy side are (chloromethyl)oxirane Bisphenol A
mixed and applied to the primed surface using a phenolic Diglycidyl Ether Polymer
napless roller. Alternatively, and in some cases preferen Rohm & Haas Polysulfide Toughening Agent 23.5
ELP-3 Epoxy terminated polysulfide
tially, the topcoat (the second amine side and epoxy side) is Sherwin-Williams Corrosion Inhibitor
applied prior to the primer curing to the tack free State. In 35 Moly White 101 Zinc Molybdate
this regard the topcoat in some instances is applied within 60 Rockwood Industries
Zinc Oxide
Corrosion Inhibitor
seconds of the primer being applied. The Surface can be PhOS Plus Zn(PO)-2,-4 H2O Mixture
cleaned prior to application of the primer. The rheology of Heucotech Corrosion Inhibitor
the topcoat allows for the formation of the ridges and valleys 40
Heucorin RZ Zinc-5-Nitro-Iso Phthalate
which Supplies additional slip resistance. The resulting coat Degussa Hydrophobic Moisture Penetration
Aerosi R812 Inhibitor
ing was approximately 1-10 mm thick (1–2 mm of primer). Amorphous Fumed Silica
The coating exhibited excellent durability when subjected to Ferro UV Light Stabilizer 2.0
a standard impact test. The coating showed Surprisingly little UV 55-07051 Bis(1,2,2,6,6-Pentamethyl-4-
wear due to the impact. The impact test, conducted accord 45
Piperidinyl)Sebacate
ing to MIL-PRF-24667A (Navy), consists of dropping a 907 LaPorte IR Transparent, Darkening Pigment 1.7
Black Iron Oxide Fe3O4.
gram steel ball from a height of 244 cm onto the coated steel Lauscha Fiber Thixatrope
Surface in a 5 by 5 array consisting of 25 impacts. Impact internat. Glass Fiber Reinforcing Agent
resistance is scored by counting the number of adjacent
impact 2.5 percentage points and Subtracting this from 100. 50
98.93
A minimum score of 95% is expected for an acceptable
material according to MIL-PRF-24667A (Navy). The coat
ings described herein typically score 100 in this test.
TABLE 2b
EXAMPLE 2 55
Top-Coat Composition
The procedures of Example 1 were repeated except that Weight
Supplier/Tradename Component Percent
the primer and topcoat of Tables 2a and 2b were employed.
In this example, antimony oxide and Zinc oxide were 60
Amine Side
removed from the coating of Tables 1a and 1b, with alumina Air Products Amine Curing Agent 39.5
trihydrate and titanium dioxide being used instead. Also, the Ancamime 2074 Isophoronediamine
Zinc corrosion inhibitors were used in the primeramine side Trimethylhexamethylenediamine
and some of the glass fiber was moved from the primer B. F. Goodrich Rubber Toughening Agent 3.9
Hycar 1300X16 ATBN
epoxy side to the primeramine side. Likewise, the amounts 65 Aminoethyl piperazine
of zinc corrosion inhibitor and black iron oxide were Alcan Chemicals Fire Retardant 9.4
increased in the primer epoxy side.
 US 7,037,958 B1
15 16
were tested to determine the amount of polythioether that
TABLE 2b-continued corresponds to a standard polysulfide formulation. The for
Top-Coat Composition mulations are shown in Table 3A, with the results of the tests
shown in Table 3B.
Weight The formulation in Table 3A were used to form cured
Supplier/Tradename Component Percent compositions of a primer coating and topcoat coating. The
Alumina Trihydrate Al2O3.3H2O resulting cured coatings were tested to determine Shore D
H-10 hardness and flexibility. Flexibility was measured using a
is nium Pigment and IR Reflector 19.7 four-point bend configuration in an Instron test machine
Lauscha Fiber Thixatrope 1.6 operated in compression (ASTM D6272). The four-point
Internat. Glass Fiber Reinforcing Agent bend test generated data for flexural modulus and the
B-1S-F -- -- -

Atlantic Equipment Aggregate 26.1 ultimate yield stress, which indicate flexibility and strength,
Eng. Aluminum respectively. The data is shown in Table 3B.
Aluminum Powder 15
TABLE 3A
Total 10O2
Epoxy Side Resin
Poly- Polythioether Epoxy resin Hard- hard
XMS
aldyle GY6010 E. ,
enol, 4,4'-(1- 48.4 sulfide (PERMAPOL (ARYLDYTE ener ele
methylethyidene)bis-, polymer 20 Sample (ELP3) 5534) GY6010) type ratio
with (chloromethyl)oxirane A. 25.83 O 74.17 A. 2.33
Bisphenol A Diglycidyl Ether mixture
Polymer O
Rohm & Haas Polysulfide Toughening Agent 16.1 Ancamine
ELP-3 Epoxy terminated polysulfide HY 2964
LaPorte IR Transparent Darkening Pigment 4.8 25 and Hycar
Black Iron Oxide Fe3O4. 13 OOX16
Lauscha Fiber Internat. Thixatrope 1.9 B O 25.83 74.17 A. 2.29
B-1S-F Glass Fiber Reinforcing Agent mixture
Ferro UV Light Stabilizer 2.0 O
UV 55-07051 Bis(1,2,2,6,6-Pentamethyl-4- Ancamine
Piperidinyl)Sebacate 30 HY 2964
Atlantic Equipment Eng. Aggregate 25.8 and Hycar
Aluminum Powder Aluminum 13 OOX16
C O 20.67 79.33 A. 2.2O
99 mixture
O
35 Ancamine
The primer sides and topcoat sides were applied to a clean HY 2964
steel plate Substrate according to Example 1. The cured and Hycar
coating was subjected to the impact test- of Example 1. The D O 15.51 84.49
13 OOX16
A. 2.11
cured coating showed excellent durability and Surprisingly mixture
little wear. 40 O
Ancamine
EXAMPLE 3 HY 2964
and Hycar
13 OOX16
Polythioether Formulations E O 10.33 89.67 A. 2.04
45 mixture
Several formulations were prepared using either an epoxi-
-
An oI C8lle
dized polysulfide or an epoxidized polythioether (PER- HY 2964
MAPOL polythioether, obtained from PRC DeSoto). While and Hycar
the epoxidized polysulfide is a linear pre-polymer containing 13 OOX16
di-sulfide bridges spaced periodically through the molecule, so 90.80% of the HY-2964 and 9.20% of the Hycar 1300X16
the epoxidized polythioether contains —S—bridges spaced
periodically through the molecule. While not wishing to be
bound by theory, it is thought that the sulfur linkage is more Sample A and B have equal amounts by weight of polysul
flexible than the S–S di-sulfide linkages, which results in a fide and polythioether, respectively. Sample C has 80% of
superior product when using the epoxidized polythioether ss polythioether relative to the amount of polysulfide in Sample
relative to the polysulfide. In addition, the PERMAPOL A, with the balance being made up with additional epoxy
polythioether has lower viscosity than the ELP3, which resin. Samples D and E have 60% and 40%, respectively, of
allows less polythioether being needed relative to the ELP3 polythioether relative to the amount of polysulfide in Sample
polysulfide to achieve the same rheology. Five formulations A.

TABLE 3B
Shore D Hardness Max Load at Yield (PSI Modulus at X% Deformation (PSI

Sample Meas 1 Meas 2 Meas 3 Average Meas 1 Meas 2 Meas 3 Average Meas 1 Meas 2 Meas 3 Average
Steel Paint Can 87 90 88.5 88.5
 US 7,037,958 B1
17 18
TABLE 3B-continued
Shore D Hardness Max Load at Yield (PSI Modulus at X% Deformation (PSI

Sample Meas 1 Meas 2 Meas 3 Average Meas 1 Meas 2 Meas 3 Average Meas 1 Meas 2 Meas 3 Average
Lid
ELP3 74 77 77.5 76.2 3353.2 32.56.4 3852.4 3487.3 166416.O 149941.7 1884O7.5 168,255
(Ambient Cure)
ELP3 (85F cure) 75 72.5 73.5 73.7
100% Permapol 76.5 71.5 70.5 72.8 1724.607 1971.898 1978.98S 1891.8 86007.4 82614.3 69763.3 79,461
5534
(Ambient Cure)
100% Permapol 70 69.5 75.5 71.7
5534 (85F Cure)
80% Permapol 77 79 77.5 77.8 3803.913 3728.068 3929.92S 3820.6 44612.1 55.699.7 69842.7 56,718
5534
(Ambient Cure)
80% Permapol 74.5 77 78 76.5
5534 (85F Cure)
60% Permapol 76.5 78 78.5 777 5341.757 4887.624 4949.777 5059.7 2O8745.4 222708.6 234415.8 221,957
5534
(Ambient Cure)
60% Permapol 76.5 77 81.5 78.3
5534 (85F Cure)
40% Permapol 76 76.5 76.5 76.3 6665.947 6499.856 6671.931 6612.6 3O42O3.1 28992O.S 314S18.2 302,881
5534
(Ambient Cure)
40% Permapol 81 79.5 8O.S 80.3
5534 (85F Cure)

The data in Table 3B shows that essentially the same

physical properties can be achieved using the polythioether 30
(Permapol 5534) in place of the polysulfide (ELP3), but with
only about 60% by weight of the polythioether relative to the
polysulfide.

TABLE 3C
Aluminum Aggregate Garnet Aggregate
ELP3, EPS25 Permapol ELP3/EPS25 Permapol
% Wt. %Wt. %Wt. %Wt.

Component Primer Activator:

Hardener HY2963 44.29 44.30 44.29 44.30
Hycar 1300X16 15.79 15.8O 15.79 15.8O
Mollywhite 1.85 1.90 1.85 1.90
Alumina trihydrate DH-80G 28.80 28.8O 28.80 28.8O
Aerosil R812 O.84 O.8O O.84 O.80
216O TiO2 8.42 840 8.42 8.40

Total: 99.99 1OOOO 99.99 100.00

Primer Base:

Araldyte GY6010 72.30 81.48 72.30 81.48

EPS25.ELP-3 23.90 23.90
Permapol 14.95 14.95
Black Iron Oxide O.SO O.25 OSO O.25
PhOS Plus O.80 O.8O O.80 O.80
Heucorin RZ O.08 O.08 O.08 O.O8
Aerosil R812 O.SO O48 OSO O.48
Silguest A-187 2.00 1.96 2.00 1.95

Total: 100.08 1OOOO 100.08 100.00

Topcoat Activator:
Ancamine 2074 31.60 31.8O 31.60 31.8O
Hycar 1300X16 3.22 3.2O 3.22 3.20
Alumina trihydrate 15.36 15.30 15.36 15.30
Titanium dioxide, Kronos 2160 7.12 7.10 7.12 7.10
Glass Microfiber, B-15-F 0.75 O.8O 0.75 O.80
Aluminum Tadpoles T-103 30.71 30.70
Aluminum Powder, A1-110 10.48 1O.SO
Garnet Aggregate 41.43 41.30
 US 7,037,958 B1
19 20
TABLE 3C-continued
Aluminum Aggregate Garnet Aggregate
ELP3/EPS25 Permapol ELP3/EPS25 Permapol
% Wt. %Wt. %Wt. %Wt.

Fumed Silica, CAB-O-SIL O.S2 OSO O.S2

Total: 99.76 99.99 1OOOO 100.00
Topcoat Base:
Araldyte GY6010 28.75 32.75 28.75 32.75
EPS25.ELP-3 1O.O2 1O.O2
Permapol 6.OO 6.OO
Black Iron Oxide 8.47 8.47 8.47 8.47
B-15-F Glass Fiber 1.34 1.34 1.34 1.34
Ferro UV Inhibitor, 55-07051 4.96 4.96 4.96 4.96
Aluminum Tadpoles, T-103 34.43 3445
Aluminum Powder, AL-110 11.02 11.02
Garnet Aggregate 45.45 45.47
Fumed Silica, CAB-O-SIL 1.01 1.01 1.01 1.01

Total: 100.00 1OOOO 1OOOO 100.00

The aluminum aggregate primer formulations of Table 3C 500 cycles. The results of a formulation using polythioether
were tested by bonding one-inch-wide adherends on steel 25 does not experience this level of wear until about 4,000
with a one-inch overlap using primers made using polysul cycles are exceeded.
fide and polythioether. For comparison, the primers from The polythioether formulation of Table 3C was also
two commercially available products were also tested. The subjected to tests under MIL-PRF-24667 to test resistance to
bonded assemblies were pulled apart using an Instron test wear and abrasion of a cable stimulant. As per MIL-PRF
machine. The results shown in Table 3D, and given in 30 24667, an aircraft carrier cable stimulant is rubbed over a
coating sample, with 30 pounds of pressure applied. The
absolute pounds of pull required to break the samples. Each cable is drug back and forth, with each back and forth pass
result is the average of five tests. The result for the poly equaling one cycle. Three samples were tested. MIL-PRF
thioether sample is low because one sample had to be pulled 24667 specifies that a sample passes the test procedure a
twice because it first reached the maximum level for the load 35 maximum average of 0.025 millimeter loss after 200 cycles
cell used, which weakened the adhesive bond. for abrasion of the cable, and a maximum average of 10%
weight loss per sample after 500 cycles for the coating wear.
TABLE 3D Sample 1 showed abrasion in millimeters of 0.021 after 200
Results
cycles, and 9.2% loss for the wear test after 500 cycles.
(absolute pounds of 40 Sample 2 showed abrasion in millimeters of 0.019 after 200
Sample pull to break sample) cycles, and 3.45% loss for the wear test after 500 cycles.
Sample 3 showed abrasion in millimeters of 0.008 after 200
Amercoat 138, a solvent born epoxy primer" 299 cycles, and 3.03% loss for the wear test after 500 cycles.
American Safety 440L primer" 679 Hence, all three polythioether samples passed the require
Polysulfide primer 2178
Polythioether primer (60% formulation) 2599 45 ments of MIL-PRF-24667 for these tests.
The coating made from a formulation using polythioether
"Amercoat 138 and American Safety 440L are commercially available were subjected to an impact test by dropping a two-pound
primers, which are not embodiments of this invention, and included for ball on the surface of the coating from a height of eight feet,
comparative purposes.
which is repeated twenty-five times in a five-by-five array.
The results show the Superiority of primers made using 50 The centers of the impact points are one inch apart. Failures
polysulfide and polythioether, owing so the significantly are counted when the coating chips away from the Surface
higher adhesion to steel and toughness than the commercial between adjacent impact points. According to MIL-PRF
products which lack either polysulfide or polythioether. 24667 no more than an average of two failures are allowed.
The formulations in Table 3C were also tested to deter No failures occurred in four panels tested, where the panels
mine wear properties of the coating using test MIL-PRF 55 were of a formulation made with polythioether.
24667A (U.S. Navy). This test is designed to simulate the In addition, a coating made using polythioether was tested
to measure flammability of the cured coating and its ability
wear produced by the trap cables on aircraft carriers. The test to quench a fire once initiated on the Surface. The formula
involves dragging a cable simulant across the coating for tion passed the requirements of the MIL-PRF-24657A speci
500 cycles. The simulant is a steel rod having the same 60 fications.
hardness as the steel in a cable. A thirty-pound load is The coatings made using polythioether were also subject
applied to the simulant. The sample is periodically weighed to a coefficient of friction test with the coating dry, wet by
to determine the quantity of coating removed by abrasion. sea water simulant, and coated with oil, which are intended
Normally the test proscribes 500 test cycles; however, in this to represent the extremes of conditions on an aircraft carrier
example, 5,000 test cycles were obtained. The specification 65 deck. The results showed an acceptably high coefficient of
for a U.S. Navy non-skid (MIL-PRF-24667A) requires no friction under MIL-PDF-24667A relative to a standard Sur
more than 10% of the weight of the coating be removed after face. The results are shown in Table 3E.
 US 7,037,958 B1
22
11. The epoxy topcoat of claim 1, wherein the topcoat is
TABLE 3E formulated with from about 4 to about 20 percent of the
Coefficient of Friction Sample 1 Sample 2 Sample 3
rubber toughening agent.
12. The epoxy topcoat of claim 1, wherein the epoxide
Dry (50 wear cycles) 1.09 1.15 1.16 containing toughening agent contains Sulfur.
Wet (50 wear cycles) 120 1.21 1.24
Oily (50 wear cycles) O.82 O.85 0.75 13. The epoxy topcoat of claim 1, wherein the epoxide
Dry (500 wear cycles) 1.26 1.12 1.27 containing toughening agent is a polysulfide, a polythioet
Wet (500 wear cycles) 1.46 1.11 1.34 her, or a combination thereof.
Oily (500 wear cycles) O.99 O.78 0.75
10 14. The epoxy topcoat of claim 1 wherein the rubber
toughening agent is an amine-terminated butadiene nitrile, a
Further modifications and alternative embodiments of this carboxy-terminated butadiene nitrile, or combination
invention will be apparent to those skilled in the art in view thereof.
of this description. Accordingly, this description is to be 15. The epoxy topcoat of claim 1, wherein the glass fiber
construed as illustrative only and is for the purpose of 15 has an average fiber diameter of about 0.2 to about 5 microns
teaching those skilled in the art the manner of carrying out and a surface area as measured by BET of about 0.01 to
the invention. It is to be understood that the forms of the about 25 meters squared per gram; wherein the topcoat is
invention herein shown and described are to be taken as
formulated from about 10 to about 50 percent of the amine
illustrative embodiments. Equivalent elements or materials curing agent; wherein the topcoat is formulated from about
may be substituted for those illustrated and described herein, 0.01 to about 10 percent of the epoxide-containing tough
and certain features of the invention may be utilized inde ening agent; wherein the topcoat is formulated from about
pendently of the use of other features, all as would be 0.01 to about 10 percent of the ultraviolet light stabilizer;
apparent to one skilled in the art after having the benefit of wherein the topcoat is formulated from about 0.01 to about
this description of the invention. 10 percent of the glass fiber; wherein the topcoat is formu
What is claimed is:
25 lated from about 20 to about 90 percent of the epoxy resin:
1. An epoxy topcoat comprising a cured mixture that is wherein the topcoat is formulated from about 4 to about 20
formulated from
percent of the rubber toughening agent; and wherein the
epoxide-containing toughening agent is a polysulfide, a
an epoxy resin, polythioether, or a combination thereof.
an epoxide-containing toughening agent, 30 16. An epoxy coating formulated from (a) an amine curing
optionally, an ultraviolet light stabilizer, agent, (b) an epoxide-containing toughening agent, (c) an
a pigment, epoxy resin, (d) a rubber toughening agent other than the
a glass fiber thixotrope and impact toughening agent, epoxide-containing toughening agent, and (e) an optional
an optional abrasive aggregate, fire retardant, an optional glass fiber thixotrope and impact
an optional fire retardant, 35 toughening agent, a pigment, a corrosion inhibitor, a mois
an amine curing agent, and ture penetration inhibitor, an ultraviolet light stabilizer, an
a rubber toughening agent other than the epoxide-con optional abrasive aggregate, or a combination thereof.
taining toughening agent. 17. The coating of claim 16, wherein the coating is
2. The epoxy topcoat of claim 1, wherein the glass fiber prepared with from about 20 to about 60 percent of the
40
has an average fiber diameter of about 0.2 to about 5 microns amine curing agent.
and a surface area as measured by BET of about 0.01 to 18. The coating of claim 16, wherein the coating is
about 25 meters squared per gram. formulated with from about 0.01 to about 30 percent of the
3. The epoxy topcoat of claim 1, wherein the topcoat is epoxide-containing toughening agent.
formulated with from about 10 to about 50 percent of the 45 19. The coating of claim 16, wherein the coating is
amine curing agent. formulated with from about 0.01 to about 15 percent based
4. The epoxy topcoat of claim 1, wherein the topcoat is on the total weight of the coating of the corrosion inhibitor.
formulated with from about 0.01 to about 10 percent of the 20. The coating of claim 16, wherein the coating is
epoxide-containing toughening agent.
5. The epoxy topcoat of claim 1, wherein the topcoat is formulated with from about 0.01 to about 10 percent based
formulated with from about 0.01 to about 10 percent of the
50 on the total weight of the coating of the glass fiber.
ultraviolet light stabilizer. 21. The coating of claim 16, wherein the coating is
6. The epoxy topcoat of claim 1, wherein the topcoat is formulated with from about 0.01 to about 3 percent based on
formulated with from about 0.01 to about 45 percent of the the total weight of the coating of an moisture penetration
abrasive aggregate. inhibitor.
55
7. The epoxy topcoat of claim 1, wherein the topcoat is 22. The coating of claim 16, wherein the coating is
formulated with from about 0.01 to about 10 percent of the prepared with from about 0.01 to about 35 percent based on
glass fiber. the total weight of the coating of the fire retardant.
8. The epoxy topcoat of claim 1, wherein the topcoat is 23. The coating of claim 16, wherein the coating is
formulated with from about 0.01 to about 20 percent of the 60 prepared with from about 10 to about 90 percent based on
fire retardant. the total weight of the coating of the epoxy resin.
9. The epoxy topcoat of claim 1, wherein the topcoat is 24. The coating of claim 16, wherein the coating is
formulated with from about 0.01 to about 30 percent of the prepared with from about 4 to about 40 percent based on the
pigment. total weight of the coating of the rubber toughening agent.
10. The epoxy topcoat of claim 1, wherein the topcoat is 65 25. The coating of claim 16, wherein the coating is
formulated with from about 20 to about 90 percent of the prepared with from about 0.01 to about 30 percent based on
epoxy resin. the total weight of the coating of the pigment.
 US 7,037,958 B1
23 24
26. The coating of claim 16, wherein the coating is 5 microns and a surface area as measured by BET of about
prepared with from about 0.01 to about 10 percent based on 0.01 to about 25 meters squared per gram.
the total weight of the coating of the ultraviolet light 30. The coating of claim 16, wherein the epoxide-con
stabilizer. taining toughening agent contains Sulfur.
27. The coating of claim 16, wherein the coating is 31. The coating of claim 16, wherein the epoxide-con
prepared with from about 0.01 to about 45 percent based on taining toughening agent is a polysulfide, a polythioether, or
the total weight of the coating of the abrasive aggregate. a combination thereof.
28. The coating of claim 16, wherein the coating is
substantially free of solvents.
29. The coating of claim 16, wherein the glass fiber is 10
present and has average fiber diameter of about 0.2 to about