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US005618860A
United States Patent (19) 11 Patent Number: 5,618,860
Mowrer et al. (45) Date of Patent: Apr. 8, 1997
(54) EPOXY POLYSILOXANE COATING AND 4,250,074 2/1981 Foscante et al. ................. 260/32.8 EP
FLOORING COMPOSITIONS 4,385,158 5/1983 Mikami et al. ......................... 525/476
4,546,018 10/1985 Ryuzo et al. ...... ... 427/407.2
75) Inventors: Norman R. Mowrer, La Habra: - - - - 5.
sw-wes
2.3. Sing et al. E.
urlyama et al. .
isian, is 5,019,607 5/1991 Coltrain et al. ......................... 523/435
d Primary Examiner-Margaret W. Glass
73 Assignee: Aero literational Corporation,
aSadena, Ualli.
Attorney, Agent, or Firm-Christie, Parker & Hale, LLP
57) ABSTRACT
(21) Appl. No.: 342,414 A sprayable, trowelable epoxy polysiloxane based coating
(22) Filed: Nov. 18, 1994 and flooring composition exhibiting excellent weatherability
in sunlight and superior chemical, corrosion and impact
Related U.S. Application Data resistance after curing is made up of: (a) a resin component
which includes a non-aromatic epoxy resin having at least
63) Continuation-in-part of Ser. No. 64,398, May 19, 1993, two 1,2-epoxy groups per molecule, a polysiloxane and an
abandoned. organooxysilane; (b) an difunctional aminosilane hardener
51) Int. Cl. C08K 3/20 component; (c) an organotin catalyst; and (d) an aggregate
52) us c O. 523,421,528/27: 528/18: or pigment component. Organic solvents and flow modify
2007. ing agents may be added to facilitate spray application. The
52.5.2.G.i?: G. G. resin component, hardener component, aggregate compo
9. 106iii. 427/38 6. 427(387 nent and desired catalysts are combined in the presence of a
581 Field of Search 9 528p7 18, 15 sufficient amount of water to promote the hydrolysis of
(58) Field o east11 4.38: 525/476,5231414 42 1 417: polysiloxane and/or organooxysilane and the polyconden
6/2 wV2 12: 4 387 sation of the silanols produced by such hydrolysis. The
106/287.11, 806, 816, 712; 427/386, aminosilane and epoxide resin react to form a cured linear
epoxy polymer. The polysiloxane and/or organooxysilane
(56) References Cited undergo a hydrolysis reaction which produces silanol. The
U.S. PATENT DOCUMENTS silanol undergoes polycondensation forming a linear epoxy
3,183,198 5/1965 Wagner 260/18 modified polysiloxane polymer.
3,297,724 1/1967 McConnell et al. .................... 260/348
3,395,128 7/1968 Hale et al. ............................. 260/77.5 20 Claims, No Drawings
 5,618,860
1 2
EPOXY POLYSLOXANE COATING AND Epoxy based protective coatings possess many properties
FLOORING COMPOSITIONS which make them desirable as coating materials. They are
readily available and are easily applied by a variety of
RELATION TO COPENDING APPLICATION methods including spraying, rolling and brushing. They
adhere well to steel, concrete and other substrates, have low
This application is a continuation in part to U. S. patent moisture vapor transmission rates and act as barriers to
application Ser. No. 08/064,398, filed on May 19, 1993, now water, chloride and sulfate ion ingress, provide excellent
abandoned. corrosion protection under a variety of atmospheric expo
sure conditions and have good resistance to many chemicals
FILED OF THE INVENTION 10 and solvents.
Epoxy based materials are also formulated as surfacers or
This invention relates to epoxy resin based coating and flooring materials primarily for application over concrete.
flooring materials having improved properties of flexibility, One commercially successful epoxy based flooring material
weatherability, compressive strength and chemical resis utilizes liquid bisphenol A epoxy resin and a modified
tance. 15 aliphatic polyamine combined with graded silica sand aggre
gate as a third component. It can be spray applied and has
BACKGROUND excellent compressive, tensile and flexural strength, good
resistance to impact and abrasion and resists a wide variety
Epoxy coatings and flooring materials are well know and of chemicals and solvents.
have gained commercial acceptance as protective and deco 20 Another commercially successful epoxy based flooring
rative coatings for steel, aluminum, galvanizing, wood and material described in U.S. Pat. No. 3,794,609, utilizes liquid
concrete in maintenance, marine, construction, architectural, bisphenol A epoxy and a mixture of powdered methylene
aircraft and product finishing markets. The basic raw mate dianiline (MDA) and graded silica sand as the second
rials used to prepare these coatings generally comprise as component. The composition has excellent resistance to
essential components (a) an epoxy resin, (b) a hardener and 25 organic and inorganic acids and a wide variety of chemicals
(c) a pigment or aggregate component. and solvents. However, MDA has recently been identified as
The epoxide resins are those having more than one a carcinogen and its manufacture and use are being regu
1,2-epoxy group per mole and may be saturated or unsat lated. Further, MDA cured epoxies are not very color stable
urated, aliphatic, cycloaliphatic, or heterocyclic. The 30 and darken quickly.
epoxide resins generally contain glycidyl ester or glycidyl The resistance of epoxy based flooring and coating mate
ether groups and have a weight per epoxide of from 100 to rials to attack by solvents such as acetone and methanol can
2000. The hardener is usually chosen from the general be poor. The properties of an epoxy resin based film are
classes of aliphatic amines or aliphatic amine adducts, dependent on the type of epoxy resin and hardener, the
polyamides, polyamidoamines, cycloaliphatic amines, aro 35 chemical nature of the cure linkage and extent of crosslink
matic amines, Mannich bases, ketimines and carboxylic ing relative to chain extension and cross link density. The
derivatives. Pigments or aggregates include titanium dioxide most important commercial cure mechanisms use aliphatic
and other inorganic and organic color pigments, silica, amines, polyamides, polyamidoamines, aromatic amines
barium sulfate, magnesium silicate, calcium silicate, fumed and carboxylic derivatives. Unfortunately, amines and car
silica, garnet, feldspar, carbon black and the like. 40 boxylic derivatives result in cured materials which are
Known epoxy based flooring and coating materials often generally sensitive to acid and hydrolyric degradation. The
contain several components in addition to the epoxy resin, structural basis for this susceptibility, when using amine
hardener and pigment/aggregate. These include such addi hardeners, is the presence of the substituted nitrogen group
tives as nonreactive and reactive diluents including mono in the matrix which can be protonated by acid and undergo
and di-epoxides, plasticizer, bituminous and asphaltic 45 a series of degradation reactions. In the case of carboxylic
extenders, adhesion promoters, suspending agents and acid derived hardeners, the cured material contains ester
thixotropes, surfactants, corrosion inhibitors, ultraviolet linkages which are subject to hydrolysis catalyzed by both
light stabilizers, catalysts and rheological modifiers. acid and base.
Both the resin and hardener components may also contain Epoxy based coating and flooring materials generally do
volatile organic solvents whose primary function is to lower 50 not have good resistance to weathering in sunlight. While
viscosity thereby providing a consistency suitable for spray such coatings maintain their chemical and corrosion resis
application with conventional air, airless and electrostatic tance, exposure to the ultraviolet light component of sun
spray equipment. light results in a surface degradation phenomenon known as
Epoxy based protective coatings represent one of the most chalking which changes both the gloss and color of the
widely used methods of corrosion control. They are used to 55 original coating. Where color and gloss retention is desired
provide long term protection of steel, concrete, aluminum or required, epoxy protective coatings are typically top
and other structures under a broad range of corrosive con coated with a more weatherable coating i.e. an alkyd, vinyl
ditions, extending from atmospheric exposure to full immer or aliphatic polyurethane coating. The end result is a two or
sion in strongly corrosive solutions. For over 20 years, these sometimes three coat system which provides corrosion resis
coatings have been formulated from either a solid or liquid 60 tance and weatherability, but which is also labor intensive
epoxy resin cured with an aliphatic polyamine or polyamide and expensive to apply.
resin e.g., Shell Epon 1001 or Epon 828 epoxy resins cured A growing emphasis on compliance with government
with diethylene triamine (DETA) or Versamid 100 series environmental and health hazard regulations has prompted
polyamides. In typical two package coating systems, the coating and flooring material manufacturers and end users to
epoxy resin component is usually the vehicle for pigment 65 evaluate new coating technologies. The Clean Air Act sets
grinding and dispersion of other aggregates and various limits on both the type and amount of volatile organic
additives. compounds (VOC) and has resulted in research directed to
 5,618,860
3 4.
higher solids, solventless and waterborne protective coating (a) a resin component based on a blend of (1) a non
systems. In addition, as part of the Resource Recovery and aromatic epoxy resin having at least two 1,2-epoxy
Conservation Act, the Environmental Protection Agency has groups with (2) a polysiloxane and (3) an organoox
established minimum national standards for the manage ysilane;
ment of hazardous waste. Part of these standards deals with
the prevention of waste releases into soil and groundwater (b) a difunctional amine hardener component which may
through chemically resistant coating, lining and flooring be substituted wholly or in part with an aminosilane;
materials in the form of secondary containment structures.
Thus, while epoxy based coating and flooring materials (c) an optional catalyst;
have gained wide commercial acceptance, the need never 10 (d) a pigment or aggregate component; and
theless remains for epoxy based materials with improved (e) water.
color and gloss retention, better chemical and corrosion
resistance, and improved resistance to mechanical abuse. A protective flooring embodiment of the composition is
New epoxy coating and flooring materials are needed to prepared by combining the following ingredients:
comply with new governmental environmental and health 5 (a) a resin component based on a blend of (1) an aromatic
hazard regulations. Epoxy coatings and flooring materials
with improved color and gloss retention are needed wher epoxy resin having at least two 1,2-epoxy groups with
ever they may be exposed to sunlight. An epoxy coating (2) a polysiloxane and (3) an organooxysilane;
which doesn't chalk and does not require a weatherable (b) an amine hardener component which may be substi
topcoat is desirable. Coating and flooring materials with tuted wholly or in part with an aminosilane;
improved chemical, corrosion, impact and abrasion resis 20
tance are needed for both primary and secondary chemical (c) an optional catalyst;
containment structures, for protecting steel and concrete in (d) a pigment aggregate component; and
chemical, power generation, railcar, sewage and waste water
treatment, and paper and pulp processing industries. (e) Water.
Improved epoxy based flooring materials are needed in 25 Coating embodiments of the composition comprise in the
industrial environments such as shipping and receiving range of from about 15-45 percent by weight of the non
docks where heavy impact loading can be anticipated, for aromatic epoxy resin ingredient, 15 to 45 percent by weight
floors which must be repeatedly cleaned with steam and polysiloxane, 1 to 10 percent by weight organooxysilane, 10
aggressive chemicals, such as those found in food process
ing, meat packaging and beverage industries and where 30 to 20 percent by weight amine hardener, and up to about 4
spills of caustic, acid and highly reactive chemicals cannot percent by weight catalyst.
be avoided. Flooring embodiments of the composition comprise in the
Heretofore, epoxy coatings with improved weatherability range of from about 5-20 percent by weight of the epoxy
have been obtained by modification with acrylic resin or by resin ingredient, to 10 percent by weight polysiloxane, up to
curing inherently weatherable epoxide resins i.e., sorbitol 35 2 percent by weight organooxysilane, 2 to 5 percent by
glycidyl ethers, hydrogenated reaction products of bisphenol
A and epichlorhydrin, and more recently the epoxy func weight amine hardener, and up to about 4 percent by weight
tional coetherified melamine resins from Monsanto with catalyst.
polyamide, cycloaliphatic amine or carboxyl functional The epoxide resins useful in forming coating embodi
acrylic or polyester resins. Another approach has been to use 40 ments of this invention are non-aromatic hydrogenated
epoxidized polyester resins in combination with certain
carboxyl functional vehicles. While these coatings exhibit resins which contain more than one 1,2-epoxy groups per
improved weatherability, their chemical and corrosion resis molecule and more preferably two 1,2-epoxy groups per
tance is generally inferior to the epoxy resin based coatings molecule. The weight per epoxide of such resins are within
previously described. the range of from 100 to about 2000. Preferably the epoxide
Epoxy based flooring materials with improved chemical 45
resistance have been developed from epoxy novalac resins resins contain glycidyl ether orester groups, are liquid rather
and modified cycloaliphatic and aromatic amine hardeners. than solid and have weight per epoxide in the range of from
Epoxy movalac based flooring materials generally cannot be about 100 to about 500. Epoxide resins useful in forming
sprayed at 100% solids because of their high viscosity. flooring embodiments of this invention include aromatic
Aromatic amine hardeners, i.e. methylene dianiline and 50 epoxy resins.
diethyltoluene diamine are either carcinogenic or suspect Polysiloxanes useful in coating and flooring embodiments
carcinogens. These materials generally have excellent
chemical resistance, however, their weatherability is very of the present invention have the formula:
poor. Discoloration may often occur indoors. R1
Therefore, it is an object of the present invention to 55
provide modified epoxy based coatings with improved R2-O R2
chemical, corrosion and weathering resistance. s-o
R
Another object of this invention is to provide solventless, F.

modified epoxy based flooring materials with improved

resistance to weathering and improved solvent, acid and 60 where each R is selected from the group consisting of the
base resistance and which exhibit high tensile and compres hydroxy group and alkyl, aryl and alkoxy groups having up
sive strength and excellent resistance to impact and abra to six carbon atoms. Each R is selected from the group
S10.
consisting of hydrogen and alkyl and aryl groups having up
SUMMARY OF THE INVENTION to six carbon atoms and wherein n is selected so that the
65
A protective coating embodiment of the composition is molecular weight of the preferred polysiloxanes may be in
prepared by combining the following ingredients: the range of from 400 to about 2000.
 5,618,860
S 6
Organooxysilanes useful in coating and flooring embodi resin with the polyamine to form a cured linear epoxy
ments of the present invention have the formula: polymer, hydrolysis of the polysiloxane and/or organoox
ysilane to form silanol, and the polycondensation of silanol
pR. to form an epoxy-modified polysiloxane polymer. The com
R-Si-OR. positions formed by combining the above-identified ingre
OR4
dients can be cured in situ on the surface of a substrate is
desired.
where R is selected from the group consisting of aryl, alkyl,
and cycloalkyl groups containing up to six carbon atoms and 10
DETAILED DESCRIPTION
where R is independently selected from the group consist The present invention provides an epoxy-modified pol
ing of alkyl, hydroxyalkyl, alkoxyalkyl and hydroxyalkoxy ysiloxane coating and flooring material with improved prop
alkyl groups containing up to six carbon atoms. The epoxy
resin, polysiloxane and organooxysilane are combined to erties. When formulated as a coating material, compositions
form the resin component. of the present invention have greatly improved resistance to
The hardener component comprises an amine selected 15 ultraviolet light and weathering in sunlight as well as
from the general classes of aliphatic amines, aliphatic amine improved chemical and corrosion resistance when compared
adducts, polyamidoamines, cycloaliphatic amines and to conventional epoxy resin based coatings. Coatings of the
cycloaliphatic amine adducts, aromatic amines, Mannich present invention have color and gloss retention approaching
bases and ketimines which may be substituted wholly or in those exhibited by aliphatic polyurethanes and may, depend
part with an aminosilane having the general formula: ing on application, obviate the need for topcoating. Chemi
cal resistance is also improved over the prior art. The
enhanced weatherability is believed to be due to the forma
where Y is H(HNR) and where a is an integer from two to tion of a linear epoxy polymer structure, rather than a
about six, each R is a difunctional organic radical indepen cross-linked epoxy structure, as will be discussed in greater
dently selected from the group consisting of aryl, alkyl, 25 detail below.
dialkylaryl, alkoxyalkyl, and cycloalkyl radicals, and R can When formulated as a flooring material, compositions of
vary within each Y molecule. Each X can be the same or the present invention have greatly improved chemical resis
different, and is limited to alkyl, hydroxalkyl, alkoxyalkyl tance and compressive strength and exhibit high tensile
and hydroxyalkoxyalkyl groups containing less than about strength and impact resistance compared to prior art epoxy
30
six carbon atoms. At least 0.7 equivalents of amine or 0.2 flooring materials and surfacers.
moles of aminosilane per equivalent of epoxy are present in The epoxy polysiloxane coating embodiment of the com
the hardener component. Amine hardeners useful informing position is prepared by combining in the presence of water;
coating embodiments of this invention are difunctional, (a) a resin component comprising a non-aromatic epoxide
where 'a' in the formula set forth above for the aminosilane resin, polysiloxane and organooxysilane;
is one. Amine hardeners useful in forming flooring embodi 35
ments of this invention are polyfunctional. (b) a hardener component;
A preferred catalyst is an organotin catalyst having the (c) an organotin optional catalyst; and
general formula (d) a pigment and/or aggregate component.
40
The epoxy flooring embodiment of the composition is
prepared by combining in the presence of water;
R-in-R, (a) a resin component comprising an aromatic epoxy
R8 resin, polysiloxane and an organooxysilane;
(b) a hardener component;
where Rs and R are selected from a group consisting of 45 (c) an optional organotin catalyst; and
alkyl, aryl, and alkoxy groups having up to eleven carbon (d) a pigment and/or aggregate component.
atoms, and R, and Rs are selected from the same groups as The coating and flooring composition may also contain
Rs and R or from a group consisting of inorganic atoms other components such as, rheological modifiers, plasticiz
such as halogens, sulphur or oxygen. ers, thixotropic agents, antifoam agents and solvents and the
The coating embodiment of the composition according to 50 like to achieve the desired properties sought by the user.
the present invention comprises a fine particle size pigment With respect to the resin component, it comprises ablend
or aggregate material, preferably with 90 percent by weight of epoxide resin, polysiloxane and organooxysilane. Suit
greater than 325 mesh U. S. Sieve size. The flooring able epoxy resins useful informing coating embodiments of
embodiment of the composition according to the present this invention are non-aromatic hydrogenated epoxy resins
invention comprises a coarse or a mixture of coarse and fine 55 that contain more than one and preferably two 1,2-epoxy
particle size aggregate material, preferably at least about 85 groups per molecule. Preferably, the epoxide resins are
percent by weight of the aggregate component will be liquid rather than solid, have an epoxide equivalent weight
between 10 and 200 U. S. Sieve size. of about 100 to about 2,000, and more preferably in the
Water should also be present in an amount sufficient to range of from about 100 to 500 and have areactivity of about
bring about hydrolyric polycondensation of polysiloxane 60 tWO.
and silane. The coating and flooring embodiments of the Preferred epoxide resins are non-aromatic hydrogenated
composition of the present invention may additionally con cyclohexane dimethanol and diglycidyl ethers of hydroge
tain certain catalysts to improve cure time, solvents to nated Bisphenol A-type epoxide resin, such as Epon DPL
improve spray atomization and application, and rheological 862, Eponex 1510, Heloxy 107 and Eponex 1513 (hydro
modifiers to improve flow characteristics. 65 genated bisphenol A-epichlorohydrin epoxy resin) from
Curing of the coating and flooring embodiments of the Shell Chemical in Houston, Tex.; Santolink LSE-120 from
compositions involve the simultaneous reaction of the epoxy Monsanto located in Springfield, Mass.; Epodil 757 (cyclo
 5,618,860
7 8
hexane dimethanol diglycidylether) from Pacific Anchor groups having less than six carbon atoms to facilitate rapid
located in Allentown, Pa.; Araldite XUGY358 and PY327 hydrolysis of the polysiloxane, which reaction is driven by
from Ciba Geigy located in Hawthorne, N.Y.; Epirez 505 the volatility of the alcohol analog product of the hydrolysis.
from Rhone-Poulene located in Lousiville, Ky., Aroflint 393 R and R groups having greater than six carbon atoms tend
and 607 from Reichold located in Pensacola, Fla.; and to impair the hydrolysis of the polysiloxane due to the
ERL4221 from Union Carbide located in Tarrytown, N.Y. relatively low volatility of each alcohol analog. Methoxy,
Other suitable non-aromatic epoxy resin include DER 732 ethoxy and silanol functional polysiloxanes having in
and DER 736. Such non-aromatic hydrogenated epoxide selected molecular weights are about 400 to about 2000
resins are desired for their limited reactivity of about two, which are preferred for formulating coating and flooring
which promote formation of a linear epoxy polymer and 10 materials of the present invention. Methoxy, ethoxy and
prohibits formation of a cross-linked epoxy polymer. It is silanol functional polysiloxanes having molecular weights
believed that the resulting linear epoxy polymer formed by of less than 400 would produce a coating and flooring
adding the hardener to the epoxide resin is responsible for composition that would be brittle and offer poor impact
the enhanced weatherability of this composition. resistance. Methoxy, ethoxy and silanol functional polysi
The use of Such non-aromatic epoxide resins to form a 15
loxanes having molecular weights of greater than 2000
weatherable protective coating has never before been produce a coating and flooring composition having both a
explored because of the limited reactivity of the epoxide viscosity outside the desired range of from about 3,000 to
resin and, therefore, the perceived inability of the resin to 15,000 centipoise (cP) at 20° C., and are too viscous for
cure to form a protective coating. application without adding solvent in excess of current
A preferred coating composition comprises in the range of 20
volatile organic content (VOC) requirements.
from 15 to 45 percent by weight epoxide resin. If the coating Especially preferred methoxy functional polysiloxanes
composition comprises less than 15 percent by weight are: DC-3074 and DC-3037 from Dow Corning; GESR191
epoxide resin, chemical resistance of the coating will be and SY-550 from Wacker located in Adrian, Mich. Silanol
compromised. If the coating composition comprises greater functional polysiloxanes include, but are not limited to, Dow
than 45 percent by weight epoxide resin, the weatherability 25
Corning's DC840, Z6018, Q1-2530 and 6-2230 intermedi
of the coating will be compromised. A particularly preferred ates. A preferred coating composition comprises in the range
coating composition comprises approximately 25 percent by of from 15 to 45 percent by weight polysiloxane. A preferred
weight non-aromatic epoxide resin. flooring composition comprises in the range of from one to
Preferred epoxide resins for flooring materials, surfacers, ten percent by weight polysiloxane. If the coating and
are blends of Shell Epon 828 (bisphenol A-epichlorohydrin 30
flooring composition comprises an amount of polysiloxane
epoxy resin) with difunctional epoxide reactive diluents Outside each range, the coating and flooring composition
such as neopentylglycol diglycidylether, resorcinol digly produced will display inferior weatherability and chemical
cidyletherandcyclohexanedimethanoldiglycidylether, resistance. A particularly preferred coating composition
bisphenol F epoxy resins i.e., Shell Epon DPL862 (bisphe comprises approximately 30 percent by weight polysilox
nol F-epiclorohydrin epoxy resin) and epoxy phenol novalac 35
ane. The preferred flooring composition comprises approxi
resins Such as: Epalloy 8250 (epoxy novalac resin) from mately 3 percent by weight polysiloxane.
CVC located in Cherry Hill, N.J.; Araldite EPN 1139 from With respect to organooxysilane used to make up the resin
Ciba Geigy; and DEN432 and DEN438 from Dow Chemi component, preferred organooxysilanes have the general
cal. These epoxide resins display good chemical resistance. formula.
Aparticularly preferred epoxy resin for flooring and surfacer 40
compositions is Epalloy 8250.
A preferred flooring composition comprises in the range
(R.
of from 5 to 20 percent by weight epoxide resin. If the R-Si-OR.
OR4
flooring composition comprises less than five percent by
weight epoxide resin resistance to alkaline chemicals will be 45 where R is selected from the group consisting of alkyl and
compromised. Additionally, the cost to manufacture the cycloalkyl groups containing up to six carbon atoms and aryl
composition using an offsetting amount of polysiloxane and groups containing up to ten carbon atoms. R is indepen
organooxysilane would be prohibitive. If the flooring com dently selected from the group consisting of alkyl, hydroxy
position comprises greater than 20 percent by weight alkyl, alkoxyalkyl and hydroxyalkoxyalkyl groups contain
epoxide resin, its resistance to organic acid and solvent 50 ing up to six carbon atoms. It is preferred that R comprise
would be less than desirable. A particularly preferred com groups having up to six carbon atoms to facilitate rapid
position comprises approximately 15 percent by weight hydrolysis of the organooxysilane, which reaction is driven
epoxide resin. by the evaporation of the alcohol analog product of the
With respect to the polysiloxane used to make up the resin hydrolysis. Ra groups having greater than six carbon atoms
component, preferred polysiloxanes include, but are not 55 tend to impair the hydrolysis of the organooxysilane due to
limited to, those having the following formula: the relatively low volatility of each alcohol analog.
Particularly preferred organooxysilanes are trialkoxysi
lanes such as Union Carbide's A-163 (methyl trimethoxy
silane), A-162 and A-137, and Dow Corning's Z6070 and
60 Z6124. A preferred coating composition comprises in the
range of from one to ten percent by weight organooxysilane.
A preferred flooring composition comprises up to about two
where each R1 is selected from the group consisting of the percent by weight organooxysilane. If the coating and floor
hydroxy group and alkyl, aryl, and alkoxy groups having up ing composition comprises an amount of organooxysilane
to six carbon atoms. Each R is selected from the group 65 outside each range, the coating and flooring composition
consisting of hydrogen and alkyl and aryl groups having up produced will display inferior impact resistance and chemi
to six carbon atoms. It is preferred that R and Rcomprise cal resistance. A particularly preferred coating composition
 5,618,860
9 10
comprises approximately five percent by weight organoox A difunctional aminosilane is desired because such aminosi
ysilane. The preferred flooring composition comprises lanes have a reactivity of two, i.e., have only two amine
approximately 0.7 percent by weight organooxysilane. hydrogens, that reacts with the non-aromatic expoxy, also
Accordingly, a preferred coating composition according having a reactivity of two, to form a linear non-cross linked
to practice of this invention may comprise a weight ratio of 5 epoxy polymer having improved weatherability.
polysiloxane to organooxysilane of approximately six to These amines and aminosilanes are preferred because
one. A preferred flooring composition may comprise a
weight ratio of polysiloxane to organooxysilane of approxi they produce coating compositions exhibiting superior
weatherability in terms of both color and gloss retention. A
mately four to one. preferred coating composition comprises in the range of
The hardener component comprises an amine chosen 10 from 10 to 20 percent by weight amine and/or aminosilane.
from the general classes of aliphatic amines, aliphatic amine If the coating composition comprises an amount of amine or
adducts, polyamidoamines, cycloaliphatic amines and aminosilane outside this range, a coating composition hav
cycloaliphatic amine adducts, aromatic amines, Mannich ing inferior weatherability and chemical resistance will be
bases and kerimines which may be substituted wholly or in produced. Aparticularly preferred coating composition com
part with an aminosilane having the general formula: 15 prises approximately 15 percent by weight amine and/or
Y-Si-O-X) aminosilane.
The preferred polyamines and aminosilanes for flooring
where Y is H(HNR) and where one, each Ris a difunctional and concrete surfacer compositions of the present invention
organic radical independently selected from the group con are aliphatic amines, methylene bis dianiline, diethyltoluene
sisting of aryl, alkyl, dialkylaryl, alkoxyalkyl, and 20 diamine, methylene bis diethylaniline, methylene bis diiso
cycloalkyl radicals, and R can vary within each Y molecule. propylaniline, Versamine I70 and 671 CE from Henkel
Each X can be the same or different, and is limited to alkyl, located in Ambler, Pa., Ciba Geigy's XUHY350,
hydroxalkyl, alkoxyalkyl and hydroxyalkoxyalkyl groups XUHY310, and XUHY315, Pacific Anchor's Ancamine
containing less than about six carbon atoms. At least 0.7 2264, 2280, and 2168, NC541 from Cardolite located in
equivalents of amine or 0.2 moles of aminosilane per 25 Newark, N.J., Euredur 3265 and 3266 from Schering Berlin
equivalent of epoxy may be present in the hardener com located in Dublin, Oh., Hils'AO698, and 12328-1 from
ponent. PCR located in Gainsville, Fla. These polyamines and
Preferred aminosilanes include, but are not limited to:
aminoethyl aminopropyl triethoxysilane, n-phenylamino compositions are
aminosilanes preferred because they produce flooring
having superior chemical resistance. A par
propyl trimethoxysilane, trimethoxysilylpropyl diethylene 30 ticularly preferred aminosilane for chemically resistant
triamine, 3-(3-aminophenoxy) propyl trimethoxy silane, flooring compositions is Dow Corning's Z6020 (aminoethyl
amino ethyl amino methyl phenyl trimethoxy silane, 2 aminopropyl trimethoxy silane). A preferred flooring com
amino ethyl 3 aminopropyl, tris 2 ethylhexoxysilane, n-ami position comprises in the range of from two to five percent
nohexyl aminopropyl trimethoxysilane and trisaminopropyl by weight polyamine or aminosilane. If the flooring com
trismethoxy ethoxy silane. 35 position comprises an amount of polyamine or aminosilane
The manufacturers and trade names of some aminosilanes outside this range, a flooring composition having inferior
useful in the present invention are listed in Table 1 weatherability and chemical resistance will be produced. A
TABLE 1.
particularly preferred flooring composition comprises
approximately four percent by weight polyamine or ami
Aminosilanes 40 nosilane.
Accordingly, a preferred coating composition according
Manufacturer Product Designation to practice of the present invention may comprise a weight
Dow Corning Z6020, XI-6100, XI6150 ratio of polysiloxane to amine and aminosilane of approxi
Union Carbide A1100, A1101, A1102, A1108, A1110, A120 mately two to one. A preferred flooring composition may
Wacker
A1126, A1130, A1387, Y9632
ED117
45 comprise a weight ratio of polysiloxane to polyamine and/or
HSls A0696, A0698, A0699, A0700, A0710, A0720, aminosilane of approximately three to four. Additionally, a
A0733, A0733, A0742, A0750, A0800 preferred coating may comprise a weight ratio of amine and
PCR 12328-1 aminosilane to organooxysilane of approximately three to
one. A preferred flooring composition may comprise a
The hardener component for a preferred coating compo- 50 weight ratio of polyamine and aminosilane to organooxysi
sition comprises a difunctional aminosilane having the gen lane of approximately six to one.
eral formula: In the modified epoxy based coating and flooring com
positions of the present invention, the proportion of hardener
Y-Si-O-X) component to resin component can vary over a wide range,
55 regardless of whether the amine hardener is chosen from the
where Y is H(HNR) and where a is one, R is a difunctional general classes of amines, or an aminosilane of the general
organic radical independently selected from the group con formula above, or any combination thereof. In general, the
sisting of aryl, alkyl, dialkylaryl, alkoxyalkyl, and epoxy resin component is cured with sufficient amine hard
cycloalkyl radicals, where X is limited to alkyl, hydroxalkyl, ener to provide at least from about 0.7 to about 1.2 amine
alkoxyalkyl and hydroxyalkoxyalkyl groups containing less 60 equivalent weight per 1 epoxide equivalent weight or with at
than about six carbon atoms. At least 0.7 equivalents of least 0.2 moles of aminosilane per epoxide equivalent
amine or 0.2 moles of aminosilane per equivalent of epoxy weight. If the amount of amine hardener added provides less
may be present in the hardener component. than 0.7 amine equivalent weight per epoxide equivalent
Preferred aminosilanes are difunctional silanes including weight, the coating and flooring composition produced will
aminopropyltrimethoxysilane and aminopropyltriethoxysi- 65 exhibit a slow cure time and have inferior weatherability and
lane. A particularly preferred aminosilane for coating com chemical resistance. If the amount of amine hardener added
positions of the present invention is Union Carbide A1100. provides greater than 1.2 amine equivalent weight per
 5,618,860
11 12
epoxide equivalent weight, the coating and flooring compo gates includes those previously described for the first
sition produced will exhibit surface blushing or greasiness. embodiment. A preferred flooring composition comprises in
With respect to the pigment or aggregate component, the the range of from 50 to 90 percent by weight aggregate
present invention embraces two principal embodiments that material. If the flooring composition comprises less than 50
are dependant on whether the composition is used as a percent by weight aggregate the offsetting raw material cost
coating or a flooring.
In the first embodiment, the modified epoxies of the will be too high and the flooring composition produced will
present invention are formulated for application with con exhibit poor compressive strength. If the flooring composi
ventional air, airless, air-assisted airless and electrostatic tion comprises greater than 90 percent by weight aggregate
spray equipment, brush or roller and are intended for use as 10 the flooring composition produced will be too viscous to
protective coatings for steel, galvanizing, aluminum, con permit application. A particularly preferred flooring compo
crete and other substrates at dry film thicknesses in the range sition comprises approximately 70 percent by weight aggre
of from 25 micrometers to about two millimeters. Accord
ingly, the pigment or aggregate is a fine particle size gate material. -
material, preferably with at least 90 weight percent greater The coarse particle size pigment or aggregate component
than 325 mesh U. S. sieve size, and is selected from organic 15
can be mixed with the resin component to form a two
and inorganic color pigments which may include titanium package system or packaged as a separate, third component
dioxide, carbon black, lampblack, zinc oxide, natural and or any combination thereof. The modified epoxy flooring
synthetic red, yellow, brown and black iron oxides, toluidine materials of the present invention are typically applied at
and benzidine yellow, phthalocyanine blue and green, and
carbazole violet, and extender pigments including ground 20 0.06 to 0.50 inches (1.5 to 13 millimeters) in thickness using
and crystalline silica, barium sulfate, magnesium silicate, roller, trowel and screed application methods.
calcium silicate, mica, micaceous iron oxide, calcium car Water is an important ingredient of the present invention
bonate, Zinc powder, aluminum and aluminum silicate, and should be present in an amount sufficient to bring about
gypsum, feldspar and the like. both the hydrolysis of the organooxysilane and/or the pol
A preferred coating composition comprises up to 50 25 ysiloxane and the subsequent condensation of the silanols.
percent by weight fine particle size aggregate. If a clear The sources of water are mainly atmospheric humidity and
coating composition is desired the coating composition may adsorbed moisture on the pigment or aggregate material.
be prepared without the pigment or aggregate component. Additional water may be added to accelerate cure depending
Clear coating compositions may be used as decorative finish
coat or as a sealing coat in flooring compositions. If the 30 on ambient conditions, such as the use of the coating and
coating composition comprises less than about ten percent flooring composition in arid environments. A preferred
by weight fine particle size aggregate the raw material cost coating and flooring composition comprises up to a stoichio
is generally too high and the coating composition produced metric amount of water to facilitate hydrolysis. Coating and
exhibits poor hiding power, i.e., it may not cover in one coat. flooring compositions prepared without added water may
If the coating composition comprises greater than 50 percent 35 not contain the amount of moisture needed for the hydrolysis
by weight fine particle size aggregate the coating composi and condensation reactions, and may therefore produce a
tion produced is too viscous for application. A particularly coating and flooring composition having an insufficient
preferred coating composition comprises approximately 20 degree of ultraviolet, corrosion and chemical resistance.
percent by weight fine particle size aggregate. Coating and flooring compositions comprising greater than
The pigments or aggregates are typically added to the
epoxy resin portion of the resin component and dispersed about two percent by weight water tend to hydrolyze and
with a Cowles mixer to at least 3 Hegman fineness of grind polymerize to form an undesirable gel before application. A
or alternatively ball milled or sand milled to the same particularly preferred coating and flooring composition
fineness of grind before addition of polysiloxane and orga comprises approximately one percent by weight water.
nooxysilane components. Selection of a fine particle size 45 If desired, water may be added to either the epoxide resin
pigment or aggregate and dispersion or milling to about 3 or polyamine hardener. Other sources of water may include
Hegman grind allows atomization of mixed resin and cure trace amounts present in the epoxide resin, polyamine hard
components with conventional air, air-assisted airless, air ener, thinning solvent, or other ingredients. Water may also
less and electrostatic spray equipment and provides a be incorporated by using kerimines or alcohol-solvent-water
smooth, uniform surface appearance after application. 50
mixtures as described in U. S. Pat. No. 4,250,074 herein
In the other embodiment of the present invention, the incorporated by reference. Regardless of its source, the total
modified epoxies are formulated as flooring materials or
surfacers and the pigment or aggregate comprise a mixture amount of water contained in a particularly preferred coating
of coarse and fine particle sizes. At least from about 85 and flooring composition should be the stoichiometric
percent to about 95 percent of the pigment or aggregate 55 amount needed to facilitate the hydrolysis reaction. Water
component has between 10 and 200 mesh U. S. sieve size exceeding the stoichiometric amount is undesirable since
(coarse) and from about 5 to about 15 percent is greater than excess water acts to reduce the surface gloss of the coating
325 mesh U. S. sieve size (fine). A range or mixture of or flooring composition.
aggregate sizes is used to improve packing efficiency and Up to four percent by weight catalyst may be added to the
optimizes the amount of low cost aggregate used to produce 60 resin component or as an entirely separate component to
the composition. The fine sized aggregate particles can be speed drying and curing of the modified epoxy coating and
thought of as filling in the spatial voids between the coarse
sized aggregate. The integration of fine and coarse sized flooring materials of the present invention. Useful catalysts
aggregate helps to improve the compressive strength of the include metal driers well known in the paint industry e.g.
flooring material. 65 zinc, manganese, cobalt, iron, lead and tin, each in the form
Preferred coarse aggregates are aluminum oxide, garnet, of octoates, neodecanates and napthenates. Suitable cata
pumice and silica sand. Preferred fine particle size aggre lysts include organotin catalysts having the general formula
 5,618,860
13 14
up the hardener component, the amine moiety of the ami
nosilane undergoes the epoxy-amine addition reaction and
the silane moiety of the aminosilane undergoes hydrolytic
5 polycondensation. In their cured form, the modified epoxy
coating and flooring materials of the present invention exist
where Rs and R are selected from a group consisting of as linear epoxy-modified polysiloxane which have substan
alkyl, aryl, and alkoxy groups having up to eleven carbon
atoms, and R, and Rs are selected from the same groups as tial advantages over conventional epoxy systems.
Rs and R. or from a group consisting of inorganic atoms 10 In a preferred coating composition, the non-aromatic
such as halogens, sulphur or oxygen. Dibutyl tin dilaurate, epoxy rein reacts with the difunctional aminosilane to form
dibutyl tin diacetate, organotitanates, sodium acetate, and a linear epoxy polymer that combines with the polysiloxane
aliphatic secondary or tertiary polyamines including propy
lamine, ethylamino ethanol, triethanolamine, triethylamine, to form an epoxy-modified polysiloxane coating via insutu
and methyl diethanoi amine may be used alone or in formation of a linear cycloaliphatic/aliphatic epoxide poly
combination to accelerate hydrolytic polycondensation of 15 mer with pendant alkoxy silane groups.
polysiloxane and silane. A preferred catalyst is dibutyl tin The isolated reaction of epoxide resin and polyamine, to
dilaurate.
Modified epoxy coatings of the present invention are form cured epoxy is believed to be as follows:
generally low in viscosity and may be spray applied without
addition of solvent. However, organic solvents may be 20
added to improve atomization and application with electro
static spray equipment or to improve flow and leveling and
appearance when applied by brush, roller, or standard air and
airless spray equipment. Exemplary solvents include esters,
ethers, alcohols, ketones, glycols and the like. The maxi 25
mum amount of solvent added to the coating or flooring The secondary amine hydrogens may also react as follows:
composition of the present invention is limited by govern
ment regulation under the Clean Air Act to approximately
420 grams solvent per liter of the coating or flooring
composition. 30
The epoxy polysiloxane coating and flooring composition
of the present invention may also contain rheological modi
fiers, plasticizers, antifoam agents, thixotropic agents, pig
ment wetting agents, bituminous and asphaltic extenders, OH
antisettling agents, diluents, UV light stabilizers, air release 35
agents and dispersing aids. A preferred coating and flooring Hydrolyric polycondensation reactions of organooxysi
composition may comprise up to about ten percent by
weight such modifiers and agents. lanes and polysiloxanes of the present invention are believed
The epoxy polysiloxane coating composition of the to occur in a stepwise fashion. The first reaction is hydrolysis
present invention is supplied as a two package system in 40 of organooxysilane e.g., trialkoxysilane or methoxy func
moisture proof containers. One package contains the tional polysiloxane, in the presence of water and catalyst to
epoxide resin, polysiloxane, organooxysilane and pigment form the corresponding silanols with liberation of alcohol as
or aggregate component, additives and solvent if desired.
The second package contains polyamine and/or aminosilane illustrated in Reaction 1.
and optionally catalysts or accelerating agents. 45
Reaction 1
The epoxy polysiloxane flooring or surfacer composition
of the present invention is typically supplied as three pack Hydrolysis of Organooxysilane i.e., Trialkoxysilane
age systems in moisture proof containers. The first package 3H2O
contains epoxide resin, polysiloxane, organooxysilane, color R-Si-(OX), A SeRSi(OH)3 +3XOH
pigments and additives. The second package contains 50 and/or
polyamine and/or aminosilane hardeners and catalysts if
desired. The remaining package is a coarse or mixture of Hyrdolysis of Alkoxy Functional Polysiloxane
coarse and fine particle size pigments or aggregates.
The epoxy polysiloxane coating and flooring composition R R R
of the present invention can be applied in ambient tempera 55
tures in the range of from -6°C. to 50°C. At temperatures ch-i-o-i-o--ch is
below -18°C. cure is severely retarded. However, the coat bx bx bx
ing and flooring composition of the present invention may R R R
be applied under bake or cure temperatures up to 150°C. to
200°C. 60
While not wishing to be bound by any particular theory, CH-i-o-i-o-Si-Chi 3XOH
OH OH OH
it is believed that the curing of the modified epoxy coating
and flooring materials of the present invention involves the The second reaction involves the condensation of the
reaction of an epoxide resin with polyamine to form a cured
epoxy polymer, and hydrolyric polycondensation of polysi 65 silanols produced by the hydrolysis of organooxysilane and
loxane and organooxysilane to produce alcohol and a pol polysiloxane i.e. trialkoxysilane and alkoxy functional pol
ysiloxane polymer. When an aminosilane is utilized to make ysiloxane, to form polysiloxane and water
 5,618,860
15 16
Reaction 2
The coating composition prepared by combining a difunc
Silanol Condensation tional aminosilane with a non-aromatic epoxy resin dis
places improved resistance to caustic, is weatherable, allows
infinate recoatability, provides abrasion resistance better
than a polyurethane (which is completely unpredictable
OH OH
because siloxane polymers and epoxy polymers have terrible
abrasion resistance).
The coating and flooring compositions of the present
Both reaction rates are strongly pH dependent, but under invention are capable of achieving complete cure at an
optimum conditions hydrolysis and condensation begin to 10
ambient temperature range of from -6° C. to 50° C. How
occur within minutes. The same factors which accelerate ever, some applications of the coating or flooring composi
hydrolysis of alkoxysilanes and condensation of silanols tion of the present invention may achieve complete cure
also accelerate condensation of silanol and their alkoxysi during a baking process at temperatures up to 150° C. to
lane and methoxy functional polysiloxane precursors. The 200° C.
overall pathway for the hydrolysis and full condensation of 15 The coating and flooring compositions of the present
organooxysilane and polysiloxane is complicated. Presented invention exhibits an unexpected and surprising improve
in FIG. 1 is a model for trialkoxysilane hydrolysis and ment in chemical corrosion and weathering resistance as
condensation reproduced from the Hills Corporation Silicon well as high tensile and compressive strength and excellent
Compounds Register and Review. impact and abrasion resistance.
F.G. 1

HYDROLYSIS - G C
O
R R N
Ro-5-OR ->RO-Si-OR -G Ro-5-oh -Ge. Ho-5-oh ED
OR OH OH OH N
\ V V S
V V V A
\ V V T
\ \ R V R I
O
Ro-5-os= -Ge. Ro-5-os = -Ge. Ho-5-os = N
OR OH OH
\ V
V V
V V
V V
R
so-s-os=
OR
Ho-5-os
OSE
=
\
\
V
\
S so-5-os. E
OSis

The silanols generated from hydrolysis of alkoxysilane These and other features of the present invention will
may also condense with hydroxyl groups available on the 55 become more apparent upon consideration of the following
surface of siliceous pigments or aggregates such as ground examples. Refer to Table 2 for a description of the ingredi
glass, quartz and silica. The same silanols may also con ents used in Examples 1 through 9. In each example, the
dense with the hydroxyl groups formed from reaction of ingredients used are combined in the proportions described
epoxide resin and polyamine. by weight in grams.
Ultimately, the chemical and physical properties of the to
epoxy polysiloxane coating and flooring materials of the TABLE 2
present invention are affected by judicious choice of epoxy Ingredient Description
resin, organooxysilane, polysiloxane, polyamine or aminosi
lane hardener and pigment or aggregate components as well Epon 828 Shell epoxy resin. Eq. Wit. = 190
as the relative rates of reaction of epoxy resin with hardener 65 Epon DPL862 Shell epoxy resin. Eq. Wt. = 165
and hydrolyric polycondensation of organooxysilane and Eponex 1513 Shell epoxy resin. Eq. Wit. = 230
Epalloy 8250 CVC epoxy resin. Eq. Wit. = 170
polysiloxane.
 5,618,860
17 18
mixture was stirred until uniform. The resin blend had a
TABLE 2-continued Brookfield viscosity of approximately 3,800 cF at 70° F.
Ingredient Description (20°C) and a calculated equivalent weight of 265 grams per
equivalent.
Epodil 757 Pacific Anchor cyclohexanedimethanol
diglycidyl ether
Aroflint 607 Reichold epoxide resin EXAMPLE 3
A-163 Carbide methyl trimethoxysilane
DC-3074 Dow Corning methoxy functional The same ingredients and procedure used to prepare the
polysiloxane resin and pigment blend of Example 1 was used, except that
A-1100 Carbide aminopropyl trimethoxysilane O 356 grams of Aroflint 607 (epoxide resin) were used instead
Y-9632 Carbide proprietary aminosilane of 385 grams of Eponex 1513 (epoxide resin). The resin
Z6020 Dow Corning aminoethyl aminopropyl
trimethoxy silane blend had a Brookfield viscosity of approximately 6,800 cp
ED-117 Wacker proprietary aminosilane at 70° F (20° C) and a calculated equivalent weight of 338
Euredur 3265
Ancamine 1942
Schering Berlin polyamine Eq. Wt. = 400
Pacific Anchor polyamine Eq. Wit. = 70
grams per equivalent.
DCH-99% Dupont diaminocyclohexane 15
Araldite R972 Ciba Geigy methylene bis dianiline Eq. COMPARISON EXAMPLE 4
Wit. = 48
Nuosperse 657 Pigment wetting agent A resin and pigment blend was prepared by combining
Tioxide RTC 60 Titanium dioxide
F-75 40 mesh silica sand 711 grams of Epon 828 (epoxide resin), 5 grams of
Crystal Silica #70 70 mesh silica sand 20 Nuosperse 657 (pigment wetting agent), 5 grams of BYK
Silicosil 325 U.S. Silica silica flour 080 (antifoaming agent), 10 grams of Dislon 6500 (thixo
Dislon 6500 King Industries thixotrope tropic agent) and 338 grams of Tioxide RTC 60 (titanium
BYK 080 BYK-Chennie defoamer
dioxide). The ingredients were added to a 1 quart can and
dispersed to less than 5 Hegman fineness of grind using an
air-motor powered Cowles dissolver. The mixture was
EXAMPLES 1 THROUGH 4 thinned with 100 grams of xylene to reduce viscosity and
then mixed until uniform. The resin blend had a Brookfield
Examples 1 through 4 describe the preparation of the resin viscosity of approximately 12,000 cP at 70° F (20° C) and
component and the combination of the pigment or aggregate the calculated equivalent weight was 313 grams per equiva
material of the present invention as used for coating pur 30 lent.
poses. In each example, the types and proportions of ingre
dients used to make up the resin and pigment blend are Three hundred grams of the resin blend of Example 1 was
slightly varied. A portion of each resin and pigment blend as mixed with 48 grams of Union Carbide A-1100 (aminopro
prepared in each example is then combined with a various pyl trimethoxysilane) and 20 grams of butyl acetate (organic
hardener components and solvents in different proportions solvent). The mixture was then spray applied to sandblasted
as shown in Table 3. Each resulting coating composition was 35 steel test panels using a DeVilbiss air-atomizing spray gun.
tested for cure time, weathering resistance, corrosion resis The epoxy polysiloxane coating dried to touch in less than
tance and chemical resistance as shown in Table 3. one hour and was dry through in about eight hours. The
coating composition displayed initial 60 gloss of 90.
EXAMPLE 1. 40
The resin blends of Examples 1, 2 and 3 and Comparison
Example 4 were mixed with the hardeners and solvents
A resin and pigment blend was prepared by combining shown in Table 3 and applied to test panels in a similar
385 grams of Eponex 1513 (epoxide resin), 5 grams of C.
Nuosperse 657 (pigment wetting agent), 5 grams of BYK The epoxy polysiloxane coating composition prepared
080 (antifoam agent), 10 grams of Dislon 6500 (thixotropic according to Table 3 were tested for curing time, weathering
agent) and 338 grams of Tioxide RTC60 (titanium dioxide). 45
resistance, corrosion resistance and chemical resistance
The ingredients were added to a one quart can and dispersed according to the following ASTM and industry test methods:
to 5 Hegman fineness of grind using an air-motor powered 1. ASTM G53, sometimes called QUV accelerated weath
Cowles dissolver. This required about 20 minutes, after ering, is an accelerated test intended to simulate the
which time 25 grams A-163 (trimethoxysilane) and 432 deterioration of coatings caused by sunlight and water
grams DC-3074 (polysiloxane) were added and the com 50
as rain or dew. Test panels are exposed to alternating
bined mixture was then stirred until uniform. The resinblend ultraviolet light and condensing humidity cycles. Deg
had a Brookfield viscosity of approximately 10,000 cPat 70° radation is measured by loss of gloss or rusting and
F. (20° C.) and a calculated equivalent weight of 315 grams blistering of the coating.
per equivalent.
2. ASTM B117 measures the corrosion resistance of
EXAMPLE 2 coated panels exposed to salt spray (fog) under pre
scribed conditions. Panels are checked periodically and
A resin and pigment blend was prepared by combining rated for blistering and rusting according to ASTM
390 grams of Epodil 757 (epoxide resin), 5 grams of D1654. The rating test method uses a 1 to 10 scale with
Nuosperise 657 (pigment wetting agent), 5 grams of BYK 10 indicating no change.
080 (antifoam agent), 10 grams of Dislon 6500 (thixotropic 3. Chemical Resistance, Union Carbide Method C117,
agent) and 338grams of Tioxide RTC 60 (titanium dioxide). measures the resistance of coatings to ten different
The ingredients were added to a one quart can and dispersed reagents. One milliliter of each reagent is placed on the
to 5 Hegman fineness of grind using an air-motor powered test coating and covered with a watch glass. After 24
Cowles dissolver. This required about 20 minutes, after 65 hours, the reagents are removed and any change is rated
which 10 grams A-163 (trimethyoxysilane) and 432 grams on a scale of 1 to 10 with 10 indicating no change, 8
DC-3074 (polysiloxane) were added and the combined indicating some change, 6 indicating major change, 4
 5,618,860
19 20
indicating partial failure and 2 indicating complete 1. ASTM G14 determines the energy required to rupture
failure. a surfacer or flooring system and is a measure of its
Gloss retention in QUV accelerated weathering, salt fog ability to withstand mechanical damage in service.
testing and chemical spot tests clearly show that epoxy 2. ASTM C-307 Tensile Strength, ASTM C-579 Com
polysiloxane coatings compositions of the present invention pressive Strength and ASTM C-580 Flexural Strength
have improved chemical, corrosion and weathering resis are tests for measuring degree of cure, load bearing
tance compared to conventional epoxy coatings composi capability and maximum stress at the moment of crack
tions. ing or breaking for chemically resistant mortars, grouts
and monolithic surfacers.
TABLE 3 10
TABLE 4
COATING COMPOSITION
FLOORING COMPOSITION
Weight (grams)
Weight (grams)
Example 1 300 300 300 300
15
Example 2 - -- - - 300 - - Example 5 6 6A 7 8 9
Example 3 - - - - 300 -
Comparison - - - - - - 300 Epalloy 8250 81.0 - - - -
Example 4 Epon 828 - 81.0 81.0 - 100 100
butyl acetate 20 20 20 20 15 20 25 Epon DPL862 - - 81.0 --
A100 48.3 - - 57.9 - - DC3074 15.0 5.0 15.0 15.0 -
ED-17 - 54.9 - - --- - w 20 A-163 4.0 40 4.0 4.0 - ---
Y-9632 --- - 48.0 - - 45.0 -- Z6O20 27.0 23.0 23.0 - -
DCH-99% - -- - 15.0 - --- - Euredur 3265 -- -- --- --
Versamid 25 w- - -- --- - 86.3 Ancamine 1942 - - 24.0 25.8
Test Results Araldite R972 an - - - - 21.3

BYK 080 20 2.0 2.0 2.0 2.0 2.0

Dry film 6 6 6 6 6 6 6 25 F-75 Sand 3360 336.0 336.0 336.0 336.0 336.0
thickness (mm) Crystal Silica #70 840 84.0 84.0 84.0 840 840
Dry to touch 1 1 12 15 1.5 1 1.5 Silicosil 325 30.0 30.0 30.0 30.0 30.0 30.0
(hours) Mechanical Test Results
Dry through (hours) 8 6 10 16 16 12 20
QUV Accelerated Direct Impact Pass - - Pass Fail Fail
Weathering 30 200 in lbs
Compressive 18,540 - - - 11,200 7,000
60° gloss -initial 90 91 90 86 75 22 65 Strength (psi)
1 day w- 91 91 65 -- --- 3 Tensile 3,400 r - 2,900 2,300
7 days 52 90 66 48 58 13 I Strength (psi)
21 days - 75 36 - --- ---- --- Flexural 5,500 mer - - 5,300 3,400
Salt Fog - 35
Strength (psi)
(1000 hours) Chemical Resistance - 24 hour Spot Tests
blistering 10 10 - - - - 10 NaOH (50%) 10 10 10 10 10 10
rusting 10 10 - - - - 8 HCl (Conc.) 10 10 6 10 6 8
Chemical Resistance H2SO (Conc.) 10 10 6 0 8 8
phenol 10 8 4. 8 4 8
NaOH (50%) 10 O - - - - 10 40 HPO (Conc.) 10 10 4 10 8 10
HCl (conc.) 10 10 - - - --- 8 acetOne 10 10 10 10 8 10
HSO(conc.) 10 10 - - - - 4. NHOH (Conc.) O 10 10 10 10 10
phenol 8 8 - - - - 4. ethanol 10 10 10 10 10 10
HPO,(conc.) O 10 --- - - - 6 acetic Acid 10 8 4 10 6 10
NHOH 10 O - - -- -- 10 cene 10 O 10 10 10 10
ethanol 10 10 --- - -- 10 45
acetic acid (conc.) 8 8 - - - 4
Clele 10 10 - - - 10 Example 6A is the same as Example 6 except that the
acetone 10 10 - - - - 10 epoxy resin was dried over 4A molecular sieves for 24 hours
and the pigment/aggregate blend was heated for 48 hours at
50
110° C. and allowed to cool overnight in a desiccator at 20°
EXAMPLES 5THROUGH 9 C. and 0% humidity before use. The dried epoxy resin,
polysiloxane, organooxysilane, defoamer, aminosilane and
Examples 5 through 9 describe the preparation of the dried pigment/aggregate blend were mixed for two minutes
epoxy polysiloxane composition of the present invention as using a Jiffy mixer and troweled onto a steel panel. The
used for flooring or surfacer purposes. The flooring compo coated panel was then placed in a desiccator at 20° C. and
sitions are prepared using the ingredients and in the propor 55 0% relative humidity and allowed to cure. After 36 hours,
tion in grams as shown in Table 4. Each flooring composi Example 6A was tacky compared to Example 6 which was
tion was prepared by adding the ingredients to a 1 quart can dry hard. After 7 days at 20° C. and 0% RH, the chemical
and mixing with a Jiffy mixer until uniform. Each flooring resistance of Example 6A was not as good as the chemical
composition was trowel applied at one eighth inch thickness resistance of Example 6. This illustrates the importance of
onto 4"x12"X/8" sandblasted steel panels for chemical spot 60 water in the epoxy polysiloxanes of the present invention.
tests and impact testing. Tensile, flexural and compressive The compressive strength specimens of Examples 5 and 6
strength specimens were cast into the corresponding ASTM and comparative Examples 8 and 9 were immersed for 7
molds. Testing was conducted after 7 days cure at 70° F (20° days in 50% sodium hydroxide, 98% sulfuric acid and
C.) and 50% relative humidity. Chemical resistance was methyl ethyl ketone. The specimens were removed from the
tested using by using Union Carbide Method C117. Direct 65 test fluid, rinsed with water and allowed to dry for 48 hours
impact, compressive, tensile and flexural strength was tested before measuring compressive strength. Examples 5 and 6
using the following ASTM test methods: retained greater than 92% of their initial compressive
 5,618,860
21 22
strength in all three test fluids. Comparative Example 8
retained greater than 90% of its initial compressive strength
in 50% sodium hydroxide, however, the specimens were where Y is H(HNR) and where a is one, R is a difunctional
completely degraded in 98% sulfuric acid or MEK. Com organic radical independently selected from the group con
parative Example 9 had percent retention of initial compres sisting of aryl, alkyl, dialkylaryl, alkoxyalkyl, and
sive strength of 92% and 80% in 50% sodium hydroxide and cycloalkyl radicals, and where X is limited to alkyl, hydrox
MEK, respectively, however the specimens in 98% sulfuric alkyl, alkoxyalkyl or hydroxyalkoxyalkyl groups containing
acid were completely degraded. less than about six carbon atoms.
Examples 5 through 9 clearly show that surfacer and 4. The coating composition as recited in claim 1 wherein
flooring compositions of the present invention have 10
the composition additionally comprises at least one metal
improved chemical resistance, higher compressive strength catalyst to facilitate cure at ambient temperature, wherein
and higher impact resistance compared to conventional the catalyst is selected from the group consisting of zinc,
epoxy resin based materials. manganese, cobalt, iron, lead, and tin each in the form of
Although the present invention has been described with octonates, neodecanates, or naphthanates.
considerable detail with reference to certain preferred varia 5. The coating composition as recited in claim 1 com
tions thereof, other variations are possible. Therefore, the 15 prising at least one additional ingredient selected from the
spirit and scope of the appended claims should not be limited group consisting of rheological modifiers, plasticizers, anti
to the preferred variations described herein. foam agents, thixotropic agents, pigment wetting agents,
What is claimed is: bituminous and asphaltic extenders, antisettling agents, dilu
1. An epoxy-polysiloxane polymer coating composition ents, UV light stabilizers, air release agents, dispersing aids,
20 and mixtures thereof.
prepared by combining: 6. The coating composition as recited in claim 1 wherein
water; the pigment or aggregate material comprises a fine particle
a polysiloxane having the formula size material selected from the group consisting of organic
and inorganic color pigments, at least 90 percent by weight
of the pigment being greater than 325 mesh U.S. sieve size.
R R2
25
7. The coating composition as recited in claim 6, com
si-o
R
prising up to 50 percent by weight aggregate material based
on the total weight of the composition.
2.
8. The coating composition as recited in claim 6, com
prising a weight ratio of polysiloxane to organooxysilane of
where each R is selected from the group consisting of the 30
approximately six to one, a weight ratio of polysiloxane to
hydroxy group and alkyl, aryl and alkoxy groups having up hardener of approximately two to one, and a weight ratio of
to six carbon atoms, each R is selected from the group hardener to organooxysilane of approximately three to one.
consisting of hydrogen and alkyl and aryl groups having up 9. An epoxy-polysiloxane polymer coating composition
to six carbon atoms and, wherein n is selected so that the prepared by combining:
molecular weight for the polysiloxane is in the range of from 35
a polysiloxane selected from the group consisting of
about 400 to 2,000; methoxy, ethoxy, and silanol functional polysiloxanes
an organooxysilane having the formula having a molecular weight in the range of from about
400 to 2,000;
pR. an organooxysilane having the formula
R-Si-OR.
OR4 pR.
where R is selected from the group consisting of aryl,
R-Si-OR.
OR
45
alkyl, and cycloalkyl groups containing up to six car
bonatoms and where R is independently selected from where R is selected from the group consisting of aryl,
the group consisting of alkyl, hydroxyalkyl, alkoxy alkyl, and cycloalkyl groups containing up to six car
alkyl and hydroxyalkoxyalkyl groups containing up to bonatoms and where R is independently selected from
six carbon atoms; 50 the group consisting of alkyl, hydroxyalkyl, alkoxy
a difunctional aminosilane hardener component that con alkyl and hydroxyalkoxyalkyl groups containing up to
denses through its silane groups with the polysiloxane; six carbon atoms;
a non-aromatic epoxide resin having more than one a difunctional aminosilane hardener component that con
1,2-epoxy groups per molecule with an epoxide equiva denses through its silane groups with the polysiloxane
lent weight in the range of from 100 to about 2,000 that 55 having the general formula
undergoes chain extension by reaction with the amine
groups in the polysiloxane to form a fully cured non
interpenetrating polymer network epoxy-polysiloxane
polymer; and where Y is H(HNR) and where a is one, R is a
a pigment or aggregate component. 60 difunctional organic radical independently selected
2. The coating composition as recited in claim 1 wherein from the group consisting of aryl, alkyl, dialkylaryl,
the non-aromatic epoxide resin is selected from the group of alkoxyalkyl, and cycloalkyl radicals, and where X is
cycloaliphatic epoxide resins consisting of hydrogenated limited to alkyl, hydroxalkyl, alkoxyalkyl or hydroxy
cyclohexane dimethanol and diglycidyl ethers of hydroge alkoxyalkyl groups containing less than about six car
nated Bisphenol A epoxide resins. 65 bon atoms;
3. The coating composition as recited in claim 1 wherein a non-aromatic epoxide resin that undergoes chain exten
the difunctional aminosilane has the general formula sion by reaction with the amine groups in the polysi
 5,618,860
23 24
loxane to form a fully cured epoxy-polysiloxane poly a non-aromatic epoxide resin;
Inler, a polysiloxane selected from the group consisting of
an organotin catalyst, and methoxy, ethoxy, and silanol functional polysilox
a sufficient amount of water to facilitate hydrolysis and anes having a molecular weight in the range of from
polycondensation to form a fully cured coating at 400 to 2,000;
ambient temperature. an organooxysilane having the formula
10. The coating composition as recited in claim 9 wherein pR.
the non-aromatic epoxide resin contains more than one
1,2-epoxy groups per molecule and has an epoxide equiva
lent weight in the range of from 100 to 2,000. 10 R-Si-OR.
OR4
11. The coating composition as recited in claim 9 further
comprising additives up to approximately ten percent by where R is selected from the group consisting of
weight of the total composition, wherein the additives are aryl, alkyl, and cycloalkyl groups containing up to
selected from the group consisting of flow modifiers, rheo 15
six carbon atoms and where R is independently
logical modifiers, plasticizers, antifoam agents, thixotropic selected from the group consisting of alkyl, hydroxy
agents, pigment wetting agents, bituminous and asphaltic alkyl, alkoxyalkyl and hydroxyalkoxyalkyl groups
extenders, antisettling agents, diluents, UV light stabilizers, containing up to six carbon atoms; and
air release agents, and dispersing aids. water, and
12. The coating composition as recited in claim 9 com 20
curing the resin component at a temperature below about
prising a fine particle size pigment or aggregate material 100 F. by adding to the resin component:
selected from the group consisting of organic and inorganic an aminosilane with two active hydrogens that con
color pigments, wherein the aggregate material comprises at denses through its silane groups with the polysilox
least 90 percent by weight aggregate having a U. S. mesh ane, whereby the non-aromatic epoxide resin under
size greater than 325 based on the total weight of the goes chain extension by reaction with the amine
aggregate material. 25 groups in the polysiloxane to form a fully cured
13. The coating composition as recited in claim 9 com epoxy-polysiloxane polymer; and
prising in the range of from 15 to 45 percent by weight an organotin catalyst.
non-aromatic epoxide resin, in the range of from 15 to 45 18. A method as recited in claim 17 wherein during the
percent by weight polysiloxane, in the range of from one to step of forming the resin component one or more ingredient
ten percent by weight organooxysilane, in the range of from 30 is added that is selected from the group consisting of
10 to 20 percent by weight hardener, and up to 50 percent by pigments, aggregates, flow modifiers, rheological modifiers,
weight aggregate based on the total weight of the compo plasticizers, antifoam agents, thixotropic agents, pigment
sition. wetting agents, bituminous and asphaltic extenders, antiset
14. The coating composition as recited in claim 13 tling agents, diluents, UV light stabilizers, air release agents
comprising approximately 25 percent by weight non-aro 35 and dispersing aids.
matic epoxide resin, 30 percent by weight polysiloxane, five 19. A non-interpenetrating polymer network epoxy-pol
percent by weight organooxysilane, 15 percent by weight ysiloxane polymer coating composition prepared by com
amine ingredient, 20 percent by weight aggregate, and the bining:
remaining percent by weight solvent and additives based on Water,
40
the total weight of the composition. a polysiloxane having the formula
15. The coating composition as recited in claim 10
wherein the non-aromatic epoxide resin is selected from the
group of cycloaliphatic epoxy resins consisting of hydroge
nated cyclohexane dimethanol and diglycidyl ethers of 45
hydrogenated Bisphenol A epoxide resins.
16. The coating composition as recited in claim 9 wherein
the polysiloxane has the formula where each R is selected from the group consisting of
the hydroxy group and alkyl, aryl and alkoxy groups
R
s -0
50 having up to six carbon atoms, each R2 is selected from
the group consisting of hydrogen and alkyl and aryl
R1 groups having up to six carbon atoms and, wherein n is
selected so that the molecular weight for the polysi
loxane is in the range of from about 400 to 2,000;
where each R is selected from the group consisting of the 55 a difunctional aminosilane hardener component that con
hydroxy group and alkyl, aryl and alkoxy groups having up denses through its silane groups with the polysiloxane
to six carbon atoms, each R is selected from the group and has the general formula
consisting of hydrogen and alkyl and aryl groups having up
to six carbon atoms and, wherein n is selected so that the
molecular weight for the polysiloxane is in the range from 60
about 400 to 2,000, and wherein the polysiloxane is present where Y is H(HNR) and where a is one, R is a
in the range of from 15 to 45 percent by weight of the total difunctional organic radical independently selected
composition. from the group consisting of aryl, alkyl, dialkylaryl,
17. A method for making a fully-cured thermosetting alkoxyalkyl, and cycloalkyl radicals, and where X is
epoxy-polysiloxane polymer coating composition compris 65 limited to alkyl, hydroxalkyl, alkoxyalkyl or hydroxy
ing the steps of: alkoxyalkyl groups containing less than about six car
forming a resin component by combining: bon atoms;
 5,618,860
2S 26
an organooxysilane having the formula alkyl and aryl groups having up to six carbon atoms
and, wherein n is selected so that the molecular
pR. weight for the polysiloxane is in the range of from
R-Si-OR, about 400 to 2,000;
OR4 5 a non-aromatic epoxide resin having more than one
1,2-epoxy groups per molecule with an epoxide
where R is selected from the group consisting of aryl, equivalent weight in the range of from 100 to about
alkyl, and cycloalkyl groups containing up to six car- 2,000;
bon atoms and where R is independently selected from 10 an organooxysilane having the formula
the group consisting of alkyl, hydroxyalkyl, alkoxy
alkyl and hydroxyalkoxyalkyl groups containing up to pR.
six carbon atoms; and R-Si-OR
non-aromatic epoxide resin having more than one
1,2-epoxy groups per molecule with an epoxide equiva- 15 OR4
lent weight in the range of from 100 to about 2,000 that
undergoes chain extension by reaction with the amine where R is selected from the group consisting of
groups in the polysiloxane to form a fully cured non aryl, alkyl, and cycloalkyl groups containing up to
interpenetrating polymer network epoxy-polysiloxane six carbon atoms and where R is independently
polymer. 20 selected from the group consisting of alkyl, hydroxy
20. A method for making a fully-cured thermosetting alkyl, alkoxyalkyl and hydroxyalkoxyalkyl groups
epoxy-polysiloxane polymer coating composition compris containing up to six carbon atoms; and
ing the steps of: Water,
forming a resin component by combining: curing the resin component at ambient temperature by
a polysiloxane having the formula 25
adding to the resin component:
an organotin catalyst, and
an aminosilane with two active hydrogens that con
R2-O si-o R2 denses through its silane groups with the polysilox
R1 30 ane, whereby the non-aromatic epoxide resin under
goes chain extension by reaction with the amine
where each R is selected from the group consisting groups in the polysiloxane to form a fully cured
of the hydroxy group and alkyl, aryl and alkoxy epoxy-polysiloxane polymer.
groups having up to six carbon atoms, each R is
selected from the group consisting of hydrogen and ck k >k k k
 UNITED STATES PATENT ANDTRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5,618,860 Page 1 of 2
DATED : April 8, 1997
INVENTOR(S) : Norman R. Mowrer; Raymond E. Foscante; J. Luis Rojas
It is certified that error appears in the above-indentified patent and that said Letters Patent is hereby
corrected as shown below:

On the title page, Abstract, line 7, change "an difunctional” to

-- a difunctional --.
Column 1, line 19, change "well know” to -- well known --.
Column 2, line 41, change "hydrolyric" to -- hydrolytic --.
Column 5, line 60, change "hydrolyric" to -- hydrolytic --.
Column 6, line 6, after "ingredients' insert -- and which --.
Column 7, line 4, change "Rhone-Poulene" to -- Rhone-Poulenc --.
Column 7, line 67, change "Rcomprise” to -- R comprise --.
Column 9, line 13, change "kerimines” to -ketimines --.
Column 9, line 18, replace "where one” with -- where a is one --.
Column 9, line 23, change "hydroxalkyl” to -- hydroxyalkyl --.
Column 9, line 47, change "HSls” to -- Hills --.
Column 9, line 59, change "hydroxalkyl" to -- hydroxyalkyl --.
Column 10, line 4, change "non-cross linked” to -- non-cross-linked --.
Column 12, line 20, change "inches” to -- inch --.
Column 12, line 49, change "kerimines' to -ketimines --.
Column 13, line 14, change "diethanoi" to -- diethanol --.
Column 13, line 65, change "hydrolyric" to -- hydrolytic --.
Column 14, line 11, replace "rein” with -- resin --.
Column 14, line 13, change "insutu' to -- in situ --.
Column 14, line 36, change "hydrolyric" to -- hydrolytic --.
Column 14, line 67, after "water” insert a period.
Column 15, line 66, change"Hydrolyric"to --Hydrolytic--.
Column 16, line 4, change "infimate” to -- infinite --.
Column 17, line 35, after "with" delete "a".
Column 19, line 65, after "tested" delete "using".
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5,618,860 Page 2 of 2
DATED : April 8, 1997
INVENTOR(S) : Norman R. Mowrer; Raymond E. Foscante; J. Luis Rojas
It is certified that error appears in the above-indentified patent and that said Letters Patent is hereby
corrected as shown below:

Column 22, lines 6,7, change "hydroxalkyl” to -- hydroxyalkyl

Column 22, line 63, change "hydroxalkyl” to -- hydroxyalkyl
Column 23, line 38, replace "amine ingredient” with -- hardener
Column 23, line 60, after "range” insert -- of--.
Column 24, lines 19,20, replace "a temperature below about 100°F.” with
-- ambient temperature --.
Column 24, line 65, change "hydroxalkyl” to -hydroxyalkyl

Signed and Sealed this

Twelfth Day of May, 1998

Aftest: (a (e?o
BRUCE LEHMAN

Attesting Officer Commissioner of Parents and Trade marks