US0094.

99712B2

(12) United States Patent (10) Patent No.: US 9,499,712 B2

Rokowski et al. (45) Date of Patent: Nov. 22, 2016
(54) NFRARED REFLECTIVE CLEAR COATING C09D 5/004; C09D 7/1208; C09D 183/04;
COMPOSITIONS FOR ELASTOMERC CO9D 119/02
WALL AND ROOF COATINGS See application file for complete search history.
(71) Applicants: Dow Global Technologies LLC, (56) References Cited
Midland, MI (US); Rohm and Haas
Company, Philadelphia, PA (US) U.S. PATENT DOCUMENTS

(72) Inventors: Joseph M. Rokowski, Barto, PA (US); 5,911,963 A * 6/1999 Krivak .................. CO1B33/193
423,335
Beata A. Kilos, Midland, MI (US); 7,768,602 B2 8, 2010 LaFleur et al.
Scott T. Matteucci, Midland, MI (US) 2009,0241450 A1 10/2009 Italiane et al.
2012/010O289 A1 4/2012 Egan et al.
(73) Assignees: Rohm and Haas Company, 2013,00897O6 A1 4/2013 Wen et al.
Philadelphia, PA (US); Dow Global
Technologies LLC. Midland, MI (US) FOREIGN PATENT DOCUMENTS

(*) Notice: Subject to any disclaimer, the term of this EP

EP
1735.387
242O868
A2
A3
12/2006
2, 2012
patent is extended or adjusted under 35 EP 258683.6 A1 5, 2013
U.S.C. 154(b) by 0 days. JP 2007 177143 A 7/2007
WO 2013065733 A1 5, 2013
(21) Appl. No.: 14/755,116
OTHER PUBLICATIONS
(22) Filed: Jun. 30, 2015
Kong et al., Advances in Elastomers I, 2013, Springer, p. 30.*
(65) Prior Publication Data
US 2016/OOO9938 A1 Jan. 14, 2016 * cited by examiner
Related U.S. Application Data Primary Examiner — Satya Sastri
(60) Provisional application No. 62/023.298, filed on Jul. (74) Attorney, Agent, or Firm — Andrew E. C. Merriam
11, 2014.
(57) ABSTRACT
(51) Int. C.
C09D 33/00 (2006.01) The present invention provides compositions for use as
CSK 7/26 (2006.01) elastomeric roof coatings having excellent infrared (IR)
C09D 5/33 (2006.01) reflectivity which comprise (i) one or more elastomeric
C09D 83/04 (2006.01) copolymer having a measured glass transition temperature
C09D 3.3/08 (2006.01) (measured Tg) of from -100 to 0° C. and one or more
C09D 5/00 (2006.01) mesoporous filler, preferably a mesoporous filler that is
C09D 7/12 (2006.01) Substantially free of organic groups or residues, the mes
(52) U.S. C. oporous filler chosen from mesoporous silica, mesoporous
CPC ............... C09D 133/00 (2013.01); C08K 7/26 aluminosilicates and mesoporous alumina, wherein the com
(2013.01); C09D 5/00 (2013.01); C09D 5/004 position has a pigment volume concentration (% PVC) of
(2013.01); C09D 7/1208 (2013.01); C09D from 0.1 to 15%. Such compositions provide aqueous or
133/08 (2013.01); C09D 183/04 (2013.01) Solvent borne clearcoats that can go over existing, already
(58) Field of Classification Search painted or colorcoated roof or wall substrates to preserve
CPC C08K 3/003; C08K 3/36: C08K 2003/2227; their finish or appearance.
C08K 7/24: CO8K7/26: C09D 133/00;
C09D 133/08: C09D 133/10; C09D 5700; 9 Claims, No Drawings
 US 9,499,712 B2
1. 2
NFRARED REFLECTIVE CLEAR COATING one or more elastomeric polymer having a measured Tg of
COMPOSITIONS FOR ELASTOMERC from -100 to 0°C., or, preferably, from -80 to -5°C., and
WALL AND ROOF COATINGS (b) from 0.1 to 25 wt.%, or, preferably, from 0.25 to 15 wt.
The present invention relates to coating compositions for %, or, more preferably, from 1 to 10 wt.% of one or more
roof and wall coatings having excellent infrared reflecting
5 mesoporous filler chosen from mesoporous silica, mesopo
properties comprising an elastomeric polymeric binder and rous aluminosilicates and mesoporous alumina, the mesopo
a mesoporous filler, as well as to methods of using the rous filler preferably being substantially free of organic
compositions and coatings made thereby. More particularly, groups or residues, wherein the composition has a pigment
it relates to aqueous acrylic emulsion polymer or polysilox 10
volume concentration (% PVC) of from 0.1 to 15% or,
ane elastomeric roof coatings, the compositions having a preferably, from 0.5 to 10%.
pigment volume concentration (% PVC) of from 0.1 to 15% 2. The composition of 1, above, wherein the one or more
or, preferably, from 1 to 10%, and to coated wall and roof polymer is chosen from aqueous acrylic emulsion copoly
Substrates made from Such coating compositions. mers, polysiloxanes, their mixtures and their combinations,
Elastomeric roof coatings have recently become popular preferably, two stage aqueous acrylic emulsion copolymers
as an inexpensive solution for extending the life of many 15
having a hard stage with a measured glass transition tem
kinds of roofs, including roofs from organic materials, such perature (measured Tg) of 0° C. to 70° C. and a soft stage
as built up roofs, modified bitumen roofs and membranes, with a measured Tg of from -60 to 0°C., preferably, -10°
sprayed polyurethane foam roofs, thermoplastic polyolefin C. to -40° C.
membranes, ethylene propylene diene rubber (EPDM) roofs, 3. The composition of 1 or 2, above, wherein the one or
as well as aluminum and metal roofs and even tile roofs. more mesoporous filler is mesoporous silica.
White elastomeric roof coatings have been useful in reduc 4. The composition of 3, above, wherein the mesoporous
ing energy costs as they reflect heat off of roofs, especially silica has an average pore size of from 1 to 100 nm, or,
in urban areas where the roofs before coating are often black preferably, from 2.5 nm to 50 nm, or, more preferably, from
or dark in color. Meanwhile, markets outside the US satisfy 3 to 40 nm, or, even more preferably, from 10 to 18 nm.
demand for deep tint and vivid colors which tend to fade or 25
6. The composition of 1, 2, 3, 4, or 5 above, which
bleach over time.
White or light colored pigmented exterior coatings are composition is a clearcoat composition.
applied to walls roofs, pavements, structures etc. to mini 7. The composition of 1, 2, 3, 4 or 5 above, further
mize heat gain by increasing Solar reflectivity primarily comprising an IR reflective pigment, preferably, a complex
through the use of conventional white opaque pigments such inorganic pigment, Such as a Cr—Fe pigment.
30
as titanium dioxide and Zinc oxide and colored opaque 8. In another aspect of the present invention, methods of
pigments such as iron oxide. Such white pigments reflect using the compositions of any of 1 to 7, above, comprise
visible light and infrared (IR) radiation, each of which applying the composition to a painted Substrate, a coated
account, respectively, for about 45% and 50% of total solar Substrate, a roofing shingle or a roofing Substrate and letting
reflectance. However, white or colored opaque coatings are it dry.
generally not used on steep slope shingled roofs because the 35
9. In yet another aspect of the present invention, coated
opaque color does not provide color variation associated roofing or wall Substrates comprise a roofing or wall Sub
with the intricate granule design and placement of asphalt strate coated by the method of 8, above.
shingles. In addition, high IR reflective coatings are limited Unless otherwise indicated, all temperature and pressure
to white or light pastel colors. Deeptone colors have rela units are room temperature and Standard pressure (1 atmo
tively high IR reflectance only when special IR reflective 40 sphere).
pigments are used. Such IR reflective pigments are limited All phrases comprising parentheses denote either or both
in color selection and cannot be blended to match color hue
without reducing the IR reflectance through interference of the included parenthetical matter and its absence. For
reflectance of each color in the coating. Accordingly, only a example, the phrase “(meth)acrylate' includes, in the alter
very limited range of finishes are available for IR reflective native, acrylate and methacrylate.
45
roof and wall coatings. As used herein, the term "ASTM refers to publications
Recently, U.S. patent publication 2013/0089706A1, to of ASTM International, West Conshohocken, Pa.
Wen et al. disclosed infrared reflective coatings comprising As used herein, the term “(meth)acrylate” means acrylate,
polymer and dispersed IR reflective clusters of titanium methacrylate, and mixtures thereof and the term “(meth)
dioxide (TiO) primary particles cemented with plus pre 50
acrylic used herein means acrylic, methacrylic, and mix
cipitated silica and/or alumina. The IR reflective clusters are tures thereof.
white pigments; see 0040. The coatings were colorcoat As used herein, the term "pigment volume concentration'
compositions from white paint bases that were applied to or % PVC refers to the quantity calculated by the following
metal coils and to roofing granules; however, each coating formula:
color had to be separately formulated; and no deep tint
compositions were enabled. 55
There clear remains a need for coatings that enable a (volume of pigment(s) +
finish having any color or hue to reflect radiation in the IR volume of extender(s) + volume of filler(s)
wavelength range. PVC (%) =
Total dry volume of coating
x 100
The present inventors have sought to solve the problem of
providing effective infrared (IR) reflective roof and wall 60
coating compositions that provide excellent infrared reflec As used herein, the term “polymer refers, in the alter
tance in coatings of any color on any Substrate. native, to a polymer made from one or more different
monomer, such as a copolymer, a terpolymer, a tetrapoly
STATEMENT OF THE INVENTION mer, a pentapolymer etc., and may be any of a random,
65 block, graft, sequential or gradient polymer.
1. In accordance with the present invention, compositions As used herein, the term “mesoporous filler” means refers
for infrared reflecting roof and wall coatings comprise (i) to a porous oxide material composed of an oxide of silicon,
 US 9,499,712 B2
3 4
aluminum, aluminosilicate, or combination thereof, wherein benzene, heating the mixture, adding under shear an oxide
the filler has an average pore size of from 2 to 100 nm or, precursor and heating and aging for 12 to 72 hours at a
preferably, 2.5 nm to 50 nm calculated using Nadsorption temperature of from 20 to 80° C., for example 35 to 60° C.
and a BET calculation based on the N adsorption/desorp to form the gel and, optionally, heating to a higher tempera
tion isotherm. Such methods are disclosed in the article ture (e.g., from 35 to 140°C., or, preferably, 60 to 110° C.)
"Recommendations for the Characterization of Porous Sol with or without a pore shaping agent for 11 to 36 hours out
ids. J. Rouquerol et al.; Pure & Appl. Chem. Vol. 66, No. of the total aging time (12 to 72 hrs.) to make the gel, and
8; PP 1739-1758; 1994. then filtering and washing the precipitate in water and
As used herein, the term "solids' or “total solids' means ethanol, optionally followed by calcining the product. Such
for an aqueous composition all parts of the aqueous com 10 methods are disclosed in detail in U.S. Pat. No. 6,592,764
positions of the present invention except for water and B1 and U.S. Publication No. 2009/0047329, both to Stucky.
volatiles or VOCs that would evaporate under conditions of Suitable oxide precursors may include, for example, metal
ambient or outdoor application temperature and pressure alkoxides, e.g., silicon alkoxides, like tetraethylorthosilicate
(the “use conditions'). (TEOS), tetramethylorthosilicate (TMOS) and aluminum
As used herein, the term “polymer solids' refers to the 15 alkoxides, like aluminum isopropoxide; silicates or alumi
polymerized monomers, chain transfer agents and non nates such as Sodium silicate, ammonium silicate and
Volatile Surfactants in any emulsion (co)polymer. Sodium aluminate; and silicon or metal halides, e.g., silicon
As used herein, the term “measured glass transition tem chloride (SiCl). Preferably, oxide precursors are inorganic
perature' or “measured Tg refers to the glass transition and include silicates and/or aluminates, such as sodium
temperature of a material as determined by Differential aluminate. Where the mesoporous filler is to include a
Scanning calorimetry (DSC) scanning from -90° C. to 150° combination of oxides, the ratios of the oxide precursors can
C. at a rate of 20° C./min on a DSCQ2000 manufactured by be varied to provide a desired ratio of oxides in the final
TA Instrument, New Castle, Del. The Tg is the inflection product.
point of the curve of heat flow vs. temperature or the Suitable amounts of the oxide precursors may range from
maximum value on the plot of its derivative. 25 about 1 to 25 wt.%, based on the total weight of the total
As used herein, the term “substantially free of organic reaction medium, including water and solvent. The weight
groups or residues' means that a given material has 1000 ratio of total (one or more) oxide precursors to total (one or
ppm or less, or, preferably, 500 ppm or less of Such organic more) structure directing agents ranges from 4:5 to 20:1, or,
groups or residues as determined by FTIR (where an Si preferably, 1:1 to 5:1.
O—C bond is at 1032 cm-1) or NMR as is known in the art. 30 Suitable structure directing agents for use in sol-gel
As used herein, unless otherwise specified, the term mesoporous filler production of the present invention can be
“weight average particle size’ for any pigment, extender or selected from a variety of polymers, block co-polymers,
filler refers to a particle size measured by light scattering self-assembling polymers, nanoparticles, biologically active
using a BI-90 particle size analyzer (Brookhaven Instru agents, and the like, according to the desired geometry of the
ments Corp. Holtsville, N.Y.) and taking the weight average 35 final product. In one embodiment, the structure directing
of the particle size distribution. agents are amphiphilic polyoxyalkylenes and self-assem
As used herein, the term “weight average molecular bling block co-polymers such as the PluronicsTM P123TM 9
weight” or “MW' refers to the weight average molecular a triblock PEO-PPO-PEO polymer (5800 Da) or FI27TM
weight of a polymer as measured by aqueous gel permeation (BASF, Leverkusen, Del.).
chromatography (GPC) against a polyacrylic acid (PAA) 40 Suitable amounts of the structure directing agents range
standard of a copolymer that is hydrolyzed in KOH. from about 0.5 to 10 wt.%, based on the total weight of the
As used herein, the phrase “wt.%' stands for weight total reaction medium, including water and solvent.
percent. Suitable polymer Swelling agents are any which readily
The compositions of the present invention enable the dissolve the structure directing agents and form an emulsion
provision of a clear coating film having the ability to reflect 45 in water, for example, trimethylbenzene.
infrared radiation and lower the temperature of coated Suitable acids acting as catalysts may be inorganic acids,
Surfaces which remain visibly transparent, thereby revealing such as HCl or phosphoric acid, or carboxylic acids like
the color, shading and Surface contour of a shingle or other formic or acetic acids, or malic acid.
roofing, wall or pavement Substrate below the clear coating. Optionally, pore shaping agents can be used. Suitable pore
The coating compositions of the present invention form 50 shaping agents are fluoride salts, for example Sodium, potas
films with relatively high IR reflectivity and are universally sium, ammonium or tetraalkylammonium fluoride. Suitable
applicable to any colored roof or substrate. Further, the amounts of the pore shaping agents range from about 0.1 to
present invention enables high levels of IR reflectivity 2 wt.%, based on the total weight of the total reaction
without reformulation of each individual color coating that medium, including water and solvent.
would otherwise incorporate IR reflective color pigments. 55 The methods for making the mesoporous fillers of the
The compositions of the present invention enable coatings present invention result in mesoporous silica and/or alumina
having a level of IR reflectivity as measured by ASTM that are Substantially free of organic groups or residues. Such
C1549 (2002) ranging from 25% or more, or, preferably, as methyl or alkyl groups or hydrocarbon results. That the
40% or more, or, more preferably, 50% or more. mesoporous fillers of the present invention are substantially
The mesoporous filler of the present invention is a silica, 60 free of organic groups or residues can be observed by using
an alumina or an aluminosilicate. Such mesoporous fillers techniques such as NMR or FTIR in a manner that is readily
may be made by Sol-gel polymerization as is known in the known to those familiar with the art.
art. For example, mesoporous fillers are made in an oil in Where the oxide precursors of the present invention are
water emulsion by dissolving in an acidic (-pH3, prefer themselves organic, e.g., tetraethyl orthosilicate, a mesopo
ably s2, or, more preferably, s1) aqueous solution a struc 65 rous filler that is Substantially free of organic groups or
ture directing agent, Such as an amphiphilic nonionic block residues will result when the mesoporous filler is formed at
copolymer, adding a polymer Swelling agent, Such as trialkyl a pH of s2, or combinations thereof.
 US 9,499,712 B2
5 6
The coating compositions of the present invention have a monomers. Examples of Suitable acid monomers may
low % PVC to insure that they remain flexible in use. The include, for example, maleic acid or anhydride, phospho
mesoporous fillers may be present in the compositions of the alkyl (meth)acrylate, meth)acrylamidopropane Sulfonate
present invention in the amount of from 0.5 to 25 wt.%, or, and, preferably, methacrylic acid (MAA), acrylic acid (AA)
preferably, from 1 to 10 wt.%, based on the total solids of 5 and itaconic acid.
the composition. Higher loadings of the filler are possible in Preferably, to prevent weatherability or outdoor durability
compositions comprising softer and more flexible lower problems, the amount of vinyl aromatic monomers should
glass transition temperature polymers. range 19.5 wt.% or less or, preferably, 10 wt.% or less, or,
Preferably, the compositions of the present invention are more preferably, 5 wt.% or less, based on the total weight
clearcoat compositions wherein the elastomeric polymer and 10 of monomers used to make each of the emulsion copoly
the mesoporous filler have similar refractive indices in air CS.
which differ by less than 0.3, preferably, by less than 0.2, or, Preferably, to increase the mechanical properties made
more preferably, less than 0.15. from the aqueous elastomeric polymer compositions of the
Exceptionally high transparency in the coating or coating present invention, the emulsion copolymers comprise the
composition for use as a clearcoat is not necessary in the 15 copolymerized product of a (meth)acrylonitrile in the
present invention as some turbidity is acceptable. In the case amount of 11 wt.% or less or, preferably, 8 wt.% or less,
of emulsion copolymer compositions, turbidity is common based on the total weight of monomers used to make each of
in the wet polymer; however, emulsion copolymers formu the emulsion copolymers.
lated with solely the mesoporous filler of the present inven Adhesion promoter monomers such as hydrolysable
tion generally dry clear. silane functional (meth)acrylates, such as (meth)acryloy
In compositions other than clearcoats where the mesopo loxypropyl trialkoxy silanes, and ureido (meth)acrylates
rous silica and or alumina are combined with IR Reflective may be included in the soft vinyl or acrylic monomer
color pigments, the present invention enables the provision composition. Suitable amounts of Such adhesion promoter
of compositions for deeply colored or deep tint coatings monomers may range from 0 to 5 wt.%, based on the total
having high (>25%, or, preferably, >40%) IR reflectivity. 25 weight of monomers used to make the emulsion copolymers,
Suitable IR reflective pigments include, for example, or, preferably, 0.1 to 4 wt.%.
complex inorganic pigments containing oxies of two or Elastomeric acrylic emulsion copolymers can be polym
more metals, such as Cr—Fe pigments. An example of a erized by emulsion polymerization techniques well known
suitable IR reflective color pigment includes, for example, in the art, e.g., by aqueous polymerization in the presence of
Cool ColorTM or EclipseTM IR reflective pigments from 30 an initiator and one or more Surfactant.
Ferro (Cleveland, Ohio) or Ferro Green 24-10204 (Ferro, Elastomeric acrylic emulsion copolymers useful in the
Cleveland, Ohio) or any pigment or colorant having a present invention are readily formed as is known in the art
refractive index in air of 1.7 or more that reflects light in the by methods for making emulsion copolymers from hydro
infrared wavelength regions of 0.7 to 2.5 microns. phobic monomers, which are mostly but not all soft acrylic
Acrylic emulsion copolymers suitable as the elastomeric 35 monomers (a) Suitable for use in the present invention. For
polymers of the present invention are well known in the art. example, U.S. Pat. No. 5,521.266, to Lau, discloses suitable
Such emulsion copolymers comprise the emulsion copoly polymerization processes suitable for forming emulsion
merization product of one or more soft vinyl or acrylic copolymers made from one or more hydrophobic monomer.
monomer, Such as butyl acrylate, ethylhexyl acrylate or For example, the hydrophobic monomer can be complexed
lauryl methacrylate, with from 0.1 to 5 wt.%, based on the 40 with a macromolecular organic compound having a hydro
weight of all monomers used to make the emulsion copo phobic cavity by mixing them to form a complexed mixture,
lymer, of at least one addition polymerizable carboxylic acid and charging the complexed mixture, along with any other
monomer, Such as methacrylic acid, and, as needed, with monomers to a reaction vessel. Alternatively, a macromo
harder vinyl or acrylic monomers such as styrene, acrylo lecular organic compound having a hydrophobic cavity may
nitrile and methyl methacrylate. As is known in the art, the 45 be added to the reaction vessel before, during or after the
monomer mixture is selected to give a desired calculated Tg. monomer mixture has been charged. Suitable macromolecu
Preferably, to improve weatherability in coatings com lar organic compounds having a hydrophobic cavity may
prising them, the emulsion copolymer of the present inven include, for example, cyclodextrin and cyclodextrin deriva
tion comprises the copolymerization product of a monomer tives; cyclic oligosaccharides having a hydrophobic cavity
mixture that contains no styrene or vinyl aromatic monomer. 50 Such as cycloinulohexose, cycloinuloheptose, and cycloinu
Suitable vinyl or acrylic monomers (a) for use in the soft loctose; calyxarenes; and cavitands. The ratio of Soft acrylic
monomer composition may include, for example, butyl monomer to the macromolecular organic compound having
acrylate, ethyl acrylate, methyl acrylate, ethylhexyl acrylate a hydrophobic cavity may range from 1:5 to 5000:1, pref
(EHA), octyl methacrylate, isooctyl methacrylate, decyl erably 1:1 to 1000:1.
methacrylate (n-DMA), isodecyl methacrylate (IDMA), lau 55 To improve blister resistance and adhesion, Suitable elas
ryl methacrylate (LMA), pentadecyl methacrylate, stearyl tomeric emulsion copolymers useful in the present invention
methacrylate (SMA), octyl acrylate, isooctyl acrylate, decyl have a weight average molecular weight of from 10,000 to
acrylate, isodecyl acrylate, lauryl acrylate (LA), the (C2 to 750,000, preferably, from 50,000 to 500,000. Such emulsion
Cs) alkyl methacrylates, cyclohexyl acrylate and cyclo copolymers may be made by conventional methods, such as,
hexyl methacrylate. 60 for example, including in the polymerization a wide variety
To improve stability in aqueous systems, the elastomeric of chain transfer agents. These include, for example, alkyl
emulsion polymers of the present invention include acid mercaptains, halogen compounds, and other well-known
functionality. Suitable ethylenically unsaturated acid func agents. A chain transfer agent such as, for example, n-do
tional monomers are included in the feed of the soft mono decylmercaptain may be used in amounts ranging from 0.1
mer composition and may include addition polymerizable 65 wt.%, based on the weight of total monomers used to make
carboxylic acids, salts thereof, anhydrides thereof, and phos the emulsion copolymer, to 2.0 wt.%, or preferably, 0.2 to
phorous containing or Sulfur containing acid functional 1.0 wt.%, or, more preferably, 0.25 to 0.8 wt.%. Preferably,
 US 9,499,712 B2
7 8
the chain transfer agent is hydrophobic, such as n-dodecyl Suitable hydrophilic dispersants may include, for
mercaptan (n-DDM or DDM) or any C to Cls mercaptan. example, copolymer dispersants like TamolTM 851 (Napoly
Suitable emulsion copolymers for use as elastomeric (MAA)) or 1124 (poly(AAco-hydroxypropyl acrylate)) dis
polymers may be made by gradual aqueous emulsion addi persants (Dow Chemical, Midland, Mich.), or RhodolineTM
tion polymerization in one or more stages, as is conventional 286N dispersants (Rhodia, Cranberry, N.J.), Disponil TM Fes
in the art. Single stage and multistage emulsion copolymers 77, a fatty alcohol polyglycol ether sulfate available from
are equally Suitable for making IR reflective coatings and (Cognis, Cincinnati, Ohio) polybasic acid salts, such as
films. Preferably, for the purpose of lowering tack in coat potassium tripolyphosphate (KTPP), polycarboxylic acid
ings made from clearcoat compositions or any other com salts, copolymer acid salts, alkali soluble resin Salts, phos
position having a % PVC of 20% or less, the elastomeric 10
pho ethyl methacrylate (PEM) polymer and copolymer
polymer of the present invention comprises two stage aque dispersants, mono or oligo-phosphorous or Sulfur containing
ous acrylic emulsion copolymers having a hard stage with a acid salts, which can be organic or inorganic, e.g., KTPP or
measured glass transition temperature (measured Tg) of 0°
C. to 70° C. and a soft stage with a measured Tg of from -60 Sulfonates. To avoid excessive water sensitivity, and pos
to 0°C., preferably, -10° C. to -40° C. 15 sible loss of adhesion, any dispersants should be used in
For multistage or two stage aqueous acrylic emulsion amounts of 2 wt.% or less, based on the total polymer solids
copolymers the overall measured Tg is within the range of in the compositions.
the inventive elastomeric polymer (-100 to 0° C.) if the The compositions of the present invention may addition
weighted average of the measured TgS for each of the ally comprise one or more of thickeners, such as hydroxy
respective polymer stages is within the inventive range; So, ethylcellulose (HEC) or modified versions thereof, UV
for example, a two-stage polymer comprising 50 wt.% of absorbers, Surfactants, coalescents, wetting agents, thicken
one stage having a measured Tg of -80° C. and 50 wt.% one ers, rheology modifiers, drying retarders, plasticizers, bio
stage having a measured Tg of 20°C., would be reported as cides, mildewicides, defoamers, colorants, and waxes.
having an overall measured Tg of -30° C. To insure enhanced weatherability, the compositions of
Suitable siloxane polymers useful as elastomeric poly 25 the present invention may preferably include one or more
mers in the present invention are well known in the art and UV absorber or light stabilizer, such as benzophenone
include polysiloxanes, such as polydimethylsiloxanes, and (BZP), or butylated hydroxytoluene (BHT) or hindered
copolymerization products thereof with hydrolysable silane amines in the total amount of from 0 to 1 wt.%, based on
functional acrylic monomers which can also be polymerized the total solids of the composition, preferably, 0.05 wt.% or
into acrylic emulsion copolymers to form hybrid polymers. 30
more or up to 0.5 wt.%.
Siloxane polymers are generally formulated as solvent borne Preferably, improved adhesion is observed in coatings
coatings in organic solvents, such as glycol alkyl ethers. The made from compositions comprising one or more hydroly
hybrid polymers may generally be formulated as emulsion sable silanes or alkoxysilanes, which preferably have two or
copolymers using Surfactants, such as nonionic Surfactants. three hydrolysable groups. Suitable amounts of epoxysilane,
A Suitable example of a siloxane polymer useful in the 35
present invention is Geniosil TM WP-1 or WP-2 (Wacker aminosilane, vinyl alkoxysilane are the same. Combinations
Chemie AG, Munchen, Del.). of the epoxysilanes and aminosilanes may be used.
To better enable effective let down of the elastomeric Suitable aminosilanes may comprises an amino-alkyl
polymer onto mesoporous fillers and IR reflective pigments, functional group and is hydrolysable, having, for example,
the compositions of the present invention preferably com 40 one or more alkoxy group or aryl(alkyl)oxy functional
prise one or more dispersant, e.g., a hydrophilic dispersant, group. Preferably, the amino silane has two or more amino
Such as a polyMAA or a polyacid salt, e.g., alkali(ne) metal functional groups and two or, more preferably, three hydro
salt, for example, polyMAA, its Nasalt. Any dispersant that lysable groups, i.e., tri-alkoxy.
can stabilize the pigments, and/or fillers and wet out Sub Examples of suitable aminosilanes include MomentiveTM
strate Surface in use may be used. Suitable dispersants 45 SilguestTMA-1120 (Momentive Performance Materials,
include both hydrophobic and hydrophilic dispersants, and Albany, N.Y.) or Dow-Corning Z-6020 (Dow Corning,
are, preferably, hydrophilic dispersants. Midland, Mich.), each of which are aminoethylaminopropyl
Hydrophilic dispersants contain the polymerization prod trimethoxysilanes. Other suitable silanes include, for
uct of less than 30 wt.%, preferably 20 wt.% or less of example, Dow Corning Z-6040, which is glycidoxypropy
monomers other than hydrophilic monomers like alkyl 50
trimethoxysilane, and Silduest WetlinkTM 78, (Momentive
(meth)acrylates, dienes or olefins, based on the total weight Performance Materials, Albany, N.Y.), a glycidoxypropyl
of monomers used to make the copolymer. More preferred methyl diethoxysilane.
hydrophilic Surfactants have a weight average molecular Silanes may be used in amounts ranging from 0.2 wt.%
weight of 5,000 or more, preferably 8,500 or more. Hydro or more, or up to 2.0 wt.%, preferably, 0.5 wt.% or more,
phobic dispersants include emulsion copolymer dispersants 55
or block copolymer dispersants comprising more than 20 wt. or, preferably 1.5 wt.% or less, or, more preferably, 0.7 wt.
%, based on the total weight of copolymerized monomers, of % or more, based on the total weight of emulsion copolymer
any block of polymer that would not form a water soluble Solids.
homopolymer (>50 g/L dissolves at room temp upon simple The aqueous compositions of the present invention may
mixing) at the weight average molecular weight of the 60 be prepared by mixing the elastomeric binder with conven
dispersant block in use. Thus, if a block of a monomer in a tional components in high speed dispersion equipment Such
block copolymer has a weight average molecular weight of as a Cowles disperser, or a Sigma mill for caulks and
1,000 in the dispersant, then to determine if the dispersant is sealants.
hydrophobic, a homopolymer having a weight average To formulate the aqueous compositions of the present
molecular weight of 1,000 of the same monomer used to 65 invention with a silane, the silane can be added with stirring,
make the block in the dispersant would be evaluated to see Such as overhead stirring, preferably before pigments or
if it is water soluble. fillers are added.
 US 9,499,712 B2
9 10
The Solids level of aqueous coating compositions of the at 1.0 and acceptable readings above 0.25. Where a given
present invention may range 40 wt.% or higher and up to 80 material is coated on a base film, Such as a polyester film, the
wt.%, preferably, 50 to 70 wt.%, based on the total weight Solar Reflectance of the base film is measured separately
of the compositions. before coating application and the measured reflectivity is
In another aspect, the present invention provides methods subtracted from the value measured for the coated base film.
of using the compositions of the present invention compris In the Examples that follow, the following chemical
ing applying the coating compositions of the present inven abbreviations are used: BA: Butyl acrylate; BZP: Benzo
tion to a Substrate, followed by drying, e.g., at ambient phenone: MMA: Methyl methacrylate: AA: Acrylic acid;
temperature and humidity or at elevated temperature and MAA: Methacrylic acid; EHA: Ethyl hexyl acrylate; IA:
ambient humidity. Drying can comprise, for example, ambi 10
Itaconic acid; UMA: Ethylene ureido ethyl methacrylate:
ent drying. n-DDM: n-dodecyl mercaptan.
The compositions of the present invention can be used on In the IR Reflectivity Examples in Tables 1 and 2, below,
any weatherable substrate, such as a roof or a wall, with and in the Solar Reflectance Examples in Table 3, below,
Suitable Substrates being asphaltic coatings, roofing felts, coating films of the indicated coating material were cast on
synthetic polymer membranes; modified bitumen mem 15
clear MylarTM polyester (DuPont, Wilmington, Del.) films
branes; foamed polyurethane, such as, spray polyurethane using a Gardner Block Multiple Clearance square applicator
foam; metals, such as aluminum; previously painted, (Paul N. Gardner Company Inc., Pompano Beach, Fla.) and
primed, undercoated, worn, or weathered Substrates. Such as dried to give coatings having the indicated film thickness of
metal roofs, weathered thermoplastic polyolefin (TPO), 625 to 700 microns (25-28 mils).
weathered poly(vinyl chloride) (PVC), weathered silicone The elastomeric polymer used in Examples 1 to 4, below
rubber and weathered EPDM rubber. Less preferred roofing was a two-stage aqueous acrylic emulsion copolymer
Substrates may include cementitious Substrates and previ (Acrylic Emulsion Copolymer 1) having a 55 wt.% solids
ously painted cementitious Substrates. content and 85 wt.% of a soft stage and 15 wt.% of a hard
The compositions are preferably used as topcoats or stage, an overall copolymerized acid monomer content of
topcoat maintenance coatings, especially if formulated with 25
2.36 wt.%, based on the total weight of monomers used to
UV absorbers or light stabilizers, or can be used as the make the copolymer, and an overall measured Tg of -35°C.
basecoat or maintenance basecoats in two coat Systems, e.g., The mesoporous silica used in the examples below has an
with a topcoat or mastic. average pore size of 13-14 nm and is substantially free of
EXAMPLES 30
organic groups.

The following Examples illustrate the advantages of the TABLE 1.

present invention. Unless otherwise indicated, all conditions IR Reflectivity Values for Acrylic Films
of temperature are room temperature (22-24°C.) and all film thickness of 625 to 700 microns (25-28 mills
units of pressure are 1 atmosphere. 35
Test Methods: IR
Example Reflectivity
The following test methods are used in the Examples.
Clarity: 1* Acrylic Emulsion Copolymer 1 4% (0.04)
The transparency of a given coating is measured by visual 2* Acrylic Emulsion Copolymer 1 (30 wt.%) + Ion 40% (0.4)
inspection of the coating film, with a Subjective 1-10 scale. 40 Exchange Resin (crosslinked vinyl copolymer bead)
(70 wt.%)
An acceptable clarity rating is 8 or more, or, preferably, 9 to 3 Acrylic Emulsion Copolymer 1 (30 wt.%) + mesoporous 70% (0.7)
10 (window glass clear). Haze: Coatings are visually silica (70 wt.%)
inspected for haze, with a subjective 1-10 scale, 10-best. *Comparative Example
Acceptable is 8 or higher.
IR Reflectivity: 45 As shown in Table 1, above, the inventive mesoporous
Measured in accordance with ASTM C1549 (2002), this silica provides coating compositions having greatly
is the reflected incident light from a given coating or film in enhanced IR Reflectivity.
the wavelength region 0.7 to 2.5 microns as measured by a
solar reflectometer (model no. SSR-ER, Devices and Ser TABLE 2
vices Co., Dallas, Tex.) calibrated according to manufactur 50
er's instructions. IR radiation is a fraction of both the IR Reflectivity of Various Materials at 10 wt.% loading in Acrylic
wavelength region of visible light and of Solar reflectance. Emulsion Copolymer (90 Wt. 90 acrylic emulsion copolymer 1
Range measured is from 0 to 1.0, with full reflectance at 1.0 IR Reflectivity
and acceptable readings of 0.25 or higher. Where a given 254 micron Film Clarity
material is coated on a base film, Such as a polyester film, the 55 Example Thickness 10 = best
IR Reflectivity of the base film is measured separately 1A* Ad Nano TM Zinc O.14 9
before coating application and the measured reflectivity is 2A* Zeelan Z-Light TM O.19 8-9
subtracted from the value measured for the coated base film. Spheres W-1000?
Solar Reflectance: 3A* Cabot Nanogel TM TLD O.28 7
2O1
Measured in accordance with ASTM C1549 (2002), this 60
4A* Expancel TM-461 DE O48 6
is the fraction of the incident solar energy which is reflected 2070
by a given substrate or film in the wavelength range of 0.30 5A* Degussa EXPTM: 3300 O.12 10
to 2.5 microns which includes some IR radiation some Silica flatting agent
6A* Potters 60P18 O.318 8 (grainy)
ultraviolet (UV) radiation. It is measured by a solar reflec Glass Bead
tometer (model no. SSR-ER, Devices and Services Co., 65 4 Mesoporous Silica 0.337 8 (Smooth)
Dallas, Tex.) calibrated according to manufacturers instruc
tions. Range measured is from 0 to 1.0, with full reflectance
 US 9,499,712 B2
11 12
TABLE 2-continued reflectance at low loadings and in a fairly thin film. Even at
low loadings with thicker films, the mesoporous filler of the
IR Reflectivity of Various Materials at 10 wt.% loading in Acrylic present invention provides excellent solar reflectance above
Emulsion Copolymer (90 wt.% acrylic emulsion copolymer 1 50%.
IR Reflectivity
254 micron Film Clarity We claim:
Example Thickness 10 = best
1. A composition useful in an infrared reflecting wall or
Zinc oxide (Evonik Industries AG, Essen DE; mfggiven particle size: 100-170 nm); roof coating comprising (i) one or more elastomeric polymer
*Ceramic (Alkali Alumino Silicate) microsphere (Zeelan Industries, 3M, St. Paul, MN,
mfg. particle size = 15-25 microns;
Hydrophobically treated amorphous silica (Cabot Corporation, Billerica, MA); 10 having a measured glass transition temperature (measured
Polymeric beads (CAS # 25214-39-5) isobutene gas filled (Akzo Nobel, Sundsvall, Tg) of from -100 to 0°C. and chosen from aqueous acrylic
Sweden);
Pyrogenic, polysiloxane surface modified silica, mfg. particle size = 9 microns (Evonik);
emulsion copolymers, polysiloxanes, and their combina
Fused glass, mfg. particle size = 16-20 microns (Potters Industries, Malvern, PA); tions, and (b) from 0.1 to 25 wt. '% of one or more
*Comparative Example. mesoporous filler chosen from mesoporous silica, mesopo
15 rous aluminosilicates and mesoporous alumina, wherein the
As shown in Tables 1 and 2, above, the mesoporous filler composition has a pigment volume concentration (% PVC)
of the present invention provides excellent IR reflectivity at of from 0.1 to 15%.
both lower and higher loadings. In addition, the mesoporous 2. The composition as claimed in claim 1, wherein the
filler of the present invention enables acceptable clarity in a elastomeric polymer has a measured Tg of from -80 to -5°
coating so that a user can retain the color or look of the C.
clearcoated Substrate. In comparison the Example 3A silica, 3. The composition as claimed in claim 1, wherein the one
which is mesoporous contains organic material, gives nearly or more mesoporous filler is mesoporous silica.
20% lower IR reflectivity and inferior coating clarity in 4. The composition as claimed in claim 3, wherein the
comparison to the present invention. mesoporous silica has an average pore size of from 1 to 100
25 .
TABLE 3 5. The composition as claimed in claim 4, wherein the
Solar Reflectance vs. Level of MPS and Film Thickness
mesoporous silica has an average pore size of from 2.5 nm
to 50 nm.
Mesoporous 6. The composition as claimed in claim 1, wherein the
Silica
30 mesoporous filler is substantially free of organic groups or
Wt. 90 in Solar Reflectance at Wet Coating Thickness residues.
emulsion 12.7 m 25.4 m 50.8 m 101.6 m 7. The composition as claimed in claim 1, which compo
copolymer (5 mil) (10 mil) (20 mil) (40 mil) sition is a clearcoat composition.
2O 0.4 O49 O.63 0.73
8. The composition as claimed in claim 1, further com
15 O3S O42 O.S6 O.66 35 prising an IR reflective pigment.
10* * NA 0.337 O.475 O.SO1 9. A method of using the composition as claimed in claim
5 O.317 O412 O.S23 O.63S 1, comprising applying the composition to a painted Sub
strate, a coated Substrate, a roofing shingle or a roofing
As shown in Table 3, above, the mesoporous silica filler Substrate, and letting it dry.
of the present invention provides more than 30% (0.3) solar k k k k k