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Патент USA US3053728

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3,053,714
Patented Sept. 11, 1962
2
1
3,053,714
INTUMESCENT COATING
Kenneth N. Edwards, Worthington, Ohio, assignor, by
mesne assignments, to Wood Conversion Company,
St. Paul, Minn, a corporation of Delaware
No Drawing. Filed May 16, 1957, Ser. No. 659,480
11 Claims. (Cl. 154-44)
This invention relates to intumescent, organic coatings.
More particularly, this invention relates to intumescent,
coating which will intumesce when exposed to the heat
of ?ame.
It is an object of this invention to provide an intu
mescent asphalt coating wherein the intumescent agent
is Water-insoluble but compatible with the asphalt.
A further object of this invention is to provide an intu—
mescent asphaltic coating which retains the properties
of weather resistance, resistance to rotting, vapor-barrier
characteristics, and adhesive properties of asphalt.
It is a further object of this invention to provide an
asphalt coatings containing phenol-aldehyde resins in
asphaltic coating which will intumesce when exposed to
combination therewith.
the heat of a ?ame and form a cellular, thermoset, skele
tal, self-supporting structure which supports and helps
retain the asphalt in place.
sistance ofwor-ganic coatings to ?re“, Due to the fact that
thew?iam?ic coating material 1s combustible, a truly ?re 15 Another object of this invention is to provide an as—
phaltic coating which will intumesce when exposed to
proof organic coating appears to be improbable. So-called
?ame and prevent or retard run-off of the asphalt.
?reproof organic coatings, therefore, are generally meant
Considerable effort has been directed to improve re
Another object of this invention is to provide an as
to mean coatings which will provide some protection of
the coated substrate to ?ame or intense heat and helps
to retard or impede the progress of the ?re. When the
phalt coating (which will intumesce when exposed to ?ame
and provide a cellular layer which will help to insulate
organic coating itself does not inherently have these prop
erties, other materials are sometimes added to impart ?re
the coated substrate from the heat of the ?re.
Applicant has discovered that an asphalt coating con
retardant properties to the coating. This is accomplished,
taining certain heat-hardenable phenol-aldehyde resins
in general, by the addition of materials which evolve an
will intumesce upon exposure to heat of a ?ame. Ap
by the addition of intumescing agents. Gas-evolving ma
hardenable phenol-aldehyde resin, as hereinafter de?ned,
in combination with asphalt, will form a coating which,
inert gas upon exposure to or contact with ?re, or else 25 plicant has discovered that the combination of a heat
terials are believed to function ‘as a diluent of the at
mosphere in the area of the combustible materials and
thereby retard or inhibit the oxidation of the combustible
upon exposure to the heat of a ?ame, will swell, bubble,
or puff, to produce a ?rm, resinous, expanded ?lm which
components of the organic coating. Such certain mate 30 helps to shield the substrate from the fire and also to re
tain the asphalt in place.
rials are halogeneated natural or synthetic resins and in
The phenolic resins incorporated with the asphalt to
organic carbonate, sulfate or phosphate salts, such as
produce the coatings of this invention are the heat-harden
chlorinated natural rubber, chlorinated naphthalene,
able, initial condensation products formed in the ?rst
chlorinated diphenyls, chlorinated hydrocarbons, amid
aldehyde resins, Zinc carbonate, and ammonium phos 35 stage of the reaction in the preparation of thermoplastic
and thermosetting phenol-aldehyde resins and which ini
phate.
Perhaps the most important single property for a ?re
retardant organic coating is intumescence. This is the
property of swelling or puf?ng when exposed to the heat
of a ?ame.
tial condensation products can further condense with the
formation of rwater of condensation upon the application
of heat. These initial condensation products are called
Such swelling of the coating results in a 40 “resoles” and are sometimes referred to as “A stage
resins.” As is known, the heat-hardenable resoles con
cellular insulating layer between the ?re and the sub
strate. Examples of intumescent 'agents which have been
used in coating formulations, either alone or in com
bination with each \other, are ammonium phosphate, ver
sist mainly of complex mixtures of alcohols of phenol and
phenol derivatives having a relatively high hydroxyl con
the exception of African Isano oil, the better intumescent
agents are water-soluble and, therefore, produce organic
tent and a relatively low molecular weight. The resoles
are liquid or sirupy semisolid materials which are’ neither
thermoplastic nor thermoset resins, but which can be
further condensed with formation of water of condensa
tion to produce resitols which are higher molecular
throughout the composition. This is objectionable in the
ventless pheno'lics by those skilled in the ?eld of paint
miculite, casein, starch, African Isano oil, carbamic phos
phoric acid, urea, and methylene disalicyclic acid. With
Weight, fusible, thermoplastic, phenolic resins. The resi
coatings having poor Water resistance. -It has been re
ported that water-soluble intumescent agents in some in 50 tols are sometimes called “B stage resins.” The resitols
may be further condensed with formation of additional
stances will leach out and weather away from the coat
water of condensation to produce resites (sometimes
ing, thereby reducing or eliminating the ?re-resistant prop
called C stage resins) which are infusible thermosetting
erty of the coating. In addition, extensive grinding of the
coating material with solid intumescent agents is neces 55 resins.
The resoles are sometimes referred to as liquid, sol
sary in order to assure thorough dispersion of the agent
and coating technology. The term “liquid” in conjunc
case of asphalt.
tion with the term “solventless” is used to include resoles
Asphalt is frequently used as a protective coating for
wood, paper, and metal, because of its excellent prop 60 which are su?iciently advanced in condensation toward
the resitol stage so as to be of a sirupy, semisolid con—
erties with regard to weather resistance, resistance to
sistency, but exclude solvent solutions of resitols which
rotting, its ability to act as a vapor barrier, and also be
are often referred to in the art as “liquid phenolics.” It
cause of its adhesive qualities. In addition, it is an in
should be understood, of course, that the resitols and
expensive product relative to other coating materials.
resites are ‘different from the resoles in many physical
Asphalt coatings, however, are not Without their draw
65 properties.
backs, the primary one being that it is combustible and
Phenol and formaldehyde are most commonly used in
will ?ow upon application of heat, thereby exposing the
the manufacture of phenol-aldehyde resins. Substituted
substrate to the ?ame. In addition, because of its com
phenols may also be used. These phenols should have
bustible nature and its run-off characteristics, the asphalt
oftentimes will carry the ?re elsewhere and contribute to 70 at ‘least two of the 2, 4, and 6 positions on the benzene
ring free of substitution in order to be able to progres
the spreading of the ?re.
sively condense with the aldehyde and methylol groups
It is an object of this invention to provide an asphaltic
t
3653111 :15.
'
fit-(iii
3,053,714
3
4
upon the application of heat. Many examples of suit
that the maximum mixing temperature which can be
able substituted phenols can be mentioned and they in
used will depend upon the particular resole used. Thus,
clude the aliphatic, aromatic, and hydroxy-substituted
the rate of advancement of resoles consisting predomi
phenols, for example. The most commonly used substi
nantly of the methylol substituted phenol ethers, as de
tuted phenols are the amyl—, butyl-, and cyclohexyl-sub 5 scribed, will begin to increase within the range of 170°
stituted phenols, cresol, bisphenol and resorcinol, for ex
to 485 " F. When using these resoles, the mixing tem
ample. The rate at which resoles will resinify, i.e., con—
perature during preparation preferably should not ex
dense to higher molecular weight products into resitols
ceed 300° F. At these temperatures, thorough mixing
or resites, will vary with the location and extent of sub
can be obtained and the mixture applied in the form of
stitution of the phenols. Advantages can be taken of 10 a hot-melt coating without any foaming action.
this phenomenon to prepare coatings in accordance with
In some instances it may be desirable to apply the coat
the invention to withstand varying degrees of heat be
ing ‘of this invention in the form of an emulsion or dis
fore intumescence. The structure of the aldehyde is of
persion rather than as a hot-melt coating. For this pur
less importance than the structure of the phenol in these
pose the asphalt and resole may be combined in a uni
heat-hardenable resoles, and the only practical limitation 15 form aqueous emulsion or dispersion, for example. The
on the aldehydes is that of expense. Formaldehyde, para
coating may be applied to the substrate in any suitable
formaldehyde, furfural, and polymeric furfural are by
manner, such as by brushing or spraying.
far the most common aldehydes used in phenol-aldehyde
Other ingredients commonly added to asphalt coatings
resin manufacture.
for the improvement of ?re-retardant properties or other
For purposes of a complete disclosure and clear un
properties may also be added. For example, gas-evolv
derstanding of this invention, the constituents of these
ing materials which may inhibit the combustion of the
resoles, as presently understood by those skilled in the
asphalt when exposed to the ?re may be added. Com
art, are identi?ed. As stated, the resoles consist mainly
pounds helpful in the control-ofIrtiuoorganisrns dele
of complex mixtures of alcohols of phenol and substi
terious to the substrate mayalso be addedhjgqwtheppalirrlg
tuted phenols. Mono-, di-, and trialcohols of phenol are 25 formulation. This is particularly desirable when the coat
known to exist in the resole. For example, in the case
ing is to be used for the protection of wood or paper
of a resole prepared from phenol and formaldehyde,
substrates. “Pentachlorophenol, a conventional asphalt
saligenin and di- ‘and tri-methylol-su‘bstituted phenols
coating additivef‘exhibits microbiocidal properties and al
have been identi?ed. Also present are simple condensa
so improves the ?re resistance of asphalt. Known ?ame
tion products of phenol and the methylol-substituted 30 retardant plasticizers, such as the mixed cggesylukphenylm-Mw
phenols 'wherein a methylol group on one phenol mole
gphosphates may also be added. Other plasti' zers, such
cule has condensed with an ortho or para hydrogen atom
in an adjacent phenol or methylol-substituted phenol to
yield methylol-substituted phenols linked by means of a
Estimate hydrocarbon plasticizing agents may be used.
Polychlorinatecl polyphenyl compounds reduce the ?am
mability and improve the durability of asphalt coatings.
methylene bridge. These products, dihydroxy diphenyl- 35 Surface active agents may also be added to the asphalt.
methanes, for example, contain methylol groups and are
Oftentimes these agents help reduce the run-off tendencies
capable of further condensation until resitols or resites
are obtained. In the case of other aldehydes and sub—
stituted phenols, the resoles will consist of analogous con
of asphalt in its heated condition. These additional in
gredients may be added to the asphalt-resole coating com
position of this invention in the amounts usually added
to other asphalt coatings. The proportions of the resole
densation products.
{The resole may also consist of etheri?ed products of
to the asphalt may vary over a very wide range.
Actual
methylol-substituted phenols, that is, alkenyloxybenzenes
ly, the proportions of the resole used will depend upon
the degree of intumescent properties desired.
wherein the alkenyl group is attached to the phenolic oxy
The following examples illustrate the combination of
gen and contains at ‘least three carbon atoms, for exam
ple, allyl, methallyl, crotyl, butenyl, etc., as well as halo 45 coating asphalt with resoles and other desirable ingre
genated derivatives thereof. Particularly suitable resoles
dients, such as microbiocidal agents, plasticizers, wetting
agents, and ?ame-retardant ingredients which evolve
for the purpose of this invention are the unsaturated
ethers marketed under the trade name Methylon 75108
inert, incombustible gases upon the application of the
by General Electric Company, comprised of a mixture of
heat of a ?ame. The ingredients are added to each other
and heated to a suitable temperature, with stirring to
mono-, di- and trimethylol-substituted phenol allyl eth
obtain complete and uniform mixture. The resoles are
ers. These resoles are produced by reacting phenol and
formaldehyde at relatively low temperatures in the pres—
preferably added last, and the entire mixing is preferably
ence of an alkali to form methylol-substituted alkali met
kept at as low a temperature as possible.
al phenates. The mixture of the phenates is then reacted
with an allyl halide to produce methylol phenol allyl 5
ethers. These heat-hardena'ble resoles and methods of
making them are described in US. Patents 2,579,329,
2,579,330, and 2,579,331. The phenolic ethers condense
with formation of Water of condensation upon the appli
temperature is usually from about 210 to 230° F. In
each example the coating was applied in the form of a
hot-melt to one side of 43 pound kraft paper. The
coating was permitted to cool and then was tested for
intumescence by applying the ?ame from a gas burner
cation of heat and are particularly suitable resoles for 6 O
combination with asphalt in the formulation of intumes—
cent coatings in accordance with this invention.
The asphalt and the resole are thoroughly mixed with
each other to form a uniform mixture. It is desirable to
heat the components in order to obtain a thorough and 65
test described in ASTM designation: D777~46. The
char length of this test is reported for each example.
The following samples are offered as a speci?c dis
closure of the invention and are not to be interpreted
complete mixture of the asphalt and the resole.
directly in contact with the coating. The ?ammability of
the coated paper was determined in accordance with the
in a limiting sense.
The
temperature of the components during the mixing should,
A suitable
Example I
Ingredients:
Percent amount
of course, be below that temperature at which advance
Asphalt
ment or substantial advancement of the resole may oc
Resole (methylol substituted phenol ethers)____ 40
____ __
__
_
4O
cur. Prolonged heating, of course, should be avoided be 70
Pentachlorophenol _______________________ __ 20
cause of the reactive nature of resoles. It is preferred
The resole is a mixture of allyl ethers of phenol hav
that the degree of resini?cation of the resole be su?icient
ing from 1 to 3 methylol groups linked singly at the
1y advanced toward the resitol stage so that upon the
ortho and para positions on the benzene ring. The penta
advent of heat of a ?ame, the resultant foamed mass
chlorophenol functions to inhibit the growth of deleterious
will quickly thermoset into a heat barrier. It is obvious 75 microorganisms and also advantageously functions as a
3,053,714
6
the coating is highly suitable in the manufacture of batt
?re-retardant agent in the evolution of inert gases upon
the application of heat. The coating swelled into a re
sultant foamed mass and quickly thermoset into a heat
barrier upon contact with the ?ame. The char length
insulation wherein the insulation is a batt of ?bers, either
vegetable or mineral or both, retained between two liners
such as kraft paper. The asphalt coatings of this inven
tion may be used to coat the inner surfaces of the kraft
was 2.92 inches.
liners, and also the outer surfaces if desired. The asphalt
Example 11
Ingredients:
coating on the inner surfaces of the kraft liners serves as
Percent amount
Asphalt
30
Resole (methylol substituted phenol ethers)____ 42
a moisture barrier and sometimes as an adhesive to
Plasticizing hydrocarbon oil
of the asphalt and also helps to hold the liner in place.
Although this may only be temporary, it helps to impede
bond the liners to the ?ber batt. Upon exposure to heat
Chlorinated hydrocarbon resin ____________ __ 12 10 of a ?re, the coating of this invention will intumesce and
form a thermoset structure which retards the run-off
Pentachlorophenol ______________________ __ 12
(spindle oil)
__
3.5
or retard the spread of the ?re and offers a means to
localize the ?re until the ?re can be brought under
control.
Another application for these coatings is on wooden
railroad trestles to protect against brush ?res. The
Wetting agent ___________________________ __ 0.5
The resole and the pentachlorophenol were the same
as in Example I. The chlorinated hydrocarbon resin ex
hibits ?re retardance in the same manner as the penta
chlorophenol but, however, has no apparent microbiocidal
properties. The wetting agent is a high molecular weight,
trestles are susceptible to damage by ?res from the brush
which collect at the base of the trestles. The coatings
of this invention afford a degree of protection against
such ?res, and also advantageously afford some degree
of protection against future ?res in the formation of a
nonionic surfactant prepared by ‘condensing ethylene oxide
with a hydrophobic base formed by condensation of
propylene oxide with propylene glycol.
The wetting
agent reduces the run-off characteristics of asphalt under
heat. This coating produced a foamed thermoset mass
upon contact with the ?ame. The char length was 3.63
inches.
heat barrier over the surface of the wood until mainten~
ance crews can make their inspection and repair tours.
Since the intumescent thermosetting. resoles also are
water-insoluble, the asphalt coatings of this invention are
especially useful for this purpose because they also ex
hibit weather resistance, rot resistance, and desirable va
Example III
Ingredients:
Percent amount
Asphalt ________________________________ __ 28
Resole (methylol substituted phenol ethers)____ 40
Chlorinated hydrocarbon resin ______________ __ 12
Mixed cresyl phenyl phosphates ____________ __ l9
Wetting agent
__ 1
The resole, the chlorinated hydrocarbon resin, and the
wetting agent were the same as the previous examples.
The mixed cresyl phenyl phopshates function as a ?ame
retardant plasticizer. The coating produced a foamed
thermoset mass upon contact with the ?ame. The char
length was 3.12 inches.
Example 1V
Ingredients:
Asphalt
Percent amount
28
Resole (phenol-furfural) __________________ __ 35
Polychlorinated polyphenyl ________________ __ 35
Wetting agent
__
2
The resole consisted of the initial condensation prod
ucts of the reaction of polymerized furfural with phenol.
30
por-barrier properties.
As various embodiments could be made in the invention
described herein, and since many different changes can
be made in the embodiments set forth, it is to be under
stood that all material disclosed is to be interpreted as i1
lustrative and not in a limiting sense, except as otherwise
set forth in the claims.
What is claimed is:
1. An article having a solid ?re-retardant coating com
prising in uniform admixture an intumescent thermoset
table composition of asphalt and a heat-hardenable ?uid
resole comprised of a mixture of alkenyloxybenzenes hav
ing from 1 to 3 methylol groups in the ortho and para
positions on the benzene ring.
2. Thermal insulation comprising an insulation ?ller,
a liner on at least one face of said ?ller, and an intumes
cent thermosettable solid coating on the inner surface
of said liner adjacent to the ?ller adhesively uniting the
?ller to the liner, said coating comprising in uniform ad
mixture asphalt and a heat-hardenable ?uid resole.
The polychlorinated polyphenyl functions to plasticize
3. Thermal insulation comprising a combustible ?brous
and improve the durability of the asphalt and also acts
insulation ?ller, a paper mat liner on at least one face of
said ?ller, and an intumescent thermosettable solid coat
as a gas evolving agent. The wetting agent was the same
as in the previous example. The coating formed a foamed
ing on the inner surface of said liner adjacent to the ?ller
thermoset mass which remained in place after removal
adhesively uniting the ?ller to the liner, said coating com
of the ?ame. The char length was about 1.25 inches.
55 prising in uniform admixture asphalt and a heat-harden
able ?uid resole.
Example V
4. Thermal insulation comprising an insulation ?ller,
Ingredients:
Percent amount
a liner on at least one face of said ?ller, and an intumes_
Asphalt ________________________________ __ 28
cent thermosettable solid coating on both surfaces of said
Resole _________________________________ __ 35
60 liner, the coating on the surface of the liner adjacent to
Polychlorinated polyphenyl ________________ __ 25
Epoxy resin
Wetting agent
_
__
_
10
__
2
The resole, the polychlorinated polyphenyl, and the
the ?ller adhesively uniting the ?ller to the liner, said
coating comprising in uniform admixture asphalt and a
heat-hardenable ?uid resole.
"
5. Thermal insulation comprising a combustible ?brous
wetting agent were the same as in the previous example. 65 insulation ?ller, a paper mat liner on at least one face of
said ?ller, and an intumescent thermosettable solid coat
The epoxy resin, which is a glycidal polyether of a poly
ing on both surfaces of said liner, the coating on the
hydric phenol has a molecular weight of about 600 to
inner surface of said liner adjacent to the ?ller adhesively
900 and an epoxide equivalent of about 180. The epoxy
uniting the ?ller to the liner, said coating comprising in
resin was added for the purpose of augmenting the ther
uniform admixture asphalt and a heat-hardenable ?uid
mosetting properties of the resole. The resultant foamed
resole.
thermoset mass remained in place after removal of the
6. Thermal insulation comprising an insulation ?ller,’
?ame. The char length was 3.75 inches.
liners on opposite faces of said ?ller, and an intumescent
These coatings have numerous applications, particu—
thermosettable solid coating on the inner surface of each
larly in the building ?eld as a ?re-resistant coating for
wood, paper- or ?ber-board, and metals. For example, 75 of said liners adjacent to the ?ller adhesively uniting the
3,053,714
7
?ller to the ‘liner, said coating comprising in uniform ad
10. Thermal insulation comprising an insulation ?ller,
mixture asphalt and a heat-hardenable ?uid resole.
7. Thermal insulation comprising a combustible ?brous
insulation ?ller, paper mat liners on opposite faces of said
?ller, and an intumescent thermosettable solid coating on
the inner surface of each of said liners adjacent to the
of the liner, said coating comprising in uni-form admix
?ller adhesively uniting the filler to the liner, said coat
ing comprising in uniform admixture asphalt and a heat
prising in a uniform intumescent thermosettable composi
hardenable ?uid resole.
a liner on at least one face of said ?ller, and an intumes
cent thermosettable solid coating on at least one surface
ture asphalt and a heat-hardenable ?uid resole.
11. An article having a solid ?re-resistant coating com
tion a basic content of asphalt admixed with a heat-hard
enable ?uid resole.
8. Thermal insulation comprising an insulation ?ller, 10
liners on opposite faces of said ?ller, and an intumescent
thermosettable solid coating on both surfaces of each of
said liners, the coating on the inner surface of each of
said liners adjacent to the ?ller adhesively uniting the
?ller to the liner, said coating comprising in uniform 15
References Cited in the file of this patent
UNITED STATES PATENTS
1,336,403
1,911,131 '
1,956,866
admixture asphalt and a heat-hardenable ?uid resole.
, 2,025,929
9. Thermal insulation comprising a combustible ?brous
2,033,411
insulation ?ller, paper mat liners on opposite faces of said
2,489,228
?ller, and an intumescent thermosettable solid coating on
both surfaces of each of said liners, the coating on the 20 2,501,995
2,518,241
inner surface of each of said liners adjacent to the ?ller
2,521,912
adhesively uniting the ?ller to the liner, said coating com
2,581,640
prising in uniform admixture asphalt and a heat-harden
2,667,425
able ?uid resole.
Weiss ________________ __ Apr. 6, 1920
Langenberg et al _______ __ May 23, 1933
Keller ________________ __ May 1, 1934
Young ______________ __ Dec. 31, 1935
Carson ______________ __ Mar. 10, 1936
Rudd ________________ __ Nov. 22, 1949
Dillehay ____________ __ Mar. 28,
McCarthy ____________ __ Aug. 8,
Greenlee ____________ _._ Sept. 12,
Fasold et al. __________ _._ Ian. 8,
Bierly ________________ __ Jan. 26,
71
1950
1950
1950
1952
1954
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