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Патент USA US3077467

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c
3,977,458
Patented Feb, 12, 1963
3
2
pletely or partially neutralised with ammonia or a lower
3,077,458
NQN-AQUE?Ud FIRE RETARDANT ‘CQMPGSKTEUN
CGMPRIMNG A UREA FGRMALDEHYDE CON
_DENSATE
.
,
.
Gerrit Queiie, Amsterdam, Netherlands, and Cyril Aubrey
Red-Earn, London, and Raymond Thompson, East
Molesey, England, assignors, by mesne assignments, to
Alirn (Iorporation, New York, N.Y., a corporation of
alkyl amine.
The use of a‘medium other than water ‘has the advan
tage that:
(a) The "composition ‘may be formed and'stored as an
entity, since ionisation and condensation cannot take
place sufliciently until the‘solv'ent evaporates as the ap‘
plied coating dries;
-New York
(b) Water-resistant and water-‘insoluble ?lm forming
No Brewing. Fiied May 25, 1958, SenNo. 737,532,
ingredients, which are ‘usually insoluble in water and
Ciaims priority, application Great Britain May 27, 1957 10 therefore increase the moisture resistance of ‘the ?nished
7 tllaims. (Cl. 26tl—2.5)
coating, may be incorporated in‘ solution: and
(c) The Water-soluble ingredients will‘not now crystal
It is 'generally'acknowledged thatthe mostsuccessful
lise as the-solvent of the medium evaporates, and since
way of imparting ?re retardance to'a combustible mate
rial such as ‘wood or'materials made therefrom (e.g. 15 a mixture of relatively long liquid life is produced, ?llers
or pigments may be intimately dispersed 'in'the medium
cardboard, hard or ‘soft ?bre insulation board and the
by mechanical milling and the cornbined‘rcsult is that a
like) isby ‘applying a surface coating which is poten
coating of enamel-like ‘appearance can be produced.
tially intumescent. Such a coating swells‘ under heat or
It is generally preferred that the non-aqueous in
direct ?ame to produce .a puffed-up, non-glowing insulat
ing cellular mat which insulates the substrate material 20 tumes'cent‘?re retardant composition according to the in
vention shall comprise not only urea but also a phenol,
from the heat source and at the same time excludes
oxygen. The principle is also advantageous in delaying
heat transfer to a treated metal surface.
each partiallycon‘densed' wlt'h'fo'rmaldehydein an' organic
solvent medium. ‘A ‘particularly suitable‘organic solvent
is one that‘is 'or ‘comprises ‘a lower-‘aliphatic alcohol,
Typical among such products is'a composition which
incorporates a foaming ingredient (e.g. mono- or di 25 such as'm'ethanol'or‘ethanol. ‘Such'alcohol'may be used
together with‘anaromatic‘ hydrocarbon such as xylene.
ammonium phosphate), urea and formaldehyde in a state
‘If the ‘compositionis required ~to‘ give ‘a surface ‘coat
of condensation and an amylaceous substance such as
ingot an opaque'or enamelslike‘character there is incor
starch. These ingredients in a ?nely pulverized state ‘are
porated therein a substantial amount of a water-insoluble
mixed in optimum proportions, together with inert pig
ments which impart colour and/ or opacity to the coating, 30 ?ller or pigment which may be for example rutile, ana
tase, asbestine, mica, vermiculite and/ or antimony oxide.
and applied to the potentially combustible surface as an
aqueous slurry or suspension. Suclia composition is
described in British patent speci?cation No. 632,844.
There are two main disadvantages with the above com
In this case it is particularly desirable that‘ thecomposi
positions. Firstly, the curing of the coating is brought 35
about by the chemical condensation of urea and form
In the case that the composition is required to produce
a transparent surface coating, the foaming ingredient
tion should include phenol as wellas ureacondensed with
formaldehyde.
aldehyde, catalysed by mono-ammoniurn'phosphate or
should be a salt or salts, with ammonia or an amine,
other acid source; these three ingredients (which com
bination produces with heat one of the best foam mats
of an organic partial ester of orthophosphoric acid,
before the composition is to be applied as a coating.
otherwise the whole solidi?es in the container. The dis
when the organic solvent ‘medium evaporates from an
because ammonium phosphates such as mono- or di
known) cannot, therefore, be mixed for many hours 40 ammonium phosphates are liable to‘ become opaque
applied coating.
In some cases, instead ofincorporating a straight urea
composition as two components which have to be in" 45 formaldchyde condensation product in the composition,
there may be employed an~alkylated,e.g. butylated,'urea
timately mixed before use, and this 'is frequently in
advantage is overcome in practice by packaging the
formaldehyde resin. This may be particularly useful
convenient. Secondly, the most effective foaming ingre
when
preparing compositions for producing ‘transparent
dients are highly water-soluble, and coatings produced
surface
coatings, and his then desirable that the foaming
from compositions containing these ingredients are water
ingredient shouldbe an organophosphoric acid ester as
sensitive and subject to e?lorescence throughout their 50 hereinbefore mentioned.
life. Moreover, since they are water-soluble, the slurry
A plasticizer is usefully incorporated in the composi
referred to is in fact a saturated solution, and as the
water evaporates from the applied coating, undesirable
crystals are grown, providing a ?nished surface of rough
texture.
The main obg'ect of the present invention is to produce
intumescent compositions which will overcome the afore
tion, particularly in the case of a composition for pro
ducing transparent surface coatings, and‘particularly'use
ful plasticizers are ‘glyceryl-a-tolyl ether and glyceryl'di
tolyl ether.
As hereinbefore indicated, the compositions of the
invention may incorporate, as a‘further addition, a Water
said disadvantages and which will be adapted to produce
resist-ant and water-insoluble ?lm-forming resin.
The following indicates howtypical-compositions ac~
60 cording-to the invention may be produced:
have an enamel-like appearance.
Urea and formaldehyde (or asubstance'such as hexa
An intumescent composition according to theinvention
methylene tetramine which liberatesformaldehyde), to
is essentially non-aqueous and comprises urea and form
gether with a phenol ‘or a substituted-phenol; are. mixed
aldehyde partially condensed in a volatile organic solvent
together and s-tirred‘into an appropriateprioportion (in
medium, and a foaming ingredient which may be an
surface coatings which may be transparent or which may
ammonium phosphate, cg. a mono- and/or di-ammoni
um phosphate, or a salt or salts, with ammonia or an
amine (preferably a lower alkyl amine), of an organo
partial ester of orthophosphoric acid.
A particular
example of a foaming ingredient of the latter type is
a mixture of mono-butyl and di-butyl phosphates together
with a minor amount of free orthophosphoric acid com
dioated .by examples hereinafter) »of 1 a non-aqueous
solvent, more particularly a lower ‘aliphaticalcolrol. A
certain degreeof condensation is. then allowed orcaused
to take place bylreeping the mixture for latime at a '.pre—
1 determined
temperature,
‘or
during ; a .sequence ;:of
time/temperature conditions. This will be-made' ,clear
' by stating that if methanol is used as a‘solvent asuitable
vheating sequence is a period of gentle refluxing at 65 .to
3,077,458
3
4
70° C. for about 11/: hours, whereafter the ethanol or
substituted phenol is added, and which is then followed
by refluxing for a period of between 1A2 to 4 hours. It is
not possible to assess the precise degree of resin con
densation which results from this procedure but it may
be said that the optimum is when the condensation prod
ganic solvent medium evaporates from an applied coating.
However, by replacement of the monoammonium phos
phate by a mono- or d-i-substi-tuted organo partial ester
of orthophosphoric acid, a coating which dries and re
mains transparent is obtained.
Example VII
uct has a viscosity, at room temperature, in the range
of 20-30 seconds No. 4 Ford cup. The pnoduct, which
constitutes the resin ‘or binder constituent of the com
The resin or binder is prepared in the manner desmibed
hereinbefore, and mixed with the other ingredients to
position, is then cooled and thereafter the ?nely pulverised 10 form a composition typi?ed by:
foaming ingredient and ?ller or pigment (if required)
are stirred in.
Parts by
weight
The mixture may then be raised again
to a temperature of, say, 60° C. for a 1/2 hour to eifect
Urea ____________________________________ __
11.4
further condensation. Final mixing and dispersion may
Parafornraldehyde
15.9
be effected by mechanical means such as are typically 15
Phenol __________________________________ _..
used in the paint industry.
The following ‘are examples of formulations for the
Ethanol
production of non-aqueous intumescent ?re retardant
compositions according to the invention in accordance
with the procedure indicated generally above.
________________________ __
36.1
Monobutyl phosphoric ‘acid ________________ __
Dibutyl phosphoric acid ___________________ __
12.5
5.3
Ammonia (anhydrous) ____________________ __
20
I Example 1
Piara-chloro-meta-xylenol
15 .0
Glyceryl a-tolyl ether _____________________ __
7.5
100.0
weight
25 Glyceryl a-tolyl ether acts as a plasticizer in the above
composition, and serves toincrease resistance to crazing
(“cold-checking”). As an alternative to glyceryl a-tolyl
ether, this material may be replaced by an equal weight
Formaldehyde _____________________________ .._ 15.9
Phenol ___________________________________ __
4.1
Methanol _________________________________ __ 28.1
of glyceryl di-tolyl ether. Para-chloro-meta-xylenol also
Mono-ammonium phosphate _________________ -1 27.0
Anatase __________________________________ __
2.7
Asbestine _________________________________ __
10.8
2.2
__________________ _ _
Percent by
Urea _______________________________________ -i 11.4
4.1
_________________________________ __
30 serves to increase resistance to crazing, but more par
ticularly to increase moisture resistance.
As an alternative to the use of the particular resins
100.0
prepared as described hereinbefore, the materials which
impart ?re retard-ance and those which plasticize the
resin may be mixed advantageously with a bu'tylated urea
fornraldehyde resin syrup of ‘the type commercially avail
able. The proportion of resin syrup to other materials
Example 11
As Example I but with resorcinol or para-chloro-meta
xylenol instead of phenol.
Example Ill
(excluding solvents) necessary to produce a coating with
good drying properties consistent with an adequate stor—
As Examples I or IE but with some or all of the anatase
replaced by antimony oxide. Not only is the antimony 40 age life has been found to be much higher than in Ex
ample VII, ‘and a typical composition is as follows:
oxide merely an alternative “?ller” to the \anatase, but
under ?re conditions it is reactive with chlorine-contain
Example VIII
ing compounds if such are present in the composition and
Parts by
forms antimonyl chloride, which is Well known as a
weight
?ame-extinguishing gas.
Butylated urea formaldehyde syrup, 55% solids
Example IV
in butanol/xylol _______________________ __
Monobutyl phosphoric acid _______________ .._
As any of the above examples but with some of the
Dibutyl phosphoric acid __________________ __
inert ?ller replaced by a material such as mica or vermicu
lite which will exfoliate under ?re conditions to give added 50 Monomethylamine _______________________ __
Ethanol ________________________________ __
?lm thickness. These materials are also more refractory
Para-chloro-meta-xylenol __________________ _._
than the carbonaceous/phosphate foam mat, and hence
Glyceryl a-tolyl ether _____________________ __
give increased resistance to ?re.
Example V
As any of the above examples but with a silicone (e.g.
an organo polysiloxane) incorporated to increase water
repellency.
'
Example Vl
75
7.25
3.10
1.50
5.65
5.00
2.50
100.00
55
Additional resistance to “cold-checking” may be imparted
by the addition of up to 10% of tris ?-chloroethyl phos
phate, weight by weight, to the mixture of Example VIII.
What We claim is:
As any of the above examples but with a water-resist 60
1. A substantially non-aqueous intumescent ?re
ant resin or other compound incorporated (e.g. a cyclic
retardant composition comprising a condensation prod
ketonic resin or urea formaldehyde-toluene sulphonamide
uct and a foaming ingredient in admixture in a 1 to 2
complex). Additions of the order of up to 10% of these
carbon atom alkanol as solvent, said condensation prod
ingredients on the composition given in Example I im
uct being a 1 to 2 carbon alkanol soluble urea-formalde
part useful properties, especially with reference to re
hyde condensation product and said foaming ingredient
sistance to moisture.
being selected from the group consisting of ammonium
There are many occasions when a transparent rather
and lower alkyl-arnine salts of from mono to dibutyl esters
than an opaque lacquer is required; e.g. when a wooden
of o-phosphoric acid.
or veneered surface is to be ?ame-proofed but at the same
2. A composition according to claim 1 in which the
time it is desired to retain the attractive appearance of 70 foaming ingredient is formed by reacting ammonia with
the natural grain. Such a lacquer cannot be obtained
merely by the elimination of the opaque pigments (e.g.
anatase, asbestine, mica) from the compositions given
in Examples I to V1; the foaming ingredient (e.g. ain
monobutyl phosphoric acid.
3. A composition according to claim 2 in which the
foaming ingredient is formed by reacting monomethyl
monium phosphate) also becomes opaque when the or 75 amine with dibutyl phosphoric acid.
8,077,458
5
6
4. A composition according to claim 1 in which the
composition is produced from the following com
ponents:
Parts by
weight
Urea
Parts by
weight
____________________________________ __
Paraformaldehyde
5
Butylated urea formaldehyde syrup, 55% solids
Phenol
__
Ethanol
___
11.4
_________________________ .._ 15.9
____ __
4.1
..
36.1
75
Monobutyl phosphoric acid __________________ __
5.3
Monobutyl phosphoric acid _________________ __ 7.25
Dibutyl phosphoric acid _____________________ __ 3.10
Ammonia (anhydrous) _____________________ __
2.2
in butanol/xylol _________________________ __
Monomethylamine _________________________ __ 1.50
Ethanol
Para-chloro-meta-xylenol ____________________ __ 15.0
p 10 Glyceryl a-toly-l ether _______________________ __
__________________________________ __ 5.65
Para-chloro-meta-xylenol ____________________ __ 5.00
Glyceryl a-tolyl ether ______________________ __ 2.50
5. A composition according to claim 1 in which the 15
resin is a urea, phenol and formaldehyde condensation
product having a viscosity, at room temperature, in the
range of 20-30 seconds No. 4 Ford cup.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,650,206
Stock _______________ __ Aug. 25, 1953
2,676,162
Marotta _____________ __ Apr. 20, 1954
785,977
Great Britain __________ __ Nov. 6, 1957
FOREIGN PATENTS
6. A composition according to claim 5 in which the 20
phenol is para-chloro-meta-xylenol.
7. A composition according to claim 5 in which the
composition is produced from the following components:
7.5
OTHER REFERENCES
Ellis: “Chemistry of Synthetic Resins,” volume 1,
pages 672-678, copyright 1935, Reinhold Pub. Corp,
New York.
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