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Patented Dec. 24, 1946
2,413,163
UNITED STATES PATENT vOFFICE
2,413,163
V FLAMEPROOF ORGANIC FIBROUS MATE
RIAL AND COMPOSITION THEREFOR
Osborne Coster Bacon, Penns Grove, N. J ., as
signor to E. I. du Pont de Nemours & Company,
Wilmington, Del., a corporation of Delaware
No Drawing. Application December 24, 1943,
Serial No. 515,586
11 Claims. (Cl. 260—3)
2
This invention relates to compositions suitable
for producing a weather-resistant ?ameproof
?nish upon readily combustible ?brous material,
?ameproo?ng composition which is adapted to
such as paper, wood, leather and textiles of ani—
mal or vegetable origin. This invention further
' composition of the above nature which is stable
relates to novel, weather-resistant and ?ame
handled in commerce and stored for considerable
periods for ultimate use by a consumer. Other
be applied to the ?brous material from an aque
ous bath. An additional object is to provide a
against ‘separation of ingredients, and may be
proof ?brous materials produced by the use of
said compositions.
-
and further important objects of this invention
will appear as the description proceeds.
Now, according to this invention, the afore
going objects are achieved by incorporating into
For the purpose of tl'iisspeci?cation and the
subjoined claims, a ?anieproof ?brous material is
de?ned as one which, if tested in a draft-free
room by putting in contact with an initiating
?ame, will not continue to ?ame of its own ac
cord for more than 5 seconds after removal of
said initiating ?ame, and will not sustain com
bustion by afterglow beyond the charred area
upon removal of said initiating ?ame.
It will be clear therefore that the material
the flameproo?ng coating composition, in addi
tion to the metallic oxide and chlorinated or
ganic compounds aforenoted, an anti-tendering
6 agent which is the water-soluble reaction prod
uct of formaldehyde upon a mixture of a water
soluble alkaline~amine-proteinate and a reagent
of the group which form water-soluble interme
diate resins with formaldehyde, such as urea,
adipamide, melamine and phenol. Typical re—
action products of this kind are described in U. S.
Patents Nos. 2,262,770 and 2,262,771. In the lat
ter patent aqueous formaldehyde is added to a
within the above de?nition may be actually con
sumed by ?re as long as it is in contact with a
?ame, provided it will not continue to burn after
the ?ame is removed.
,
Flameproof ?brous materials of the above qual
ities in gen?'al are not novel. It is old to coat
solution of triethanolamine caseinate containing
pap-er and t "'iles with heavy metal oxides such 25 urea, the quantity of formaldehyde being su?l
as oxides of tin, lead, antimony, arsenic, bismuth,
cient to react ?rst with the solubilized protein
titanium and the like, and to decrease their com
and then with the urea. It is stated therein that
bustibility thereby. It is also old to impregnate,
the urea or its reaction product with formalde
coat, saturate, or otherwise surface-treat textile
hyde exerts a solubilizing action upon the formal
fabrics with heavy metal oxides and water-in
soluble, chlorine-containing organic compounds
having ?re and waterproo?ng qualities. The lat
ter are generally applied from an organic solvent,
30
dehyde-protein reaction product, wherefore the
entire composition is water-soluble and may be
diluted considerably without precipitation. In
cidentally, I have found that the said reaction
which sometimes also acts as a vehicle for the
products also act as dispersing agents for the
metallic oxide.
.
'
35 other materials in the coating composition, and
A full discussion of such chlorine-containing
since they form an insoluble ?lm upon heating
organic compounds is given in the text herein
above 100° 0., they act further as binding agents
below. All appear to be operative for the pur
for the other ingredients, especially pigments
pose in question by virtue of their property of
where such are employed. These factors enable
liberating HCl when exposed to intense heat or 40 me to apply the ?ameproo?ng composition to the
light, Unfortunately, they retain this behavior,
?ber from an aqueous bath, thus obviating the
at a very slow rate of course, at ordinary tem
need for organic solvents with their attendant
peratures and under ordinary sunlight‘ as well.
?re hazard, toxicity and high cost. It also gives
The liberated HCl attacks the ?brous material,
the entire composition stability against separa
and as a consequence the latter in due time de
velops the faulty quality of tendering, that is
loss of tensile strength, especially when exposed
45 tion or settling, thus enabling my novel ?ame
proof composition to be handled as an article of
commerce and to be stored for inde?nite periods.
to weather.
Furthermore, the added protein-resin reaction
It is accordingly an object of this invention to
products overcome the sticky ?nish obtainable
produce ?ameproof ?brous material, for instance 50 with some of the chlorinated organic materials,
cellulosic textile material, which shall not de
and they do not affect adversely the ?exibility
velop appreciable tendering in outdoor use. A
of the treated material at low temperatures.
further object of this invention is to provide
For simplicity, I shall refer hereinafter to the
coating compositions for achieving the purpose
above reaction product of formaldehyde upon a
aforesaid. A still further object is to provide a 65 mixture of an alkaline-amine proteinate and urea
3
aerarea
4
or its equivalent (phenol, melamine, etc.) as the
“protein-resin reaction product" or “protein
resin composition,” although it will be clear from
tomary special agents may be added to the coat
ing composition to achieve special effects such as
mildew resistance, rot-resistance, plasticity, col
the above discussion that the mass is an aqueous
oring, etc. Particularly worthy of note as such
suspension containing water-soluble constituents CI auxiliary or special agents are: Salicylanilide
and does not actually become converted into a
water-insoluble resin until applied to the fiber
(mildew resistance);
zinc-dimethyl-dithiocar
bamate (mildew and rot-resistance); inorganic
coloring pigments such as lead chromate, iron
oxides, chrome oxides, and organic pigments such
and heated to 100° C. or over.
The protein material entering into the compo
sition of the aforegoing protein-resin reaction 10 as vat dyes, azo dyes and phthalocyanines; or
products may be of either animal or vegetable‘
ganic colors which are soluble in the chlorinated
origin; for example, casein, glue, soyabean protein
compound; para?in wax (waterproo?ng); and
or zein. All of these are characterized by the
plasticizers such as tricresyl phosphate and the
butyl phthalates. Additional buffering agents,
' common property that they will react ‘with am
monia, quaternary ammonium bases, 01‘ aliphatic 15 for instance water-insoluble calcium or mag
amines, especially polyalkylol amines, to produce
nesium carbonates may also be added.
compounds soluble in water. I shall refer here
The amount of protein-resin reaction product
inafter to such compounds as “solubilized pro
used is usually determined by the amount of dis
teins” or as “aikaline-amine-proteinates." The
persing agent needed and the ?exibility of the
other component may be the reaction product of 20 applied ?lm desired.
formaldehyde and an amide such as urea or
In general, the four fundamental ingredients
adipamide, formaldehyde and an amine such as
of the present fiameproo?ng compositions may
melamine, or formaldehyde and phenol.
be varied in amount as follows:
The chlorine-containing compound employed
Per cent
for flame-proo?ng may be one of the group con
sisting of chlorinated parai?n wax, chlorinated
fatty acids, chlorinated fish oil, chlorinated vege
table oil, chlorinated rubber, and chlorine-con
Protein-resin composition __________ __
Metal compound ___________________ __
taining resins prepared by polymerizing com
Water ____________________________ __
pounds containing the vinylidine group HzC=C<, .
the said compounds having a chlorine content of
They may be applied to the ?brous material in
concentrated form (up to 80% solids), or they
from 20% to 80%. The ?ameproofing-property
of the treated material generally increases with
the chlorine content of the treating agent, al
though intermediate percentages of chlorine, say
40 to 65%, are preferred in most cases.
The
metal compound may be antimony trioxide, tetra
oxide or pentoxide, tin oxides, bismuth oxides,
5 to 40
5 to 40
Chlorine-containing organic compound_ 10 to 40
5 to 40
may be diluted with water. The method of ap
plication may be dipping, brushing, spraying, or
other means of coating or impregnating. The
application to textile fabrics is generally carried
out by immersion, squeezing and drying at ele
vated temperatures. The composition does not
need to penetrate deeply to be effective. Good
‘arsenic oxides or any water-insoluble compound
penetration of the interstices of materials such
of these metals which will yield the oxide when 40 as cotton cloth is desirable when colored com
heated, for instance the respective sul?des or the
positions are applied. Sufficient penetration is
metals themselves.
usually obtained when the material is absorbent
In the customary practice with ?ameproo?ng
such as bleached cotton while unbleached cotton
compositions of the above type, the usual method 7
is usually resistant to wetting by water and resists
of application is to disperse the metal oxide in
penetration.
an organic solvent solution of the chlorine-con
Agents which lower the surface tension of
taining compound and apply the mixture in one
water may be'added to assist wetting. Alcohols
operation. Such a material corresponds to a
are the preferred wetting assistants, since they do
solvent-carried paint.
not interfere with the effect of waterproo?ng
According to my preferred mode of operation 50 agents where such are required. Ethyl alcohol
the anti-tendering agent of this invention, in
is soluble in water while hexyl alcohol may be
other words, the aforesaid protein-resin reaction
dispersed in the composition'or added as a sepa
product, may be employed to produce aqueous
, rate dispersion.
-'
suspensions of the aforegoing mixed ?ameproof
The drying step in the? application of these
ing agents, wherein it acts both as a dispersing 55 products may be carried out at ordinary tempera
agent and as a protective bu?er against the de
tures or at temperatures up to 300? F. 'or higher.
velopment of excessive concentrations of hydro
The higher temperatures are preferred when
gen chloride. However, if desired, the protein
fastness to water is required. However, consid
resin buffering agent of this invention and the
erable fastness to water may be obtained by dry
chlorinated organic ?ameproo?ng agent above 60 ing at room temperature.
discussed may be applied to the fabric separately,
The compositions of this invention may be ap
from separate organic solutions or aqueous sus
plied to any readily in?ammable ?brous material
pensions.
such as wool, silk, cellulosic fabrics, ropes, sheets
As already noted, the protective agent of this
or articles of wood or paper to render them re
.invention acts also as a dispersing agent, and as 65 sistant to burning. .
a binding agent for the other ingredients. How
Treated \materials such as cotton fabrics, pa
ever, additional, extraneous dispersing agents and
per, rope and wood require varying amounts of
binding agents may be added if desired. Like
added ?nish to obtain a ?ameproo?ng e?ect.
wise, fungicides may be added in the form of in
Heavy weight fabrics can be proofed with less
soluble pigmentsvor in the form of compounds 70 added ?nish per unit weight than light-weight
soluble in the chlorinated organic agent; again,
fabric since the ?nish does not completely pene
if desired, they may be added as a separate dis
persion. Waterproo?ng materials may be simi
larly added when desired.
In addition to the foregoing, any of the cus
trate, and approximately the same amount is re
quired for the same surface area.
Without limiting my invention, the following
75 examples are given to illustrate my preferred
9,418,108
-
mode of operation. Parts mentioned are by
weight.
6
PA“ 11. Purmnou or m Fmmnoormc
‘
COATING_C01IPOSITIOR
PAar I. PREPARATION or rm: Paornm-Rnsm
RzAcnon Pnonocr
‘
‘
Example 1
Parts
10
Casein
'
_ Example 5.—Basic formula
Triethanolamine ______________________ __
4
Parts
Protein-resin reaction-product (from Ex
ample 4)
15.5
Antimony oxide (Sb3O3) _______________ -_
20.5
Chlorinated para?ln wax (42% Cl) _____ __
43.5
Water
20.5
Urea
18 10
40% formaldehyde solution; _____________ __
50
Water
18
Total __________________________ __ 100.0
100
The antimony trioxide was dispersed in the
protein-resin agent by high-speed agitation us
'
Total
‘
I
The above composition was prepared by adding 15 ing a soda mixer at room temperature. The chlo
rinated paraffin wax, containing approximately
the casein to a solution of the urea and tri
42% chlorine, was then added along with 5 parts
ethanolamine in water, soaking for 15 minutes at
of water, and dispersed as above. The remaining
about 25° C., heating to about 60° C., then add
15.5 parts of water were then added with stirring.
ing the formaldehyde solution at 60° C; and cool
20 A medium viscosity, white, stable dispersion was
ing the mixture to room temperature.
obtained.
Example 2
Example 6.--Variation of the basic formula
.
'
.
Parts
Casein
5
Triethanolamine
______ ____ ___________ .._
.
3.5
Melamine
7.5
Parts
25 Protein-resin reaction-product (from Ex
40% formaldehyde solution_____-________ 20
ample 4)
Antimony oxide
Water
Chlorinated para?in wax (42% Cl.) ______ __
50
Water
25 =
64
15
10
Total
100 30
Total
100
The above composition was prepared by dis
solving 3 parts of triethanolamine in 15 parts of
The procedure was as in Example 5. A stable
water; adding the casein, allowing to soak for 15
dispersion was obtained.
minutes at about ‘25° C., and then heating to
Example 7.—Variation of the basic formula
about 60° C. The melamine and the remainingv 35
0.5 part of triethanolamine were added to the
Parts
formaldehyde solution and likewise heated to
Protein-resin reaction-product (from Ex
about 60° C. The two solutions were then mixed
ample 4)
_
15
jointly with 49 parts of hot water (60'' C.), and
40
40 Antimony oxide
the mixture was cooled to room temperature.
Chlorinated para?in wax (42% Cl) _______ __ 20
Water ..
__..
25
Example 3
Parts
Total
100
Casein
5
Triethanolamine _________.._______________
3
Procedure, as in Example 5. A stable disper
Phenol ..
'
10
sion was obtained.
40% formaldehyde solution ______________ __ 20
Example 8.—Use of a fungicide, calcium carbon
Water
__
62
‘ ate and a waterproo?nll agent
100 50
Total ‘
.
ample 4)
utes at about 25° C.‘ and then heating to about
60° C. and adding 47 parts of water at 60° C. fol
lowed by the phenol dissolved in the formalde
h‘yde solution also heated to about 60° C., and
60
Parts
Soyabean protein _______________________ __
Triethanolamine _______________________ __
Urea
____-
'
10
4
18
40% formaldehyde solution ___________ _Y____
50
Water
18
__
____
168.0
Antimony oxide __________________ _;___
149.0
Calcium carbonate ___________________ __
salicylanilide ________________________ __
129.0
10.0
Re?ned para?ln wax _________________ __
9.0
Glue
cooling the mixture.
Example 4 -
Parts
Protein-resin reaction-product (from Ex
This composition was‘ prepared by dispersing
the casein in 15 parts of water containing the tri
ethanolamine, by soaking, as above, for 15 min
'
_
1.8
Chlorinated para?in wax (42% Cl) ____ __
385.0
Water ______________________________ __
148.2
Total _________________________ __ 1000.0
The antimony oxide, calcium carbonate and
salicylanilide were added to the protein-resin
agent in a heavy duty mixer and dispersed by
viscous milling; 15 parts of water and the chlo
rinated para?in wax were added, and a good dis
persion of the wax was‘ obtained by continued
milling; 129 parts of water were then added fol
This composition was prepared in the same 70 lowed by the re?ned paraffin wax dispersed in
manner as Example 1, using soyabean protein in
19.2 parts of water containing the glue as a
stead of the casein in that example. The com
dispersing agent. A stable, ?uid, white emulsion
position of this example is available in commerce,
was obtained. Fabric treated with this compo
and was therefore used inmost of the examples
sition was more waterproof than fabric treated
of Part II, hereinbelow.
75 with the compositions of Examples 5, 6 and '7.
Total
___________________________ __ 100
an
a
amazes
The dispersion was prepared by viscous milling.
Example 9.--Use of a fungicide soluble in the
chlorine-containing compound
The ?rst seven ingredients were mixed in the
order named; 20 parts of water were then added;
the chlorinated para?in wax was then added
slowly, followed by the re?ned para?in wax dis
persed in part of the water containing the glue,
Parts
Protein-resin reaction-product (from Ex
ample 4) ___________________________ .__
Antimony Oxide _______________________ __
Magnesium carbonate _________________ __
150
150
100
Chlorinated paraffin wax (42% Cl) _____ __
300
Pentachlor phenol ____________________ __
20
Water _____
Total
and ?nally the remaining water. A stable, olive
drab dispersion was obtained.
280
10
Parts
prepared by viscous milling in ‘essentially the
same manner as in Example 8.
white dispersion was obtained.
A stable, ?uid,
Example 10.-Use of colored pigments to give a
sand shade
Parts
Protein-resin reaction product (from Ex
ample 4) _________________________ __
Antimony oxide _' ___________________ __
Magnesium carbonate _______________ __
Lamp black ________________________ __
274.50
123.00
109.00
0.51
Yellow iron oxide ___________________ __
9.22
Red iron ___________________________ __
0.77
Chlorinated para?in wax (42% Cl) _____
338.00
_____________________________ _ _
Total
Example 13.-Incorporating pigments in the
chlorine-containing compound
__________________________ __ 1000
The pentachlor phenol was dissolved in the
chlorinated para?fin wax and the dispersion was
. Water
8
.
145.00
Chlorinated para?ln wax (42% Cl) .... __
Copper phthalocyanine blue __________ __
15 Chrome yellow ______________________ __
A brown metallized azo color _________ __
375.59
3.22
19.32
6.77
Antimony oxide _____________________ __
Magnesium carbonate _______________ __
Protein-resin reaction-product _______ __
170.70
85.42
338.98
20
-
-
'——
Total ...... __‘_ ________________ __
1000.00
All the ingredients except the protein-resin
agent were mixed and then ground to a smooth
paste by means of a roller-type ink mill. The
25 resulting mixture was then thoroughly mixed
with the protein-resin reaction product from
Example 4. A stable, olive-drab paste, readily
dispersible in water by stirring, was obtained.
- Example 14
30
Compositions similar to those described in
Example 5 were prepared using 15 parts of the
reaction products obtained in Examples 1, 2 and
3 as protein-resin compositions. Stable disper
________________________ __ 1000.00
The pigments and 20 parts of water, followed
by the chlorinated para?in wax, were dispersed
in the protein-resin agent by viscous milling. 35 sions were obtained.
The remaining water was then mixed in. A sand
colored, ?uid, stable dispersion was obtained.
Example 15.—-Use of a casein-urea formaldehyde
resin composition in an olive-drab colored
Example 11..—Injra-red, re?ecting, olive-drab
shade
Parts
Protein-resin reaction-product ________ __
Antimony oxide _____________________ _...
Zinc dimethyl dithiocarbamate ______ -1-
7.0
90.0
7.0
A blue alkyl ether of dioxydibenzanthrone
24.0
Copper phthalocyanine _______________ __
6.0
Magnesium carbonate ________________ __
90.0
Chlorinated para?in wax (42% Cl) ____ __
300.0
Water
141.0
Parts
Casein _______________________________ _.-
220.0
115.0
Yellow iron oxide ____________________ __
Red iron oxide _______________________ __
______________________________ __
?a‘meproo?ng composition
40
1.5
Triethanolamine _____________________ __
Urea
,
Formaldehyde solution (37%) __________ __
45 Water
. Antimony oxide
- Calcium
.6
2.7
_
7.5
-
2.7
12.5
carbonate ____________________ __
12.5
__
Lead chrnmnha
6,0
' Lamp black
_
2.5
Chlorinated paramn wax (42% Cl) ______ __
37.5
Water
13.0
60 Red iron oxide
_--
1.0
.... .._
___
Total _________________________ __ 1000.0
The dispersion was prepared by viscous milling.
Total ___________________________ __ ' 100.0
The ingredients were added to the mill in the
above order, except that 75 parts of the water
The casein, triethanolamine, urea, formalde
hyde and 2.7 parts of water were first combined
as described in Example 1. The resulting prod
uct was used in place 01 the protein-resin agent
from Example 4, and the above composition was
were added intermittently with the magnesium
carbonate to maintain the proper viscosity for
milling. An olive-drab colored, stable dispersion
was obtained.
6" prepared in the same manner as in Example 10.
Example 12
‘
Protein-resin reaction-product ____-_____
Lamp black
128.0
______
24.0
Antimony oxide ______________________ __
128.0
Calcium carbonate ___________________ __
118.0
Chrome yellow ______________________ __
Red iron oxide _____________ __‘ _______ __
65.0
11.0
Zinc dimethyl dithiocarbamate _______ __
Chlorinated para?in wax (42% C1) ____ __
Glue ________________________________ __
Re?ned para?in wax _________________ __
Water
______________________________ __
Example 16.—Composition containing a vim/li
dine chloride polymer
Parts
'
Parts
65 Protein-resin reaction-product _________ __
Antimony oxide _______________________ __
Calcium carbonate ___________________ __
Lead chromafe
»
Lamp blank
10.0
354.0 70 Red iron oxide________________________ __
'
Water
2.0
25
1.0
4
Polyvinylidine chloride dispersion (18%
10.0
150.0
Total _________________________ _.. 1000.0
'
12
10
10
6
solids) _____________________________ __ 150
75
Total..______; ____________________ _.. 195.5
2,418,103
9
10
The pigments were dispersed in the protein
resln agent and water by means of high-speed
agitation. The polyvinylidine chloride emulsion
Char-length, before leachingJnches--. 1% to 1%
Char-length, after leaching___do_-__ 1% to1%
was then added. A stable olive-drab colored dis
persion was obtained.
pletely under the same tests.
Untreated ‘control samples burned up com
Example 17.-Use of antimony sul?de in place of
Example 19.—In,fra-red re?ectant dyed fabric
antimony oxide
Protein-resin reaction-product ___________ __
15
Black antimony sul?de __________________ __
Chlorinated para?ln wax (42% Cl) _______ __
25
35
The composition described in Example 8 was
applied to burlap colored green and having an
10 infra-red re?ectance of about 30% at 800 milli
microns wave length. The composition was di
luted with an equal weight of water and applied
Water ___
'70
by immersion, squeezing to 130% liquor take-up,
Parts
Paar In. FLAMEPROOFING Fnmous MATERIAL
and drying over night in the atmosphere. An
15 other similarly treated sample was dried at, ap
proximately 110‘3 C. Both samples were leached
24 hours by immersion in gently running water
at 20-25“ C. Osnaburg ,fabric colored earth red
and having an infra-red re?ectance of about
20 25% at 800 millimicrons was treated in the same
manner. The shade and infra-red re?ectance
of the treated samples was only very slightly
Example 18.—C'otto,n duck, Basic formula
‘changed by the treatment. The resistance to
burning of all samples was found to be as fol
Total _____________________________ __ 145
The antimony sul?de was dispersed in the pro
tein-resin agent and 10 parts of the water by
high-speed agitation, followed by the chlorinated
para?in wax and the remaining water.
black dispersion was obtained.
A stable
The compositions obtained in Examples 5, 6 and
'7 were diluted with water and alcohol as follows:
Parts
ows:
Flaming time ____ __' _________ _______-seconds__ 0
Char-length __________________ __inches__ 3 to 4
Composition of Example 5, _6 or 7 ____ __'_____ 140
Water
Denatured
50 80.
alcohol ______________________ __
10 -
-
Example 20.—Oz7en mesh fabric’
The composition described in Example 10 was
diluted with water and denatured alcohol in the
Total"; __________________________ __ 200
following proportions and applied to unbleached
cotton netting made on a Lever’s warp knitting
The diluted treatment baths were applied to 35 machine and weighing approximately 5 ounces
unbleached cotton duck, weighing approximately
per square yard.
12 ounces per square yard, by immersing the fab
ric in the diluted treatment bath, squeezing be
‘ Parts
tween rubber rollers to leave in the fabric an
Composition described in Example 10 _____ __ 180
amount equal to 80% of the Weight of the ?ber, 40 Water _________________________________ __ 105
and‘then drying on steam heated‘ copper drums
Denatured alcohol _________________ __,____.. 15
at 110° to 115° C. After drying, the samples
were found to have gained about 45% in weight.
Total ______________ _-___e_ ________ __ 300
The resistance to burning of the samples thus
The netting, approximately 29 feet square, was
prepared was compared with untreated material 45
folded to 8 thicknesses and impregnated with the
as follows:
above mixture‘ by passage through a padding
Strips were cut 10 inches warpwise by 2 inches
machine equipped with one dip roll in the pad
?llingwise and 10 inches ?llingwise by 2 inches
box and two squeeze rolls. The netting was dried
warpwise. A Bunsen burner, enclosed to exclude
drafts, was adjusted to give a luminous ?ame 11/2 50 at room temperature on a pin frame and then
heated in air at 125 to 130° C. for 20 minutes.
inches high.
Samples of the conditioned fabric were tested as
The test strip was suspended vertically with
follows:
the center of the lower end extending into the
Resistance to burning was determined by burn
above ?ame % of an inch. The strip was allowed
to remain in the ?ame for 12 seconds; it was 55 ing 0.3 cubic centimeter of absolute alcohol in ‘a '
cylindrical copper cup 1Arinch high having a ca
then removed, and the time that the sample
Dacity of 1 cubic centimeter placed under a 7
continued to ?ame was noted. After all burn
inch square of the netting held at a 45° angle
ing ceased, the length of char caused by ?am
to horizontal, the bottom of the center of the
ing and glowing was measured. The char
length was determined by suspending a weight 60 cup being 11/2 inches from the center of the test
fabric. The size of the burned area was taken
of 1 pound from one of the legs of the now V
as a measure of its resistance to burning.
shaped lower end of the sample, raising gently
Other samples of treated netting were leached
the end of the other leg to support both Weight
24 hours by immersion in gently running water
and sample. thereby causing some tearing at the
\
apex of the V, and then measuring the total 65 at 25-30° C.
Still other examples of treated netting were
depth of the V resulting from both burning and
exposed for 300 hours in‘ a National weather unit.
tear.
The resistance to burning was determined as
Resistance to burning was also determined
in the following table.
after the treated fabric was subjected to a 24
hour leach by immersion in gently running water 70
'~
Dimensions of burned area
at 20-25’ C.
Untreated ____________ __ Burned up completely
The average values of 5 tests for each sample
Treated ___________________ __inches__ 11/2 x 2
and treatment-bath were as follows:
Flaming time, both before leaching and after
leaching 0 to 2 seconds.
-
Treated and leached _________ _..do____ 1% x 2
Treated and exposed 300 hours in
weathering unit __________ __inches__ 11/2 x 3%
2,413,163
12
11
Example 21.—Paper
?ameproo?ng showed excellent ?ame and char
The composition described in Example 8 was
mixed with water and paper pulp and precipi
tated on the pulp by adding a solution of alu
Example 26.~C'otton duck. Using antimony sul
minum sulfate. A sheet of paper was made from
The composition given in Example 17 was ap
resistance.
-
_
?de
the mixture by screening out the pulp and dry
ing the sheet. The ?nished sheet contained ap
proximately 38.5% chlorinated para?in wax and
15% antimony oxide. The sheet was very re
plied to cotton duck by dipping, squeezing and
' drying. Flame tests showed no after?aming, and
a char-length of one inch.
sistant to burning. The same composition was iii PABT~IV. Tssrme ms Pnorncrrvn ACTION or THE
coated on a sheet of paper to give approximately
PROTEIN-RESIN REAGENT
100% added weight after drying. The product
Example 27
Compositions as described in the following
was very resistant to burning.
Example 22.—-Wood
15 table were prepared by dispersing the ingredients
applied to strips of pine wood approximately
in water by high-speed agitation and were ap
plied to 12-ounce cotton duck as described in Ex
12 x 1 x 116 inches by dipping the wood in a bath
ample 14 to deposit approximately 20% chlori
The composition described in Example 5 was
consisting of equal parts of composition and
nated para?in wax weight on the fabric.
water. The dipped wood was allowed to drain 20 Samples of the fabric so treated, and l ttreated
and dry at room temperature. About 12 treated
fabric were exposed in a Fade-Ometer for 50
sticks were stacked in the shape of an inverted
hours, and the loss in tensile strength compared
cone and two paper towels placed under the
with untreated, unexposed fabric was deter
structure. The paper towels were lighted with a
mined. The resulting data are given in the fol
25
match. This procedure was duplicated with un
lowing table:
Weight of added agent in per cent of
weight oi ?ber
S amp1e
5 ll on tion me dium
.
Chlorinated
Protsresin
c 1 1
(42% 01)
(fr. Ex. 4)
a“ "m -
para?. wax react-prod.
“be “Te
Untreated... Control_____
20
1)1“
oss081111“
pp
strength
Stoddard solvent 1
30
63
Water ____________________ __
2i
_ Water and Stoddard solvent 1."
15
Water _________________________ _.
17
l A petroleum distillate known to the dry cleaning industry as Stoddard solvent.
1 The protein-resm agent was applied irom water and dried, prior to treatment with chlorinated paraffin
from Stoddard solvent.
Example 28
treated sticks. The treated sticks did not catch
?re and the paper towels under them burned very
slowly. Four additional towels were added with
out igniting the treated wood. The untreated
sticks and the two paper towels under them
burned up very rapidly.
In the prior art, it has been suggested to coun
tera/ct the tendering action of ?ameproo?ng
chlorinated organic compounds by incorporating
. into the coating composition opaque, inorganic
pigments and water-insoluble alkaline materials
such as lamp black, zinc oxide, calcium carbonate
and yellow iron oxide. To compare the protec
tive action (against tendering of the treated ma
terials) of my novel compositions of this inven
tion against the above compositions of the prior
art, the following additional tests were carried
out.
Example 23.-Wool
A cutting of undyed wool serge fabric was
treated with the composition described in Ex
ample 8 by immersion, squeezing and drying in
air at approximately 90° C. The added dry
weight was approximately 50%. An untreated
strip of the wool fabric burned up completely
when tested according to the procedure given
5:
in Example 14, while a treated strip was only
charred about 11/2 inches and showed no after
?aming.
Ezample 24.—-R_egenerated cellulose
.
‘
Chlorinated para?in
40% chlorine
wax
Parts
containing
20
Antimony oxide _____________________ __
60
A sample of light dress material made of re
generated cellulose ?bers was treated with the
composition described in Example 13 by immer
sion, squeezing and drying in air at 250° F. The
dry take-up on the treated fabric was 40%. The 65
treated fabric was very resistant to burning when
tested according to the procedure described in
Example 14; the length of char was 2 inches.
Example 25.—C'0tton duck. Using a vinylidine 70
type chlorine-containing resin
The composition described in Example 16 was
applied to cotton duck by dipping, squeezing and
drying to give 20% added weight based on the
weight of the original dry fabric. A test for
Composition A:
7
Zing oxide
1
Calcium carbonate __________________ __
3
Yellow iron oxide ___________________ __
6
Lamp black _________________________ __
1
Black iron oxide ____________________ __
2
' Chlorinated
rubber
containing
67%
chlorine __________________________ __
xylol
___
5
55
Total __________ _'_ ________ __'____ 100
Composition B: The same as Composition A,
except that the quantity of xylol employed was
reduced to 14 parts, and the mixture was emulsi
?ed in water containing 10.0 parts of the protein
rcsin reaction-product obtained in Example 4.
The above compositions were applied to #10
2,41a,1es
duck cotton fabric by immersion, padding and
drying to deposit approximately 20% 01' the chlo
I
14
Organic compounds of lower chlorine content,
say 25 to 30%, may also be used, provided larger
rinated para?in wax based on the weight of the
untreated fabric. The treated fabrics were then
exposed in a Fade-Ometer for 50 hours. and
the loss in tensile strength due to exposure was
quantities of the compound are employed. The
quantity of any given agent is in general selected
determined for the warp threads by comparison
ticular type of ?brous material.
so as to give a hydrogemchloride equivalent not
less than a predetermined minimum for any par
with samples of the same treated fabrics before
According to this invention, the above ma
exposure. It was found that the samples treated
terials are dispersed in water using a protein=
with Composition A lost 66% of their original 10 formaldehyde-resin
water-soluble reaction prod
tensile strength, while those tested by Composi
not as the dispersing agent, which becomes a
tion B suffered no measurable loss whatever.
water-insoluble film when dried for a long time
Example 29
at ordinary temperatures or for shorter times at
Various cotton fabrics were treated with the 15 higher temperatures. The protein component
may be casein, soyabean protein, glue, gelatin or
compositions prepared hereinabove in Examples
other
protein material which is normally rendered
10, 11 and 12, respectively, ‘by immersion, pad~
water soluble by the aid of alkaline agents and
ding and drying to deposit approximately 20% of
water-insoluble by the action of heat, acids or
the chlorinated paraffin wax, based on the weight
of the untreated fabric. The treated fabrics 20 aldehydes. The alkaline solubilizing agent may
be any water-soluble alkaline amine or quater~
were then exposed in a Fade-Ometer for various
nary ammonium base, although aliphatic amines
lengths of time and the loss in tensile strength
(especially triethanolamine) are preferred. The
was determined as above. Found:
most suitable aldehyde is formaldehyde and the
most suitable resin base is urea. 'Oth'er resin
Composition oi—
Type of fabric
Extgglsgre Loss 25 i’orming agents which could be used in lieu of
urea are adipamide, succinamide, oxamide or
other
amides capable of forming water-soluble
Hours
Per cent
methylol derivatives which can be insolubilized
by condensation to a resinous state. Phenol
Example 12. . _
> Y
#10 duck __________ __
50
3
Example 10. . . _
. . _ __
Tricot netting _____ __
Example 11 _ _ . _
. . _ --
Levers netting .... ..
.
200
2
100
7
a0, formaldehyde and melamine formaldehyde may
also serve as the resin-forming agent.
The es
Samples of two commercial fiameproofing ?n
ishes applied to tricot netting and tested under
sential requirement is that the dispersing-and
?lm-forming agent shall prevent the degrada~
the same conditions showed a tensile strength
tion of cellulose treated with an unstable chlo
loss of 70% in 200 hours and 94% in 150 hours, 35 zine-containing organic compound. The de
respectively.
Samples of cotton fabrics treated with compo
sitions of the present invention have also been
grading agent may be chlorine, hydrogen chlo
ride,- hydrochloric acid or metallic chlorides
formed from the metallic pigments used. '
subjected to long storage and outdoor exposure
The compositions described in the examples
without appreciable loss in tensile strength.
40 vmay be prepared within a wide range of temper
It will be understood that the above examples
atures, say from 32° F. to 212°F., although room
are merely illustrative and that wide variations
temperature is preferred for convenience.
in the details thereof may be practiced without‘
The order of addition of the various ingre
departing from the spirit of this invention. Thus,
dients of these compositions is not critical except
in lieu of the chlorinated para?in wax and anti 45 to maintain the optimum conditions for manu
mony oxide employed in the majority of the
facturing, especially consistency, and to obtain a
above examples, any other combination of known,
practical, ?re-resisting materials may be em—
ployed.
The essential ?re-resisting materials of pres
ent-day practice are organic compounds con
taining 20 to 80% chlorine by weight and an
usable product. For example, it is logical to start
with at least some of ‘the water and the dis
persing agent and then add the materials to be
It may also be desirable to combine
60 dispersed.
part of the materials in one mix and part in
another and then mix the two parts. For ex
oxide of the metals arsenic, antimony, bismuth
ample, the metallic oxide may be dispersed along
with calcium carbonate and coloring pigments
The chlorine-containing organic compounds 65 and the dispersion mixed with another dispersion
include chlorinated para?in wax, chlorinated
of the chlorine-containing organic material and
fatty acids, chlorinated turpentine, chlorinated
optionally other ingredients. Where additional
.para?in oils, chlorinated vegetable oils, chlo
water-proo?ng or mildew-proo?ng properties are
rinated rubber, vinyl chloride polymers, chlo
required in a composition, compatible dispersions
or tin.
-
rinated vinyl chloride polymers, polyvinylidine 60 of either or both of such agents may be added.”
chloride and other chlorine-containing organic
Compatible color dispersions may also be added
compounds which are unstable at the ignition
temperature of cellulosic materials.
' _
separately.
The pigments may be ,?nely divided to begin
It will be recognized- that all the compounds
with and be easily defiocculated, or it may be
indicated hereinabove are non-volatile at tem 66 necessary to mill or grind the pigments in the
peratures up to 300° F.
~
vehicle. The pigments may be dispersed in the
In all the above, the chlorinated organic com
water phase directly or they may be ground in
pounds found most suitable in our invention are
the chlorinated organic material and the mix
those which possess at least 40% 01' combined
ture dispersed in the water phase. The water
chlorine and which are adapted to liberate at 70 phase may even be dispersed in the oil phase
least 50% of this combined chlorine in the form
(chlorinated organic compound) at some stage
of hydrogen chloride upon being heated alone for
of preparation, although in the ?nal stages,
especially when diluted for use, the continuous
400° 0.. which corresponds to the'average kin
phase is generally water since dilution tends to
dling point of untreated paper or'textile ?ber. 18 invert the “water-in-oil" system.
five minutes at a temperature between 300 and
2,413,168
15
The dispersed compositions may be prepared
by any suitable means, such as by viscous milling.
grinding in a paint or ink mill, or by high-speed
agitation in a more ?uid state.
The chlorine-containing material may be a
solid dispersed as a pigment, or it may be a
liquid at ordinary temperatures and be dispersed
rine content is not less than 20% by weight and
which liberates at least half of said chlorine, in
the form of hydrogen chloride, upon being heated
to a temperature between 300 to 400° C.; and said
joint protective and dispersing agent being a
water-soluble, acid-insoluble reaction product of
‘the group obtained by reacting (a) formaldehyde,
in aqueous medium with (b) a protein which had
been rendered water-soluble by reaction with an
carried out under a wide range of conditions of 10 aliphatic amine and (c) a reagent selected from
the group consisting of phenol, melamine, urea
temperature (32° F. to 212° F.), concentration
and diamides of aliphatic dicarboxylic acids hav
(diluted with water or applied as prepared), and
ing not more than 6 carbon atoms per molecule;
mechanical means of application, such as coat
‘in the form of droplets,
The application of the compositions may be
ing, spreading, brushing, immersion, spraying,
said joint protective and dispersing agent being
The composition may even be precipitated 15 further characterized by its capacity to form an
insoluble ?lm upon being dried, and by its
on material from a dilute bath by adding alum
capacity to react with hydrogen chloride which
or other agents.
may be slowly liberated by said organic ?ame
The impregnated material may be dried in any
proo?ng material upon storage of the treated
suitable manner, although greater durability to
water is obtained at higher temperatures and 20 ?brous material, thereby counteracting the
tendering action which said liberated hydrogen
longer periods of drying.
chloride otherwise exerts upon said ?brous mate
The protective protein-resin may be applied
separately to the material to be treated and still
rial.
2. An aqueous composition for ?ameproo?ng
be effective in preventing damage by chlorine
containing materials applied to the same ma 25 organic ?brous material, comprising a stable,
homogeneous, aqueous suspension of at least
terial.
three components, namely (1) antimony oxide,
The principal use of the novel compositions of
(2) an organic fiameproo?ng agent and (3) a
this invention is to render textile fabrics re
joint protective and dispersing agent; said
sistant to burning. Materials of most interest
are ducks for tents and paulins, and other fabrics 30 organic ?ameproo?ng agent being a chlorine
containing, non-volatile water-insoluble, organic
such as netting, burlap and Osnaburg, awnings,
compound whose chlorine content is not less than
upholstery, tobacco cloth, and similar materials
20% by weight and which liberates at least half
which may vbe subjected to leaching by rain,
of said chlorine, in the form of hydrogen chloride,
water, exposure to sunlight, and weathering in
upon being heated to a temperature between 300
general. Fabrics not to be exposed to leaching
to 400° C.; and said joint protective and dispers
may also be advantageously treated. Treatments
ing agent being a water-soluble, acid-insoluble
are effective on cotton, regenerated cellulose and
reaction product obtained by reacting with (a)
wool?bers.
formaldehyde upon an aqueous mixture compris
The compositions are also useful for treating
ing (11) a protein solubilized by reaction with an
paper articles, rope, cellulose sponge, padding,
alkanol amine and (c) urea; said joint protective
stu?ing and insulating materials, such as straw
etc.
and. wood shavings, wood, especially framework
and dispersing agent being further characterized
for houses and in attics and cellars of completed
by its capacity to form an insoluble ?lm upon be
buildings.
ing dried, and by its capacity to react with hydro
The principal advantages of my novel com- r
positions are that they will not damage the
treated material when exposed to light or heat
under normal conditions of use, for instance,
prolonged outdoor exposure; ‘they do not con
tain toxic or inflammable materials; they are ap
plicable from water; they are practically odor
less, and the treated materials are non-tacky;
the compositions are easily mixed with water,
requiring no mechanical equipment for emulsi
?cation', and ?exible materials remain ?exible
after treatment, even if subjected to extremely
low temperature.
In the claims below the term “non-volatile” as
gen chloride which may be slowly liberated by
said organic flameproo?ng material upon storage
of the treated ?brous material, thereby counter
acting the tendering action which said liberated
hydrogen chloride otherwise exerts upon said
?brous material.
3. An aqueous composition for ?ameproo?ng
organic ?brous material, comprising a stable,
homogeneous, aqueous suspension of at least
three components, namely (1) antimony oxide,
(2) an organic ?ameproo?ng agent and (3) a
joint protective and dispersing agent; said
organic ?ameproo?ng agent being a non-volatile,
water-insoluble, chlorinated para?in hydrocar
applied to the chlorine-containing, organic ?ame
bon whose chlorine content is between 20 and
that the agent will not evaporate at temper
dispersing agent being a water-soluble, acid in
soluble reaction product obtained by reacting
‘ proo?ng agents is to be construed as meaning 60 80% by weight; and said joint protective and
atures up to 300° F.
I claim as my invention:
1. An aqueous composition for ?ameproo?ng
with formaldehyde upon an aqueous mixture of
urea and triethanol-amine—soyabean-proteinate;
organic ?brous material, comprising a stable, 65 said joint protective and dispersing agent being
homogeneous, aqueous suspension of at least
further characterized by its capacity to form an
insoluble ?lm upon being dried, and by its
three components, namely (1) an inorganic
capacity to react with hydrogen chloride which‘
?ameproo?ng agent, (2) an organic ?ameproof
may be slowly liberated by said organic flame
ing agent and (3) a joint protective and dispers
ing agent; said inorganic ?ameproo?ng agent 70 proo?ng material upon storage of the treated
?brous material, thereby counteracting the
being ametai compound of the group consisting
tendering action which said liberated hydrogen
of the oxides and sul?des of antimony, arsenic,
bismuth and tin; said organic ?ameproo?ng
chlloride otherwise exerts upon said ?brous mate
ria .
agent being a chlorine-containing, non-volatile
water-insoluble, organic compound whose chlo 75 4. A ‘process of flameproo?ng organic ?brous
2,418,188
17
18
material, which comprises impregnating said
organic ?ameproo?ng agent being polyvinylidene
?brous material with an aqueous composition of
matter as de?ned in claim 1, and drying the tex
chloride; and said joint protective and dispersing
agent being a water-soluble, acid insoluble re
‘ tile material whereby to remove the moisture, and
action product obtained by reacting with for
simultaneously convert the protective agent into
maldehyde upon an aqueous mixture of urea and
a water-insoluble form on the ?ber.
triethanol-amine-soyabean-proteinate; said joint
protective and dispersing agent being further
'
5. A process of ?ameproo?ng organic ?brous
material, which comprises‘ impregnating said
characterized by its capacity to form an insoluble
?lm upon being dried, and by its capacity to react
matter as de?ned in claim 2, and drying the tex
with hydrogen chloride which may be slowly
tile material whereby to remove the moisture,
liberated by said organic ?ameproo?ng material
and simultaneously convert the protective agent
upon storage of the treated ?brous material,
into a water-insoluble form on the ?ber.
thereby counteracting the tendering action which
6. A process of ?ameproo?ng organic ?brous
said liberated hydrogen chloride otherwise exerts
material, which comprises impregnating said
upon said ?brous material.
?brous material with an aqueous composition of'
11. An aqueous composition for ?ameproo?ng
matter as de?ned in claim 3, and drying the tex
organic ?brous material, comprising a stable,
tile material whereby to remove the moisture,
homogeneous, aqueous suspension of at least
and simultaneously convert the protective agent
three components, namely (1) antimony oxide,
into a water-insoluble form on the ?ber.
20 (2) an organic ?ameproo?ng agent and (3) a
7. Fibrous organic material impregnated with
joint protective and dispersing agent; said
a ?ameproo?ng composition as de?ned in claim 1
organic ?ameproo?ng agent being chlorinated
and as modi?ed on the ?ber by drying the im
rubber; and said joint protective and dispersing
pregnated material.
agent being a water-soluble, acid insoluble re
8. Fibrous organic material impregnated with 25 action product obtained by reacting with for
?brous material with an aqueous composition of
a ?ameproo?ng composition as de?ned in claim 2
and as modi?ed on the ?ber by drying the im
pregnated material.
9.}Fibrous organic material impregnated with
maldehyde upon an aqueous mixture of urea and
triethanol-amine-soyabean-proteinate; said joint
protective and dispersing agent being further
characterized by its capacity to form an insoluble
a ?ameproo?ng composition as defined in claim 3 30 ?lm upon being dried, and by its capacity to react
and as modi?ed on the ?ber by drying the im
with hydrogen chloride which may be slowly
pregnated material.
liberated by said organic ?ameproo?ng material
, 10. An aqueous composition for ?ameproo?ng
upon storage of the treated ?brous material,
organic ?brous material, comprising a stable,
thereby counteracting the tendering action which
homogeneous, aqueous suspension of at least 35 said liberated hydrogen chloride otherwise exerts ,
three components, namely (1) antimony oxide,
upon said ?brous material.
(2) an organic ?ameproo?ng agent and (3) a
joint protective and dispersing agent; said
OSBORNE COSTER BACON.
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