U.S. patent number 3,767,452 [Application Number 05/224,346] was granted by the patent office on 1973-10-23 for flameproofing combustible sheet materials.
This patent grant is currently assigned to Raduner and Co., A.-G.. Invention is credited to Alfred E. Lauchenauer.
United States Patent |
3,767,452 |
Lauchenauer |
October 23, 1973 |
FLAMEPROOFING COMBUSTIBLE SHEET MATERIALS
Abstract
A flameproofing agent is applied to combustible sheet material
in a pattern in which small areas of high concentration of
flameproofing agent are distributed substantially uniformly on the
sheet material and alternate with areas of low to zero
concentration of the flameproofing agent.
Inventors: |
Lauchenauer; Alfred E.
(Thurgau, CH) |
Assignee: |
Raduner and Co., A.-G. (Horn,
CH)
|
Family
ID: |
9779314 |
Appl.
No.: |
05/224,346 |
Filed: |
February 7, 1972 |
Foreign Application Priority Data
|
|
|
|
|
Feb 12, 1971 [GB] |
|
|
4,552/71 |
|
Current U.S.
Class: |
428/196;
297/DIG.5; 428/921; 427/288 |
Current CPC
Class: |
D06M
23/00 (20130101); D06M 23/16 (20130101); D06Q
1/00 (20130101); Y10S 428/921 (20130101); Y10T
428/2481 (20150115); D06M 2200/30 (20130101); Y10S
297/05 (20130101) |
Current International
Class: |
D06M
23/00 (20060101); D06M 23/16 (20060101); D06Q
1/00 (20060101); B44d 005/00 (); C09k 003/28 () |
Field of
Search: |
;117/37R,136,137,138 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Konopacki; Dennis C.
Claims
What is claimed is:
1. A process for flameproofing combustible sheet material which
comprises applying to said sheet material a pattern of a
flameproofing agent in which small areas of high concentration of
flameproofing agent are distributed substantially uniformly on said
sheet material and alternate with areas of low to zero
concentration of flameproofing agent, said areas of low to zero
concentration not exceeding said areas of high concentration by a
factor of about 10, and the distance between said areas of high
concentration being less than about 10 times the thickness of said
sheet material, the total amount of flameproofing agent applied to
said sheet material being from about 2 to about 30 percent, by
weight, based on the weight of said sheet material.
2. The process according to claim 1 wherein the total amount of
flameproofing agent applied to said sheet material is from about 5
to about 15 percent, by weight, based on the weight of said sheet
material.
3. The process according to claim 1 wherein the distance between
said small areas of high concentration of flame-proofing agent is
less than about five times the thickness of said sheet
material.
4. The process according to claim 1 wherein the total area of the
areas of low to zero concentration of flameproofing agent does not
exceed the total area of the small areas of high concentration of
flameproofing agent by a factor of more than about 5.
5. The process according to claim 1 in which the distance between
the edges of adjacent small areas of high concentration of
flameproofing agent is not more than about five times the mean
diameter of said areas of high concentration.
6. The process according to claim 1 in which the distance between
the edges of adjacent small areas of high concentration of
flameproofing agent is not more than about three times the mean
diameter of said areas of high concentration.
7. The process according to claim 1 wherein said sheet material
comprises textile sheet material.
8. The process according to claim 1 wherein said small areas of
high concentration of flameproofing agent comprise a regular
pattern of disconnected dots on the surface of said sheet
material.
9. A flameproof sheet material comprising an ordinarily combustible
sheet material having a flameproofing agent applied thereto in a
pattern in which small areas of high concentration of the
flameproofing agent are distributed substantially uniformly on said
sheet material and alternate with areas of low to zero
concentration of flameproofing agent, said areas of low to zero
concentration not exceeding said areas of high concentration by a
factor of about 10, and the distance between said areas of high
concentration being less than about 10 times the thickness of said
sheet material, the total amount of flameproofing agent applied to
said sheet material being from about 2 to about 30 percent, by
weight, based on the weight of said sheet material.
10. A flameproof sheet material according to claim 9 wherein the
total amount of flameproofing agent applied to said sheet material
is from about 5 to about 15 percent, by weight, based on the weight
of said sheet material.
11. A flameproof sheet material according to claim 9 wherein the
distance between said small areas of high concentration of
flameproofing agent is less than about five times the thickness of
said sheet material.
12. A flameproof sheet material according to claim 9 wherein the
total area of the areas of low to zero concentration of
flameproofing agent does not exceed the total area of the small
areas of high concentration of flameproofing agent by a factor of
more than about 5.
13. A flameproof sheet material according to claim 9 wherein the
distance between the edges of adjacent small areas of high
concentration of flameproofing agent is not more than about five
times the mean diameter of said areas of high concentration.
14. A flameproof sheet material according to claim 9 wherein the
distance between the edges of adjacent small areas of high
concentration of flameproofing agent is not more than about three
times the mean diameter of said areas of high concentration.
15. A flameproof sheet material according to claim 9 wherein said
sheet material comprises textile sheet material.
16. A flameproof sheet material according to claim 9 wherein said
small areas of high concentration of flameproofing agent comprise a
regular pattern of disconnected dots on the surface of said sheet
material.
Description
The present invention relates to the flameproofing of sheet
materials.
Hitherto the flameproofing treatments of sheet material, in
particular textile sheet material such as fabrics has been carried
out by padding onto such sheet material solutions or dispersions of
suitable flameproofing agents, i.e., by impregnating the sheet
material with aqueous or non-aqueous solutions or dispersions of
such agents followed by squeezing between the rollers of a mangle
to remove the excess of thebath. Since rather high amounts of
flameproofing agents are necessary to achieve a substantial
reduction of the rate of burning or of flame propagation, such
flameproofing or flame-retarding treatments tend to affect the
handle of treated textile sheet material seriously, i.e., they
cause stiffening due to the reduction of fiber to fiber and yarn to
yarn mobility. In the case of synthetic thermoplastic material,
which has a much lower bath take-up than cellulosic or wool fibers,
it is in most cases impossible to apply by padding amounts of
flame-retarding agents sufficient to produce improvements in the
flame-retardance, and one had to resort to coating, which affects
the properties of the sheet material, and in particular the handle
to such an extent that such coated fabrics could no longer be used
for apparel fabrics and other textile applications.
All these flameproofing or flame-retarding treatments produced a
continuous coating or an enclosure of all individual fibers of the
entire sheet material, and it was believed that it was important to
have the agent distributed as uniformly as possible over the
surface of fibers, yarns and fabrics.
According to the present invention an improved and more universally
obtainable flame-retardant effect can be achieved if agents having
a flame-retarding action are present on sheet material, in
particular textile sheet material, in the form of a pattern only
locally, i.e., where areas with a high concentration of the agent
alternate with areas with low to zero concentration of such agents,
and where the average distance between areas of high concentration
of flame-retarding agents preferably is at most ten times,
preferably less than five times the thickness of the sheet
material.
The present invention also includes a process for imparting
flame-retardant properties to sheet material by applying agents
which have a flame-retarding action to said sheet material in the
form of a pattern, in which areas with a high concentration of the
agent alternate with areas with low to zero concentration of such
an agent.
This local application of flame-retarding agents has been found to
produce at the same total concentration of the agent on the weight
of the sheet material, flame-retarding effects of at least the same
magnitude as with a uniform distribution (all-over distribution) of
flame-retarding agents even though there is no or relatively little
flame-retarding agent present between the areas of high
concentration. The handle, stiffness or drape of sheet material
containing flame-retarding agents only locally is much less
affected than by a uniform application in the same concentration of
the same flameproofing agent. By the term "flame-retarding agent"
is to be understood any agent which, when applied to a certain
sheet material, is capable of reducing the rate at which a flame
propagates itself along this sheet material, or which reduces the
ease of ignition of this sheet material, i.e., which for instance
increases the time during which the sheet material has to be
exposed to a defined source of heat such as a flame until it
ignites, or which increases the amount of heat required to ignite
the sheet material, or which enhances the ease of extinction of the
flame on the burning sheet material.
Many different methods have been proposed for the evaluation of
flame-retarding or flameproofing effects, either by determining the
rate of propagation of a flame through a sample of sheet material,
which may be at any angle between 0.degree. to 90.degree. to the
horizontal plane, by measuring the oxygen consumption rate of a
flame on the material to be tested, the rate or ease of ignition,
ignition temperatures, ease of extinction, length of the charred
area and so on. Such methods are for instance described in Textile
Chemist and Colorist 2 (1970), p. 123-125. Such flame-retarding
agents may act either by giving off gases which do not support
combustion and thus displace oxygen in the air present in and
around the sheet material exposed to a flame, by forming a
virtually non-combustible coating around the components of the
sheet material if exposed to ignition temperatures, by catalytic or
chemical interaction with the material of the sheet material or
components thereof, or with gases developing during burning, by
influencing thermal decomposition characteristics (such as for
instance by lowering the thermal decomposition temperature of the
material to below its ignition temperature), the ignition
temperature or the heat of combustion or the heat capacity of the
sheet material or components thereof. The mechanism of the action
of flame-retarding agents is still not completely understood. Such
agents are believed to act by decomposing at temperatures equal to
or below the temperature of the flame and-or to have a catalytic
effect at these temperatures on gases given off during burning, on
the burning material itself, or both. In some cases they may act by
dissipating heat or by decomposing into non-combustible gases.
Different types of flame-retarding agents are known which all may
be used for products and processes according to the present
invention per se or in mixtures. Agents giving off non-combustible
gases comprise halogen compounds having a relatively low
decomposition temperature, in particularly organic chloro and bromo
compounds, compounds containing boron, nitrogen compounds, in
particular ammonium salts of acids and nitrogen compounds where
nitrogen is bonded to other atoms with preferably only one bond.
Most widely used among flame-retarding agents whose active
ingredient remains predominantly in the charred product, are
inorganic and in particular organic phosphorous compounds, which at
least in the case of cellulose are believed to change catalytically
the mechanism of thermal decomposition. Other elements present as
active ingredients in flame-retarding agents are molybdenum,
antimony, silicon, aluminum and other polyvalent atoms. Agents
preferred for the present invention are phosphorous compounds and
agents at least partly acting in the gas phase, such as nitrogen,
halogen and boron compounds, in particular in mixture with
phosphorous compounds.
All these agents according to the present invention may be present
in or may be applied per se or in mixtures to sheet material, in
particular fibrous sheet material, such as paper, woven, knitted or
non-woven fabrics, but also in sheets of foam, plastics, and wood.
They are present in the form of an irregular or random or a regular
pattern, where the areas of high concentrations of those agents may
or may not be interconnected, i.e., where the agent may be present
for instance in the form of dots (not interconnected) or lines
alone or dots interconnected by lines, or in any other pattern
where between areas of high concentration on the agent there are
areas with relatively low or zero concentration of the
flame-retarding agent. The total amount of flame-retarding agents
applied to the sheet material is between 2 and 30 percent, usually
between 5 and 15 percent of the weight of the sheet material
depending on the agents used and flame-retarding requirements. The
areas of high concentration may lie within the body of the sheet
material, i.e., imbedded in the sheet material without adding to
its thickness (this is particularly useful if the sheet material is
relatively thick) or they may only partly penetrate in the sheet
material or sit virtually only on its surface (thus increasing the
thickness of the sheet material) on either or both sides or faces
of the sheet material.
Generally speaking the total area of the areas of low or zero
concentration of the flame-retarding agent should not exceed the
total area of the area of high concentration by a factor of more
than 10, preferably 5. The distance between the edges of high
concentration areas should not be more than five times, preferably
three times or less than the median diameter of the high
concentration area, and the distance between high concentration
areas should be less than 10 times, preferably five tiems or less
the thickness of the sheet material. In the case of thin sheet
material (for instance up to the thickness of a poplin fabric or of
print cloth) the flame-retarding material may sit on the surface of
the sheet material on either or both sides depending on the pattern
and the flame-retardancy requirements, without substantially
penetrating into the sheet material.
This minimizes stiffness due to blocking of interfiber movement. In
the case of thicker sheet material it is advantageous to have more
flame-retarding material present within the structure of the sheet
material, particularly if a high degree of flame-retardancy is
required. More blocking of interfiber mobility will, however, take
place which will result in increased stiffness, which stiffness of
course will still be lower than if the flame-retarding agent would
be distributed evenly throughout the sheet material.
Flame-retarding agents may be present in pure form or together with
thermoplastic or non-thermoplastic binders, finishing agents, white
or colored pigments, etc. They may be applied in the form of
dispersions, emulsions, dry powders or pastes by known methods such
as printing, dry powder application (scattering, powder-dot
transfer), and spraying. These agents may at the time they are
applied already be polymeric or they may be subsequently
transformed into polymers, be chemically modified or reacted with
other agents present or with the sheet material or components
thereof.
The sheet material may consist of cellulose or derivatives thereof,
of proteinic material such as present in wool, of synthetic
thermoplastic polymers such as polymerisates, co-polymerisates or
mixed polymerisates of acrylic, vinylic, olefinic monomers, of
lactams or lactones, or they may be polycondensates of
poly-hydroxy-compounds and poly-hydroxylic acids, of
poly-carboxylic acids and polyamines, of poly-hydroxy compounds and
isocyanates or mixtures of such polymers. These polymers may be
present as fibers in the form of textile fabrics (woven, knitted or
non-woven), as films, sheets containing or consisting of one or
more polymeric components, as paper, cardboard or woodlike sheet
material, sheets of foam or laminates of two or more of the sheet
materials mentioned. Such sheet material, if present in the form of
textile fabrics, may be given the flame-retarding treatment
according to the present invention at any stage of finishing, but
preferably this treatment is applied as one of the last steps in
the finishing sequence. Such sheet material, whether present in the
form of textile fabrics or otherwise, may be coated with polymeric
material and/or be mechanically deformed for instance by embossing
or pressing prior or subsequent to being given the flame-retarding
treatment according to the present invention. By the term "sheet
material" is to be understood a shape that is thin in relation to
its length and breadth. It may be sheetlike in the sense of sheets
of fabrics of paper or of films, where a thin material is present
in lengths exceeding the width by a factor of 10, 20 or more or it
may consist of parts cut from such sheets or formed in that way. It
has been found possible to apply flame-retarding agents according
to the present invention in a discontinuous form on only one side
of the face of the sheet material or on both. A one-sided localized
application is particularly useful in cases where fabrics in actual
use are exposed to the accidental action of an incendiary only from
one side and where the flame-retarding agent thus can be located on
the invisible side of the material where it cannot unfavorably
affect other properties as would the same agent if distributed
evenly throughout the sheet material.
The discontinuous, pattern-like application of flame-retarding
agents also has the advantage that one may apply agents in the form
of pigments, powders, in molten form, in the form of soluble or
insoluble polymers, dispersions, emulsions, etc., i.e., one has a
much wider choice of formulation and thus may use agents which
could not be used by conventional methods leading to a uniform
distribution throughout the sheet material or by coating. Even
though there are areas where there are high concentrations of the
flame-retarding agent than if the same agent is distributed
uniformly throughout the sheet material, there always will be areas
in between the high concentration areas which are not affected at
all by the presence of the flame-retarding agent and thus will bend
very easily. Total stiffness thus is much lower than if the same
amount of the same agent is uniformly distributed over the sheet
material.
Following is a description by way of example only of methods of
carrying the invention into effect.
Example I
A cotton broad cloth which had been desized, bleached, mercerized
and given a wash and wear finish was treated with a paste
containing 2.4 g. Carbopol as a thickening agent and 20 g.
diammonium phosphate as the flame-retarding agent in 100 ml of
water was printed on one side in a pattern of dots, each dot having
a diameter of 0.8 mm. and the dots being disposed in rows so that
the distance between the edges of adjacent dots is 1 mm. and the
total high concentration area is 20 percent of total cloth area.
The amount of flame-retarding agent applied to the fabric was 5
percent of the weight of the fabric.
Example II (Comparison)
The fabric of Example I was padded in an aqueous solution of
diammonium phosphate as a flame-retarding agent, the add-on being
adjusted in such a way that the fabric also contained 5 percent
diammonium phosphate, uniformly distributed thereon. The treated
sample of Example I in which the flame-retarding agent was present
in a discontinuous form had a softer handle than the sample of
Example II in which the agent was distributed uniformly throughout
the fabric. The two samples and an untreated control were tested
according to AATCC 33-1962 (45.degree. configuration of the
fabric).
Sample 1 (dots): Burning time 6.4 sec.
Sample 2 (uniform distribution): Burning time 6.5 sec.
Control (untreated): Burning time 4.0 sec.
Example III
Examples I and II were repeated, the add-on of diammonium phosphate
this time being 10 percent on the weight of the fabric. When
subjected to the same burning test neither fabric sample
burned.
Example IV
The sample treated according to Example I was wrapped around a
piece of polyurethane foam. The same was done with an untreated
control. A gas flame (length 2 cm) was directed towards the two
samples for 7 seconds. The foam wrapped in the control started to
burn immediately, while the flame on the foam wrapped in fabric
treated according to Example I died after the gas flame had been
removed, both when the dots were on the inside or on the outside of
the wrapping fabric.
Example V
Example I was repeated for a 50:50 cotton/polyester blend
(shirting), the treatment being applied to one side only, and the
amount of flame-retardant being present on the fabric in an amount
of 5 percent by weight on the weight of the fabric. On conducting
burning tests at 45.degree. configuration of fabric and on contact
with a gas flame for one second a slight melting of the polyester
was noted and the flame died after a second. An identical test on
an untreated control resulted in melting and burning of the
polyester.
Example VI
Example V was repeated for a polyester blouse material. In the
burning tests, the treated material melted slightly and the flame
died immediately on removal from the gas flame. The untreated
melted and burned.
Example VII
A cotton poplin (desized, bleached, mercerized and vat dyed, weight
120 g/m.sup.2) was padded in an aqueous solution containing 400 g
water and 600 g Flammentin AC (a 50 percent solution of an organic
compound containing halogen, phosphor and nitrogen atoms, made by
Quehl, Speyer, Germany). The solids add-on after squeezing and
drying was 25 percent on the weight of the fabric (sample A,
treated control).
A second sample was prepared in the same way, but with an add-on of
only 20 percent solids (sample B, treated control B).
On two samples (samples C and D) of the same poplin, the same
flameproofing agent (Flammentin AC) was screen-printed in the form
of a thickened paste (522,5 g Flammentin AC, 50 percent solids;
322,5 g Meyprogum AC 7 as thickening agent. Meyprogum is
galactomannane, sold by Meyhall Chemical AG, Kreuzlingen,
Switzerland).
Sample C: printing screen with circular holes arranged in a regular
pattern, 25 percent of screen area open, add-on in solids (arranged
in the form of dots separated by areas of fabric containing no
flameproofing agent): 13 percent
Sample D: As sample B, but 34 percent of printing acreen open,
solids add-on 19 percent.
After printing, the samples B and C were dried as sample A.
Testing of all samples: Strips 25 by 2 cm in vertical position were
ignited by contact (2 seconds) with a gas flame at the lower edge
of the strip.
Sample add-on of flame Test Result proofing agent (A) (treated
control): 25% does not ignite uniform distribution of flame
proofing agent (B) (treated control): 20% ignites, stops uniform
distribution burning after 5 seconds (B):discontinuous 13% ignites,
flame distribution stops burning after 5 seconds (C):discontinuous
19% does not ignite distribution Untreated control -- ignites,
complete- ly burnt after 12 seconds
Example VIII
A cotton/polyester blend (50/50) after desizing and bleaching was
padded in a solution of 200 grams/liter of diammonium phosphate,
then squeezed and dried. The add-on of solids was 12 percent on the
weight of the fabric (sample A, treated control).
To the same fabric (sample B) the same amount of the same
flameproofing agent was applied by printing by means of the screen
printing method described in Example 7, 34 percent of the screen
being open. The flameproofing agent thus was present on the sample
in the form of dots separated by areas of fabric not containing any
flameproofing agent. The area covered by dots was about one third
of the total area.
Flammability tests were carried out as described in Example 7.
Sample Add-on Flammability (A) uniform distribution 12% ignites,
stops burn- of flame proofing agent ing after 4 seconds (B) local
application of 12% does not ignite flame proofing agent
* * * * *