Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Case 1-11578~
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Process for 1ameproofing organia fibrous material with
phosphonic acid salts
The invention provides a process for flameproofing
organic fibrous m~terial which comprises treating said ma-
terial with an aqueous solution containing 25 to 500 g/l of
a phosphonic acid salt of the formula
r /H 1 G3 (1),
11 0
_ O _
wherein R represents ethyl or preferably methyl and ~
represents an alkali metal cat~on or ammonium cation, and
drying it.
The alkali metal cations are derived for ~xample from
1ithium~ potasslum or in particular rrom sodium~ The
monoammonium salts are preferred to t~e alkali metal salts.
The invention provides in particu~ar a process where~n
monoammonium m~th~lphosphonate is used 2S flame-retaxdant.
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The salts of the formula (1) employed according to
the invenkiQn are obtained by reactlon o the corresponding
acids with the corresponding ba~es and are ordlnarlly in ~hs
form of 30 to 50% aqueous ~olutlon~. The alkylpho~phonlc
acids themselves are known for example from J. Am. Soc. 75,
3379 ~f. (1953). The same applies also to the alkylphosphon-
ic acld alkali metal sal~-s, which are disclosed for example
ln US patent specificatlon 3,894,386~ Monoammonium methyl-
phosphonate and monoa~monlum ethylphosphonate are al~o kno~n
frrm e.g. Chem. A~s_r., 8th Collëctive Formulae Index tl367-
1971), p~ 186 F. col. 1.
The process of the invention is carried out in
general by the spray-on metho~ and also in particular by
the pad method. The immersion or slop-pad methods ~or
example are also eligible.
As the phosphonic acid salts of the formula sl) are
water-soluble, it is normally not necessary to add solubi-
lising assistants to the treatmenk baths~ Li uors or spray
solutions. However, conventlonal fabric so~teners, ~urfac-
tants or buffer substances, such as urea, dicyandiamide,
hexamethylenetetramine, acid ammonium sulfates or phosphates
or sodium acetate can be concurrently used with advantage.
In the ~referred pad method, the phosphonic lcld
salt solutions are applied to the ibrous material ko a
liquor pick-up of 60 to 110, preferably 60 to 100 a.;d es-
pecially 65 to 80% by weight, and the lmpregnated m~texial
is subsequently drled at a temperature bekween 60~ and 120C,
preferably however below 100C, for example betwse~l 60 and
100C and in particu'.ar between 70~ and 90C~
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The process of the present invention is suitable
for flameproofing organic fibrous material, including wood,
preferably paper, for example wall-papers, or especially
textiles in any stage o processing, such as filaments,
yarns, bobbins, bonded fibre webs, knits, wo~ens or finished
garment pieces, or furnishing materials, such as carpets,
furniture coveringsl curtains or fabric-covered wall-papers.
The organic ribrous material to be provided with
the flame-retardant finish can be of natural or synthetic
origin or can consist of blends of natural and synthetic
fibres. Suitable natural fibres are in particular keratin-
ous or cellulosic fibres, including fibres made from re-
generated cellulose, such as linen, hemp, sisal, ramie,
preferably wool, cotton and/or rayonl staple fibres or fi-
lament viscose.
In addition to pure cellulose fibresl blends there-
of with synthetic fibres are also suitable. The cellulose
content of such blends is preferably 20 to 80~. Examples of
suitable syntnetic fibres are polyesterl preferably acrylo-
nitrile copolymerl or in particular polyacrylonitrile fi~-
res- Although less preferred/ cellulose acetate fibres, for
example cellulose 2 1/2-acetate and cellulose triacetate
and fibres obtained from crosslinked polyvinyl alcohols,
for example acetates or ketals of polyvinyl alcohols, are
also suitable.
In addition, however, to cellulose fibres and their
blends with synthetic fibres, man-made synthetic fibrous
material is particularly preerred, especially that made
from polyester or especially polyacrylonitrile or acrylo-
nitrile copolymers. Polyacrylonitrile wall-papers can be
particularly well flameproofed according to the invention.
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Such polyester fibres are derived in particular rom te-
rephthalic acid, fox example from poly~ethylene glycol te-
rephthalate) or poly(4-cyclohexylenedimethylene terephthal-
ate).
The acrylonitrile content of acrylonitrile copoly-
mers is desirably at least 50~ by weight and preferably at
least 85% by weight of the copolymer. The copolymers are in
particular those in the production of which other vinyl
compounds, for example vinyl chloride, vinylidene chloride,
methacrylates, acrylamide or styrenesulfonic acids, have
been used as comonomers.
The aqueous solutions with which these fibrous ma-
terials are treated contain ordinarily 25 to 500 g/kg of
the phosphonic acid salt of the formula (1).
Especially when treating man-made synthetic fibrous
materials, for example polyester material, by the preferred
pad method, bath concentrations of 25 to 100 g/kg often
suffice, particularly when the ammonium salt is used. Pre-
ferably, however, the padding is carried out using bath
concentrations of 200 to 450 g/kg, especially when flame-
proofing polyacrylic fibres.
The pH value of the solutions employed in the pre-
sent invention is normally from 4 to 8 and is adjusted by
the addition of a base, for example an alkali hydroxide,
ammonia, or buffer substances of the indicated kind.
The amounts of compound of the formula (1) required
to obtain a sufficient flame-retardant effect vary depend
ing on the nature of the fibre and material and are normal-
ly between 2 and 25%, based on the weight of the fibre.
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The process of the present invention does not pro-
vide permanent flame-retardant effects, for which reason
the treated fabrics should not be given a washin~-o.
The process o~ the present ~nvention is distingulsh-
ed in particular by the fact that a very wide variety of
substrates can be provided with an effective flame-retar~
dant finish by means of it and that the compositions em-
ployed do not have a corxosive action - a feature which is
especially advantageous when stapling treated wall-papers,
for example in decorating.
The flame-retardant finishes of the present inven-
tion have virtually no effect on the lightfastness of dyed
or whitened polyester and polyacrylonitrile fabrics. The
good compatibility of the phosphonic acid salts used ac-
cording to the invention with most textile finishing agents,
such as water and oil repellents, stiffeners and fabric
softeners, is particularly advantageous.
A further advantage of the pro~ess of the invention
resides in the low add-ons required for flameproofing poly-
ester fibres.
In the following Examples the parts and percentages
are by weight.
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Exa~ple 1: Different fabrics are padded with an aqueous
liquor of the composition indicated in Table I and drled
for 30 minutes at 80C. After conditioning for 12 hours
at 45% relative humidity, the flame-retardant efect ac-
cording to DOC FF 3-71 (ignition time 3 seconds) is carried
out. The results are also reported in Table I.
Untreated fabrics burn away.
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Example 2: The fabrics listed in Table II are padded with
aqueous liquors of the composition also indicated in the
table. The results o the flame-retardant test after co~
ditioning and drying as described in Example 1 are like-
wise reported in the table. The flame-retardant test is
also carried out in accordance with DOC FF 3-71, but with
the ignition time stated in Table II. The untreated cor-
responding fabrics burn aw,ay completely.
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Example 3: A viscose fabric having a welght per unit area
of 180 g/m2 is padded with an aqueous liquor which contains
200 g/l of monoammonium methylphosphonate ~40%) and ZOO g/l
of polyvinyl acetate ~50%) and has a pH value of 5.5. The
liquor pick-up is 90% and the add-on of phosphonate after
drying at 120C for lO minutes is 7.2%. The fabric is then
coated by the floating blade coating method on both sides
with an aqueous viscous solution consisting of 1000 parts
of polyvinyl acetate (50~), 150 parts of monoammonium me-
thylphosphonate (40%), lO parts of hydroxyethyl cellulose
(lOO~) and 30 parts of ammonia (30%). The pH of the solution
is 8 and the add-on is 140 g/m2 on each side of the fabric.
The coated fabric is dried for 5 minutes at 120C and
further processed to light protective lamellae which are
tested in accordance with DOC FF 3-71 with an ignition time
of 3 seconds. The after-flame time and tear length of the
warp is o seconds and 5.5 cm respectively and the after-flame
time and tear length of the weft is o seconds and 5 cm re-
spectively. Light protective lamellae prepared without mono-
ammonium methylphosphonate on the other hand burn away
completely.
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