Note: Descriptions are shown in the official language in which they were submitted.
lOS608Z
This invention relates to textile materials and,
in particular, to the class of materials including those known
as outerwear fabrics which consist essentially of hydrophobic
synthetic fibers. This invention relates more particularly
to processes for treating synthetic fiber-containing materials
to impart durable water and oil repellency and materials so
protected.
As a result of the development of polymers con-
taining fluoroaliphatic radicals, a variety of methods for
treating fabrics to provide resistance to aqueous and oily
stains has been developed. Depending upon the intended field
of use, these treatments have been more or less durable
and have conferred varying degrees of resistance to abrasion,
laundering, dry cleaning and such other conditions as are
encountered by the fabric during its use. In general, each
particular type of fabric and each particular use has required
a somewhat different treatment, sometimes involving different
treating resins, for optimum economic performance.
- 1- ~ ~ .
~(~5608Z
In particular, excellent durable treatments have
been pro~ided for fabrics consisting of blends of synthet~c
and cellulosic fibers in which the treating materials in-
cludes both a fluoroaliphatic radical-containing polymer
and an aminoplast resin of the sort typified by the con-
ventional durQble-press resins described in U.S Patents
Nos. 2,783,2~1 and 2,974,432. ~ypically, such fabrics have
contained ~rom between 25 to 75% of each fiber component.
The aminoplast resln deposits primarlly upon the cellulosic
fibers durlng treatment and seems to have served to pro-
vlde improved durability of the fluorochemical treatment
toward laundering and dry cleaning.
Recently fabrics con~isting substantially com-
pletely of hydrophoblc synthetic fibers, typically those ~
ba~ed on polyamides (e.g. , nylon) and polyesters (e.g., ;; -
polyethyleneglycol terephthalate) have become popular for
outerwear, light-weight, brightly colored garments particu-
larly use~ul in sportY wear, such as ski ~ackets, wind
breakers, and the like. Su^h garments obviously encounter
2~ a variety of soils, are worn in the rain and under adverse
conditions, and should advantageously di~play the highest
resistance to water as well as to staining and soiling con-
ditions. Such garments also requlre frequent cleaning, and
such cleaning may be either laundering or dry cleaning, de-
pending piimarily upon the whims of the user
--2--
: .,~ ......
-
lOS608Z
Heretofore, there has been no satisfactory method for pro-
viding such fabrics with the combination of soil and stain
resistance with a high level of water repellency which would
be durable under the ordinary cleaning procedures. ~urable-
press resins applied in sufficient concentration to provide
durability produce a hand that is harsh and stiff and com-
pletely unacceptable to the customer, perhaps because of the
lack of hydrophilic fibers in the fabric. Other materials
such as upholstery and carpet fabrics may also be made of
100% synthetic fibers.
This invention re~ates to a process in which dur- -
ably launderable and dry-cleanable oil and water repellency
can be conferred on fabrics consisting essentially of hydro-
phobic synthetic fibers by applying to said fabric a blend
of a fluoToaliphatic group-containing mateTial and a car-
bodiimide in proportions of from lO:90 to 95:5 and preferably
from 20:80 to 80'~20 fluoroaliphatic radical-containing mater-
ial to carbodiimide. The blend may be applied as a sus-
pension or solution in either aqueous or non-aqueous media.
-- 3 --
105608Z
The present invention provides the process for conferring durably
launderable and dry-cleanable repellency to oil and water on fabrics con-
sisting substantially completely of hydrophobic synthetic fibers consisting
essentially of applying to said fabric a blend, in volatile aqueous or non-
aqueous medium, of at least 0.3% by weight of from about 10 to 95 parts of -~
(A) fluoroaliphatic radical-containing substantially linear vinyl
polymer containing from 10 to 60 percent by weight thereof of fluorine in
the form of fluoroaliphatic groups terminating in CF3 groups, said fluoro-
aliphatic groups, each containing at least three fully fluorinated carbon
atoms and from about 90 to 5 parts of
~ B) a solvent-soluble carbodiimide consisting essentially of from 1
to a plurality of carbodiimide groups, wherein the carbodiimide groups form
at least 12% of the molecule except for:
~ 1) terminal and pendent fluoroaliphatic groups when present;
(2) terminal organic radicals connected to carbodiimide groups, said
terminal organic radicals being free from isocyanate-reactive hydrogen atoms
and being substituted or unsubstituted by a fluoroaliphatic radical; and
(3) when two or more carbodiimide..groups are present polyvalent organic t
groups, or residues of polyisocyanates linking successive carbodiimide groups,
said polyvalent organic groups or said residues of polyisocyanates being sub-
stituted or unsubstituted by a fluoroaliphatic group, and thereafter vaporiz-
ing said medlum whereby a coating of said blend is deposited on said synthetic
fibers.
The present invention also provides a durably launderable and dry- :
cleanable, oil and water repellent fabric consisting substantially completely
of hydrophobic synthetic fibers having a coating thereon of a blend, in
proportions of from about 10:90 to 95:5, of
(A) fluoroaliphatic radical-containing substantially linear vinyl
polymer containing from 10 to 60 percent by weight thereof of fluorine in
the form.of fluoroaliphatic groups terminating in CF3 groups, said fluoro-
aliphatic groups each containing at least three fully fluorinated carbon
atoms, and
r ~
~ ~ I ~ -3a-
105608Z
(B) a carbodiimide consisting essentially of from 1 to a plurality of
carbodiimide groups, wherein the carbodiimide groups form at least 12% of the
molecule except for:
(1) terminal and pendent fluoroaliphatic groups when present;
(2) terminal organic radicals connected to carbodiimide groups, said
terminal organic radicals being free from isocyanate-reactive hydrogen atoms
and being substituted or unsubstituted by a fluoroaliphatic radical; and
(3) when two or more carbodiimide groups are present polyvalent organic
groups, or residues of polyisocyanates linking successive carbodiimide groups,
said polyvalent organic groups or said residues of polyisocyanates being
substituted or unsubstituted by a fluoroaliphatic group, said coating being
in amount to provide from 0.02 to 0.5% by weight of carbon-bonded fluorine
on the abric.
The present invention also provides a blend, in proportions of
from about 10:90 to 95:5, in volatile aqueous or non-aqueous medium of a to-
tal of at least 0.3~ by weight of
(A) fluoroaliphatic radical-containing substantially linear vinyl
polymer containing from 10 to 60 percent by weight thereof of fluorine in
the form of fluoroaliphatic groups terminating in CF3 groups, said fluoro-
aliphatic groups each containing at least three fully fluorinated carbonatoms, and
(B) a carbodiimide consisting essentially of from 1 to a plurality of
carbodiimite groupsl wherein the carbodiimide groups form at least 12% of the
molecule except or:
(1) terminal and pendent fluoroaliphatic groups when present;
(2) terminal organic radicals connected to carbodiimide groups, said
terminal organic radicals being free from isocyanate-reactive hydrogen atoms
and being substituted or unsubstituted by a fluoroaliphatic radical; and
(3) when two or more carbodiimide groups are present polyvalent organic
graups, or residues of polyisocyanates linking successive carbodiimide groups~
said polyvalent organic groups or said residues of polyisocyanates being
substituted or unsubstituted by a fluoroaliphatic group.
~ ~ -3b-
. . .
105608Z -
A preferred 1uoroaliphatic radical-containing material is a
sub~tantially linear vinyl polymer containing from 10 to 60 percent by
weight of the polymer of fluorine in the form of fluoroaliphatic groups
terminating in CF3 groups and containing at least three fully fluorinated
carbon atoms and preferably 3 to 18 fully fluoronated carbon atoms. Acrylates
and methacrylates are readily available and very convenient vinyl polymers and
are particularly preferred.
The carbodiimides consist essentially of from 1 to a plurality,
preferably not over 20, of carbodiimide groups, terminal organic radicals
free from isocyanate-reactive hydrogen atoms connected to carbodiimide and,
when two or more corbodiimide groups are present, also polyvalent, preferably
divalent, organic linking groups which are residues of a polyisocyanate
between succissive carbodiimide groups. Fluoroaliphatic groups may form
parts of terminal or linking groups.
The treating solution is applied by padding, spraying or other
conventional means and the vehicle or solvent is vaporized to leave a coating
of the blend on the fibers. The components can be applied in a series of
applications, or, more conveniently, as a single blend. A blend of vinyl
polymer and carbodiimide combined in a ratio of 10:90 to 95:5 may be prepared
in the desired aqueous or nonaqueous medium and diluted as needed to form
2Q the treating solution. The fabric is found to be oil and water repellent,
launderable and dry-cleanable with substantial retentiOn of repellent
properties and to posses a pleasant hand.
~D ~4~
~056082
Any of the art-recognized fluoroaliphatic radical-
containing polymers useful for the treatment of fabrics to
obtain oil and water-born stain repellency can be used in-
cludlng condensation polymers such as polyesters, polyamides,
polyepoxldes and the like, and vinyl polymers such as
acrylates~ methacrylates, polyvinyl ethers and the like.
M~ny of these are disclosed in the reference in Table l.
The preferred class of fluoroaliphatic radical-
containing vinyl polymers is composed of the acrylate and
methacrylate polymers and random copolymers. In any event,
it is essentlal that the vinyl polymer contain a fluoroali-
phatic radical termlnatlng in a CF3 group and containing at
least three fully fluorinated carbon atoms, preferably a
perfluoroalkyl group. The polymer may contain as little
as 10% of its welght of fluorine in the form of fluoroali-
phatic radlcal~, and as much as 60~ for maxlmum resistance
to dry cleaning. It i8 preferred that the polymer contain
from about 15% to 45~ by weight of fluorine. The fluoroali-
phatic polymer is applied to the treated fabric so as to
provide between 0.02 and n.5% by weight of carbon-bonded
fluorine on the fabric, preferably n.os - n.25~ by weight.
Although higher levels of fluorine can be applied to provide
use~ul products, the increased cost is not usually warranted
by lncrease in performance.
-5-
llD5 6 0 8Z
Table I
_ . _
Inventors U. S. Pat. No. Tltle
Ahlbrecht, 2,642,416 Fluorinated Acrylates
Reid and Husted and Polymers
Ahlbrecht, 2,8~3,615 Fluorocarbon Acrylate and
Brown and Smith Methacrylate Esters and
Polymers
Bovey and Abere 2,826,564 Fluorinated Acrylate and
Polymers
Ahlbrecht and 3,1~2,103 Perfluoroalkyl Acrylate
Smith Polymers and Process of
Producing a Latex thereof
Johnson and 3,256,230 Polymeric Water and Oil
Raynolds Repellents
Johnson and 3,256,231 Polymeric Water and Oil
Raynolds Repellents
Fasick and 3, ~82,905 Fluorine Containing Esters
Raynolds and Polym~rs thereof
Smith and 3,329,661 Compositlons and Treated
Sherman Articles thereof
Smith and 3,356,628 Copolymers of Perfluoro
Sherman Acrylates and Hydroxy Alkyl
Acrylates
Farah and 3,407,183 Acrylate and Methacrylate
Gllbert Esters and Polymers thereof
Kleiner 3,412,179 Polymers of Acrylyl Per-
fluorohydroxamates
Sweeny and 3,420,697 Perfluoroalky-substituted
~la.uw Polyamide Oil-repellency
Compound and Textile Mat-
erlals Treated therewith
Pacini 3.445.491 Perrluoroalkylamido-
alkylthlo Methacrylates
and Acrylates and Inter-
mediates therefor
Eygen and 3,470,124 New Fluorinated Compounds
Carpentier and Their Preparation
Brace 3,544,537 Poly(perfluoroalkoxy)- ~
polyfluoroalkylacrylate-
type ~sters and Their
Polymers
T~ndy 3,546,187 Oil and Water Repellent
Polymerlc Compositions
-6_
-
1~56~82
Carbodiimides are conveniently obtained by con-
densation of isocyanates in the presence of sultable
catalysts as descr~bed, for example, in the patents of
Table 2 and by Campbell et al., J. Org. ChemO J Vol. 28
pages 2069-2075 (1963)o
Table 2
Inventor U.S. Pat. No. Title
Balon 2, 85~J 518 Chemical Process
Campbell and 2, 85~J 473 Production of Carbodiimides
Verbanc
Campbell 2J 941~ 966 Carbodlimide Polymers
Smeltz 2, 941~ 983 Urethane-Terminated
Polycarbodiimides
Hoe8chele 3J 450~ 562 Celluloslc Materials
Coated with An Organic
Polycarbodiimlde
Brltish 1, 224J 635 Stabilized Polyester
Patent Shaped Artlcles
The carbodiimides employed in the invention can
be of more or less conventlonal types includlng termlnal
hydrocarbon radicals or the~ may include fluoroaliphatic
radlcals as noted above. Fluoroallphatic radical-containing
carbodllmides were not known heretofore and are particularly
useful in fabrlc treatments. The carbon-bonded fluorine of
these polymers whlch ranges from about 15 to about 45 per-
cent 18 included within the totals of fluorine applied to
the fabric, iOe., 0.02 to 0.5% by weightO
-7-
~05608Z
In general, carbodiimides formed from dl_isocya_
nates with or without monoisocyanates are represented
for con~enience by the general formula.
B --~N=C=N-A~-n-N=C-~-B
where n is 0 or an integer from l to at least 20 and
preferably fr~m l to lO. A and B are as defined below.
The A groups or B groups may each be the same or different.
Carbodiimides in which n is 20 and hlgher are useful but
... ... .
offer no known advantages
In the above general formula, A is a divalent
organic group which may include pendent fluoroallphatic
radlcals llnking succe~sive carbodilmlde group~ when n
is l or more. Illustrative linking groups include alky-
lene, such as ethylene, lsobutylene, and the like of 2
to about 10 carbon atoms, aral~ylene, such a~ -CHzC~H4CH2-,
of up to lO carbon atoms, arylene, such as tolylene,
-C~H~(CH3)-, of up to about lO carbon atoms, polyoxaalky-
lene ~uch a8 -(C2H40)XC2H4-, contalning up to about 5 oxa
groups and combinations of the various type~. It will be
recognlzed that the A group is the resldue of an organlc
dlisocyanate, that is, the divalent radical obtalned by
remoYal of the i~ocyanate group from an organic dli30cyanate
Sultable organlc dl~ocyanates may be simple, e.g., toluene
diisocyanate, or complex, as formed by the reaction of a
simple diisocyanate wlth a di- or polyol ln proportions to
glve an isoCyanate terminated polyurethane.
Although carbodiimldes generally and preferably
include dlvalent A groups, some of the A group~ can be,
for example trivalent or tetr~valent derived from
_~ ':
~05608Z
triisocyanates or tetraiso^yanates such as polymethylene-
polyphenyl isocyanates, e.g., OCNC~H4CH~C6H3(NCO)CH2C~H4NCO.
When A is trivalent or tetravalent, branched or even cross_
linked polycarbodiimides result. A mixture of A groups
containing some t~ivalent groups can be used to provide
branched polycarbod~imides which retain the desirable
solubility and thermoplasticity of the linear carbodiimides
resulting from carbodiimides having divalent A groups.
The carbodilmide groups (-N=C=N-) should represent
at least 12~ of the molecule except for terminal and pend-
ent fluoroaliphatic radicals present.
Substituents may be present in A groups provided
they contain no isocyanate-reactive hydrogen atomsj that
iB, groupB ~uch as -OH are normally excluded. Simple un-
substltuted organic linking groups free from non-aromatlc
unsaturatlon are preferred. The organic linklng group
depends on the polylsocyanate compound employed such as:
- CH~- ~ -CH2 - ,CH~ ~ J
$o2
or _ CeH3(CHs)NHCO2C2H4~C2H402CHN(CH9)CeH9
1056082
The terminal groups, or ELgroups, are preferably
monovalent radicals of monoisocyanate compounds which may
be aliphatic as C4H9-, aralkyl as C6H5CH2-, aryl as C6H5-,
and preferably fluoroaliphatic such as C4F9C2H4-, and
C7Fl~CH202CNHC~H4(CH3)-, (derived from tolylene diisocya-
nate and l,l-dihydroperfluorooctanol)0 Numerou~ other
terminal groups are operable in the compounds and process
of the invention. When only diisocyanates are used to
form the polycarbodiimldes, the B groups are monovalent
radlcals derived from diisocyanates and include an isocya-
nate group (or an hydrolysis product of such a group).
The terminal B group8 may be the same or different.
~ecause the monoisocyanate terminates the carbodii-
mlde molecule, the relative proportion of monoisocyanate
to dilsocyanate used in the reaction determines the average
value of n in the above formulaJ 0 when no diisocyanate i6
used upwards ~o that with about 10 mole percent of mono-
l~ocyanate and 90 percent of dlisocyanate n will average
about 20 as wlll be readlly apparent.
The inventlon ls more partlcularly described
herelnbelow by examples of the preparation of suitable
components for the process of the inventlon and by examples
showing the effectlveness of the process of the invention
ln providing oil and water repellency durable to washing
and/or drycleanlng. In these example~, all parts are by
welght. The testing procedures employed in these examples
are as follows:
_10--
~56~8Z
Synthetic fabrics of 100% filament nylon and
100~ spun and 100~ fllament polyester are treated with
the blended formulat~on at a predetermined level of fluoro-
aliphatic component on the fabric. This level ls conveniently
set to give a particular weight of carbon-bonded fluorine
on the fabric, usually of the order of 0~05 to about 0.5
by weightO
The water repellency of the tested fabrics is
measured by Standard Test Number 22-52, published in the
1952 Technical Manual and Yearbook of the American Associ-
ation of Textlle Chemists and Colorists, Vol. 28, page 136.
The spray rating i8 expressed on a O to 100 scale where
100 is the hlghest possible ratlngO For outerwear fabrics
partlcularly, a spray rating of 70 or higher is consldered
desirable.
The oil repellency test American Association o~
Textlle Chemist8 and Colorists Standard Test 118L196 ls
based on the resistance to penetratlon of oils of varying
~?~ viBcositieso Treated fabrics resistant only to NuJol, a
common type of mineral oil, and the least penetrating of
the test oils, are given a ratlng of 1, whereas fabrics re-
sistant to heptane, the most penetrating of the test oils,
are given a value of 8. Other intermediate valueR are de_
termined by use of other pure substances. The oil repellency
corresponds to the oil which does not penetrate or wet the
fabrlc a~ter 3 mlnutes contact. Higher numbers indlcate
better oil repellency. In general, an oil repellency of 3
or greater 18 deslrable.
~r k
105~;08Z
The ~undering cycle employed is as follows:
The treated fabrics are laundered in a mechanically agitated
automatic washing machine capable of containing a 4 kg. load,
using water at 60 C0 and a commercial detergent and then
tumble-drled in an automatic dryer for 20 minutes at 88 C.
before being tested, They are not ironed after drying.
Drycleaning is performed by a commercial dry-
cleanlng establishment and the fabrics are not pressed or
heated after the drycleaning process. Perchloroethylene
(C2Cl4) is the solvent used for the drycleaning procedure.
Carbodllmides are usually made ~rom dilsocyanates
and monolsocyanates ln an inert solvent such as methyl
i~obutyl ketone, conveniently at a conc~ntration of about
40% of dissolved materials, to whlch 18 added about 1~ of
the weight of the material~ of a phospholine oxide or other
suitable catalyst. The reactlon mixture is prepared so
that any water 18 removed before addltion of isocyanates
and i8 heated until reaction ls essentially complete. The
reactlon mixture can be emulsified in water and further
diluted with water before appllcation. The fabrlc treatlng
~olution can be prepared by blending emulslons of carbodii-
mide and fluoroaliphatic radical-contalning polymers, to-
gether wlth any desired compatible ad~uventsO Alternatlvely,
the polycarbodilmide and fluoroaliphatlc radlcal containing
polymer can be prepared i~solution_and the ~olution blen~ed,
dlluted lf necessary and applied, for example, to fabrics
that would be undesirably affected by water~ The proportions
depend on the amount needed to give a treatlng solution which
-12-
.
'
11)56~82
will provide the correct concentration of solids, carbodiimides
plus fluoroaliphatic-radical contalning polymer, to attain the
desired weight of treatment at the level of wet pickup chosen.
This level is herein set at 50~ where not otherwise denominated
to ~ive comparability of results. Thus for 50~ wet pickup, a
0.3~ concentration provides 0.15% solids pickup which at 50~
fluorine content gives 0.075% fluorine on the fabric. The latter
fluorlne content is used in these examples, unless otherwise
indicated, to permit ready comparisons.
Example 1
A solùtion o' 101.6 parts (0.17 mol) of C8Fl7S02N(CH2CH20H)2 in
265 parts of methyl isobutyl ketone (MIBK) is first dried by dis-
tilling 30 parts of the solvent. Then 54 parts (0.31 mol) of
2,4-toluene diisocyanate are added and the solution refluxed for
2 hours to form a prepolymer diisocyanate. The solution is then
cooled to 65-75 C., and 1 part of 3-methyl-1-phenyl-3-phospholine_
l-oxide i8 added followed by 3 hours further refluxing. A film
cast from thi3 solution is weak and brittle and contains the
characteristic carbodiimide infrared absorption pea~ at 4.69 mi-
crons. The solution contains the carbodiimide designated Polymer A
which is predominantly represented by the formula:
OC~ NC0
IN~C02~ 2~4
Cl 2H4O2CNH ICE~Fl70zS_N
~- SO2C~Fl7 l l
dzH402C~H NHCO2C2H4
~- NSC=N - ~
L CH3 L n CH3
-13-
10560BZ
It will be seen that this structure corresponds to the
general forrnula above in which the group designated as
"A" is:
~--NCO~CHaCH2i ~CH202~
and the "B" group is -A-NC0.
To 100 parts of this polycarbodiimide in 121 parts of
MIBK is added 4 parts of polyoxyethylene sorbitan noo-
leate emulsifier, 4 parts of C8F17S02N(CH3)C2H4N(CH3)3jCl
emulsifier and 225 parts of distllled water The mixture
is then emulsified using a high shear mixer The emulsion
is employed in fabric treatments.
Example 2
A solution of 90 parts (0.15 mol) of C8Fl7S02N(C2H5)CH2CH20H
in 320 parts of methyl isobutyl ketone is first dried by
distilling and discarding 24 parts of the solvent and 82.4
parts (0.473 mol) of 2,4-toluene diisocyanate are added
and the solution is refluxed for 3 hours. After cooling
the solution to 65 - 75 C., and adding 1.8 parts of
3-methyl-1-phenyl-3-phospholine-1-oxide to it, the solution
is refluxed for a further 3 hours A film cast from this
-14_
105608Z
solution is.weak and brittle and contains the characteristic
carbodiimide absorption peak at 4.79 micror~s. The solution
contains the carbodiimide designated as Polymer B which
is represented by the formula: CH3
~ C=l~ ~_OCHeC~1025C=F 7
C2H5 H C2H5
in ~hich it will be seen that the IrAI! group is -C~3H3CH3-
and the "B" group i5 C8F17S02N(C2Hs)-C2H4~2CNHC~H3(CH3)-
~
To 100 parts of this polycarbodiimide in 1~8 parts of methyl
isobut.yl ketone iB added 2.5 parts of polyoxyethylene sorbi-
tan monooleate emulsifier (available under the Trademark
Tween 80), 2,5 parts of C8Fl7S02N(CH3)C2H4N(CH3)3Cl and
265 parts of dlstilled water. The mixture ls then emulsified.
Example 3
To a solution of 27 parts of
C~3Fl7SOzN~CH3)C2H402CC (CH3)=CH2,
2;85 parts of ethylhexyl methacrylate and 0.15 parts of
glycldyl me~hacrylate in 12 parts of acetone and 48 parts of
20 wat.er are added 1.5 parts of polyethoxylated quaternary
ammonium chlorlde emulslfler, 0.05 parts t-dodecyl mercap_
tan and 0.05 parts of potaqslum persulfate. The mlxture is
degassed, blanketed under nltrogen and then heated to 65 C.,
and the polymerization allowed to proceed with agltatlon for
25 16 hours. A fllm cast from this material is hard and brittle.
The random copoly,mer having pendent fluoroaliphatic groups
is deslgnated Polymer C.
-15-
:
r -
1~5~;08Z
Example 4
The procedure o~ Example 2 is repeated using
CBFl7S02N(CH3~C2H40H and a lower amount (27.5 parts; 0,16 mol)
of tolylene diisocyanate. The resultant carbodiimide desig-
nated Polymer D is represented by the structure:
C8Fl7S02~C2H402CNH ~
~ -CH3
CeFl7S02~C2H~02C ~ c~3
A further series of fluoroaliphatic ca~bodiimides
is prepared by the above procedures using the materials
and molar proportions indicated in Table III and designated
as shown there.
-
1C~5608Z
,o~
~, ~ 2 2
N
0 c ~ p~N ~ N
. H ,_1 ,1 ~1 æ~ ~
H ~ ~ ~ O ~ h :
. ;~ + + ++ + 0 j~
; O
l ~ ~ ~ .
. U~ N U) ,j~l 111 N 111 N U) N
C) Pi ~ P~ u~ C
N .I N I N I N I N l O --I
C.~ ;i'i C~; ~; C~ C C~; 5~
oN ~ æ O O ~
C~ _~ ~
0 . 0 0 0 ¢ ~ ~O
l V V V U V 0 C
O ~
: ~ 0
0 S~ ~0
, ~ ~ ~ ~ o H O ~1 O
1~ ~ C~ ~ ~o ~ ,:
O
O h
-~ D ~ 0 O~ m
., .~ ~ .
1~56082
g ~ :
0 ~ ~J
, ~ ~ C
~ ~ I O ~a
a~ ~1 V
~; ~ ~ N E~ fi
+ ~ U~ 4)
+ e ~ + + ~, ,
~ o + C O ~ O
a~ X ,~ o
,1 0 o Lq ~ 0 ~
~ ~ c ~ 0 0 e
a) ~ ~ ~ a~ ~ :
. O O
~a ~ z O ~
~ ~ ~ .
:
..
~ ,1 N .-1 ~
' ~
' .
~ \
10560~Z
For purposes of provlding fluoroaliphatic poly-
mers, a number of materlals are prepared or obtained
commercially. These also are designated by letters.
Polymer U designates a commercially available
materlal believed to be a 50/50 blend of poly(2-ethyl-
hexyl methacrylate) and poly(l,l,2,2-tetrahydroperfluoro-
alkyl methacrylate) in which the alkyl group has an average
composition of about lO carbon atoms. This is available
under the Trademark Zepel D.
Polymer V designate6 a 50/50 blend of two poly-
mers. One is made by emulsion polymerizing for 16 hours
at 50 C. a mixture of 50 parts methyl methacrylate and
60 parts of tridecyl acrylate in 126 parts of water and
54 parts of acetone in the presence of 2 parts of
G~Fl7SO2N(CH9)C2H4N(CH3~2HCl a~ emulsifier and 3 parts
of a commercial polyoxyethylene lauryl ether as another
emulsifier and using 0.2 parts of potas~ium per~ulfate
as catalyst. The other polymer is prepared, using the
same amounts of emulsifler and catalyst and same reactlon
condltions, from 93.5 parts of C8Fl7so2N(c2Hs)c2H4ococ(cH3)~cH
and 6.5 parts of lsoprene ln 144 parts of water and 36 parts
of acetone with the addltlon of 0.75 parts of t-dodecyl
mercaptan.
Polymer W 18 llke the latter polymer used in
Polymer V, but prepared from equal amounts of C8Fl7SO2-
N(C2H5)C2H40COC(CH3),CH2 and chloroprene a3 described in
Example III D of U. S. Patent No. 3,068,187.
-1~
1056082
Polymer X i~ prepared as In the above procedures,
heating a reaction mixture of 90 parts C8F~7S0zN(CH3)C2H4_
OCOO(CH3)=CH2, and 10 parts butylacrylate in 160 parts
water and 40 part~ acetone with 0.2 part~ t-dodecyl mer-
captan and 0.2 parts potassium persulfate using 5 parts of
a commercial polyethoxylated quaternary ammonium chloride
emulsifier at 65 C. for 16 hours.
As noted herelnaboveJ fabrics of 100% filament
nylon and both 100% spun and 100% fllament polyester are
treated by standard procedures with various blends of fluoro-
allphatic vinyl polymers and carbodiimides and rated for
oil and water repellency a~ter treatment and agaln after
5 launderlngs and ln some ca~es also after 5 drycleanings.
The data are pnesented in the followlng tables in which
Nylon- 100~ filament nylon
Polyester F3 100% filament polye~ter
Polyester S- 100% spun polyester
Initlal = dsta before laundering etc.
Laundered- data after 5 launderings
Drycleaned~ data after 5 drycleanings.
Except as noted, the fabrlcs are treated to contaln
0.075~ carbon bonded ~luorine. Proportlons of polymer~
blended together are indlcated as, e.g., 65C + 35B, and ~or
controls or comparisons where there is no blend, as e.g., lOOC.
The r~tings are given for conciseness as a fraction, e.g., 5/100,
ln whlch the numerator (5) is oll ratlng and denomlnator
(100) 1~ spray r~tlng.
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105608Z
Example 24
To a 25 gallon glass-lined kettle equipped with agitator,
condenser, and provision for heating and cooling, are added 58
parts of C8Fl7S02N(C2H5)C4H80H and 1~5 parts of MIB~ solvent.
The solution is heated to about 115 C. and 25 parts of solvent
removed by distillation to ensure anhydrous conditions The
kettle is cooled to about 90 C., 52 parts of 2,4-toluene diisocy_
anate added and the solution heated to 115 C. for a further
3 hours. The solutlon is next coo~ed to 50 C. and 5 parts of
a 20% by weight solutlon of 2,2,3,4,4-pentamethyl-1-phenylphos_
phetane oxide in methylene chloride added, and the solution is
then again slowly heated to 115 C., care being taken to avoid
excessive foaming. The solution is malntained at 115 C., with
agltation for about 3 hours, or until the isocyanate groups are
essentially completely reacted as lndlcated by the lnfra-red ab-
sorptlon spectrum. The product is a 40~ by weight solution of:
CH3 _ CH3 -
C~Fl7S02~-C4HeO ~ ~ ~N=C= ~ ~0C4H8~02SC~Fl7
2Hs _ = 2 2Hs
A fabric-treatlng concentrate 18 prepared by dissolving
90 parts of a fluoroaliphatic radical-containing methacrylate
copolymer (35% fluorlne ln the form of fluoroaliphatlc radlcals)
ln 115 parts of MIBK and 260 parts of CzF3Cl3, and adding 25
parts of the above polycarbodiimide product solution.
For treatment of fabrics whose structure would be
damaged by exposure towater, such as textured or velvet uphol-
stry fabrics, a solvent system 18 preferred. For treatment
of a medium-weight 100 percent nylon velvet, for example,
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.. . ~ ...: . . . . .. . ..
- .. - ~... ;., . . , . , .. . . - - . . , ~ ~ .
1056082
the above concentrate, is diluted to about 0.4% solids with
trichloroethylene. Improved water resistance can be ob-
tained by the addition of a fluorine-free water repellant,
such as Ool~ by weight of the solution of a stearato-chrome
complex. The fabric is sprayed in a ventilated spray booth
with the dilute solution to about 50~ wet pick up, then
dried in a circulating air oven at 110 C. for about ~ min-
utes, until the solvent has evaporated and the fabric has
reached oven temperature. The resulting treated fabric has
an oil rating of 6 and a spray rating of 75. The stain re-
sistance remains even after extens~ve abrasion.
... .. .
1~)5608Z -
Example 25
A branched polycarbodiimide is prepared by adding
to 57.5 parts of dry MIBK (Methyl Isobutyl Ketone)
C8Fl7S02N(C2H5)C2H40H 28.6 parts
2,4_Toluene diisocyanate 7.8 parts
OCNC~H4CH2C~H3(NCO)CH2C~H4NC~ 2.1 parts
me solution is refluxed for 3 hours, then cooled
to 90 C. and 1.7 parts of a 22% by weight solution of
pentamethyl-l-phenylphosphetane oxide added. The resulting
solution i8 heated to reflux and maintained there for t~o
hours. A further o.86 parts of catalyst solution is added
because the presence of unreacted -NC0 is shown by infrared
absorptlon and refluxing i8 continued for an additional
hour. The resulting clear solution is free from -NC0, but
exhibits the characte~lBti~ absorption peak of carbodiimide
at 4.69 microns. Emulsions and solution~ containlng this
polycarbodiimide product and a fluoroaliphatlc group con-
taining acrylate copolymer confer durable oll and water
resistance on treated fabrics.
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