CA1056082A - Outerwear fabric treatment - Google Patents

Abstract

A B S T R A C T

Durably launderable and dry-cleanable repellency to water and oil is conferred on fabrics consisting essentially completely of hydrophobic synthetic fibers by application of a blend of a fluoroaliphatic vinyl polymer and a carbodiimide, preferably comprising fluoroaliphatic groups.

Description

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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.

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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 : .,~ ......

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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.

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-(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.

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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.

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~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.

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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

~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 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:

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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.

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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 .
' 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 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_ 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 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.

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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.

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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.

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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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, 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, -26_ .. . ~ ...: . . . . .. . ..
- .. - ~... ;., . . , . , .. . . - - . . , ~ ~ .

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.

.. . .. . . . . -

Claims (11)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. The process for conferring durably launderable and dry-cleanable repellency to oil and water on fabrics consisting 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 fluoro aliphatic 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 sub-stituted or unsubstituted by a fluoroaliphatic group, and thereafter vaporiz-ing said medium whereby a coating of said blend is deposited on said synthetic fibers.

2. The process according to claim 1 for conferring durably launderable and dry-cleanable repellency to oil and water on fabrics consisting substan-tially 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 fluoroaliphatic groups each containing at least three fully fluorinated carbon atoms, and from about 90 to 5 parts of (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 fluoro aliphatic 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 and thereafter vaporising said medium whereby a coating of said blend is deposited on said synthetic fibers.

3. A process according to claim 1 or 2 wherein the solvent soluble carbodiimide is represented by the formula wherein n is 0 to at least 20, A is a divalent organic residue of a diiso-cyanate which is substituted or unsubstituted by a pendent fluoroaliphatic radical but is free from isocyanate-reactive hydrogen atoms, said A groups linking successive carbodiimide groups when n is 1 or more, B is a terminal monovalent aliphatic, aralkyl, aryl or fluoroaliphatic group which is sub-stituted or unsubstituted by an isocyanate group or hydrolysis product there-of and N=C=N are carbodiimide groups which form at least 12% of the molecule except for fluoroaliphatic groups present in either A or B groups.

4. The process according to claim 2 or 3 wherein the fluoroaliphatic radical containing vinyl polymer is an acrylate or methacrylate.

5. The process according to claim 2 wherein the carbodiimide includes fluoroaliphatic radicals at least in terminal groups.

6. The process according to claim 5 wherein the carbodiimide includes fluoroaliphatic radicals in terminal and linking groups.

7. The process according to claim 6 wherein fluoroaliphatic radicals contain from 3 to 18 fully fluorinated carbon atoms.

8. 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 (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 fabric.

9, A blend, in proportions of from about 10:90 to 95:5, in volatile aqueous or non-aqueous medium of a total 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 carbon atoms, and (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.

10. A durably launderable and dry-cleanable oil and water repellent fabric according to claim 8 wherein the carbodiimide is represented by the formula wherein n is 0 to at least 20, A is a divalent organic residue of a diiso-cyanate which is substituted or unsubstituted by a pendent fluoroaliphatic radical but is free from isocyanate-reactive hydrogen atoms, said A groups linking successive carbodiimide groups when n is 1 or more, B is a terminal monovalent aliphatic, aralkyl, aryl or fluoroaliphatic group which is sub-stituted or unsubstituted by an isocyanate group or hydrolysis product thereof and N=C=N are carbodiimide groups which form at least 12% of the molecule except for fluoroaliphatic groups present in either A or B groups.

11. A blend according to claim 9 wherein the carbodiimide is re-presented by the formula wherein n is 0 to at least 20, A is a divalent organic residue of a diiso-cyanate which is substituted or unsubstituted by a pendent fluoroaliphatic radical but is free from isocyanate-reactive hydrogen atoms, said A groups linking successive carbodiimide groups when n is 1 or more, B is a terminal monovalent aliphatic, aralkyl, aryl or fluoroaliphatic group which is sub-stituted or unsubstituted by an isocyanate group or hydrolysis product there-of and N=C=N are carbodiimide groups which form at least 12% of the molecule except for fluoroaliphatic groups present in either A or B groups.