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Publication numberUS3896251 A
Publication typeGrant
Publication dateJul 22, 1975
Filing dateJul 19, 1973
Priority dateMar 6, 1972
Also published asDE2310801A1, DE2310801B2
Publication numberUS 3896251 A, US 3896251A, US-A-3896251, US3896251 A, US3896251A
InventorsLanducci Dennis P
Original AssigneeMinnesota Mining & Mfg
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Outerwear fabric treatment
US 3896251 A
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Description  (OCR text may contain errors)

United States Patent Landucci 1 July 22, 1975 [5 OUTERWEAR FABRIC TREATMENT 2.941.966 6/1960 Campbell 260/25 3.150.000 91964 E 11 1-1. .1 1171395 [75] Dennis Landucci Lake Elmo 3.232.790 211966 E2621: :1 :1 11711395 P- Minn- 3,236,672 2/1966 5116116 61111. 1. 106/287 3,256 23l 6/1966 .lOhflSOrl 61 111.. 260/296 [73] Asslgnee' m M and S t 3.450.562 6/1969 HOESCl'lClB 117/155 am 3,544,537 12/1970 Bffl 1. 260/895 Paul 3,575 s99 4 1971 P1 61 260/174 22 Filed: July 19 1973 3,598,514 8/1971 S6110 61 211. 8/1151) 3.816.495 6/1974 11111116161611 260/453 AL [21] Appl. No: 380,702

Related US. Application Data Primary Examiner-P. E. Willis, Jr. [63] C0l'lllrlUal10n-lfl-p2llt Of 861. N6. 232,186, M61611 6, Alrvmey. Agenh Or FfrmAl9Xflfld9r1 $19191 &

1972, abandoned. DeLaHunt [52] US. Cl. 428/290; 260/296; 427/372;

427/385; 427/390 1571 ABSTRACT [51] 11' CL 15/321DO6T" 15/52 Durably launderable and dry-cleanable repellancy to 1581 held of Search 8/1 117/13551 13818 N water and oil is conferred on fabrics consisting essen- 117/1388 F1 A1 161 P1 UH1 161 tially completely of hydrophobic synthetic fibers by UN, 16] UP; 260/295 F1 453 AR! AT application ofa blend of a fluoroaliphutic vinyl polymer and a carbodiimide, preferably comprising [56] References cued fluoroaliphatic groups.

UNITED STATES PATENTS 2.803.615 8/1957 Ahlbl'CChl 61611 260/296 7 Clams N0 Drawmgs OUTERWEAR FABRIC TREATMENT This application is a continuation-in-part of my copending application Ser. No. 232,186, filed Mar. 6, 1972, now abandoned.

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 fibercontaining materials to impart durable water and oil repellency and materials so protected.

As a result of the development of polymers containing 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 dur ing 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.

In particular, excellent durable treatments have been provided for fabrics consisting of blends of synthetic and cellulosic fibers in which the treating materials includes both a fluoroaliphatic radical-containing polymer and an aminoplast resin of the sort typified by the conventional durable-press resins described in U.S. Pat. Nos. 2,783,231 and 2,974,432. Typically, such fabrics have contained from between 25 to 75 percent of each fiber component. The aminoplast resin deposits primarily upon the cellulosic fibers during treatment and seems to have served to provide improved durability of the fluorochemical treatment toward laundering and dry cleaning.

Recently fabrics consisting substantially completely of hydrophobic synthetic fibers, typically those based on polyamides (e.g., nylon) and polyesters (e.g., polyethyleneglycol terephthalate) have becomme popular for outerwear, light-weight, brightly colored garments particularly useful in sports wear, such as ski jackets, wind breakers, and the like. Such garments obviously encounter a variety of soils, are worn in the rain and under adverse conditions, and should advantageously display the highest resistance to water as well as to staining and soiling conditions. Such garments also require frequent cleaning, and such cleaning may be either laundering or dry cleaning, depending primarily upon the whims of the user. Heretofore, there has been no satisfactory method for providing such fabrics with the combination of soil and stain resistance with a high level of water repelency which would be durable under the ordinary cleaning procedures. Durablepress resins applied in sufficient concentration to provide durability produce a hand that is harsh and stiff and completely 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 I percent synthetic fibers.

It is a principal aim and object of this invention to provide durable water and oil repellency for textiles consisting essentially of synthetic fibers. Other aims and objects will become apparent hereinelsewhere.

In accordance with these and other aims and objects of the invention, it has been found that durably launderable and dry-cleanable oil and water repellency can be conferred on fabrics consisting essentially of hydrophobic synthetic fibers by applying to said fabric a blend of a fluoroaliphatic group-containing material and a carbodiimide in proportions of from l0:90 to 95:5 and preferably from 20:80 to :20 fluoroaliphatic radical-containing material to carbodiimide. The blend may be applied as a suspension or solution in either aqueous or non-aqueous media.

A preferred fluoroaliphatic radical-containing material is a substantially linear vinyl polymer containing from 10 to 60 percent by weight of the polymer of fluorine in the form of fluoroaliphatic groups terminating in CR, groups and containing at least three fully fluorinated carbon atoms. Acrylates and methacrylates are readily available and very convenient vinyl polymers and are particularly preferred.

The carbodiimides consist essentially of from I to a plurality, preferably not over 20, of carbodiimide groups, terminal organic radicals free from isocyanatereactive hydrogen atoms connected to carbodiimide and, when two or more carbodiimide groups are pres ent, also polyvalent, preferably divalent, organic linking groups which are residues of a polyisocyanate between successive carbodiimide groups. Fluoroaliphatic groups may form parts of terminal or linking groups.

The treating solution is applied by padding, spraying or other conventional means a perfluoroalkoxyl group having up to 4 carbon atoms, cyano, carboxy, carbamoyl, 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 :5 may be prepared in the desired aqueous or nonaqueous medium and diluted as needed to form 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 possess a pleasant hand.

Any of the art-recognized fluoroaliphatic radicalcontaining polymers useful for the treatment of fabrics to obtain oil and water-born stain repellency can be used including condensation polymers such as polyesters, polyamides, polyepoxides and the like, and vinyl polymers such as acrylates, methacrylates, polyvinyl ethers and the like. Many of these are disclosed in the reference in Table l.

The preferred class of fluoroaliphatic radicalcontaining vinyl polymers is composed of the acrylate and methacrylate polymers and random copolymers. ln any event, it is essential that the vinyl polymer contain a fluoroaliphatic radical terminating in a CF group and containing at least three fully fluorinated carbon atoms, preferably a perfluoroalkyl group. The polymer may contain as little as 10 percent of its weight of fluorine in the form of fluoroaliphatic radicals, and as much as 60 percent for maximum resistance to dry cleaning. it is preferred that the polymer contain from about 15 percent to 45 percent by weight of fluorine. The fluoroaliphatic polymer is applied to the treated fabric so as to provide between 0.02 and 0.5 percent by weight of carbon-bonded fluorine on the fabric, preferably 0.05 0.25 percent by weight. Although higher levels of fluorine can be applied to provide useful products, the increased cost is not usually warranted by increase in performance.

Table l lnventors US. Pat. No. Title Ahlbrecht, 2,042,416 Fluorinated Acrylates Reid and and Polymers Husted Ahlbrecht. 2.803.615 Fluorocarbon Acrylate and Brown and Methacrylale Esters and Smith Polymers Bovey and 2.826.564 Fluorinated Acrylate and Abere Polymers Ahlbrecht and 3.l02,l03 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 Fasiclt and 3,282,905 Fluorine Containing Esters Raynolds and Polymers thereof Smith and 3,329,66l Compositions 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 Gilbert Esters and Polymers thereof Kleiner 3,412,179 Polymers of Acrylyl Perfluorohydroxamates Sweeny and 3,420,697 Perfluoroalky-substituted Liauw Polyamide Oil-repellency Compound and Textile Materials Treated therewith Pacini 3,445.49l Perfluoroalkylamidoalkylthio Methacrylates and Acrylates and lntermediates therefor Eygen and 3.470.l24 New Fluorinated Compounds Carpentier and Their Preparation Brace 3 544.537 Poly( perfluoroalkoxy polyfluoroalkylacrylatetype Esters and Their Polymers Tandy 3,546,187 Oil and Water Repellent Polymeric Compositions Carbodiimides are conveniently obtained by condensation of isocyanates in the presence of suitable catalysts as described, for example, in the patents of Table 2 and by Campbell et al., J. Org. Chem., Vol. 28, pages 2069-2075 {1963).

The carbodiimides employed in the invention can be of more or less conventional types including terminal hydrocarbon radicals or they may include fluoroaliphatic radicals as noted above. Fluoroaliphatic radicalcontaining carbodiimides were not known heretofore and are particularly useful in fabric treatments. The carbon-bonded fluorine of these polymers which ranges from about l5 to about 45 percent is included within the totals of fluorine applied to the fabric, i.e., 0.02 to 0.5 percent by weight.

C H (CH )NHC0 C H c s o canicagc a In general, carbodiimides formed from di-isocyanates with or without monisocyanates are represented for convenience by the general formula:

where n is O or an integer from I to at least 20 and preferably from 1 to 10. 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 higher are useful but offer no known advantages.

In the above general formula, A is a divalent organic group which may include pendent fluoroaliphatic radicals linking successive carbodiimide groups when n is I or more. Illustrative linking groups include alkylene, such as ethylene, isobutylene. and the like of 2 to about l0 carbon atoms, aralkylene, such as CH,C,H.C- H,, of up to l0 carbon atoms, arylene, such as tolylene, C.H,(Cl-l;), of up to about 10 carbon atoms. polyoxaalkylene such as (C,H O),C,H containing up to about 5 oxa groups and combinations of the various types. lt will be recognized that the A group is the residue of an organic diisocyanate. that is, the divalent radical obtained by removal of the isocyanate group from an organic diisocyanate. Suitable organic diisocyanates may be simple, e.g.. toluene diisocyanate. or complex, as formed by the reaction ofa simple diisocyanate with a dior polyol in proportions to give an isocyanate terminated polyurethane.

Although carbodiimides generally and preferably include divalent A groups, some of the A groups can be, for example trivalent or tetravalent derived from triisocyanates or tetraisocyanates such as polymethylenepolyphenyl isocyanates. e.g., OCNC l-l CH,C H (NCO)CH C H NCO. When A is trivalent or tetravalent, branched or even crosslinked polycarbodiimides result. A mixture of A groups containing some trivalent groups can be used to provide branched polycarbodiimides which retain the desirable solubility and thermoplasticity of the linear carbodiimides resulting from carbodiimides having divalent A groups.

The carbodiimide groups (N=C=N) should represent at least 12 percent of the molecule except for terminal and pendent fluoroaliphatic radicals present.

Substituents may be present in A groups provided they contain no isocyanate-reactive hydrogen atoms; that is, groups such as -OH are normally excluded. Simple unsubstituted organic linking groups free from nonaromatic unsaturation are preferred. The organic linking group depends on the polyisocyanate compound employed such as:

The terminal groups, or B-groups, are preferably monovalent radicals of monoisocyanate compounds which may be aliphatic as C l-l aralkyl as C,H,CH,-. aryl as C H and preferably fluoroaliphatic such as C F C ll and C F, Cl-l O,CNHC,l-l.(Cl-l,). (derived from tolylene diisocyanate and l,ldihydroperfluorooctanol). Numerous other terminal groups are operable in the compounds and process of the invention. When only diisocyanates are used to form the polycarbodiimides, the B groups are monovalent radicals derived from diisocyanates and include an isocyanate group (or an hydrolysis product of such a group). The terminal B groups may be the .same or different.

Because the monoisocyanate terminates the carbodiimide molecule, the relative proportion of monoisocyanate to diisocyanate used in the reaction determines the average value of n in the above formula, 0 when no diisocyanate is used upwards so that with about mole percent of monoisocyanate and 90 percent of diisocyanate n will average about as will be readily apparent.

The invention is more particularly described hereinbelow by examples of the preparation of suitable components for the process of the invention and by examples showing the effectiveness of the process of the invention in providing oil and water repellency durable to washing and/or drycleaning. In these examples, all parts are by weight. The testing procedures employed in these examples are as follows:

Synthetic fabrics of 100% filament nylon and 100 percent spun and 100 percent filament polyester are treated with the blended formulation at a predetermined level of fluoroaliphatic component on the fabric. This level is 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 percent by weight.

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 Association of Textile Chemists and Colorists, Vol. 28, page 136. The spray rating is expressed on a 0 to 100 scale where 100 is the highest possible rating. For outerwear fabrics particularly, a spray rating of 70 or higher is considered desirable.

The oil repellency test American Association of Textile Chemists and Colorists Standard Test 1 18-196 is based on the resistance to penetration of oils of varying viscosities. Treated fabrics resistant only to Nujol, a common type of mineral oil, and the least penetrating of the test oils, are given a rating of 1, whereas fabrics resistant to heptane, the most conventionally of the test oils, are given a value of 8. Other intermediate values are determined by use of other pure substances. The oil repellency corresponds to the oil which does not penetrate or wet the fabric after 3 minutes contact. Higher numbers temperatures better oil repellency. In general, an oil repellency of 3 or greater is desirable.

The laundering 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 C. and a commercial detergent and then tumble-dried 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 drycleaning establishment and the fabrics are not pressed or heated after the drycleaning process. Perchloroethylene (C Cl is the solvent used for the drycleaning procedure.

Carbodiimides are usually made from diisocyanates and monoisocyanates in an inert solvent such as methyl isobutyl ketone, conveniently at a concentration of about 40 percent of dissolved materials, to which is added about 1% of the weight of the materials of a phospholine oxide or other suitable catalyst. The reaction mixture is prepared so that any water is removed before addition of isocyanates and is heated until reac tion is essentially complete. The reaction mixture can be emulsified in water and further diluted with water before application. The fabric treating solution can be prepared by blending emulsions of carbodiimide and fluoroaliphatic radical-containing polymers, together with any desired compatible adjuvents. Alternatively, the polycarbodiimide and fluoroaliphatic radical containing polymer can be prepared in solution and the solution blended, diluted if necessary and applied, for example, to fabrics that would be undesirably affected by water. The proportions depend on the amount needed to givea treating solution which will provide the correct concentration of solids, carbodiimides plus fluoroaIiphatic-radical containing polymer, to attain the desired weight of treatment at the level of wet pickup chosen. This level is herein set at 50 percent where not otherwise denominated to give comparability of results. Thus for 50 percent wet pickup, a 0.3 percent concentration provides 0. l 5 percent solids pickup which at 50 percent fluorine content gives 0.075 percent fluorine on the fabric. The latter fluorine content is used in these examples, unless otherwise indicated, to permit ready comparisons.

EXAMPLE 1 A solution of l0l.6 parts (0.17 mol) of C,F SO,N(CH CH OH in 265 parts of methyl isobutyl ketone (MIBK) is first dried by distilling 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 6575 C., and 1 part of 3-methyl-lphenyl-B-phospholine-l-oxide is added followed by 3 hours further refluxing. A film cast from this solution is weak and brittle and contains the characteristic carbodiimide infrared absorption peak at 4.69 microns. The solution contains the carbodiimide designated Polymer A which is predominantly represented by the and the B" group is -A-NCO. To 100 parts of this polycarbodiimide in l2l parts of MIBK is added 4 parts of polyoxyethylene sorbitan monooleate emulsifier, 4 parts of C F SO=N(CH )C H N(CH CI emulsifier and 225 parts of distilled 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 C F,-,SO,N(C,H )CH,CH,OH 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 3methyl-l-phenyl-3- phospholine-l-oxide to it, the solution is refluxed for a further 3 hours. A film cast from this solution is weak and brittle and contains the characteristic carbodiimide absorption peak at 4.79 microns. The solution contains the carbodiimide designated as Polymer B which is represented by the formula:

in which it will be seen that the A" group is C H C- H;, and the 8" group is C F -,SO,N(C H )C H O,CNHC H;,(CH To I00 parts of this polycarbodiimide in 138 parts of methyl isobutyl ketone is added 2.5 parts of polyoxyethylene sorbitan monooleate emulsifier (available under the Trademark Tween 80), 2.5 parts of C F SO N(CH )C H..N(CH CI and 265 parts of distilled water. The mixture is then emulsified.

EXAMPLE 3 To a solution of 27 parts of C F SO N(CH )C H,O CC(CH )=CH 2.85 parts of ethylhexyl methacrylate and 0.15 parts of glycidyl methacrylate in l2 parts of acetone and 48 parts of water are added 1.5 parts of polyethoxylated quaternary ammonium chloride emulsifier, 0.05 parts t-dodecyl mercaptan and 0.05 parts of potassium persulfate. The mixture is degassed, blanketed under nitrogen and then heated to 65 C., and the polymerization allowed to proceed with agitation for 16 hours. A film cast from this material is hard and brittle. The random copolymer having pendent fluoroaliphatic groups is designated Polymer C.

EXAMPLE 4 The procedure of Example 2 is repeated using C F SO N(CH )C H OH and a lower amount (27.5 parts; 0.16 mol) of tolylene diisocyanate. The resultant carbodiimide designated Polymer D is represented by the structure:

CaF17s02 C H O CN- H H 2 5 A further series of fluoroaliphatic carbodiirnides is prepared by the above procedures using the materials and molar proportions indicated in Table III and designated as shown there.

Table Ill Polymer Example Designation Reactants 5 E C..F,,so,N c,H.oH 3 mol (OCN-CJL-fiCl-l,

H -co 2":

P 6 F .F11SO,NC,H.OH 3 mol Q c H; NCO

NCO a": l

\. 7 G u n -;H OH 5 mol H C A NCO Table ll] Continued Polymer Example Designation Reactants NCO l 8 H c r som-c mon nocm on 2 mol H c. 5. NCO

NCO i 2H5 m a f y 9 l c r-", sons-canon c r somcm om, 10 mo! u 3C \b NCO Mw-5500 A series of non-fluorinated carbodiimides is prepared using the same general procedures as above on the mol proportions of reactants shown in Table IV,

Table IV Polymer Example Designation Reactants 10 M Stearyl alcohol l mol NCO I ll N Butanediol 2 mols H355 NCO MW-1000 Phenyl isocyanate 2 mols H NCO l3 P Stearyl alcohol 3 mols NCO NO I I4 Q MW-5000 Stearyl alcohol 5 mol NCO plus 2 mol 0H -terminated polydiethylene glycol polyester of adipic acid For purposes of providing fluoroaliphatic polymers, a number of materials are prepared or obtained commercially. These also are designated by letters.

age composition of about l0 carbon atoms. This is available under the Trademark Zepel D.

Polymer V designates a 50/50 blend of two polymers.

Polymer U designates a commercially available mate- 65 One is made by emulsion polymerizing for 16 hours at rial believed to be a 50/50 blend of poly( Z-ethylhexyl methacrylate) and poly( l l ,2,Z-tetrahydroperfluoroalkyl methacrylate) in which the alkyl group has an aver- 50 C. a mixture of 50 parts methyl methacrylate and 60 parts of tridecyl acrylate in I26 parts of water and 54 parts of acetone in the presence of 2 parts of Polymer W is like the latter polymer used in Polymer V, but prepared from equal amounts of C F SO N(C,.

H,)C,H,OCOC(CI-I )=CH, and chloroprene as described in Example Ill D of U.S. Pat. No. 3,068,187.

Polymer X is prepared as in the above procedures,

after treatment and again after 5 launderings and in some cases also after 5 drycleanings. The data are presented in the following tables in which Nylon= 100% filament nylon Polyester F 100% filament polyester Polyester S 100% spun polyester Initial data before laundering etc.

Laundered= data after 5 launderings Drycleaned data after 5 drycleanings.

Except as noted. the fabrics are treated to contain h in a reac1i0nmim f90 -r C F SO N(CH 0.075 percent carbon bonded fluorine. Porportions )C H OCOC(CH )=Cl-I and 10 parts butylacrylate in 160 parts water and 40 parts acetone with 0.2 parts tdodecyl mercaptan and 0.2 parts potassium persulfate using 5 parts of a commercial polyethoxylated quaterof polymers blended together are indicated as. eg... 65C+35B. and for controls or comparisons where there is no blend. as e.g.. 100C. The ratings are given for conciseness as a fraction. e.g.. 5/100. in which the nary ammonium chloride emulsifier at 65 C. for 16 nllmel'illor 1 15 Oil rating and denominator i hours spray rating.

Table V Initial Laundered Treatment Polymer Blend Nylon Polyester S Polyester F Nylon Polyester 8 Polyester F 1 65C B 2/100 5/95 6/100 2/95 4/95 5/95 2 50C 50D 5/100 6/95 5/90 4.5/90 6/100 4.5/85 3 65C 35A I/l00 6/100 5/100 l/I00 3.5/100 /100 4 65X 35A 2/100 6/100 4/[00 3/85 3/95 4/85 5 65C 35E 5/100 5.5/100 5.5/100 4/100 35/80 4/90 6 65C 35F 5.5/100 5.5/100 5.5/100 3/90 25/75 5/80 7 65C 350 1.5/100 4/80 5/100 2/95 4.5/80 4.5/95 8 C 50H 5/100 6/85 5.5/100 3/90 5/85 4.5/95 9 C 351 2/100 5/l00 5/100 l/l00 5/95 4/95 10 100C 2.5/100 5/100 5/95 15/75 2.5/50 2/50 I l 100C 5/95 6/80 5.5/l00 0/00 2/70 2/50 applied at 0 089% carbon-bonded fluorine on fabric. Certain of the above were also SUhJCClCd to drycleaning with the results shown in Table VI Table VI Initial Drycleaned Treatment Polymer Blend Nylon Polyester 5 Polyester F Nylon Polyester 5 Polyester F 3 65C 35A l/l00 6/100 5/100 2/75 25/70 5/70 4 65X 35A 2/100 6/100 4/100 3/70 3/70 4.5/ 1 l 100C 5/95 6/80 5.5/100 5/50 0/0 3/50 applied at 0.089% carbon-bonded fluorine solids on fabricv As noted hereinabove, fabrics of 100% filament nylon and both 100 percent spun and 100 percent filament polyester are treated by standard procedures with Various fluoroaliphatic vinyl polymers are used with the same fluoroaliphatic carbodiimide and the data are tabulated in Table VII.

Table VII Initial Laundered Treatment Polymer Blend Nylon Polyester S Polyester F Nylon Polyester S Polyester F 12 65U 35B 6/100 6/85 5/100 4/90 4/70 2/75 l3 65V 358 6/95 5/85 5/85 5/95 4/75 3/80 14 65W 358 5/95 5/80 5/95 4.5/ 45/80 4/85 15 65C 358 5/100 5/100 6/100 4.5/ 5/80 3.5/95 I6 IOOU 7/95 6/70 0/60 0/50 0/50 0/50 I! 100V 5/100 5/85 l/BO 3/50 3/50 3/50 l8 100W 5/100 5/100 5/100 5/90 5/80 3/85 19 I(X)B 2/70 4/85 2/70 0/70 l/80 0/70 various blends of fluoroaliphatic vinyl polymers and carbodiimides and rated for oil and water repellencv Non-fluorinated carbodiimide blends are compared in the data of Table VIII.

Table VI" Initial Laundercd Treatment Polymer Blend Nylon Polyester S Polyester F Nylon Polyester S Polyester F 20 65C 35M 3/95 5/l00 3/85 3/85 2] 65C 35N 5/95 6/l00 5/l00 2/75 5/85 4/80 22 65C 350 2/100 4/100 5/l00 2/85 l/80 2/85 23 65C 35? 4/!00 5/l00 l/SS 2/85 24 65C 350 2/100 5/90 5.5/l H80 2160 2/75 A further series of fluoroaliphatic radical-containing carbodiimides is also prepared by the above procedures and characterized by melting ranges and fluorine analyses. Infrared absorption spectroscopy confirms the presence of -N=C=N- groups. These carbodiimides are also useful in the fabric treatments as set forth above. Analogous polymeric carbodiimides in which the fluoroaliphatic groups contain from four through 18 fully fluorinated carbon atoms, such as C F C F C F C F O(C F O) CF(Cl-l are also found to be useful. The data on this series of carbodiimides are summarized in Table IX.

lation to ensure anhydrous conditions. The kettle is cooled to about 90 C., 52 parts of 2,4-toluene diisocyanate added and the solution heated to 1 l" C. for a further 3 hours. The solution is next cooled to 50 C. and 5 parts of a by weight solution of 2,2,14,4- pentamethyl-l-phenylphosphetane oxide in methylene chloride added, and the solution is then again slowly heated to 1 15 C., care being taken to avoid excessive foaming. The solution is maintained at 1 15 C., with agitation for about 3 hours, or until the isocyanate groups are essentially completely reacted as indicated by the EXAMPLE 24 To a 25 gallon glass-lined kettle equipped with agitainfra-red absorption spectrum. The product is a percent by weight solution of:

tor, condenser, and provision for heating and cooling. are added parts of CgF11S02N(CgH5)C4HgOH and 135 parts of MIBK solvent. The solution is heated to about 1 15 C. and 25 parts of solvent removed by distil- A fabric-treating concentrate is prepared by dissolving parts of a fluoroaliphatic radical-containing methacrylate copolymer (35 percent fluorine in the form of fluoroaliphatic radicals) in l l parts of MIBK and 260 parts of C F Cl and adding 25 parts of the above polycarbodiimide product solution.

For treatment of fabrics whose structure would be damaged by exposure to water, such as textured or velvet upholstry fabrics, a solvent system is preferred. For treatment of a medium-weight 100 percent nylon velvet, for example, the above concentrate, is diluted to about 0.4 percent solids with trichloroethylene. lmproved water resistance can be obtained by the addition of a fluorine-free water repellant, such as 0.1 percent 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 ll0 C. for about 3 minutes, 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 resistance remains even after extensive abrasion.

EXAMPLE 25 A branched polycarbodiimide is prepared by adding to 57.5 parts of dry MIBK (Methyl lsobutyl Ketone) The solution is refluxed for 3 hours, then cooled to 90 C. and 1.7 parts of a 22 percent by weight solution of pentamethyll -phenylphosphetane oxide added. The resulting solution is heated to reflux and maintained there for two hours. A further 0.86 parts of catalyst solution is added because the presence of unreacted NCO is shown by infrared absorption and refluxing is continued for an additional hour. The resulting clear solution is free from NCO, but exhibits the characteristic absorption peak of carbodiimide at 4.69 microns. Emulsions and solutions containing this polycarbodiimide product and a fluoroaliphatic group containing acrylate copolymer confer durable oil and water resistance on treated fabrics.

What is claimed is:

l. The process for conferring durably launderable aqueous 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 suitable aqueous or nonaqueous medium, in proportions of 10:90 to 95:5, of

A. fluoroaliphatic radical-containing substantially linear vinyl polymer containing from ID to 60 percent by weight thereof of fluorine in the form of fluoroaliphatic radicals terminating in CF groups, said fluoroaliphatic radicals containing at least three fully fluorinated carbon atoms, and

B. a solvent-soluble carbodiimide consisting essentially of from I to a plurality of carbodiimide groups, terminal organic radicals free from isocyanate-reactive hydrogen atoms connected to carbodiimide and, when two or more carbodiimide groups are present, polyvalent organic groups, residues of polyisocyanates, linking successive carbodiimide groups, and thereafter vaporizing said medium whereby a coating of said blend is deposited on said synthetic fibers.

2. The process according to claim I 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 suitable aqueous or non-aqueous medium, in proportions of 10:90 to :5, of

A. fluoroaliphatic radical-containing substantially linear vinyl polymer containing from l0 to 60 percent by weight thereof of fluorine in the form of fluoroaliphatic radicals terminating in CF, groups, said fluoroaliphatic radicals containing at least three fully fluorinated carbon atoms, and

B. a carbodiimide consisting essentially of from I to a plurality of carbodiimide groups, terminal hydrocarbon or fluoroaliphatic radicals free from isocyanate-reactive hydrogen atoms and connected to carbodiimide and, when two or more carbodiimide groups are present, polyvalent organic groups, residues of polyisocyanates, linking successive carbodiimide groups, and

thereafter vaporizing said medium whereby a coating of said blend is deposited on said synthetic fibers.

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

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

5. The process according to claim 4 wherein the carbodiimide includes fluoroaliphatic radicals in terminal and linking groups.

6. The process according to claim 5 wherein fluoroaliphatic radicals contain from 3 to 18 fully fluorinated carbon atoms.

7. 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 l0:90 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 CF, groups, said fluoroaliphatic groups containing at least three fully fluorinated carbon atoms,

and

B. a carbodiimide consisting essentially of from l to a plurality of carbodiimide groups, terminal organic radicals free from isocyanatereactive hydrogen atoms connected to carbodiimide and, when two or more carbodiimide groups are present, polyvalent organic groups, residues of polyisocyanates, linking successive carbodiimide groups;

said coating being in amount to provide from 0.02 to 0.5 percent by weight of carbon-bonded fluorine on the fabric.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,896,25

DATED 1 July 22, 1975 INVENIOR(S) Dennis P. Landucci It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, lines 28-31, a perfluoroalkoxyl group...

carbamoyl," should read as and the vehicle Column 5, line N2, "conventionally" should read as penetrating Column 5, line 47, "temperatures" should read as indicate Column 15, line 16, "aqueous" should read as and Signed and Scaled this fourteenth Day Of October 1975 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer (ommissimrer oj'Parents and Trademarks

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Classifications
U.S. Classification442/80, 427/393.5, 427/389.9, 524/195, 427/393.4
International ClassificationD06M15/21, D06M101/00, D06M13/432, D06M13/428, D06M15/00, D06M15/244, D06M15/277, D06M13/00, D06M13/02, D06M101/16, D06M13/395, D06M13/322
Cooperative ClassificationD06M13/432, D06M13/428, D06M13/395, D06M15/244
European ClassificationD06M13/432, D06M13/428, D06M15/244, D06M13/395