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Publication numberUS3920389 A
Publication typeGrant
Publication dateNov 18, 1975
Filing dateApr 13, 1973
Priority dateJan 31, 1973
Also published asUS3854871
Publication numberUS 3920389 A, US 3920389A, US-A-3920389, US3920389 A, US3920389A
InventorsEanzel Albert Robert
Original AssigneeDu Pont
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Textile cleaning process
US 3920389 A
Abstract
A process for simultaneous cleaning and finishing of soiled textile material in which the textile is (A) agitated in a cleaning bath consisting essentially of a major amount of a textile dry cleaning solvent and optionally minor amounts of water, and containing (1) an insoluble polyfluoroalkyl-substituted stain repellent material and (2) optionally an emulsion-promoting agent which does not adversely influence the stain repellency of the treated textile material, and then (B) is dried.
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United States Patent [191 Eanzel 11 3,920,389 Nov. 18, 1975 TEXTILE CLEANING PROCESS 75 Inventor: Albert Robert Eanzel, Wilmington,

Del. 3

731 Assignee: E. l. Du Pont d Nemours &

Company, Wilmington, Del.

22 Filed: Apr. 13, 1973 211 App]. No; 350,796

Related U.S. Application Data [63] Continuation-impart of Ser. No. 328,382, Jan. 31,

1973, Pat. No. 3,854,871.

[52] US. Cl. .Q 8/142; 8/1 15.6; 252/86;

256/56 R; 256/56 S; 260/296 F [51] Int. Cl. B32B 27/04; B44D 1/09 [58] Field of Search 8/1 15.6; 252/86;

256/56 R, 56 S; l17/l39.5 CQ, 139.5 A, 121, 135.5, 161; 260/29.6 F

[56] References Cited 7 UNITED STATES PATENTS 3,518,218 6/1970 Connick et al. 8/1 15.6

FOREIGN PATENTS OR APPLICATIONS 671,516 8/1967 7 Netherlands Primary Examiner-William R. Trenor [57] ABSTRACT A process for simultaneous cleaning and finishing of soiled textile material in which the textile is (A) agi tated in a cleaning bath consisting essentially of a major amount of a textile dry cleaning solvent and optionally minor amounts of water, and containing (1) an insoluble polyfluoroalkyl-substituted stain repellent .material and (2) optionally an emulsion-promotingagent which does not adversely influence the stain repellency of the treated textile material, and then (B) is dried. I r

2 Claims, No Drawings TEXTILE CLEANING PRocEss CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of copending application Ser. No. 328,382 filed Jan. 31, 1973, now US. Pat. No. 3,854,871. 1

U BACKGROUND on THE INVENTION 1. Field of the'lnvention r This invention relates to an improved process for cleaning'textile materials and more particularly is directed to a process for simultaneous cleaning and finishing of textiles using a bath of dry cleaning solvent whichcontai'ns an insoluble polyfluoroalkyl-substituted stain repellent and an "optional'select emulsion promoting'agent. Y

2. Prior Art Textiledry cleaning isbase d on the fact that most soiling matter is'bound to textiles by a film of oil or grease, and dissolving the oil in asolvent releases the dirt.

The solvents in'common use are: perchloroethylene, trichloroethylene, and the relatively recent introduction, trichlorotrifluoroethane.

The solvent can be used alone and will give reasonably good cleaning. The best results are obtained by filtering the solvent continuouslyduring cleaning so as to remove the releasedparticles of soiling matter and prevent redeposition. A proportion of the filtered solvent containing dissolved oil and grease is distilled after each load has been cleaned in order to prevent undue accumulation of contaminants. This system of dry cleaning is used less widely today because it is less efficient than other methods in removing stains attached by water-soluble films, such as food and beverage stains. In the alternative systems, small quantities of water are carried into the solvent in such a way as to minimize any harmful effects the water may have.

The latter system seems to be widely misunderstood outside-the dry-cleaning industry and sometimes even within the industry. It involves the use of a solvent containing a moderately highconcentration of dissolved detergent and a controlled concentration of dissolved water. The solution is used repeatedly in a process involving continuous filtration.

In practice, the concentrations used vary over the range 0.5 to 4% by volume of detergent as purchased,

and the detergents commonly contain some 50% active material. Because of the high concentration of detergent and attendant high cost, the bath cannot be discardedafter a single use. Continuous filtration to remove suspended dirt'particles as 'soon as possible is helpful in almost any type of process, but it becomes essential whenabath is reused repeatedly.

When small quantities of 'water are added to such a system,theyl become solubilized and are held quite tenaciously, The partial 'pressure' of'the water vapor in the atmosphere in equilibrium above the solution is much below that of pure water at thesame temperature, and the ratio of this vapor pressure to the saturation vapor pressure is known as the solvent relative humidity (SRH). At a given temperature and'detergent concentration, theSRl-l depends jonth'e water concentration, and it can therefore be controlled by controlling the addition of water. Practically, some water al- When textiles are immersed in a chaiged system (solvent-detergent-w'ater), an equilibrium tends to be set upbetween the water in the textiles and the water in the solvent in exactlythe same way as an equilibrium is set up between textiles and the surrounding atmosphere. The moisture. regain of. fibers in equilibrium with a charged system with an SRH of."% is the same as that which-theywould attainwhen in equilibrium with an atmosphere of 75% relative humidity at the same temperature. 1 V; g

The significance of this is that sufficient water can be added to the system to have a very marked effect in removing water-soluble soilings without. increasing the moisture regain of the fibers beyondthe level that they would have in contactwith the ordinary atmosphere. The usual risks of wettreatment, including shrinkage, loss of creases, felting of wool, etc, can be avoided. The fact that water can pass in either direction is a considerable safeguard because, if a damparticle is inadvertently included in a load, the-solventwill rapidly take up water, and the article will be exposed to much less risk than would otherwise have been true.

The effect of adding water in this way maybe judged from the fact that, after cleaning, in solvent alone, on average some 45-50% of garments need no further treatment to remove stains, whereas, after cleaning in a charged system, the proportion may be.75% or more.

The dry-cleaning machine, although basically similar to a washing machine, requires much more accessory equipment, and this is generally built into the one assembly, which includes filter, still, condenser, separator, and pumps and storage tanks, possibly with control gear for the charged system. The machine serves not merely as a washer, for the drum can also be run at high speed to give centrifugal extraction and may subsequently act as a drying tumblers In order to recover the solvent, there is a closed air-circuit. Hot air, isblown through the load,and the solvent-laden air then passes over cooling coils (or, in some designs, meetsa spray of cold water) to strip the solvent before theair is reheated to repeat the circuit. When substantially all the solvent has been removed from the load, the air-circuit is opened, and air is vented from the machine for a short time.

The solvent application of finishes to textile products bears a resemblance to the dry cleaning procedure, and many attempts have been made to apply textile finishes in dry cleaning equipment. However heretofore, so far as is known, there has been nodisclosure of a process combining the two functions of dry cleaning and finish application without substantial alteration of the normal dry-cleaning cycle.

Prior art applications of water and oil repellent compositions do not combine the treatments, but rather apply the repellentin a separate step after the cleaning operation is finished. It was usually necessary to apply awash or rinse to remove the dry cleaning detergent, which, if present, interfered with application or performance of the repellent, In the process of this invention the two'functions are combined satisfactorily through the use of a composition wherein an aqueous or nonaqueousdispersed finishing composition is dispersed in dry cleaning solvent at a low concentration such that the dry cleaning procedure can be carried forward in an essentially normal manner. The dry cleaning deter- 3 gents normally used in that operation are not necessary in the process of this invention.

SUMMARY OF THE INVENTION In summary, this invention is directed to a process for simultaneous cleaning and finishing soiled textile materials in which the textile is A. agitated in a vessel with a composition comprising a major amount of a textile dry cleaning solvent, and dispersed therein an insoluble polyfluoroalkylsubstituted stain repellent in an amount sufficient to give add-on of 0.05 to 0.5 percent, based on dry weight of textile, and then B. the treated material is dried.

A preferred embodiment of the process above is that wherein the treating composition contains additionally a minor amount of water, and wherein the treating composition contains additionally 5 to percent, based on the weight of stain repellent, of an emulsion promoting agent selected from among 1. water soluble salts of condensation products prepared by reacting methylol compounds of aminotriazines,

urea, cyclic ureas, or their ethers, with low molecular weight alcohols with aliphatic compounds containing a carbon chain of at least seven carbon atoms and a reactive hydrogen atom attached to a heteroatom and a primary or secondary amine, 7 a water-soluble salt of a primary or secondary amine, or a tertiary amine, which contains a reactive hydrogen attached to a' heteroatom; 2. acrylate and methacrylate polymers and copolymers; and I 3. hydrocarbon copolymers of 80 to 20 mol percent ethylene and 20 to 80 mol percent aminoalkyl acrylate monomers of the formula wherein R is hydrogen or methyl, R is hydrogen or alkyl of one to atoms, R, is hydrogen or alkyl of one to atoms, and n is a positive integer of from 1 through 4.

DESCRIPTION OF INVENTION four carbon four carbon In one method of carrying out this process, a waterin-oil type emulsion is first prepared by mixing an aqueous dispersion of a textile stain repellent agent into a relatively large amount of a halogenated liquid having a boiling point between 25C. and C. and a relatively small amount of an emulsion-promoting agent which does not adversely affect the performance of the repellent on the textile. The resulting water-in-oil type emulsion is added to an organic solvent functioning as a cleaning agent for textiles ,to form a very dilute extended water-in-oil type emulsion. Textile material is then agitated in contact with the dilute emulsion at ambient or elevated temperature, after which textile material is dried.

In another method of carrying out the process of the invention there is employed a non-aqueous dispersion of a fluororepellent polymer composition in an organic liquid. These compositions are best prepared by polymerization or copolymerization of appropriate monomers in non-aqueous systems to produce an organosol product which contains dispersed polymer particles, and may also contain some soluble polymer material. Some of these products can accept water, emulsifying it readily in the organic liquid continuous phase. With or without added water, these compositions can be employed in the improved textile cleaning process of the invention. Where necessary an emulsifying agent which does not adversely affect the performance of the repellent on the textile can be added to the fluororepellentorganic liquid dispersion to promote water emulsification if desired. With or without the added emulsifier, the composition is added in a very small amount to the organic solvent used as textile cleaning agent, and textile material contacted therewith as already described.

The treatment serves a plural function in that:

1. Soil or foreign material soluble in the organic solvent is removed from the textile.

2. Water soluble-soil or stain is removed by the action of the water when present.

3. The repellent is deposited on the textile to serve its designed function.

The invention has broad application in the processing and cleaning'of textiles. Where organic dry cleaning solvents are used as cleaning agents, the invention provides a method for accomplishing several desirable objectives in one simple step. The combining of a cleaning step and a stain repellent finish application is unique and very valuable to the cleaner and processor.

More specifically, in this invention textile material is cleaned and a polyfluoroalkyl-substituted oil and water repellent is deposited thereon in regular textile dry cleaning equipment with very slight alteration of the normal cleaning cycle. When water is present the unique combination of cleaning solvent, water, and stain repellent provides normal cleaning and significant stain repellent qualities to the textile products. Watersoluble stain is removed and the objectionable necessity for spotting or hand removal of stubborn stain is lessened. Of course, hand removal of water-soluble stains can be performed separately instead of combining it with dry cleaning and repellent applications.

Another application is found in textile processing where a step involving exposure of the fabric to dry cleaning type solvent for the purpose of removing processing chemicals is involved. Stain repellents in the water-in-oil type emulsion or in the non-aqueous dispersions are mixed with the solvent to provide stain repellency during the cleaning step.

For the purposes of this invention, soiled textile materials means textiles which are soiled or stained in use as well as new textiles which contain processing chemicals.

in preparing a dispersion of finishing agent in solvent, the usual dry-cleaning solvents are satisfactory, including tetrachloroethylene, trichloroethylene, 1,1,2-trichlorol ,2,2-trifiuoroethane and trichloromonofluoromethane. Stoddard solvent and others based on petroleum fractions also function satisfactorily, however, the halogenated solvents named abovepossess the advantage of lack of flammability.

Any polyfluoroalkyl-substituted or other textile finishing agents exhibiting lack of solubility in water and in the solvents employed can be used in the process of the invention. This group can include not only oil and water repellents but also members which additionally exhibit the quality of providing dry soil resistance, improved soil release during laundering and other desired properties to textile substrates. Since dry cleaning equipment does not normally provide temperatures above about 210F., those agents requiring a higher temperature cure for development of functional performance are not recommended unless the required cure temperatures can be otherwise provided, as for example in pressing or the like. Of course such agents can be applied in dry cleaning equipment where less than optimum performance is acceptable.

Oil and water repellent agents are exemplified by polyfluoroalkyl-substituted compounds which contain perfluorinated alkyl chains of at least three and as many as 16 carbon atoms. Representativeagents are polymers of fluoro monomers which can be copolymerized or extended with non-fluorinated monomers, and are listed below:

where n may be 1 to 5 and R is H or CH These'compounds are disclosed in US. Pat. No. 3,547,861.

where n is usually 3 but may be from 1 to 5, and R is H or CH These compounds are disclosed in U.S. Pat.

' c n, OR

where R is H or CH is disclosed in U.S. Pat. No. 2,803,615. Useful polymers and copolymers of such monomers are also disclosed in U.S. Pat. Nos. 3,068,187 and 3,574,791.

6 where n has a value of 3 to l4; m is an integer of from 1 toa'bout '12-; and R is H or CH are disclosed in U.S. Pat. Nos. 2,642,416, 3,102,103, 3,378,609, 3,392,046 and'3,546;l87.' v

where R, is a perfluorinatedalkyl-group of three to 17 carbons, aredisclosed in U.S. Pat. Nos. 3,386,977 and where. n is z 1; X is .O C alkyl, -(CH ),,,OH, -(CH ),,,O C'alkyl, or OH wherein m is an integer of 0 to 10; and R -is perfluoroalkyl of from 3 to 21 carbons as disclosed in U.S. Pat. No. 3,575,940, U.S. Pat. No. 26607/68, 1994/69 and 2182/70.

where R, is perfluoroalkyl of four to 18 carbons; m is an integer of 2 m6; R is an alkyl group of four to 10 carbons; and R isH or methyl as disclosed in U.S. Pat. No. 3,304,278.

where R; is perfluoroalkyl of five to 12 carbons and R is H or methyl as disclosed in U.S. Pat. No. 3,384,627. 9. Graft polymers comprising a backbone chain of a polymer susceptible to grafting by a free radical mechanism to which is grafted a homo or copolymer derived from a fluorine-containing monomer of the formula where X is oxygen" or sulfur, R is an ethylenically unsaturated hydrocarbon radical derived from a dibasic or tribasic acid, m is'an integer from 3 to 18, n is zero or an integer from 1 to 10 and sis 2 or 3 corresponding to the number of carboxyl groups of the acid from which R is derived, and optionally an ethylenically unsaturated comonomer. These compositions are disclosed in British Pat. No. 1,280,036

10. The polymer of the composition defined as follows:

An organosol containing as a dispersed phase, in an inert organic liquid as the continuous phase, a plural polymer composition resulting from polymerization of a mixture comprising A. at least 70 percent by weight of at least one eth-- ylenically unsaturated perfluoroalkyl-substituted monomer,

B. from 0.5 to 30 percent by weight of an organic hydrogen-containing polymer which is soluble in said organic liquid, and

C. at least one free-radical generating polymerization initiator,

monomer (A) having the general formula R,X-Y,

wherein R, is a monovalent perfluoroalkyl radical CF (CF where n is an integer from 2 to l3, X

is a divalent organic group free of ethylenic unsaturation, and Y is a monovalent ethylenically. unsaturated group attached tp X by a carbon, oxygen, nitrogen or sulfur atom in Y, or to an oxygen atom joined to a phosphorus atoms in Y.

These useful copolymers and the organosol compositions containing them are disclosed in British Pat. No.

' The above list is not exhaustive, but merely exemplifies suitable fluorine-containing monomers which are employed in some commercial oil and water repellent polymers for textile finishing. The polymers are available in the form of aqueous emulsions containing from 5% to 50% active ingredient (polymer) or, in some instances, as non-aqueous organosol dispersions.

In order to effectively disperse and emulsify the aforementioned fluorinated repellents and water in dry cleaning solvent, an emulsion-promoting agent may be needed which promotes dispersion but does not adversely affect the functional performance of the repellents on the treated fabric. Conventional surfactants such as alkanesulfonates, long chain alcohol sulfates,,

ethylene oxide additives of alcohols, acids, amines and phenols, alkylnaphthalenesulfonates and the like can be used, however, theytend to promote wetting and otherwise interfere with the performance of the repellent. Where these or other dry cleaning detergents are employed, their deleterious effect can be largely overcome by increasing the amount of repellent used and deposited on the textile substrate.

A number of chemical species provide the desired emulsion promoting function. Preferred among them are:

1 water soluble salts of condensation products prepared by reacting methylol compounds of aminotriazines,

urea, cyclic ureas, or their ethers, with weight alcohols with aliphatic compounds containing a carbon chain of at least seven carbon atoms and a reactive hydrogen atom attached to a heteroatom and a primary or second amine, e a water-soluble salt of a primary or secondary amine, or a tertiary amine, which contains a reactive hydrogen attached to a heteroatom; 2. acrylate and methacrylate polymers and copolymers; and

3. hydrocarbon copolymers of 80 to 20 mol percent ethylene and 20 to 80 mol percent aminoalkyl acrylate monomers of the formula low molecular i CH u 2n V wherein R is hydrogen or methyl, R is hydrogen or alkyl of one to four carbons,

R is hydrogen or alkyl'of one to four carbons, and

vn is a positive integer of from 1 through 4.

Of the above emulsion-promoting agents the copolymers of ethylene and aminoalkyl acrylate monomers are most preferred. Suitable acrylate monomers include 2-(dimethylamino)-ethyl acrylate and methacrylate, aminoethyl acrylate and methacrylate, 2-(diethylamino)ethyl acrylate and methacrylate, 2-(methylamino)ethyl acrylate and methacrylate, Z-(tbutylamino)-ethyl acrylate and methacrylate and 3- (dimethylamino)propyl acrylate and methacrylate.

The water-soluble salts of the condensation products and their preparation are described in US. Pat. No. 2,783,231 and preparation of the hydrocarbon copolymers is described in Canadian Pat. No. 900,650.

The emulsion-promoting agent is present during the treating process in a weight ratio of from about 1:20 to relative to the active component or components of the finishing agent. A ratio of 1:5 to 1:10 is preferred.

Representative of non-aqueous fluororepellent dispersions which can be employed in the process of the invention and which possess the inherent property of self-dispersion forming uniform dispersions of very fine solid particles without additional dispersant are the polymer products listed as types Nos. 9 and 10 as described hereinbefore which possess this property. Additionally the products listed under No. 10 are watersolubilizing agents, i.e., water can be added to the nonaqueous dispersion with agitation to form a uniform stable system without using a separate emulsifying agent.

The preferred manner of introducing the aqueous stain repellent to the cleaning operation is in the form of a water-in-oil type emulsion. The emulsion is prepared by mixing the repellent (which is itself preferably in the form of an aqueous dispersion) into a solution of the emulsion-promoting agent in a solvent. The solvent can advantageously be the same as used in the textile cleaning operation. The product should be uniform in composition, stable and easily handled, so that it can be added to the cleaning system in accurately known amounts with no more than a preliminary stirring or shaking. It must be extendible in the cleaning solvent so as to form and maintain a uniform treating composition. The product is not limited so far as the concentration of water and repellent material in solvent is concerned, so long as the product is uniform. Normally the emulsion product will contain from 1% to 25% of the polyfluoroalkyl-substituted stain repellent, preferably from 5% to 15%.

Where non-aqueous fluoropolymeric dispersions are employed to introduce the stain repellent and water is desired in the system, the waterin-oil emulsion can be prepared in several ways. With dispersions not requiring an emulsion-promoting agent, water in minor amounts can be added to the dispersion with mixing to prepare the desired water-in-oil emulsion, the fluoropolymer coexisting as an insoluble dispersed phase.

Where an emulsion-promoting agent is necessary in.

compatible solvent. The water can then be added priorto introducing the composition into the cleaning fluid.

By a minor amount of water as used herein, is meant from about 0.01% to about 4% by weight of the dry cleaning solvent. This'is the water actually present during the cleaningand treating operation. It may be.

derivedfrom the fluoropolymer composition, if said composition is water based, or may be added separately.

For use in textile cleaning, the above compositions are greatly diluted in the cleaning solvent.The controlling factor is the amount of repellent agent which is to be deposited on the textile material. While easily discernible results are achieved even at very low add-on of stain repellent, the preferred add-on is from about 0.05% to about 0.5% of polymer solids on the dry:

weight of the textile. Practically, the amount of repellent agent used is determined by the weight of textile material to be processed and the concentrationof solid repellent in the composition/For 50 pounds of textile material, using a composition containing 10%of a polyfiuoroalkyl stain repellent',there would be used from about 0.25 to about 2.5 pounds of the composition whether the cleaning procedure required 100 gallons or200 gallons of cleaning solvent. The concentration of repellent in the cleaning bath itself is thus very low, in the order of 0.01% by weight.

It is in this condition particularly that the process of the invention differs from prior art processes for application of stain repellents to textiles. Where the objective of a process is solely the application of an adjuvant to a garment or other textile product, a minimum amount of solvent or application medium will be employed, since the solvent or application medium will have to be purified, recovered or somehow handled for re-use. Where the process objective is solely cleaning, the greater amount of cleaning solvent used per unit weight of textile the better thecleaning will be. The process of the instant invention performs the two functions, and without the use of ordinary dry-cleaning detergents.

While the stain repellent and any emulsion-promoting agent are preferably introduced to the cleaning operation in the form of a single product, they can also be introduced separately. That is, the emulsion-promoting agent can first be dissolved in or added to the cleaning solvent, and the familiar dispersion of stain repellent added subsequently. 3 The cleaning bath containing the polyfluoroalkylsubstituted stain repellent is applied to the textile material so asto provide thorough and efficient contact between the two for a period of at least several minutes. Agitation of textile material in a perforated basket through the cleaning composition as in a dry cleaning machine is; quite satisfactory, although other similar methods of agitation can be used. In general, where the equipment affords the opportunity, it is best to mix the pure solvent cleaning liquid with the textile material first, before adding the repellentcomposition. In this manner particulate soil loosened from the textile fibers can be reinovedby filtration, 'asin the regular cycle of a dry cleaning'machine, before introduction of the repellent composition. If the repellent composition is present while circulation and filtration of the cleaning. fluid is in progress some of it may be carried along in particulate form and filtered out of the stream beforeit can be deposited on the textile substrate. Where such filtration isa part of the cleaning cycle, itis preferably omitted or by-pass ed during the period the textile material is incontact with the repellent-laden.cleaning fluid. No other alteration is necessary in any of the well-known dry cleaning machine cycles. Drying of the cleaned and treated material canbe carried out at any convenient temperature. Best results are achieved when cleaning fluid is completely removed before further processing of the textile.

While even better oil and water repellency is attained when the usual hotpressing is carried out, this step is not essential to the attainment of good oil and water repellency. i

- Textiles treated. by. the process of the invention exhibit a startling improvement in water and oil repellency and'stain resistance. When water is present, nonoily stains or sweet spots-are effectively removed during the dry cleaning procedure, and no more hand removal of stains is required than with prior dry cleaning techniques. Where the instance. of water soluble stains is higher than normal, additional water can be added with the fluororepellent composition, Water level can, be controlled by employing the solvent relative humidity concept, as hereinbefore described. Redeposition of particulate soil from the cleaning solvent appears to be minimized also in the process of the invention. I

Any of the well known commercial dry cleaning machines can be employed in the process of theinvention, Transfer or dry-to-dry machines, drum types, open pocket and split pocket types are all usable. The usual ratio of solvent to clothes (which admittedly varies widely) can be used, for instance from about 200 gallons for a 25 pound load to 100 gallons for an pound load. The usual cycle times are satisfactory exceptthat the repellent composition is best not introduced into the solvent until about one-half of the wash time has passed, and the particulate filter should be by-passed after the washing is resumed, as already mentioned.

- The following examples illustrate the invention. Parts and percentages referredto therein are by weight unless otherwise indicated.

EXAMPLE 1 In a typical small commercial dry cleaning machine there were placed 25 pounds of a variety of soiled garments for dry cleaning and 2,250 POUIldSQf perchloroethylene; The machine was previously washed thoroughly to remove any residual detergents, which might impair the efficiency of the subsequent treatment. The

cycle was started, and after about 4 to 5 minutes (onehalf the normal washing time) the filter was by-passed and one-half pound of a stain repellent composition was added. The composition contained 71.5% l,l,2 -tril l yethyl methacrylate. A detailed method for preparing this polymer is given in column 6, Example 1 of US. Pat. No. 3,462,296.

After addition of the stain repellent composition, the cycle was resumed. The garments were washed in the perchloroethylene-stain repellent for about 5 minutes and then agitation was stopped. The liquid was drained away and the load spun and dried. Upon removal the garments were found to shed water poured on them very efficiently. The incidence of sweet spots was at least as low as with the normal detergent process. There was no increase in wrinkling, and appearance of the garments after pressing was judged equal or superior to those treated by prior art processes. Handling and recovery of the dry cleaning solvent was carried out in the routine manner. There was no additional make-up or purification required.

Using the same composition and procedure, over 700 cycles were carried out successfully, with continued excellent performance in appearance, water repellency and sweet spot removal.

EXAMPLE 2 A cleaning composition was prepared by first dissolving 2 pounds of the copolymer derived from 70% ethylene and 30% dimethylaminoethyl methacrylate in 278 pounds of perchloroethylene, then mixing in, with rapid agitation, 120 pounds of an aqueous dispersion of a' copolymer prepared by polymerizing a mixture of 60 grams of cloth added, three 10 gram pieces of wool and one 10 gram piece of each of polyester, nylon and cotton. The jar was tumbled in a motor driven machine which turned the jar end over end at 55 rpm. The tumbling device is described in the AATCC Standard Test Method No. 708-1964. After cleaning for 2 to 3 minutes, tumbling was stopped and the fluoropolymer-containing composition was added. The jar was then tumbled for 5 minutes. The treated samples were removed and adhering liquid spun off in a laboratory centrifugal extractor for about seconds at high speed. The fabric pieces were then placed on a pin frame and dried in a 200F. oven for 5 minutes. They were then ready for oil and water repellency tests. The cloths were analyzed for fluorine to determine the amount of fluoropolymer exhausted from the treatment bath.

EXAMPLE 3 The water-in-oil emulsion composition contained 30% of an aqueous dispersion containing 22.5% solid copolymer derived from the above monomer mix and monomers containing 90 parts 30 70% of a solution containing 97.14 parts of trichloro- F(CF ),,CH Cl-l O CCl-l=CH where n is 3 to 14, 10 ethylene and 2.86 parts of the ethylene-dimethylaminoparts" of trifluoroethyl vinyl ether, 0.25 part N- ethyl methacrylate copolymer described in Example 1. methylolacrylamide and 0.25 part of 2-hydroxyethyl The water-in-oil emulsion thus contained 6.75% of flumethacrylate. Preparation of this copolymer is disoropolymer which contained 3.91% fluorine. closed in U.S. Pat. No. 3,546,187. A stable emulsion The composition was employed to treat test cloths of resulted. wool, polyester, cotton and nylon by the laboratory ln this'application 70 pounds of cotton-35% procedure described above. The treated cloth pieces polyester clothing were scoured at ambient temperawere analyzed for fluorine with the following results, ture'with about gallons of perchloroethylene. The shown in Table l.

' TABLE I Treatment Level Grams Grams Grams Grams Emulsion Dry Cleaning Fluorine Fluorine Fluorine Product Fluid in Bath Recovered on Cloth Polyester Wool Nylon Cotton fabric was first washed in a basket washer for about 5 minutes while particulate soil was removed by filtering the circulating solvent. Then 1.4 pounds of the emulsified product described above were added to the perchloroethylene along with 2 pounds of water to aid in removal of water soluble soil. The fabric was then washed an additional 5 minutes while by-passing the solvent filter. After 1 to 2 minutes of centrifugal extraction the fabric was dried at -170F. The treated clothes were clean and exhibited good water repellenc In the following examples, test cloths were treated according to the process of the invention on a laboratory scale. Test cloths of four different fabrics were treated in a single application bath to simulate a commercial dry cleaning load. The treating vessel was a glass jar of about 6 quarts capacity, 12 inches long and 6 inches in diameter. For each application 600 grams of perchloroethylene was placed in the jar and a total of Allowing for analytical inaccuracies, not unexpected at such low fluorine concentration, substantial exhaust of the repellent from the bath to the fiber is shown.

EXAMPLE 4 In this example there was employed a commercial product prepared according to the general procedure described in British Pat. No. 1,280,036. Analysis of the product, a white, creamy dispersion of fluoropolymer in perchloroethylene, indicated 8.5% solids content.

0 The solids contained 45.5% fluorine. Further analysis 13 in Example hereinbelow. This composition was employedto treat test cloths as in Example 3. The following data were obtained (Table II). i

14 J. Chem. Soc., 1953, 3761] and Brice and Simons TABLE 11 Treatment Level Grams Grams Grams Grams Emulsion Dry Cleaning Fluorine Fluorine 71 Fluorine Product Fluid in Bath Recovered on Cloth Polyester Wool Nylon Cotton Substantially the same degree of exhaust of repellent are known, see Pierce et al., JACS 75, 5618 (1953);

from bath to fiber is shown as in Example 3. Park et Q gem. 23, l 166 (1958). The method used by Pierce et al. and Park et al. to prepare EXAMPLE 5 these alcohols is as follows:

A commercially available copolymer was employed as a backbone polymer in the composition used in this example. The copolymer is a 80/20 butadiene/sty- 'F AgOQCCHS c'lFa-flCHzcHzozccHa rene copolymer and is sold in 50% toluene solution. l-lj These copolymers can be prepared as described in C'IFZ'IHCHZCHZOZCCHS Preparative Methods of Polymer Chemistry by Sorenson and Campbell on page 219. The book was pub- Another route discovered for preparing these alcohols lished by Interscience Publishers, Inc., New York involves the following step: 1961 The fluorinated monomer was Cl-l -C(Cl-l )CO CH Cl-l C,,F where n is an inte- (6) ger of from 3 to 14. Preparation of this monomer is dis- Catalyst closed in US; Pat. No. 3,282,905 as described below. fif CHFCHOfiCHn Q-Fe-HCHZCHOZCCm The group C,,F contains from three to about 14 HQ -carbons. Examples of this group are nC F7, m 4F9, 5 11 s 13 1 1s 2 5 sF11 9F19 10F21 and 12- F25 5 A mixture was first prepared to contain 60 parts of The methacrylate esters may be prepared from the the CH2=C(CH3)CO2CH2CH2:"F2"+1 monomer 60 alcohols c p c co Which undergo ready parts of a 50/50 toluene/butadtene-styrene copolymer terification with methacrylic acid or transesterification soluuon 9 'f toluene and '7 Part? of with alkyl methacrylates, he zoyl peroxide. Th s mixture was placed in a suitable reactor equipped with a reflux condenser and blanketed (I) 40 with nitrogen to exclude oxygen from contact with the it reaction mass. The mix was heated to 95C. and held at CJzMCHZCHzOH Z2 that temperature for 2 hours. In a second vessel another mixture was prepared to C F2 HCH2CH2OH +CH1=C CHQCO2CHS H+ contain 1 10.0 parts of the same fluorinated monomer, c r cr-r cu o,cc(cu,,)=cu 011 011 6.5 parts of toluene and 3.8 parts of a,a'

azodiisobutyronitrile catalyst. The alcohols C,,F Cl-l CH Ol-l can also be esterified After the first mixture had been held at 95C. for 2 by reaction with methacrylyl chloride. An alternate hours, the second mixture was added and the composmethod of preparing these esters is reaction (3) which ite again heated to 95C. and held at that temperature .follows: for 2 hours. After cooling to 65C. 653.2 parts of methyl chloroform were added to the charge which was (3) then mixed well for about 10 minutes keeping the tem- Q F OZCQCHQFCH2 perature at 65C. The charge was then cooled and fil- 2 z tered. The resulting organosol composition was em- 10 ed in the laboratory treatment procedure already The lodlde? C"F2"+CH2CH2I are prepared by reacting esbribed, again using test cloths of wool, polyester, n 2n+1 h ethylene (S66 Ha$Z6ldme ell J Chemcotton and nylon. The treated water and oil repellent 1949 2856; 1950 3041 and Park et WADC cloths were analyzed for fluorine with the results part S A 151014; shown in Table III below. The dry copolymer solids l 166 1958)). The iodides C,,F I are available by the 60 contained 395% fluorine methods of Haszeldine et al. [Nature, 167, 139 (1951);

TABLE 111 Treatment Level Grams Grams Grams Grams Emulsion Dry Cleaning Fluorine Fluorine 72 Fluorine Product Fluid in Bath Recovered on Cloth Polyester Wool Nylon Cotton 15 16 l'clairn: stain repellent in an amount sufficient to give 1. A process for simultaneous cleaning and finishing add-on of 0.05 to 0.5 percent, based on the dry soiled textile materials in which the textile is weight of textile, and then A. agitated in a vessel with a composition consisting B. the treated material is dried.

essen nany of 2. The process of claim 1 wherein said composition a malor amount of a textlle y Cleaning solvent; additionally contains about from 0.01% to 4% of water.

and dispersed therein a polyfluoroalkyl-substituted

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Classifications
U.S. Classification8/142, 8/115.6, 510/285, 510/287, 252/8.62, 524/544
International ClassificationD06L1/08, D06M15/277, D06M15/21, D06L1/00, D06L1/04
Cooperative ClassificationD06L1/04, D06M15/277, D06L1/08
European ClassificationD06L1/08, D06L1/04, D06M15/277