US3598515A

US3598515A - Methods fof applying soil-release compositions to textile materials

Info

Publication number: US3598515A
Application number: US803112*A
Authority: US
Inventors: Donald R Moore; Stephen B Sello
Original assignee: JP Stevens and Co Inc
Current assignee: JP Stevens and Co Inc
Priority date: 1969-02-27
Filing date: 1969-02-27
Publication date: 1971-08-10
Anticipated expiration: 1988-08-10

Abstract

TEXTILE MATERIALS CONTAINING SUBSTANTIAL PROPORTIONS OF CELLUOSIC AND/OR HYDROPHOBIC CONSTITUENTS ARE PROVIDED WITH BOTH DURABLE-PRESS AND SOIL-RELEASE PROPERTIES BY DEPOSITING ON SAID TEXTILE MATERIALS ACID CATALYZED DURABLEPRESS RESIN PRECURSORS; ACRYLIC ACID POLYMER SELECTED FROM THE GROUP CONSISTING OF ACRYLIC ACID TYPE HOMOPOLYMERS, COPOLYMERS AND TERPOLYMERS; FLUOROCARBON POLYMER; AND POLYOL DERIVATIVE. THE FLUOCARBON POLYMER CONTAINS HIGHLY FLUORINATED OLEPHOBIC AND HYDROPHOBIC PORTIONS AND NONFLUORINATED HYDROPHILIC PORTIONS.

Description

United States Patent 3,598,515 METHODS OF APPLYING SOIL-RELEASE COM- POSITIONS TO TEXTILE MATERIALS Donald R. Moore, Rutherford, and Stephen B. Sello, Cedar Grove, N.J., assiguors to J. P. Stevens and Co., New York, N.Y. No Drawing. Filed Feb. 27, 1969, Ser. No. 803,112 Int. Cl. D06m 13/12 US. Cl. 8115.6 6 Claims ABSTRACT OF THE DISCLOSURE Textile materials containing substantial proportions of cellulosic and/or hydrophobic constituents are provided with both durable-press and soil-release properties by depositing on said textile materials acid catalyzed durablepress resin precursors; acrylic acid type polymer selected from the group consisting of acrylic acid type homopolymers, copolymers and terpolymers; fluorocarbon polymer; and polyol derivative. The fluorocarbon polymer contains highly fluorinated oleophobic and hydrophobic portions and nonfluorinated hydrophilic portions.

This invention concerns improved methods and compositions for imparting soil-release characteristics to tex tile substrates which are to have a durable-press or permanent-press finish. v

More particularly, this invention relates to compositions comprising acrylic-type polymers, fluorocarbon polymers and polyol derivatives, which when used in comuncttou with durable-press resin precursors, catalysts and opt onal, textile adjuvants, produce a finish having good soil re lease upon one laundering, without compromising the durable-press finish.

With the advent of wash-and-wear, durable-press or permanent-press garments, the utilization of synthetic fibers and their blends with cellulosics and/or other natural fibers has become widespread. Garments containing substantial quantities of polyesters and other hydrophobic fibers have been particularly favored because they strengthen the abrasion resistance of cellulosic based garments and increase the crease resistance of the garments without the need for increased amounts of crosslinking resins. Unfortunately garments containing a substantial quantity of these synthetic fibers (as illustrated by polyester) have exhibited a pronounced tendency to retain soil and stains, particularly oily stains. Furthermore these fabrics or garments have been found to resist release of the soil or stains even upon exposure to repeated laundering. In all likelihood the propensity of these blends of synthetic and natural fiber to accumulate stains is due to the inherently oleophilic structure of synthetics such as polyester.

Increased resisance to the release of soil also results from the crosslinking resins employed to impart durablepress properties to fabrics. These resins are probably converted during their insolubilization to oleophilic structures. Whatever the factors that are involved, soil and stain retention in fabrics treated with thermoset crosslinking resins has been a serious and costly problem.

A recent patent, US. Pat. No. 3,377,249, discloses a process for imparting soil-release finishes to textile materials containing polyester fibers. The claimed process comprises applying to a fabric an aminoplast textile resin and a synthetic acid emulsion polymer comprising at least weight percent acid calculated as acrylic acid and curing the textile resin to impart the desired finish.

The finishing system of the above patentee is deficient in an important aspect, namely, that at least two launderings are required to remove oily soil or stains, even when 3,598,515 Patented Aug. 10, 1971 emulsion polymer of the claimed acid content is employed.

In order to overcome this problem, applicants have developed a finishing system for textiles which contains a novel soil-release composition comprising relatively small quantities of fluorocarbon polymers, certain polyol derivatives and emulsion derived acrylic acid type polymer. The finishing system also includes the durable-press resin precursors utilized in US Pat. No. 3,377,249. Not only are initial soil-release properties excellent, but the finish is durable, crease retention is excellent and the hand of the finished product is satisfactory. Inasmuch as the improvement in soil release upon one laundering is obtained at application levels where the individual components of the soil release composition (fluorocarbon polymer, acrylic acid type polymer, and polyol derivative) are ineffective the results are most unexpected. Even more startling, good initial and durable soil release has been obtained where the acid emulsion polymer contains less than the 20 weight percent acid. In view of this, applicants invention is contrary to the teaching of the art.

In practicing the present invention, samples of the textile substrate are treated With the components of the soilrelease composition, durable-press resin precursor, textile adjuvants and catalyts until the desired pickup level is achieved. The treated samples are dried between about 50 C. to 130 C., desired configurations imparted therein and the samples set by exposure to heat and pressure. The setting step is followed by curing at a sufliciently elevated temperature and for a sufliciently long time to cure the durable-press resin precursor. The cured substrate has long lasting durable-press and soil-release properties.

In preferred practice, an aqueous bath comprising 1-5% by weight solids of the acrylic acid type polymer; 0.1 to 2% by weight solids of fluorocarbon polymer; 5- 12% by weight solids of polyol derivative; 420'% durable-press resin precursor, and from about 0.1-5.0% of acid catalyst is prepared. After padding the treated substrate is passed through squeeze rollers set at about 30-50 lbs/sq. inch. The substrate is then dried at about 70 to C. so that the hereinafter described modifying amount of add-on of the active components is present on the textile substrate. Then, if desired, the substrate is pleated or creased and the configurations pressed and cured using the usual conditions commonly used in producing creased durable-press garments.

While it is convenient to apply all the components of the padding bath simultaneously, the components can be applied separately or the components can be employed in one bath varying the order of addition.

As previously stated, the soil-release compositions of this invention comprise (a) acrylic acid type polymers in conjunction with certain (b) fluorocarbon polymers defined below, and

(c) polyol derivatives defined below.

The acrylic acid type polymers are prepared by polymerizing unsaturated acidic monomers either by themselves or in the presence of esters and amides. Typical acrylic acid type monomers include among others, acrylic acid, methacrylic acid, itaconic acid, maleic acid, furmaric acid, or their mixtures. These monomers are preferably emulsion coor terpolymerized with esters of unsaturated acids or their amides. The esters are conveniently obtained by react-ing one or more of the above unsaturated acids or related acids with one or more alkyl alcohols or halogenated alcohols. Suitable esters include among many others, methyl acrylate, ethyl acrylate, the propyl acrylates, the butyl acrylates, methyl methacrylates, ethyl methacrylates, the propyl methacrylates, the alkyl fumarates, alkyl maleates, etc. The corresponding amides, such as acrylamide can be used to replace the esters, wholly or in part. Similarly, the salts of the illustrated unsaturated acids such as sodium, potassium, among others, can be used wholly or in part to replace the free acids.

The [fluorocarbon polymers which are an essential component of the soil-release compositions of this invention are fluorocarbon polymers containing highly fluorinated oleophobic and hydrophobic portions and nonfluorinated hydrophilic portions. Preferably, the highly fluorinated portions contain perfiuoroalkyl groups of at least 4 carbon atoms and the nonfiuorinated portions contain groups of the formula tC H O-h, where x is an integer of 1 to 4 and e is an integer of 4 to 20. Preferred polymers are selected from the group consisting of:

(a) The homopolymers of:

wherein R, is a fluoroalkyl radical containing 4 to 25 carbon atoms such as wherein Z is H or F, and m is an integer ranging from 3 to 24,

x is a difunctional radical selected from the group consisting of wherein R is lower alkyl (from 1 to 4 carbon atoms), b is an integer ranging from to 15, g ranges from about 1 to 4, e is an integer ranging from 4 to 20, G is an unsaturated acyl radical 0 II CR wherein R is an unsaturated aliphatic radical containing from 2 to 8 carbon atoms, and Y is wherein x is an integer ranging from 1 to 4, and

(b) Copolymers of:

R,-X-[Y] -G whereln Rf, X, G, and Y are as defined above, and vinylic monomers such as vinyl chloride, vinyl acetate, ethylene, propylene, acrylic acid, methacrylic acid, acrylate or methacrylate esters, fluorinated acrylic esters, or acrylates or methacrylates of polyethylene oxide (CH CH O) groups, and

(c) Commercially available fluorinated polymer having an average composition represented by the formula R is hydrogen or lower alkyl having from 1 to 6 carbon atoms,

d ranges from about 12 to 20, and

R and R are selected from the group consisting of hydrogen and lower alkyl having from 1 to 4 carbon atoms.

Suitable fluorocarbon polymers can be prepared following known procedures such as fiuorination, amidation, oxyalkylation, and esterification and polymerization as disclosed in the following patents.U.S.: 2,732,398; 2,803,615; 2,915,554; British: 857,689.

The following are specific illustrations of the preferred fluorocarbon monomers:

The polyol derivatives used in the soil-release compositions of this invention include the monoand dialkyl esters and alkyl ethers, as Well as the alkoxylated derivatives of polyols, particularly of polyalkylene glycol. Illustrative of these are the monoand diphthalate, citrate, oleate, laurate and stearate esters of polyethylene glycol and the monomethyl and monoethyl ethers of polyethylene glycol, as well as the mixed ester-ethers and their alkoxylated counterparts.

The textile substrates used in the present invention are textile materials containing substantial quantities of natural and/or synthetic hydrophobic thermoplastic materials in the form of yarns, slivers, filaments, tows, fibers, articles, garments and the like produced by processes such as drawing, spinning, combing, weaving, knitting, needle-punching or other non-weaving procedures. Illustrative of these substrates are cellulosics such as cotton; and synthetic polymers such as polyesters, polyamides, polyethylene, polypropylene, polyacrylonitrile or blends of these cellulosics and synthetics. The process has considerabel utility in imparting a soil-release finish to textile materials containing at least 25% by weight of these synthetics, usually from 50% by Weight and upwards. The favored synthetic substrate is polyester such as poly- (ethylene terephthalate) and poly(1,4-cyclohexylenedimethylene terephthalate). When the substrate comprises by weight of synthetic fibers the durable-press resin precursor may be omitted.

Durable-press characteristics are obtained by the use of certain acid catalyzed durable-press resin precursors which can be generically grouped as adducts of formaldehyde with amides. The products can be linear or cyclic in structure or they can comprise mixtures of one or more of these structural types. These percursors can be aliphatic, aromatic or heterocyclic and are employed along with at least a catalytic quantity of an acidic catayst.

A listing of preferred resin precursors includes:

N ,N ,N -tris(hydroxymethyl) melamine,

hexakis (methoxymethyl melamine,

the his (hydroxymethyl triazolidinones,

1,3-bis (hydroxymethyl urea,

1,3-bis(hydroxymethyl -2-imidazolidinone, 4,5-dihydroxy-1,3-bis (hydroxymethyl) -2-imidazolidinone, N,N -bis (methoxymethyl uron and 2-methoxyethyl N,N-bis (hydroxymethyl) carbamate,

among others.

Preferred acidic catalysts include metal salts such as magnesium chloride, zinc nitrate and zinc fluoroborate. The various modifiers, agents, conditioners and acids which alter characteristics other than durable press and stain release of the finished textile products are generically categorized as textile adjuvants. These adjuvants include softeners, surfactants, hand modifiers, antistatics, thickeners and the like. Illustrative of these are polyvinyl acetates of various average molecular weight ranges, thickeners such as the natural gums, ethylated starches, hydroxyethylcellulose and sodium carboxymethylcellulose, among others. Also intended to be included as adjuvants are the various wetting agents and other surfactants such as: p-(l,1,3,3-tetramethylbutyl)phenoxynna(ethyl eneoxy)-ethanol, the sodium salt of N-methyl-N-oleyltaurine, and the sodium salts of sulfonated hydrocarbons, among others. Since the role of the textile adjuvants is not critical to the inventive process, no attempt has been made to present an exhaustive or even lengthy list. Voluminous listings of the many textile adjuvants can be found in commercial brochures, chemical literature and in the soap and chemical specialties listings of the Department of Agriculture.

All of the constituents of the process of this invention can be applied to the textile substrates by any of the c0nventional impregnation methods known in the textile art. These include the preferred padding or dipping method as well as coating, spraying, or the like. The treating compositions can be in aqueous or non-aqueous form, where the solubility characteristics allow it, or in the forms of slurries, suspensions, emulsions, dispersions, and the like. Preferably, the textile substrate is dipped into a bath which is an aqueous dispersion of the constituents to be applied.

The concentration of the various components of the soil-release and durable-press finishes required is dependent upon the concentration of the materials in the treating composition (such as pad bath) the wet pickup, the effect sought and to some extent the type of textile substrate treated (the type of weave or knit and the weight of the substrate).

The following data show the ranges of the various finish components to be added in terms of parts by weight per 100 parts by weight of original fabric (this basis for indicating the weight of finish component added being hereinafter referred to as Percent Solids OWF).

Percent solids OWF The particular heating temperatures and the length of the heating cycle are not critical as long as the combination of heating temperature and time is suflicient to accomplish the drying, setting of configuration or curing of thedurable-press resin precursor, etc. For example, after application of the soil-release composiiton, the treated textile article can be dried up to the curing resin precursor.

Similarly, the setting of the crease or pleat can be accomplished using different combinations of temperature, time and pressure. For instance, the treated fabric after fabrication into a garment can be pressed on an electrically heated hot-heated garment press as follows: Steam is used for the first seconds (at 150 to 160 C.), thenthe temperature is raised between about 160 C. to 180 C., keeping the head pressure at about 85-100 pounds/sq. inch. After the final heating, vacuum is applied for from about 3 to seconds or higher to complete the operation.

The setting of the creases can be accomplished in a garment-setting oven using the combination of temperatures and times required for curing the resin precursor. For instance, a satisfactory range is about 140 C. to 170 C., for a period of time ranging from about 15-5 minutes. Again as the mode of pressing and setting the creases or pleats is not novel or critical to the invention no attempt will be made to describe them in detail.

In order to illustrate the invention as completely as possible, the accompanying examples are submitted. Unless otherwise specified, all percentages are expressed on a parts-by-weight basis. A description of the test 'methods and the terms used in the examples preccedes the examples.

Evaluation of soil release.--The following soiling agents were used, denoted respectively as vegetable oil (V), mineral oil (M), and lubricating oil (L).

Corn oil (not hydrogenated); e.g., Mazola, Best Foods Division, Corn Products Co., New York, NY.

Extra-heavy mineral oil, Saybolt viscosity between 360 and 390 at F., specific gravity between 0.880 and 0.900 at 60 F.; e.g., Nujol, Plough, Inc., New York, NY.

Used, dirty lubricating oil drained from the crankcase of an automobile.

The fabric specimen, no smaller than 24 by 24 inches, was laid on a glass plate covered by polyethylene film 3 inches square. The soiling agent was applied to the face side, using 4 drops (0.25 ml.) when liquid, or when semisolid (axle grease), using 1.2 ml. (0.25 teaspoon) spread as a circular spot approximately 2.4 cm. in diameter, but not worked into the fabric. Polyethylene film 3 inches square was placed over the spotted area immediately, and a 2.5-inch diameter, 5-pound Weight was left over each spot for 30 seconds, to impart a pressure of approximately 1 pound per square inch. Then the original polyethylene films were discarded, and the specimen was sandwiched between 2 paper towels, the sandwich having been covered top and bottom with polyethylene film to prevent soiling the glass plate and the weight. The S-pound weight was then placed over the spotted area for 3 seconds to blot out excess soiling agent. (If excess soiling agent remained, it was removed at once by lightly blotting with a facial tissue.) Next, stained specimens were aged in the ordinary room atmosphere for at least 30 minutes by being hung so there was no contact between specimens.

Laundering was done in a home-type washer at approximately 50 C. in 4-pound loads using the high water level (16 gallons) with a level cupful of non-ionic detergent, and tumble dried.

Rating for residual soil used the Deering Milliken Photographic Standards for Evaluation of Soil-Release Finishes, the scale of which is from 1 to 5. No visible spot remaining was denoted by 5, and a spot barely visible by 4, with 3, 2, and l denoting progressively serious stains. The evaluation was made under ordinary overhead fluorescent room lighting of normal intensity with the test specimen flat on a table top 35:5 inches from the floor directly under the light, and viewed from all possible angles. The rating for each stainwas the lowest number assigned it from any angle.

Evaluation of wash and wear.-AATCC 88A-1964T; Test III-C for laundering: Home-type washer, 5-pound load, fullcycle, 60 C., synthetic detergent; tumble drying (TD). The number of laundering-drying cycles (as l, 2, or 5) is indicated in tables by 1L, 2L, or SL. The 5-point rating scale extends from 1 (extensively wrinkled) to 5 (perfectly smooth).

Evaluation of crease retention.AATCC 88A-1964T; Test III-C also. The rating scale is as follows: 1. (no crease remaining), 2. (slight crease), 3. (moderate crease), 4. (sharp crease), and 5. (unchanged, very sharp crease).

Percent solids OWF.Means parts by Weight of finish component added per hundred parts by weight of original fabric.

WPU.Means Wet pickup or percent wet add-on, i.e.,

Weight of wet add-onx 100 Weight of original fabric EXAMPLE 1 Unsuccessful attempts to impart a soil-release finish using the individual components of the soil-release finish The substrate used for treatment is a fabric blend of polyester (50% by weight) and cotton (50%,by weight) having a thread count (warp x filling) of 134 x 66.

The following application procedure was used. Aqueous pad baths were made up containing varying amounts of the soil-release polymer components, fluorocarbon polymer acrylic acid type polymer and polyol derivative is made in accordance with US. Pat. 2,915,554 and this alcohol is reacted with acrylic acid in accordance with plus dimethylol-dihydroxyethylene urea resin precursor 5 and Zn(NO catalyst. The fabric samples were padded the procedure of US. Pat. 2,803,615. The monomer is through squeeze rolls set to give a wet pickup of about emulsion polymerized by the method described in Exam- 55% to 66%. ple 1 of US. Pat. 2,803,615. The reaction mixture is After padding, the fabric sample was framed t the cooled and worked up by the described techniques to yield original dimensions and dried at approximately 60 C.- 10 a polymer latex having a solids content of about 36% 80 C. The dried fabric is cut into samples designated solids.

TABLE 1 Soil release Percent solids OWF I W h Original stain Stained after L 8S Acrylic Fluoro- Polyl and IL 2L 1L 2L acid type carbon derivwear,

Samples polymer polymer ative 5L V M L V M L V M L V M L 3.5 2 1/2 1 4/5 4 4 2 1 2 4/5 4 4/5 3.5 2 1 2 1/2 5 4 4 3 2 3 4/5 4 4 5 3.3 2 2 1/2 5 4/5 4/5 2 1 1/2 3 2/3 3 3.0 2 1/2 2 4 4 4 1 1 1 2 4 3 4 5 4.0 2 2 1 2 3/4 3/4 3 2 1 1 4 3 3 4 4.3 2 1/2 1 3 3 3 1 1 1 2/3 2 2/3 4.3 2 3 2 1 3 2/3 1 1/2 2 1 2/3 2/3 1 3.5 2 2/3 1 3 3 1 2/3 2/3 1 3/4 3 1 3.5 1 1 1 1 1 1 1 1 1 1 1 1 3.3 1 1 1 1 1 1 1 1 1 1 1 1 1 In addition to the acrylic acid type polymer, fluorocarbon polymer and polyol each sample contained 6.3%

and 0.7% OWF ZnNOa catal st 3 The addition of the poly as shown in Table 1. Each sample was pressed with a crease in it on an electric hot-head garment press set at 100 lbs/sq. inch at a temperature of 165 C. for seconds. Finally, vacuum was applied for 5 seconds and the durable-press finish cured by heating at 170 C. for minutes. The resulting add-on of each ingredient based on the weight of fabric (OWF) as well as the wash-andone laundering.

EMBODIMENT A OWF dimethylol dihydroxy ethylene urea y ol derivative was necessary to formulate the mixture of the acrylic acid type polymer, resin precursor and catalyst.

EXAMPLE 2 A soil-release composition comprising a mixture of 80% by weight ethyl acrylate, 10% by weight acrylic acid, 10% by weight acrylamide terpolymer, fluorocarbon polymer and the monooleate ester of polyethylene glycol The fabric substrate used for treatment is the same one employed in Example 1. A pad bath is made up containing the above emulsion derived acrylic acid terpolymer, the fluorocarbon polymer of Example 1, the monooleate ester of polyethylene glycol, zinc nitrate catalyst and dimethylol-dihydroxyethylene urea resin precursor.

The samples were padded, dried, framed, cut, creased, pressed and cured as in Example 1. The designations of the samples and the add-on of the various components on each fabric sample appears in the accompanying Table 2 which also reflects the excellent wash-and-wear and onomer havm the structure: A m so1l-release results obtamed when the inventive mixture of a 7 soil-release components were used. CgF17S0zN(CHzGHzO)lfi 2 TABLE 2 Soilrelease Percent solids OWE Original stain Stained alter 5L Wash Acrylic Fluoroand Crease 1L 2L 3L 1L 2L acid carbon wear re .en- Q Sample polymer polymer 8L tion,8L V M L V M L V M L V M L V M L V M L 4.5 0.35 3.5 5.0 5 3 3 5 5 5 5 5 5 4 2/3 2/3 5 5 4 5 5 5 4.5 0.13 3.5 5.0 5 3 2 5 4/5 4 5 5 5 3 2/3 2 5 4/5 4/5 5 5 5 3.4 0. 35 3.5 5.0 5 4 2/3 5 5 4 5 5 5 3/4 2/3 2/3 5 4/5 5 5 5 5 3.4 0.13 3.3 5.0 5 3 2/3 5 5 4 5 5 5 4 2/3 2 5 4 3/4 5 4/5 4/5 2.3 0.35 4.3 5.0 5 2/3 2 5 5 4 5 5 5 3 2 2/3 5 5 5 5 5 5 2.3 0.13 43 5.0 5 3 2/3 5 4/5 4 5 5 5 3 2 2 4 2/3 3 5 3 3/4 1.7 0.35 4.3 5.0 5 3 2 5 5 5 5 5 5 4 2/3 2/3 5 5 5 5 5 5 1.7 0.13 4.5 5.0 4 2/3 3 5 4/5 4/5 5 5 5 3 2/3 2 3/4 2/3 3 4 2/3 3 1.2 0.35 5.0 5.0 4/5 4 /3 5 5 4 5 5 5 4 3 2/3 5 5 5 5 5 5 1.2 0.13 3.0 2.0 4 3/4 2/3 4/5 4/5 4 5 5 4/5 2 1 1 3 2 1/2 3 2 1/2 4,5 4.0 5.0 1 1 1/2 1 3 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1/2 1/2 1 NOTEL-In addition to the is prepared by methods analogous to those described in dimethylol dihy olymer, each sample had an add-on in percent solids OWF of 5.3% monooleate droxy ethylene urea and 0.7% zinc nitrate.

US. Pat. Nos. 2,915,554 and 2,803,615. In preparing this 7 monomer, the alcohol EXAMPLE 3 Soil-release compositions comprising fluorocarbon polymer, monooleate ester of polyethylene glycol, dimethylol dihydroxy urea resin precursor, acid catalyst and a by weight ethyl acrylate 10% by weight acrylic acid copolymer In this example, thefabric substrate, fluorocarbon polymer, polyol derivative, resin precursor and acid catalyst of Example 2 are used. Only the acrylic acid polymer and the concentration of the fluorocarbon differ. The application procedure and reaction conditions from padding through and including curing are identical to Example 2. The add-on of the various components based on the weight of fabric, as well as the data on wash-and-wear and soil-release appear in Table 3.

Examples 3 and 4 illustrate that excellent results can be obtained by the present invention, using an acid emulsion polymer containing less than 20 weight percent acid calculated as acrylic acid. These exmaples also illustrate that excellent results can be obtained using a relatively small amount of fluorocarbon polymer.

TABLE 3 Soil release Percent solids OWF W Original stain Stained alter 5L ash Acrylic Fluoroand Crease 1L 2L 1L 2L acid carbon wear, retention, polymer polymer L L V M L V M L V M L V M L 5. 3 0. 4 4. 5 5. 0 5 5 5 5 5 5 5 4/5 4/5 5 5 5 5. 3 0. 2 5. 0 5. 0 5 5 5 5 5 5 5 4/5 4/5 5 5 5 4. 0 0.4 4. 5 5. 0 5 5 5 5 5 5 5 4/5 5 5 5 5 4. 0 0. 2 4. 5 5. 0 5 4 4 5 5 5 405 4 4 5 5 5 2.7 0.4 4.5 5.0 5 4 4 '5 5 5 4C5 3 3 5 5 5 2. 7 0. 2 4. 5 5. 0 4/5 3 3 5 5 5 304 3/4 5 5 5 5 2. 0 0. 4 4. 3 5. 0 4/5 4 3 5 5 5 304 3/4 3/4 5 5 5 2.0 0. 2 4. 8 5.0 4/5 3 3 5 5 5 4 3 2/3 5 5 4/5 1. 3 0. 4 4. 3 4. 5 4/5 4 3 5 5 5 4/5 3/4 4 5 5 5 1. 3 0. 2 4. 3 5. 0 3/4 3 2/3 5 5 5 5 5 5 5 5 5 K 5. 3 4. 5 5. 0 3 2 '1 3/4 2/3 2/3 2 2 1 4/5 4 3 Untreated control 1 r 1 1 1 1 1 Norr-:.-ln addition to the acrylic acid polymer and fluorocarbon polymer, each sample had an add-on in percent solids OWF o! 5.3% monooleate ester of polyethylene glycol (molecular weight 860), 6.3% dimethylol dihydroxy ethylene urea and 0.7% zinc nitrate.

EXAMPLE 4 Additional soil-release finish utilizing the same fluorocarbon polymer, resin precursor, acid catalyst and 85% by weight ethyl acrylate--% by weight acrylic acid copolymer EXAMPLE 5 Soil-release finishes similar to the preceding examples except that an acrylic acid type, polymer component (60% by weight ethyl acrylate, 40% by weight acrylic acid) is utilized wherein the acrylic acid content represents more than of the polymer The same fabric, reaction conditions, finish components and procedures which were utilized in the preceding three examples were employed except that a high acrylic acid content emulsion polymerized 60% by weight ethyl acrylate, by weight acrylic acid polymer was used with the fluorocarbon polymer, durable-press resin precursor, polyol derivative and acid TABLE 4 Soil release Percent solids OWF h Original stain Stained after 5L as Acrylic Fluoroand Crease 1L 2L 1L 2L acid carbon wear, retention,

copolymer polymer 10L 10L V M L V M L V L V M L 5. 3 4. 0 5. 0 3 2 2 4 3 3/4 3 2 3 4/5 4 4 Untreated contr 1 1 1 1 1 1 1 1 1 Norm-In addition to the acrylic acid polymer and fluorocarbon polymer, each sample had an add-on in percent solids OWF of 5.3% monooleate ester of polyethylene glycol (molecular weight 860), 6.3% dimethylol dihydroxy ethylene urea and 0.7% zinc nitrate.

catalyst. The percent Solids OWF of the components and the wash-and-wear soil-release data appear in Table 5.

TABLE 5 Soil release Percent solids OWF w h Original stain Stained after 5L as Acrylic Fluoro- Retenand IL 2L 1L 2L acid type carbon tion of wear, Sample polymer polymer crease 5L V M L V M L V M L V M L 2. 7 0. 4 5. 0 3. 0 5 5 4 4 5 5 4/5 4/5 4/5 5 5 5 2. 6 0. 2 5. 0 4. 0 4 3 3 5 4/5 4/5 2 1 2 5 4 4 2. 0 0.4 5 0 4. 0 5 3/4 3 5 5 5 2/3 1/2 2 5 5 5 2.0 4 0. 2 5 O 4. 3 5 3/4 4 5 5 5 3/4 2 3 5 4 5 1. 3 0.4 5 0 4. 0 5 4/5 3/4 5 I 5 5 4 2 4 5 5 5 1. 3 0. 2 5 0 4. 5 4/5 4 4 5 5 5 3 1 2/3 5 4 5 G 2.7 5 0 3.0 2 2 1/2 2 4 4 4 1 1/2 4 3 4/1 Untreated control. 1 1 1 1 1 1 1 1 1 1 1 5 NOTE. -In addition to the acrylic acid polymer and fluorocarbon polymer, each sample had the following addcn OWF: 5.3% monooleate ester of polyethylene glycol (molecular weight 860); 6.3% dimethylol dihydroxy ethylene urea and zinc nitrate (0.7%).

EXAMPLE 6 Variations in polyol derivatives employed In this example the identical reagents and procedures employed in Example 2 were used except that the various polyol derivatives described below were substituted for the polyol derivativeused in Example 2 on a weight-byweight basis. In all instances, fabrics having both good initial and long-term soil-release and wash-and-wear properties are obtained.

Softener: Molecular weight (1) Monooleate of polyethylene glycol 660 (2) Monooleate of polyethylene glycol 1260 (3) Monooleate of polyethylene glycol 810 (4) Dioleate of polyethylene glycol 1070 (5) Monooleate of polyethylene glycol 3610 (6) Dioleate of polyethylene glycol 3870 (7) Monostearate of polyethylene glycol 3610 (8) Distearate of polyethylene glycol 3870 (9) Monooleate of polyethylene glycol monomethyl ether 1010' As the preceding discussion and examples indicate, the results obtained by the practice of this invention are both advantageous and unexpected.

For example, durable stain-release is obtained in fabrics and garments containing natural or synthetic fibers or their blends. Furthermore, unlike the soil-release compositions claimed in US. Pat. No. 3,377,249 (Marco), oily soil can be completely removed in a single laundering rather than requiring several launderings. In addition neither the quality or durability of the durable-press finish is compromised by the novel soil-release finishes of this invention.

The finding that effective and durable soil-release finishes could be obtained by treatment with acrylic acid type copolymers and terpolymers containing less than weight percent acid calculated as acrylic acid was particularly surprising in View of the teaching of the Marco patent which teaches that polymers containing less than 20 weight percent acid were inefiective and commercially unacceptable. This fact, coupled with applicants finding that complete soil-release of oily stain could be effected using only one laundering as compared to the several required by Marco, was wholly unexpected. A further unusual aspect to applicants invention is the discovery that while the individual components of the soil-release finish, fluorocarbon polymer, acrylic acid type polymer and polyol derivative are individually ineffective at the stated concentration levels in providing a durable soil-release finish, combining the same three components apparently creates a synergistic mixture which imparts an effective and durable finish.

As this specification discloses, numerous modifications, substrates and the like can be made without departing from the inventive concept. The metes and bounds of this invention are best determined by the claims which follow, read in conjunction with the specification.

We claim:

1. A process for imparting both soil-release and durable-press characteristics to a fabric containing a blend of cellulosic and polyester fibers, said process comprising applying to each 100 parts by weight of said fabric (1) from about 0.1 to 2.0 parts by weight of a fluorocarbon homopolymer wherein said fluorocarbon homopolymer is prepared from a monomer of the formula 12 wherein R' is a perfluoroalkyl radical having 6 to 10 carbon atoms,

R is hydrogen or lower alkyl having from 1 to 6 carbon atoms,

a is an integer of from 12 to 20, and

R and R 'are selected from the group consisting of hydrogen and lower alkyl having from 1 to 4 carbon atoms.

(2) from about 0.5 to 5.0 parts by weight of a copolymer of at least one unsaturated acid selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid with at least one ester of said listed unsaturated acids and/or at least one amide of said listed unsaturated acids,

(3) from about 2 to 15 parts by weight of at least one polyol derivative selected from the group consisting of ester, ether and alkoxylated derivatives of a polyalkylene glycol,

(4) 'from about 3.0 to 20 parts by weight of an acid catalyzed durable-press resin precursor which is an adduct of formaldehyde and an amide and,

(5) from about 0.1 to 5 .0 parts by weight of an acidic catalyst for said durable-press resin precursor, and

heating the textile material until the durable-press resin precursor is cured and a soil-release and durable-press finish is imparted to the fabric.

2. A process as claimed in claim 1 wherein said copolymer contains less than 20 weight percent acid calculated as acrylic acid.

3. A process as claimed in claim 1 wherein the polyalkylene glycol is polyethylene glycol.

4. A process as claimed in claim 1 wherein said copolymer is a copolymer of acrylic acid with an alkyl acrylate.

5. A process as claimed in claim 1 wherein 0.15 to 0.5 part by weight of fluorocarbon homopolymer are applied to each parts by Weight of textile material.

6. A process as claimed in claim 1 wherein said fluorocarbon homopolymer is a homopolymer of a monomer having the formula 011F178 OzN (CI-120112 OM60 CH=CH said copolymer is copolymer of ethyl acrylate and acrylic acid; and said "derivative of a polyalkylene glycol is selected from the group consisting of monooleate of polyethylene glycol, dioleate of polyethylene glycol, monostearate of polyethylene glycol, distearate of polyethylene glycol and monooleate of polyethylene glycol monomethyl ether.

References Cited UNITED STATES PATENTS 2,915,554 12/1959 Ahlbrecht et al. 260-86.1X 3,377,249 4/1968 Marco 26029.4UX 3,462,296 8/1969 Reynolds et a1. 26029.6FX

JULIUS FROME, Primary Examiner J. B. LOWE, Assistant Examiner US. Cl. X.R.

117-139.4; 260294UA, 29.6F

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 515 D d August 10, 1971 Inventor(s) Stephen B. Sello and Donald R. Moore It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 5 line 59, "hot-heated" should read Column 10, Table 3, under Soil Release, 1L, under Sample D, "4C5 should read 4/5 Sample E, "4C5 should read 4/5 Sample F, "3C4" should read 3/4 Sample G, "3C4 should read 3/4 Table 5, under Original Stain, 2L, under the V,

should read under the L,

Sample A, "4" Table 5, under Stained after 5L,

Sample G, "4/1" should read hot-head the V,

Signed and sealed this 12th day of September 1972.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. Attesting Officer- ROBER'I' GOT'ISCHALK Commissioner of Patents