US2997407A

US2997407A - Textile finishing agents

Info

Publication number: US2997407A
Application number: US560706A
Authority: US
Inventors: Edward B Lawler; Kenneth D Ballou
Original assignee: American Cyanamid Co
Current assignee: Wyeth Holdings LLC
Priority date: 1956-01-23
Filing date: 1956-01-23
Publication date: 1961-08-22
Anticipated expiration: 1978-08-22

Description

Aug. 22, 1961 E. B. LAWLER ET AL TEXTILE FINISHING AGENTS 2 Sheets-Sheet 1 Filed Jan. 23, 1956 WETT/NG SPEED {MODIFIED BRAVES TEST) www 0 0/ am W M? Z 0 Z i I10 w4 4 1 3 ww AA w w T Rm INVENTO/PS. EDWARD B. LAWLEP, KENNETH D. BALLOU BY ATTORNEY.

United States Patent 2,997,407 TEXTILE FINISHING AGENTS Edward B. Lawler and Kenneth D. Ballou, Charlotte, N.C., assignors to American Cyanamid Company, New York, N. a corporation of Maine Filed Jan. 23, 1956, Ser. No. 560,706 6 Claims. (Cl. 117-1355) This invention relates to surface active agents and to the wetting-out of textiles to which permanent and semipermanent water-repellent finishes are to be applied and to the washing, scouring, cleaning and other after-treatments of such textiles having such finishes applied theret0.

Water-repellent finishes are normally hydrophobic in nature and naturally resist wetting the textiles to which they are to be applied, consequently making their application and adherence to such textiles very diificult. As a result, therefore, relatively high concentrations of powerful wetting agents are used therewith in order to wet out the textiles to permit the application of the water-repellent finishes thereto.

Once the Water-repellent finishes are actually applied and adhered to the textiles, however, the continued presence of these Wetting-out agents is extremely undesirable inasmuch as they would serve to increase the wettability of the textiles and enhance their susceptibility to spotting by water and aqueous stains, which characteristics are wholly unwanted in water-repellent textiles. Consequently, the treated textiles are normally exposed to numerous washings, cleanings, scourings or other aftertreatments to remove the wetting-out agents which would tend to decrease the water-repellency of the textiles. This quite often involves long and extensive washing procedures and requires the passage of the textiles through about ten or even fifteen aqueous treating baths with intermediate nipping or squeezing-out of the treating liquid. Such procedures are, of course expensive, time consuming and prohibitive in the textile industry.

The present invention is based on the discovery of a new class of surface active agents possessing a sufiiciently powerful wetting-out action so as to be capable of substitution for the wetting agents presently used in the industry for such purposes but which will not diminish or interfere with the later water-repellency of the textiles whereby the treated textiles may be merely dried and/ or cured and then be capable of use as water-repellent textiles. By reason of this unusual combination of initially good wetting properties and desirably poor later rewetting properties, this class of wetting agents is capable of dispersing the water-repellent finishes in the treating bath from which it is to be applied to the textile, wetting out the textiles to permit the facile applicability of the Water-repellent finish to the textiles, and then, following a simple drying and/or curing such as the customary oven drying, not interfering with or detracting from the later desired water-repellency of materials fabricated from such textiles.

Additionally, these wetting agents are excellent for use in cleaning the fabricated water-repellent textiles after they have been worn or used and soiled inasmuch as they can be employed to remove dirt, soil, stains, stubborn spots and the like and will then permit the re-use of such textiles after a mere drying Without involving careful subsequent washing processes.

The non-rewetting, cleaning, dispersing or wetting agents used in practicing the processes of our invention are the ammonium soaps of mixtuers of rosin acid or abietic acid and higher fatty acids having a suflicient chain length of from about 8 to about 22 carbon atoms ice to impart good wetting properties to their ammonium soaps.

Additionally, it has been surprisingly discovered that, although the ammonium soaps of mixtures of these acids exhibit the desired properties, the ammonium soap of rosin acid, per se, and the ammonium soap of the higher fatty acids, per se, individually do not exhibit the desirable surface active properties required for the present invention. It is therefore believed that, when the acids are first mixed and are then employed in the form of such a mixture to produce the ammonium soap, there is some sort of synergistic action taking place either during the soap formation or during its later use whereby the desired surface active properties are obtained.

It is to be appreciated that the term rosin acid or abietic acid is not to be construed as limited to abietic acid itself which is a specific chemical compound but should be understood to cover natural or processed materials containing high percentages of abietic acid or abietic-type acids including neoabietic acid, dihydroabietic acid, tetrahydroabietic acid dehydroabietic acid, dextrcpimaric acid, isodextropimaric acid, etc.

With regard to the higher fatty acids used, considerable latitude is permitted in the selection thereof and relatively pure fatty acids may be employed or, in the interests of economy, the commercially available fatty acid mixtures may be used. For example, Emery 621 or Emery 622 which are coconut type commercial vegetable fatty acids primarily containing saturated fatty acids of from 8 to about 18 carbon atoms; or Emersol 130 or Emersol 132, which are triple pressed stearic acids primarily containing saturated fatty acids having 16 to 18 carbon atoms; or the commercial linseed fatty acids primarily containing the 18 carbon atoms unsaturated fatty acids may be employed.

These two clases of organic acids, i.e., abietic acid and the higher fatty acids, must be used in certain definite proportions in the formation of the ammonium soap in order to obtain the combination of properties for the successful practice of the invention. At least about 20% by weight and not more than about by weight of abietic acid must be used together with not more than about 80% or less than about 20% by weight of the fatty acids for reasons which will subsequently be explained.

The principles of the invention will be more complete ly understood by reference to the accompanying drawings, wherein: l

FIGURE 1 shows the wetting powers of ammonium soaps of mixtures of rosin acid and coconut fatty acids in the rangesof proportions by Weight as indicated, with the total soap concentration being 0.5% (active) in the evaluation composition. The steepness and height of the ends of the U-shaped curve sharply indicated the relative ineificiency of those compositions containing predominant proportions (close to of either rosin acids or fatty acids, whereas the low central trough strongly emphasizes the efficiency and synergistic cooperation of those compositions falling within the 2080% bounds of the present invention. The values noted in FIGURE 1 were obtained by means of the Standard Modified Draves Test at 25 C., using cotton tape.

FIGURE 2 shows the wettingand rewetting properties of ammonium soaps of mixtures of rosin acid and coconut fatty acids in the ranges of proportions by weight as indicated, with the total soap concentration being 12.5 grams in 1000 ml. water. The wetting times were obtained by means of the Standard Modified Draves Test at 25 C. using cotton tape. The rewetting results were obtained by Drop Reflectance Tests using 8 oz. denim loom goods originally treated with the agent.

The Drop Reflectance Test, using 8 oz. denim loom goods, is carried out as follows: The 8 oz. denim loom goods is padded and squeezed so as to give approximately 100% wet pick-up based on the Weight of the cloth in the test solution at the concentration listed in the appropriate table and at a bath temperature of about 160 F. The denim is then stretched on frames and is dried at a temperature of about 220 F. for approximately minutes. After conditioning overnight at room temperature and standard humidity, the denim is held taut and flat and a drop of water is placed on it and observed. The time required for this drop to soak into the denim and to lose its tendency to refict light is measured and is called drop reflectance.

The general shape of the curves is to be particularly noted in FIGURE 2. The U-shaped configuration of the wetting curve is to be compared to the inverted U- shaped curve of the rewetting curve whereby it can be ascertained that the optimum values for wetting times are normally obtained within approximately the same 20-80% range as the optimum values for the rewetting times.

It is to be observed also that the use of the ammonium soaps either of rosin acid, per se, or higher fatty acids, per se, in percentages close to 100% leave much to be desired both in wetting and rewetting times. The use, however, of the 20-80% or 80-20% proportions and intermediate values normally leads to better and shorter wetting times with longer rewetting times.

It is therefore seen that the ammonium salts of mix-- tures of from about 20% to about 80% of rosin or abietic acid with from about 80 to about 20% of oleic acid therefore will combine optimum wetting power with greatly decreased rewetting power and that the processes of our invention apply these discoveries for the treatment or aftertreatment" of textiles with water repellents to avoid the necessity of extensive washing for removal of the wetting agent that has heretofore beoen considered necessary.

While it will be evident that the principles of our invention can be applied for the cleaning of any type of water-repellent textiles including many of the synthetic fibers that inherently possess a considerable degree of water-repellency, their most important field of utility is in the application of hydrophobic finishes to cellulosic textiles such as cotton cloth, viscose and cuprammonium rayon cloth and the like as well as to woolen cloth. The most widely used finishes of this type are the heatcured mixtures of higher fatty acid amides or their formaldehyde reaction products with methylated methylol melamine described in US. Patent No. 2,357,273 and sold commercially as Permel; the higher alkylpyridinium halides such as stearylpyridinium bromide, sold as Zelan; and the silicone finishes which are essentially hydroxyalkylsilicone resins. The non-rewetting ammonium soap mixtures of the present invention may be used with any of these or similar types of permanent and semi-permanent water repellents.

The water-resistant finishes of the above described types are normally applied to cellulosic textiles such as cotton cloth in quantities of from about 3 to about 6%, based on the weight of the cloth, when the highest degree of water-repellency is desired. For the so-called spotproof or strain-proof finishes about half of these quantities are used; i.e., from about 1.5% to about 3%. The finishes are ordinarily applied by dispersing them in water, sometimes with the aid of an emulsifying or dispersing agent, and a'wetting agent is dissolved in the water in the quantity necessary to make it wet out the cloth rapidly. The ammonium soap mixtures of the present invention may be used in such baths to replace the wetting agents previously employed, and will function efficiently to obtain a rapid and uniform application of the water-proofing composition to the cloth without, however, requiring an extensive washing of the treated cloth for its removal. The ammonium salt mixtures are normally used in such baths in quantities of from about 0.1% to about 1% by weight, based on the weight of the bath, and usually in quantities of from about 0.2 to about 0.5% by weight.

After the cloth has been padded in the aqueous bath containing the water-repellent compositions, it is normal- 1y frame-dried in an oven at temperatures within the range of about 220-400 F. for times varying from about 1 /2 minutes at the highest temperature to about 10-15 minutes at the lowest temperature. The water repellent is set or cured on the cloth by this heat fireatment. The cloth is then frequently scoured or cleaned in a detergent solution to remove the emulsifying agent used in preparing the first bath as well as any unreacted or partially reacted materials such as incompletely cured synthetic resins that would reduce the spray rating of the finish. It is in this after-treatment or scouring procedure that the ammonium soaps of the present invention find their most important field of utility, for they combine good detergency with a high degree of wetting power for the water-repellent textiles and the scoured cloth does not require extensive rinsing in Water as is necessary with other surface-active agents. Instead, the scoured cloth is simply heated in driers at temperatures above 220 F. and preferably between about 250 and 400 F. for the time necessary to dry it to the desired extent, which is usually within the range of about 15-10 minutes.

Quantities of the ammonium soap mixtures of the present invention within the range of about 0.1% to 1%, and usually about 02-06% on the weight of the bath are usually employed in these scouring processes. The scouring bath may contain other ingredients if desired such as 01-05% of sodium carbonate, or preferably 0.21.0% ammonia, as ammonium hydroxide, but, of course, should not contain other Wetting agents of the type which decrease the Water resistance of the cloth. The scouring is preferably carried out at elevated temperatures on the order of l30-l60 F., although the particular scouring procedures used will of course vary with the type of cloth being treated and the impurities that must be removed. We have found that the addition of about 0.5-l% by weight of ammonia to scouring baths containing the ammonium soaps of our invention will increase the effectiveness of these Wetting agents in many cases.

The invention will be further described and illustrated by the following examples which show the application of the principles thereof to illustrative water-proofing treatments for textiles. It will be understood, however, that the invention in its broader aspects is not limited to the detailed quantities and procedures shown in these examples, the scope of the invention being defined by the appended claims.

Example 1 Surface active formulations having the following compositions by weight were prepared, the parts being given by weight.

l 1 i 2 1 3 l 4 5 i 6 855 855 855 855 855 855 Gum Rosin 10D 60 40 20 0 Oleic Acid.- O 20 40 60 80 Ammonia (26%).... 45 45 45 45 45 45 The rosin and an equal weight of water were heated together at about 100 C. until the rosin was melted; the oleic acid was then added with stirring at the same temperature and the stirring was continued until the mixture was homogeneous. The batches were then cooled to room temperature, the ammonia was added slowly and the remainder of the water was stirred in.

The wetting power of the compositions was determined in water solutions containing 0.56% and 0.28% by weight (active) of the ammonium soaps by the Standard Draves sinking test.

Rewetting times were determined by the AATCC tentative test method 2752 which consists essentially in depositing a Water droplet on fabric impregnated uniformly with a known quantity of the material under test and measuring the time in minutes before it is absorbed by the cloth. Eight ounce denim was packed in a 0.56% solution of the soaps (or 5% of the compositions), passed through squeeze rolls set for 100% pickup and oven dried at 220 F. and then tested. Wetting times (secs).

On the basis of the test results of Example 1, a 100 lb. batch of a surface active composition was prepared from a mixture containing by weight of red oil (commercial oleic acid), 10% gum rosin, 10% of aqueous ammonia containing 28% NH, and 5% of isopropyl alcohol as a clarifying agent. The rosin and an equal weight of water were charged into a jacketed kettle, heated to boiling and maintained at the boil until the rosin was completely melted. The red oil was added slowly with stirring at the same temperature and the batch was cooled to room temperature after it had become homogeneous. With continued stirring the alcohol was added followed by addition of the ammonia and when the ammonium soap formation was complete the remaining water was added. The final composition contained 22.6% solids.

The wetting power of the composition for cloth treated with a commercial water-repellent 'finish was measured in comparison with a nonionic wetting agent composition in wide commercial use for this purpose. The wetting power was measured by determining the sinking times for 1" x 1" squares of the treated cloth (8 oz. denim) in aqueous solutions containing 0.5% of sodium carbonate g wetting agents used commercially for scouring cloth after the application of permanent water-repellent finishes thereto. The tests were made by measuring the sinking time of 1" 'x 1" squares of cotton poplin treated with Permel, which is .a permanent water-repellent finish having the composition and method of application 'described in US. Patent No. 2,491,249 dated December 13, 1949. The test results (seconds) were as follows:

. NHfSoap Igepal CO Triton W-30, Cone, Percent Compositions, 633,,33.3% 38% solids 18% solids solids Rewetting Times and dried at 220 F 10 3 5 These results show that the ammonium oleyl rosinate compositions of the present invention have wetting and detergent properties comparable to those of the inost wldely used commercial wetting agents for cloth containing permanent water-repellent finishes, but possess greatly reduced wetting power thereafter (rewetting). The ammonium oleyl rosinate detergents can therefore be used successfully 'as scouring agents for cloth pretreated with Permel, Zelan, stearoguanamine-containirig compositions, silicone resins ir'iixt-iir'es iif'ifiethyl ated 'methylgl melamine with higher aliphatic alcohols and other known or approved permanent and semi-permanent water-repellent finishes without, however, resorting to an extensive scouring to remove the wetting agent from the finish. V

- Example 3 Six surface active compositions having the'proportions set forth in'Ex-ample 1 were prepared, using different fatty acids as indicated.

' RATIO OF ACID COMPONENTS .IN FORMULATIONS (BY WEIGHT) plus the wetting agents in the concentrations indicated 1 2 3 4 5 6 111 the followmg table:

Fatty Acid 100 80 60 40 20 0 tt Time, s c B03111 Ac 0 20 40 60 80 100 A ent Cone, Percent x g HN; Soap Commercial Fatty Acid 0on0. Wetting Speed (Modifiedpraves Test) Composition WettingAgent Tape S g Tune 1. 4 1.0 C onut 1 g 23 101 1.4 1.5 3.0 2.8 Fatty 9s 94 '10s 5.0 62 51 .83 101 21.0 129 117 172 26 34 49 101 Fatty Acids 139 Rewettmg tunes were determined on batches of the same cloth padded in baths containing 0.5% of sodium carbonate plus 0.63% of the detergents under test. The rewetting time of the cloth impregnated with 0.63% of ammonium oleyl rosinate was excellent and was more than 360 seconds; the rewetting time for the cloth impregnated with the commercial detergent composition was too short and was only 20 seconds.

The commercial wetting agent composition used as a standard of comparison in this test was a mixture of 12% by weight of Nonic 218 which is the condensation product of approximately 9 mols of ethylene oxide with 1 mol of l-dodecyl mercaptan, 6% by weight of Ultrawet K, a dodecyl benzene sodium sulfonate, and 82% by weight of water.

Comparative tests were also made against Igepal CO 633 and Triton W-30, both of which are well known 1 (See Figure 1 of drawings.)

Example 4 The surface active compositions ofExample 1 were prepared in the concentrations shown therein but using tall oil rosin acids (Acint ol R) in conjunction with the "oleic' acid. -These rosin acids contained 36% abietic acid, 16% neoabietic acid, 13% dihydroabietic acid, 12% tetrahydroabietic acid, 7% dextropimaric acid, 7% isodextropimaric acid and 5% dehydroabietic acid. It is to be observed that these rosin acids are similar to those occurring in wood and gum rosin. The wetting and rewetting times were comparable to those of the composition of Example 1.

Example 6 Example 5 was repeated using Acintol C containing 51% rosin acids, 2.5% palmitic acid 20% oleic acid, 18.5% linoleic acid, 0.5% linolenic acid and 7.1% unsaponifiable acid. The wetting and rewetting properties compared very favorably with the properties of the compositions of Example 1.

Example 7 .Example 5 was repeated using Acintol D containing 32% rosin acids, 6% linoleic (conjugated) acid, 25% linoleic (non-conjugated) acid, 34% oleic acid and 2% 'palmitic acid. The wetting and rewetting properties compared very favorably with the positions of Example 1.

The following table sets forth numerically the Wetting properties of the comand rewetting activity of ammonium soaps of mixtures of a fatty acids and rosin acids referred to more generally elsewhere. TABLE 1 [by weight] Gum Rosin 2O Acintol D 20 Acintol R Oleic Acid 10 Stearic Acid Coconut Fatty A nid Isopropanol 5 5 5 Ammonia (28%) 10 10 10 Water 65 65 65 Percent Gone. Wetting SpeeSd (Modified Draves Test) Tape inking Time (sec.)

RewettingiSgeed (8 oz. denim loom goods) Drop ectance Duration (mms.)

Example 8 ing and curing process, did not exert any deleterious The wetting and rewetting properties 1 of various rosincoconut fatty acid ammonium soaps were evaluated as follows:

' The Tape Wetting Times in seconds at 25 C. using a cotton tape in 50 grams of agent in 1000 ml. water in the Standard Modified Draves Test were as follows:

1 See Figure 2 of drawings.

Example 9 Treating baths for applying water-repellent finishes were prepared as follows:

Permel Resin B- Aerotcx Accelerator AS Immersion: 1 dip; 1 nip onto 5.5 oz. cotton poplin.

Pressure: 3.5 tons.

Expression: 80%.

Dry at: 225 F.

Cure at: 350 F. for 1.5 minutes.

The product of Example 2 markedly accelerated the wetting-out of the cotton poplin during the application of the water-repellent finish indicated and, after the dryeifect on the water-repellency of the cotton poplin.

The following table sets forth the normal average compositions by weight of the ranges of the various fatty acid mixtures referred to in the specification.

Although several specific examples of the inventive concept have been described, the same should not be construed as limited thereby nor to the specific substances mentioned therein but to include various other compounds of equivalent constitution as set forth in the claims appended hereto. It is understood that any suitable changes, modifications and variations may be made without departing from the spirit and scope of the invention.

We claim:

1. A method of applying a water-repellent composition to textiles which comprises Wetting out said textiles in an aqueous dispersion of said water-repellent composition by the wetting action of ammonium soaps of a mixture of from about 20% to about 80% by weight of abietic acid and from about 80% to about 20% by weight of fatty acids of from about 8 to about 22 carbon atoms and thereby applying the water repellent to the textiles and drying the textiles containing the applied water-repellent composition by heating them at temperatures of from about 220 to about 400 F.

2. A method of applying a water-repellent composition to textiles which comprises wetting out said textiles in an aqueous dispersion of said water-repellent composition containing from about 0.1% to about 1% by weight of a wetting-out agent comprising ammonium soaps of a mixture of from about 20% to about by weight of abietic acid and from about 80% to about 20% by weight of fatty acids of from about 8 to about 22 carbon atoms and thereby applying the water repellent to the textiles and drying the textiles containing the applied 9 water-repellent compositions by heating them at temperatures of from about 220 to about 400 F.

3. A method of applying a water-repellent composition to textiles which comprises Wetting out said textiles in an aqueous dispersion of said water-repellent composition by the wetting action of ammonium soaps of a mixture of from about 20% to about 80% by Weight of abietic acid and from about 80% to about 20% by weight of coconut fatty acids of from about 8 to about 18 carbon atoms and thereby applying the Water repellent to the textiles and drying the textiles containing the applied water-repellent composition by heating them at temperatures of from about 220 to about 400 F.

4. A method of applying a water-repellent composition to textiles which comprises Wetting out said textiles in an aqueous dispersion of said water-repellent composition by the wetting action of ammonium soaps of a mixture of from about 20% to about 80% by Weight of abietic acid and from about 80% to about 20% by weight of linseed fatty acids of from about 16 to about 18 carbon atoms and thereby applying the water repellent to the textiles and drying the textiles containing the applied waterrepellent composition by heating them at temperatures of from about 220 to about 400 F.

5. A method of applying a water-repellent composition to textiles which comprises wetting out said textiles in an aqueous dispersion of said water-repellent composition by the wetting action of ammonium soaps of a mixture of from about 20% to about 80% by Weight of abietic acid and from about 80% to about 20% by Weight of oleic acid and thereby applying the water repellent to the textiles and drying the textiles containing the applied 1O water-repellent composition by heating them at temperatures of from about 220 to about 400 F.

6. A method of applying a water-repellent composition to textiles which comprises: Wet-ting out said textiles in an aqueous dispersion of said Water-repellent composition by the wetting action of ammonium soaps of a mixture of from about 20% to about by weight of abietic acid and from about 80% to about 20% by weight of stearic acid and thereby applying the water repellent to the textiles and drying the textiles containing the applied water-repellent composition by heating them at temperatures of from about 220 to about 400 F.

References Cited in the file of this patent UNITED STATES PATENTS 1,362,658 Willford Dec. 21, 1920 1,732,729 Phair Oct. 22, 1929 2,052,170 Engelmann Aug. 25, 1936 2,069,823 Driesen Feb. 9, 1937 2,191,982 Doser Feb. 27, 1940 2,304,367 Morgan Dec, 6, 1942 2,350,548 D'eLaney June 6, 1944 2,362,894 Epstein Nov. 14, 1944 2,489,473 Zerner Nov. 29, 1949 FOREIGN PATENTS 2,527 Great Britain Oct. 28, 1856 OTHER REFERENCES

Claims

1. A METHOD OF APPLYING A WATER-REPELLENT COMPOSITION TO TEXTILES WHICH COMPRISES WETTING OUT SAID TEXTILES IN AN AQUEOUS DISPERSION OF SAID WATER-REPELLENT COMPOSITION BY THE WETTING ACTION OF AMMONIUM SOAPS OF A MIXTURE OF FROM ABOUT 20% TO ABOUT 80% BY WEIGHT OF ABIETIC ACID AND FROM ABOUT 80% TO ABOUT 20% BY WEIGHT OF FATTY ACIDS OF FROM ABOUT 8 TO ABOUT 22 CARBON ATOMS AND THEREBY APPLYING THE WATER REPELLENT TO THE TEXTILES AND DRYING THE TEXTILES CONTAINING THE APPLIED WATER-REPELLENT