US2448247A

US2448247A - Treatment of textiles with acyloxysubstituted aromatic acid salts

Info

Publication number: US2448247A
Application number: US15492A
Authority: US
Inventors: Carl R Bellwood
Original assignee: Cravenette Co
Current assignee: Cravenette Co
Priority date: 1948-03-17
Filing date: 1948-03-17
Publication date: 1948-08-31
Anticipated expiration: 1965-08-31

Description

Patented Aug. 31,1948

TREATMENT OF TEXTILES WITH ACYLOXY- SUBSTITUTED AROMATIC. ACID SALTS Carl R. Bellwood, Ridgefield, N. J., assignor to The Cravenette Company, U. .S. A.,,Hoboken, N. J a corporation of New Jersey No Drawing. Application March 17, 1948,

Serial No. 15,492

10 Claims. 1

This application is a continuation in art of my pending application Serial Number 496,613, filed July 29, 1943, now abandoned.

invention relates to the treatment of cell-ulosic and proteinitic fibers, and fabrics made from such fibers, to render them to an unusual degree persistently water repellent when repeatedly subjected to the customary normal washing and dry cleaning. Accordingly, garments made of such textiles (cotton, rayon, linen, jute, wool, silk, manipulated protein like casein fiber, synthetic polymers like nylon, 'etc., -etc.), when treated by-t'his process ofier serviceable protection against wetting by rain or snow, even after being dry cleaned or washed many times. In addition, cloth treated according to this process is not substantially harmed as to hand or drape; in fact, in many instances it is actually improved in those respects. There is the further advantage that, if desired in any particular case, the fibers processed as herein suggested, may be restored to substantially the condition they were in before the water-repellent quality was imparted to them. And finally, the ingredients used in the preparation of the materials employed in the process are normally readily available and comparatively cheap (some of them may be found on the market), and the technique of the application of the compounds to the cloth is simple and involves relatively little time, effort and expense.

I have discovered that certain substituted aliphatic esters, under proper conditions, will apparently undergo a reaction with the textile fibers, with the result that the water repellency ofv the fiber or any fabric made from this fiber is greatly increased; in addition, this water-repellent quality is maintained by the fiber or fabric even after manydry cleanings or washings of the type commonly employed in commercially cleaning such fabric or garment made therefrom.

Examples of starting materials that I may use in preparing the reaction compound areas follaws:

'0 O H C O 'OH O CO'CnHas '0 C D 01132:

Qrtho stearyloxyb'enzoic acid '01tholeurylcxybenzblc'acid I 0 0 )H C 00H 0 C O CuHn 0 0 0C uHi'a Para stearyloxybenzoic acid rare laurzylosybenzbic acid COOH COOH

0G0 C17H35 0 O 0 CuH'za 3-lauryloxy-2-naphthoic acid 0O OCnHz:

H0 5 SOaH 2-lauryloxy-3,G-naphthalcnedisulfonic acid 'QCOCnHzs OCOCuHza l-stcaryloxy i-i1aphthalenesulfo'nic 'acid .OOOH

'OGOOoHn SOaH 1-1auryloxy-4-naphthalencsulfonic acid COOH EH: CH:

2=stearylcxy-3Ii1ethylbenzoic Z-Iauryloxy-3-methylbenzoic acid acid Preparation of starting material and reaction compound 302 grams of stearyl chloride and 138 grams of ortho hydroxy benzoic acid or para hydroxy benzoic acid are heated together. During the heating process nitrogen which has been thoroughly dried'of moisture is bubbled through the reaction mixture to liberate the hydrogen chloride. Heating is continued until evolution of hydrogen chloride ceases. The resulting compound, ortho stearyloxybenzoic acid or para stearyloxybenzoi'c acid, which may be called the starting material, is-thencooled. 1 gram of this is dissolved in 99 cc. of water containing 0.2 gram of sodium hydroxide. about=8--10-. The finished reaction compound so prepared is presumably an approximately 1% solution of the sodium salt of ortho stearyloxybenzoic acid or of the sodium salt of para stearyloxybenzoic acid. In the same way solutions of the alkali-metal salts of the homologues of ortho stearyloxybenzoic acid or para stearyloxybenzoic acid (-foreexample, ortho or para lauryloxybenzoic acid-resulting from a variation in the length of the 'acyloxy radical-and Z-stearyloxy-B-methylbenzoic acid-resulting from a varition of the aromatic nucleus) may be prepared, Also, in the The pH of the resulting solution is same way analogues of ortho stearyloxybenzoic acid, para stearyloxybenzoic acid, ortho lauryloxybenzoic acid, and para lauryloxybenzoic acid may be prepared among polynuclear compounds such as-- 3-stearyloxy-2-naphthoic acid; 2-stearyloxy-3,6-naphthalenedisulfonic acid; 1-stearyloxy-4-naphthalenesulfonic acid.

3-lauryloxy-2-naphthoic acid; 2-lauryloxy-3,fi-naphthalenedisulfonic acid; 1-lauryloXy-4-naphthalenesulfonicacid.

The behavior of these and their analogues and homologues is roughly equivalent.

The starting materials referred to arefree acids. The reaction compound is made by bringing the free acid into solution by the addition of alkali. This process forms a solution of the alkali-metal salt of the free acid, said alkali-metal salt being herein referred to as the reaction oompound.

By way of further example: grams of the ortho stearyloxybenzoic acid or of the para stearyloxybenzoic acid may be dissolved in 95cc. of water containing 1 gram of sodium hydroxide. The pH of the resulting solutionis about-Ste 10, at any rate on the alkaline side to the extent that the compound is dissolved and so that application to the fabric is facilitated. The finished reaction compound so prepared is presumably an approximately 5% solution of the sodium salt of ortho stearyloxybenzoic acid or of para stearyloxybenzoic acid. Similarly, 5% solutions may also be prepared from homologues and analogues, which have already been discussed in connection with a 1 solution.

Pieces of cotton poplin and gabardine were dipped in the 1% solution and another set was dipped in the 5% solution, prepared as above. In each case the percentage absorption was about 80% after the samples were passed through squeeze rollers. Thus, in the case of the 1% solution the amount of active ingredient present in the cloth was 0.8% based on the dry weight of the cloth. In the case of the 5 solution, the amount of active ingredient present in the cloth was 4.0% based on the dry weight of the cloth. Each example was' dried at.120 Randbaked at 300 F. The sample was-then given awashin Water to remove products of the reaction.

Each sample was subjected to water-repellency tests as outlined in the American Association of Textile Chemists and Colorists Yearbook, vol. XIX (1942) pages 255/263, and was'found to possess a high degree -of water repellency with a spray test rating of 90. Each'sample was subjected to several dry cleaning treatments employing amachine as outlined in'Federal Specification CCC-T-191a, section XIII, paragraph 4, and following the procedure outlined in Federal Specification P. Q. D. No. 1, section F, paragraph 3d, and was found to retain most of its water repellency according to the above testing methods. "Each sample was subjected to several laundering'treatments as outlined in "the American Association of Textile Chemists and Colorists Yearbook, vol. XIX (1942), pages 244 and 245, and'was found to retain mostof its original water repellency.

The drying may be carried on at about 120 F., and the baking at a temperature of about 275- 300 F. for about 5-15 minutes. The drying and baking may be carried out as parts of a continuous operation in :a single piece of apparatus, or they maybe carriedout separately in separate apparatus. The fabriclmay lbe subjected to approximately the same conditions, and satisfactory results obtained, by passing the wet web of fabric into a dry chamber in which the air is ci-rculated and is maintained at preferably from 5 300-310 F., "the-web being continuously moved through the chamber at a speed which will cause any given portion of the fabric to remain in the chamber for approximately minutes. For about the first 5 minutes of such treatment the 10 fabric dries, EilIdifOI the remainder of the time it bakes. However the drying be done, I prefer that the 'fabric, after having the moisture removedtherefrom; be subjected to a baking temperature .of at least 275 F. and preferably 300 F.

Examples havebeen given in which the immersion of the cloth was in a solution of the sodium salt of ortho stearyloxybenzoic acid or of para stearyloxybenzoic acid adjusted to a pH of about 8-10. I prefer a solution of the order of 5%. 2 Instead of using the sodium salt, I'may -.use'the salt of potassium or other alkali metal. Also, I might use ortho or para benzenesulfonica'cidderivatives, or naphthalenesulfonic acid derivatives, or naphthoic ac-iclderivatives, or compounds hav- 05 mg acyloxy aliphatic groups containing -820 carbon atoms, in place of the ortho or para stearyloxybenzoic acid specified in the example. With reference .to the maximum number -of-carbon atoms in the. acyloxy aliphatic group, I have never reachedan upper limit. As the number-of carbon atoms is increased,.it.could-be expected that a point would be reached Where the compound would become relatively inactive. However, I have successfully used compounds. having --as many .as 26 carbon atoms in the acyloxy. aliphatic group, e..g..ortho cerotyloxybenzoic acid.

Broadly, a reaction compound as hereincontemplated may besaid to answer. to theformula (6) And groups (1) and .(2) are in ortho or para relationship in the benzene compound, and in two-three or one-four relationship in the naphthalene .series the other symbols having their usual technical meanings.

Or, the reaction compound may be said to comprise, generally, a soluble alkali-metal salt of an acyloxy-substituted aromatic acid, where the acyloxy group is aliphatic and may contain more than 7 carbon atoms, adjusted to a ,pHof the order of about 8-10.

While I have spoken of the textilefabricsan'd fibers in general. terms, it is to be understood that I contemplate the treatment of dyed, as well as undyed material, provided, of course, that there is nothing in the dye that inhibits or substantially modifies the action of, or is otherwise incompatible with the chosen reaction compound. It is within the contemplated application 'of my invention to combine two or more .of 'the reaction compounds herein mentioned, :for the ;pro-

where the other symbols having their usual technical meaning; and then drying and baking the material being treated.

2. The method of treating fibers and fabrics of the kind set forth to render them water repellent, which consists in subjecting them to the action of an aqueous solution of a compound answering to the formula X-Me (1) where (a) Ar is the divalent aromatic nucleus CeHi (b) R is a saturated aliphatic chain containing 7 or more carbon atoms X is selected from the group consisting of (--COO)- and (SOzO) Me is an alkali metal And groups (1) and (2) are in ortho or para relationshipthe other symbols having their usual technical meaning; and then drying and baking the material being treated.

3. The method as in claim 2 in which the material is dried at approximately 120 F. and baked at about 275-300 F.

4. The method as in claim 2 in which the material is dried at 120 F. and baked at 300 F.

5. The method of treating fibers and fabrics of the kind set forth to render them water repellent, which consists in subjecting them to the action of an aqueous solution of a compound answering to the formula X-Me 1 \OER 2 where (a) Ar is the divalent aromatic nucleus 010116 (b) R is a saturated aliphatic chain containing 7 or more carbon atoms X is selected from the group consisting of (C'OO) and (-SO2O) Me is an alkali metal And groups (1) and (2) are in two-three or one-four relationshipthe other symbols having their usual technical meaning; and then drying and baking the material being treated.

6. The method as in claim 5 in which the material is dried at approximately F. and baked at about 275-300 F.

7. The method as in claim 5 in which the material is dried at 120 F. and baked at 300 F.

8. The method of treating fibers and fabrics of the kind set forth to render them water repellent, which consists in subjecting them to the action of an aqueous solution of an alkali-metal salt of ortho stearyloxybenzoic acid, and then drying and baking the material being treated.

9. The method of treating fibers and fabrics of the kind set forth to render them Water repellent, which consists in subjecting them to the action of an aqueous solution of an alkali-metal salt of S-StearyIoXy-Z-naphthoic acid, and then drying and baking the material being treated.

10. The method of treating fibers and fabrics of the kind set forth to render them water repellent, which consists in subjecting them to the action of an aqueous solution of an alkali-metal salt of 1-stearyloxy-4-naphthalenesulfonic acid, and then drying and baking the material being treated.

CARL R. BELLWOOD.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,916,776 Steindorif et al. July 4, 1933 2,125,072 Kern July 26, 1938 2,146,308 Shipp Feb. 7, 1939 2,146,392 Shipp Feb. '7, 1939 2,313,741 Engelmann et a1. Mar. 16, 1943 2,337,924 Platz et a1 Dec. 28, 1943