US2793929A

US2793929A - Process of shrinkproofing regenerated cellulose fabric with alkoxymethylene quaternary ammonium compositions and product produced therefrom

Info

Publication number: US2793929A
Application number: US396339A
Authority: US
Inventors: David M Musser
Original assignee: Onyx Oil and Chemical Co
Current assignee: Onyx Oil and Chemical Co
Priority date: 1953-12-04
Filing date: 1953-12-04
Publication date: 1957-05-28
Anticipated expiration: 1974-05-28

Description

Unite This invention relates to a method for the treatment of regenerated cellulosic textile materials in order to improve their dimensional stability. Also included'within the purview of the invention are the dimensionally stable fabrics resulting from this treatment. This application is a continuation-in-part of our co-pending applications S. N. 121,633' (now Patent No. 2,681,342) and S.'N. 121,634 (now abandoned), both filed October 15, 1949.

-Heretofore, several methods have been used for shrink proofing regenerated cellulosic fabrics (i. e.,rayons prepared by the viscose or cuprammonium processes, etc.). One of the methods involves application of resins, such as melamine-formaldehyde, urea-formaldehyde or acetone-formeldehyde polymers to the fabric. is subject to many disadvantage-s, among them the serious shortcoming of increasing the weight of the fabric and thus detracting from its original hand and drape qualities. In addition, this treatment changes the nature of the fabric so that it is prone to pick up chlorine-during laundering. The resin finish is gradually removed as the fabric is laundered, until finally its effectsare substantially completely lost and the fabric shrinks excessively.

Another shrinkproofing method involves treatment of the fabric with glyoxal. This method likewise has many disadvantages among which may be mentioned its tendency to render the fabric less susceptible to direct dyeing, as well as its tendency to substantially destroy the tensile strength of the fabric. In addition, the glyoxal process is adaptable to only a carefully prepared fabric which may be dyed with a relatively small group of fast dyes.

A third method is described in U. S. Patent No. 2,351,581. I It involves the use of certain quaternary ammonium compounds having oxymethyl groups as N-substituents. This process is subject to the disadvantages of imparting hydrophobic characteristics to the fabric and results in a lowered moisture pickup. Furthermore, fabrics so-treated exhibit poor and uneven dye absorption.

It is an object of the present invention to avoid the foregoing and other disadvantages of prior art processes by means of a new method for improving dimensional stability which involves the use of a new class of compositions obtained as described in our co-pending application S. N. 121,633.

This method ats Pat n V hance the shrinkproofing properties of the products used. 1

A further object is to devise a shrinkproofing method mated with certain quaternary ammonium compositions,

followed byframing and curing of the impregnated material. In accordance with my invention I have found that if the fabric is treated as described above, it'not only retains practically all of its original desirable characteristics but is rendered surprisingly shrinkproof and pH of 3 or lower preferably about 23) at ambient or slightly elevated (i. e. about 20 C. to C.) temperatures. These compositions are all characterized by the presence of quaternary ammonium halides having a methoxymethyl group as an N-substituent.

Although it might appear that reaction of a tertiary amine with a chloromethyl ether would yield similar products, it has been found that my method, involving the use of an anhydrous tertiary amine salt, methanol and formaldehyde is not only cheaper but produces a mixture of by-products which appear to substantially en- It is evident from the foregoing that a relatively narrow class of compositions containing quaternary ammonium halides with N-methoxymethyl substituents may be employed in accordance with this invention. While all of these compositions will improve the dimensional stability of regenerated or modified cellulosic fabrics, they will not do so to the same extent. prefer to use those compositions obtained using, as the tertiary amine salt reactant, picoline hydrochloride, pyridine hydrochlorideor dimethyl benzyl amine hydrochloride; or mixtures predominating in one or more of these salts.

My invention as to process is not limited to any narrowly defined conditions. Nevertheless, for best results I prefer to impregnate the fabric by means of a solution containing from about 5 to about 10% by weight of the shrinkproofing compositions; and it is essential to maintain the pH of the solution within the range of about 2 to 5. The excess solution is advisably removed from the impregnated fabric, .for example, on padder or squeeze rolls, and the treated fabric framed to the desired dimensions. Thereafter, the impregnated fabric is cured at elevated temperatures for a short period, during which a chemical reaction probably occurs between the fabric and the shrinkproofing composition. While the conditions of this curing operation are not critical, I prefer to employ temperatures within the range of about C.

to about C. and times extending from about 2 to 10 g minutes.

I do not know the precise mechanism of the reaction whereby the regenerated or modified cellulosic textiles are dimensionally stabilized by my shrinkproofing compositions, and do not wish to be restricted to any theory; nevertheless, it is my belief that these reagents react with the cellulosic material to form a derivative of the cellulose molecule.

Following in tabular form is the results of comparative tests made using the compositionsof this invention, obtained as described in Example III, infra, under acid' and non-acid conditions:

Type of Matt. Percent pH Pick-up, Shrinkage,

- percent percent For optimum results'l Theinvention may be more readily understood by a consideration of the-following illustrative exampleswhere in quantities are stated in parts by weight unless otherwise noted.

Example I (A) To 4219 parts of refined beta-gammapicoline was added with stirring 4,627 parts of concentrated hydrochloric acid, sp. gr. 1.88, at a rate'such that. the temperature of the mixture did not exceed 100 C. The. mixture was decolorized with carbon and then heated upto 200 C. to drive off all the water and obtain substantially an anhydrous salt. After the salt had cooled to.room.tem-

perature, 1452 parts of methanol was introduced. The

pH of a 1% solution was 4.0. This value was adjustedto 2.6 by addition of 95 partsof concentrated hydrochloric acid... Then, 1360 parts of paraformaldehyde was added. The reaction temperature Was maintained at 50 C. until the product dissolved perfectly clear in water,,which required about 4 hours. Unreacted methanol, together with the methylal which formed. as a. by-product, were removed through distillation. The yield of finalproduct was. 7794 parts.

, The final products (a mixture containing -methoxy methylene beta-gamma-picolinium chloride) produced. as.

aforesaidare characterized by being semi-solidat room temperature (crystalline material admixed withliquid). At about 50 C. they completely liquify toform. a lightamber-colored, water-clear, liquid. They arecompletely soluble in water in all proportions.

(B) A measured sample of Fuji fabric (all-rayon),

desized and scoured, was padded through a 7.5% aqueous solution of a composition obtained as described in (A), which had been adjusted to pH 4.5, then framed to approximately original size and cured for about 5 minutes at 150 C. The cured fabric, after washing according to AATCC Standard Wash Test No. 3, shrank warpwise 0.3%. The untreated control under the same wash test shrank 8.0%. The loss in tensile strength as compared with control was.4.5%.

Ei'ample- II (A) One hundred and eighty-six parts of mixed picolines and 64 parts of methanol were treated with anhydrous hydrogen chloride at such a rate that the temperature of reaction did not exceed 70 C. until a total of 71 parts of gas had been introduced. The time required was approximately three hours. The pH of a 1% solution was,2.1. The mixture was then allowed to cool to 40 C. when 60 parts of paraformaldehyde was introduced. The reactionmixture wasmechanically stirred at 40.to 50 C.

until. the solution dissolved completely in water.

(B) A measured sample of greige Fuji fabric (allrayon) was treated with aqueous solution ofthe composition obtained as described in (A), which had been adjusted to pH 2.9, passed through squeeze rolls to removeexcess solution, then framed to original dimensions and cured for 5 minutes at 150 C. In .the standard wash test, the treated sample shrank 4.4% warp direction and the untreated control shrank 17%. The percent loss in tensile strength of the treated sample was 6.

Example III (A) To1158 partsof pyridine, there was..added 2045 parts concentratedihydrochloric acid (36%) gradually and with stirring. The mixture was heated up to about 200 C. to drive off all the'water and unreacted pyridine; To the cooled pyridinium hydrochloride was added 74 parts methanol. The solution was adjusted to pH 2.4. Then 55 parts of paraformaldehyde was introduced. The mixture was stirred at room temperature for 4 hours, then heated to distill otf methylal and unreacted methanol. The yield was 273 parts.

The final products (a mixture containing methoxy methyl pyridinium chloride) produced as aforesaid has the same general appearance and properties as the mixture described in Example I.

(B) A measured sample of desized Fuji fabric (all rayon) was immersed in a 10% aqueous solution, adjusted to a pH of 2.1, of the composition obtained as described in (A). It was then squeezed, framed to the measured dimensions, dried, and cured for 6 minutes at C. After washing, the treated sample shrank 0.1%; whereas the control shrank 7.5%. There was a 7.5% loss of tensile strength.

Example V (A) To 135 parts of benzyl dimethyl amine was-added gradually 102.2 parts of concentrated hydrochloric acid (36%).- The solution was heated under slight vacuum to remove 55 parts as distillate.- To the concentrated salt solution, there was then added 32 parts of methanol. Heatingwas required to effect complete solution. The pH of a one percent solution was 2.2. Then at about 60 C., 30 parts of para-formaldehyde was introduced with stirring; The solution became clear in about one hour.

(B) A measured sample of g-reige, all rayon broadcloth was treated with a 10% aqueous solution, of pH 2.5, of After the composition obtained as described in- (A). passing through squeeze rolls, it was framed 'to original dimensions, and cured at C. for 5' minutes.- The for the tertiary amine portion of the reactant any of the I following tertiary amines: dimethyl pyridine, ethyl pyridine, trimethyl pyridine, ethyl methylpyridine; propyl pyridine, tetramethyl pyridine, ethyl-dimethyl pyridine, quinoline, isoquinoline, diethyl benzyl amine, dimethyl benzyl amine, methyl benzyl dimethyl'amine, dirnethyl benzyl dirnethyl amine, ethyl methyl benzyl amine, methyl propyl benzyl amine, triethyl amine, dimethyl-isobutyl amine, and the like. These amines are all simple tertiary amines and in each instance'the quaternary-ammonium compositions formed therefrom have amethoxy methyl group as an N-substituent. Their anions are advisably chloride, but it is contemplated that other halogens or hydroxyl groups may serve as the anion;

Where the compositions are not readily soluble in water they may be dissolved in suitable inert organic solvents or mixtures thereof. As a general rule however, I prefer to apply the compositions from aqueous solution and, hence, recommend those which are soluble irr-water. By means of this invention an entirely new class of shrinkproofing agents-is made available to the manufacturer. Unlike the agents of the prior art these materials do not substantially increase the weight or detract from the drape and hand qualities of the fabrics. Likewise, they do not destroy the tensile strength of the fabric or otherwise appreciably affect their desirable qualities. They are practially permanent and so far as I am aware are easier to apply in process than any heretofore used. They may be applied usiugexisting textile machinery and are inexpensivein'comparison with many of theagents now in common use. Of additional importance is the fact thatthe compositions of this invention will notappreciably affect the "dyeing properties of the fabric.

As manyapparently widelyditferent embodiments of this invention may be made without-departing from the spirit and scope hereof, it is to be understood that the invention is not limited to the specific embodiments here of except as defined in the appended claims.

I claim:

1. A process for shrink proofing regenerated cellulose fabric which comprises impregnating said fabric, at a pH of about 2-5 with at least of an aqueous solution of an alkoxymethylene quaternary ammonium shrink proofing composition obtained by reacting an anhydrous tertiary amine hydrohalide with methanol and p-araformaldehyde at a pH of about 2-3 at temperatures between about and C., framing the impregnated material to the original dimension and curing it by heating at elevated temperatures until a shrink proof regenerated cellulose fabric is obtained.

2. The process of claim 1 wherein the aqueous solution contains about 5 to 10% of said shrinkproofing composition.

3. The process of claim 2 wherein curing is effected at a temperature of between about C. and C.

4. A shrink proof regenerated cellulose textile material produced by the process defined in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 2,125,901 Evans et al. Aug. 9, 1938 2,243,682 Reyonlds et al May 27, 1941 2,282,702 Bock et al May 12, 1942 2,330,775 Bock et -al. Sept. 28, 1943 2,351,581 Bock et a1. June 20, 1944 2,680,057 Janes June 1, 1954 2,681,342 Mussser June 15, 1954 FOREIGN PATENTS 426,482 Great Britain Mar. 28, 1935 OTHER REFERENCES Journal of the Textile Institute, April 1946, page A173, Cellulose Materials: Vulcanisation.

Claims

1. A PROCESS FOR SHRINK PROOFING REGENERATED CELLULOSE FABRIC WHICH COMPRISES IMPREGNATING SAID FABRIC, AT A PH OF ABOUT 2-5 WITH AT LEAST 5% OF AN AQUEOUS SOLUTION OF AN ALKOXYMETHYLENE QUATERNARY AMMONIUM SHRINK PROOFING COMPOSITION OBTAINED BY REACTING AN ANHYROUS TERTIARY AMINE HYDROHALIDE WITH METHANOL AND PARAFORMALDEHYDE AT A PH OF ABOUT 2-3 AT TEMPERATURES BETWEEN ABOUT 20* AND 80*C., FRAMINING THE IMPREGNATED MATERIAL TO THE ORIGINAL DIMENSION AND CURING IT BY HEATING AT ELEVATED TEMPERATURES UNTIL A SHRINK EGENERATED CELLULOSE FABRIC IS OBTAINED.