US2785948A - Process for stabilizing cellulose textile materials against dimensional changes by applying simple acetals and products resulting therefrom - Google Patents

Description

United States Patent PROCESS FOR STABILIZING CELLULOSE TEX- TILE MATERIALS AGAINST DIMENSIONAL CHANGES BY APPLYING SIMPLE ACETALS AND PRODUCTS RESULTING THEREFROM Ellis Abrams, Philadelphia, Pa., assignor to Quaker Chemical Products Corporation, Conshohocken, Pa., a corporation of Pennsylvania No Drawing. Application January 8, 1954, Serial No. 403,078

13 Claims. (Cl. 8-116) The present invention relates to the treatment of textile materials containing a substantial quantity of cellulose for the purpose of stabilizing such textile materials against shrinkage during laundering.

Although the method of stabilizing to be described herein can be applied to cellulosic materials in general, is is particularly applicable to fabrics made of either filament or staple regenerated cellulose fibers, such as viscose rayon, cuprammonium rayon and hydrolyzed cellulose acetate, or containing preponderant amounts of these fibers.

It is well known in the art to treat cellulosic materials, for purposes of dimensional control, to stabilize same against progressive dimensional shrinkage under repeated washings, with water-soluble urea or melamine formaldehyde condensates in the presence of acidic or potentially acidic catalysts. It is also Well known to apply free aldehyldes, such as formaldehyde and glyoxal, to cellulosic materials in the presence of acidic catalysts in order to achieve dimensional control.

It is a Well-known and well-recognized fact that the urea and melamine condensates possess inherent disadvantages which limit their field of usefulness. For example, some of these products emit objectionable odors during their application to textile materials and in certain cases these odors may persist in the finished fabric. In other instances objectionable odors may develop in the fabric after finishing. Some of these condensates bring about considerable tenderingand embrittle-ment of the fibers, thereby lowering the fabric tensile strength. These condensates also possess the unfortunate property of retaining chlorine. Thus, fabric treated with these condensates and subsequently bleached during laundering with chlorine-containing bleaches, will retain this chlorine and release it as hydrochloric acid when the fabric is ironed. This hydrochloric acid seriously tenders the fabric to the extent that these urea and melamine formaldeyhde condensates cannot be applied to white or pastel shades which may be bleached during laundering. Furthermore, it has been observed that the degree of durability to laundering obtained through the use of these condensates is rather limited.

Also proposed for the stabilization of cellulosic materials has been the application of formaldehyde in the presence of suitable catalysts. The application of formaldehyde has never achieved widespread commercial acceptance because of the difficulty of realizing good uniforrnity and high tensile strength. The glyoxal process has achieved some degree of success, but extreme care must be exercised in order not to cause serious discoloration and significant tensile strength losses. In this connection there has recently been proposed a method of achieving dimensional control by the application of formaldehyde in the presence of a polymeric formaldehyde acceptor, such as 'hydr-oxyethyl cellulose or polyvinyl alcohol. This process, even under ideal conditions, emits exceedingly disagreeable odors during the padding, dryleast 250 F.

2 ing and curing operations and, in fact, this odor may persist even in the finished fabric.

An object of this invention is to provide a novel method of treating cellulosic or predominantly cellulosic textile materials to protect them against objectionable progressive dimensional shrinkage under repeated launderings.

A further object is to provide a treatment which will impart a minimum degree of discoloration to the treated fabric. Further, the treated material will have a pleasing handle and will be free of objectionable odors. Moreover, the padding, drying and curing operations will be substantially free of odors.

Further advantages of the invention will become apparent from the detailed description of the discovery which follows.

-It has been discovered that the above-mentioned objects may be accomplished by treating cellulosic materials with non-volatile acetals of monoaldehydes and dialdehydes containing up to eight carbon atoms in the presence of an acidic catalyst. The term non-volatile as applied here refers to non-volatility at the curing temperature of at In using the acetals according to this invention, at no time during the padding, drying or curing operations is there a detectable odor of aldehyde. This is especially important in the case of acetals of formaldehyde.

Suitable aldehydes which may be converted to acetals in this process are formaldehyde, acetaldehyde, propanal, butanal, glyoxal, and other dialdehydes containing not more than eight carbon atoms in the monomeric form,

such as malanaldeh'yde, succinaldehyde, glutaraldehyde,v

adipaldehyde, hy-droxy adipaldehyde, benzaldehyde, telephthalaldehyde and the like. Suitable alcohols which may be combined with the above-mentioned aldehydes to form acetals are methanol, ethanol, propanol, isopropanol, butanol, methoxy ethanol, ethoxyethanol, methoxyethoxy ethanol, ethylene glycol, glycerine, and dipentaerythritol. I may also use acetals derived from other polyhydric alcohols, such as, for example, the simple formal of diethylene glycol, such as (0CHaCHzO'CH2'CI-I'O)CH2 I may also use mixed formals, such as H3C'O'CH2'O'CHz'CHz'O'CHz'O'CHa H300CH2OCH2'CH2'O'CH2CH2O'H HaC'O'CHz'O'CHz'CHz'O'CHa'CH2'O'CH2O'CH3 or mixtures thereof. In general, the acetals are prepared by reacting the al-dehydes and the alcohols in the presence of acidic catalysts by well-known procedures.

The general application of these acetals involves padding cellulosic fabric through aqueous solutions or dispersions of the acetals containing from 0.5 to 25% by weight of acetal. The padding bath must contain, in addition to the acetal, some acidic-type catalyst, such as aluminum chloride, stannic chloride, aluminum sulfate, oxalic acid, zinc chloride, sodium acid sulfate, sodium or potassium alum, dimethyl oxalate, ammonium chloride, etc., in amount of about 5% to 200% by weight of the acetal content. The treated fabric may then be dried at an appropriate temperature and is subsequently cured at a temperature of at least 250 F. for about /2 to about 10 minutes. The time of cure varies inversely with the temperature. The textile materials should be acidic during curing. The cured fabric may then be washed lightly with a detergent and a mild alkali, rinsed thoroughly and dried in a relaxed state, Fabrics so treated with these acetals will not undergo progressive shrinkage even when laundered in boiling soap solution as in American Asso-- ciation of Textile Chemists and Colorists (A. A. T. C. C'.)

1952 Standard Test Method 14-52 for cotton and linen fabrics.

The following illustrative examples will serve to explain myinv'eiition.

Example 1 'A 100 spun viscose gabardine, lightweight Shirting fabric was desized, boiled off and dried on a tenter frame. The pure finished fabric was passed through an aqueous solution containing the following materials:

8.5% di(methoxy ethoxy ethyl) formal (B. P. 305 C.) 0.6% sodium sulfate 2.4% sodium bisulfate 88.5% water The treated fabric waspassed between squeeze rolls to remove all the solution in excess of 100% pickup. The material was then dried at 180 F. on a pin frame at the dimensions it, possessed before impregnating. The dried fabric was's'ub'sequently cured at 315 F. for minutes. Since noshrinkage is permitted during the above process, the measure of the effectiveness of the operation is the residual shrinkage which occurs in the laundering tests to follow. A comparison of the behavior of the treated and the untreated fabric is given in the table below. The tensile strength of the treated fabric was not adversely affected.

WARP sHRINKAGE-A. A. T. 0. 0. STANDARD TEST METHOD 14-52 Warp Shrinkage (in/yd.)

I wash 5th wash Untreated eerie 2. a 5. 5 Treated fabric 1. 7 1. 8

Example 2 The same fabric employed in Example 1 was padded through the following solution:

5.5% di(methoxy ethyl) formal. (B. P. 207 C.) 0.6 sodium sulfate 2.4% sodium bisulfate 91.5% water Warp Shrinkage (in./yd.)

1 wash 5th wash Untreated fabric a. e 5. 4 Treated fabric 1. 5 1.6

Exizmple 3 The fabric described in. Example 1 was padded through the following solution:

3.56% glyoxal tetra (methoxy ethyl) acetal .53% oxalic acid 95.91% water g The glyoxal tetra (methoxy ethyl) acetal was prepared asdescribedii U. S. Patent 2,321,094 and was observed to boil a 3. 3 .5 mtflsn e nr The olut oa above was applied at 100% pickup to the viscose shirting .material and subsequently dried. to its original dimensions.

"Warp Shrinkage (u /y 1 wash 5th wash U utreuted fabric 4. 2 6. 3 Treated fabric 1. 9 2.0

Example 4 The fabric described in Example 1 was treated in the following solution:

3.5% malonaldehyde tetra ethyl acetal (B. P. 219 C.) .5 oxalic acid 46.0% water 46.0% isopropanol The fabric was padded through the solution to obtain a pick-up, dried at its original dimensions, and cured at 315 F. for 7 minutes. The fabric was then subjected to evaluation. The treated fabric retained good tensile and tear strength properties and retained no chlorine. Its behavior on multiple launderings is indicated in the following table:

WAR? SHRINKAG A. A. 71.. c. 0. STANDARD TEST METHOD 14-52 I Warp Shrinkage (in./yd.)

I wash 5th wash 10th wash ie tti iilillti::ij'ji:11113111133: 518 ii iii Similar results were obtained when the malonaldehyde tetra ethyl acetal was applied from an oil in water emulsion.

Similar results were obtained with other non-volatile acetals. Other suitable acetals are malonaldehyde tetra methyl acetal, malonaldehyde tetra (methoxy ethyl) acetal, glyoxal tetra methyl acetal, glyoxal tetra ethyl acetal, glyoxal tetra butyl acetal, dipentaerythritol diforma1, 1,4,5,8-naphthodioxane, Z-hydroxy adipaldehyde tetra (methoxy ethyl) acetal, succinaldehyde tetra (methoxy ethyl) acetal, and mixed acetals, such as methyl methoxyethyl formal, malonaldehyde methyl triethyl acetal and glyoxal dibutyl dimethoxyethyl acetal. The mixed acetals may be prepared by reacting thealdehyde with a mixture of the alcohols or by carrying out an exchange reaction with a given acetal with the desired alcohol. In general, I prefer to use water-soluble acetals having boiling points above C. derived from an aldehyde containing two to eight carbon'atoms and having alcohol fragments containing one to four carbon atoms. p p

The water-soluble acetals are applied to fabric with acidic catalysts from aqueous solutions. The water insoluble acetals were applied either from isopropanol solutions or from oil inwater emulsions. In all cases, no chlorine retention was observed and the degree of dimensional control was of the same order as observed in the previous examples. No obnoxious odors were noted inany of the treatment baths or during any of the pro cessing steps. I l

The term .textile material is intended to include filaments and fibers, staple or, yarns; whether in finished stages or at some intermediate stage in the production thereof, of the group consisting of natural cellulose, regenerated cellulose, such as viscose rayon, cuprammonium rayon, and hydrolyzed cellulose acetate, and mixtures thereof with other natural and synthetic fibers, such as cellulose acetate, nylon, wool, etc. The term also includes fabrics, whether knitted, woven or felted, as well as garments or other articles made from such fabrics.

I claim:

1. The process of treating a cellulose textile material which comprises applying to a cellulose textile material an aqueous bath containing an acidic catalyst and a simple acetal of a reactive aldehyde selected from the group consisting of aliphatic and carbocyclic aldehydes containing not more than 8 carbon atoms in monomeric form and mixtures of the aforesaid reactive aldehydes, and an aliphatic alcohol having from 1 to carbon atoms and from 1 to 6 hydroxyl groups and mixtures of the aforesaid aliphatic alcohols, said acetal having a boiling point above about 125 C., said catalyst being present in amount from about 5% to about 200% by weight of the acetal content in said bath, said acetal being present in the bath in amounts of about 0.5% to about 25 by weight of the bath and heating the treated textile material at an elevated temperature until said acetal reacts with the cellulose and dimensionally stabilizes the cellulose material to laundering.

2. The process of treating a cellulose textile material which comprises applying to a cellulose textile material an aqueous bath containing an acidic catalyst and a simple acetal of a reactive aldehyde selected from the group consisting of aliphatic and carbocyclic aldehydes containing not more than 8 carbon atoms in monomeric form and mixtures of the aforesaid reactive aldehydes, and an aliphatic alcohol having from 1 to 10 carbon atoms and from 1 to 6 hydroxyl groups and mixtures of the aforesaid aliphatic alcohols, said acetal having a boiling point above about 125 C., said catalyst being present in amount from about 5% to about 200% by weight of the acetal content in said bath, said acetal being present in the bath in amounts of about 0.5 to about 25% by Weight of the bath and heating the treated textile material at a temperature of at least about 250 F. for about 6 to about 10 minutes until the acetal reacts with the cellulose and dimensionally stabilizes the cellulose material to laundering.

3. The process of treating a cellulose textile material as defined in claim 2 wherein the acetal in the bath is a simple formal of diethylene glycol.

4. The process of treating a cellulose textile material as defined in claim 2 wherein the acetal in the bath is dipentaerythritol diformal.

5. The process of treating a cellulose textile material as defined in claim 2 wherein the acetal in the bath is malonaldehyde methyl triethyl acetal.

6. The process of treating a cellulose textile material as defined in claim 1 wherein the acetal in the aqueous bath is glyoxal tetra (methoxy ethyl) acetal.

7. The process of treating a cellulose textile material as defined in claim 1 wherein the acetal in the aqueous bath is malonaldehyde tetra ethyl acetal.

8. Cellulose textile material dimensionally stable to laundering made by the process of claim 1.

9. Cellulose textile material dimensionally stable to laundering made by the process of claim 3.

10. Cellulose textile material dimensionally stable to laundering made by the process of claim 4.

l1. Cellulose textile material dimensionally stable to laundering made by the process of claim 5.

12. Cellulose textile material dimensionally stable to laundering made by the process of claim 6.

13. Cellulose textile material dimensionally stable to laundering made by the process of claim 7.

References Cited in the file of this patent UNITED STATES PATENTS Great Britain Oct. 17, 1940

Claims (1)

1. THE PROCESS OF TREATING A CELLULOSE TEXTILE MATERIAL WHICH COMPRISES APPLYING TO A CELLULOSE TEXTILE MATERIAL AN AQUEOUS BATH CONTAINING AN ACIDIC CATALYST AND A SIMPLE ACETAL OF A REACTIVE ALDEHYDE SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC AND CARBOCYCLIC ALDEHYDES CONTAINING NOT MORE THAN 8 CARBON ATOMS IN MONOMERIC FORM AND MIXTURES OF THE AFORESAID REACTIVE ALDEHYDES, AND AN ALIPHATIC ALCOHOL HAVING FROM 1 TO 10 CARBON ATOMS AND FROM 1 TO 6 HYDROXYL GROUPS AND MIXTURES OF THE AFORESAID ALIPHATIC ALCOHOLS, SAID ACETAL HAVING A BOILING POINT ABOVE ABOUT 125*C., SAID CATALYST BEING PRESENT IN AMOUNT FROM ABOUT 5% TO ABOUT 200% BY WEIGHT OF THE ACETAL CONTENT IN SAID BATH, SAID ACETAL BEING WEIGHT IN THE BATH IN AMOUNTS OF ABOUT 0.5% TO ABOUT 25% BY WEIGHT OF THE BATH AND HEATING THE TREATED TEXTILE MATERIAL AT AN LEVATED TEMPERATURE UNTIL SAID ACETAL REACTS WITH THE CELLULOSE AND DIMENSIONALLY STABILIZES THE CELLULOSE MATERIAL TO LAUNDERING.