US3081144A

US3081144A - Treatment of cellulosic fabrics and the fabrics obtained

Info

Publication number: US3081144A
Application number: US61374A
Authority: US
Inventors: Gardon John Leslie; Leo S Luskin
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1960-10-10
Filing date: 1960-10-10
Publication date: 1963-03-12
Anticipated expiration: 1980-03-12

Description

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3,081,144 TREATMENT OF CELLULOSIC FABRICS AND THE FABRICS OBTAINED John Leslie Gardon, Levittown, and Leo S. Luskin, Philadelphia, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware N Drawing. Filed Oct. 10, 1960, Ser. No. 61,374 8 Claims. (Cl. 8-116) This invention relates to the treatment of cellulosic fabrics, such as those of cotton and regenerated cellulose rayon, for the purpose of imparting to them increased resilience, improved recovery from creasing, wrinkling, and other deformations, and the characteristic of having reduced shrinkage on washing so that partial or complete dimensional stabilization may be effected. The invention also embraces the treated fabrics obtained.

In accordance with the present invention, it has been found that cellulosic fabrics, woven, knitted, or otherwise formed, have reduced shrinkage on washing and acquire resistance to creasing and crushing when they are treated with a carbinol selected from the group consisting of 2,5- furandimethanol and furfuryl alcohol or by a mixture thereof. The former of these compounds has the formula Both of these compounds may be called furancarbinols and have the generic formula H0CHz 0 (CH2O)n-i H (m) wherein n is an integer having a value of 1 to 2.

While both of these carbinols serve to improve the crease resistance of cellulosic fabrics, the 2,5-furandimethanol is the more efiicient of the two. That these compounds could serve in this capacity is quite surprising since closely related compounds, such as the tetrahydro- 2,5-furandimethanol, are incapable of creaseproofing cellulose fabrics. The extent of modification by means of these carbinols may be controlled by variation in the proportion of the carbinol and by variation in the amount of catalyst employed during the treatment therewith.

The treatment with the carbinol may be effected most advantageously by means of aqueous solutions thereof in which the carbinol is dissolved at a concentration which may vary from 2 to 25% by weight. Preferably, the concentration is from 5 to 15% to obtain the maximum benefits in crease proofing and the like.

Thet reatment with the carbinol is carried out in the presence of a catalyst. Suitable catalysts are acids or acidic salts, such as citric acid, oxalic acid, potassium persulfate, potassium bisulfate, magnesium chloride, ammonium chloride, zinc nitrate, zinc fluoborate, zinc perchlorate, boron trifluoride complexes, such as the phenol complex of borontrifiuoride, and amine salts, such as the hydrochloride or sulfate of triethylamine, pyridine, morpholine, and Z-methyI-Z-aminopropanol-1. Citric acid is a preferred catalyst with relatively little tendency to cause discoloration requiring bleaching. One of the outstanding advantages of the carbinols is the fact that they need only mildly acidic catalysts making it possible to accomplish the creaseproofing treatment with a minimum loss of tensile strength in the fabric being treated.

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Conveniently, the amount of catalyst may vary from about 0.1 to 5% and is preferably in the range of 2% to 4% concentration in the aqueous solution of the carbinol.

The catalyzed solution of the carbinol is compatible with solutions or dispersions of most of the common textile finishing agents, such as synethic polymer latices and aminoplast resins or precondensates, so that they may be applied with the carbinol to produce changes in the hand or other properties of the fabric.

The aqueous solution containing the carbinol and catalyst may be applied to the fabric in any suitable manner such as spraying or impregnation. In general, it is preferable to use some method of impregnation. With piece goods, this is conveniently carried out with the various machines used for treating fabrics in open width, such as pads or jigs. However, it is not required that the impregnation be carried out in open width, and the fabric may be handled in any form. In treating garments or other articles made from cellulosic fabrics, the impregnation may be carried out in a tumble wheel, laundry machine, or other suitable equipment. After application of the solution, it is desirable to remove the excess solution by squeezing the fabric between rollers, or by shaking or centrifuging it, in order to insure a more even treatment. The fabric treated with solution may be dried, such as by air-drying at normal room temperature or by heating in a drying oven at temperatures of 60 C. and up. The drying and curing operations are preferably done with the fabric open and flat, so that it will have a smooth and even appearance when finished. In a preferred embodiment, the impregnated fabric, immediately after impregnation and without preliminary low-temperature drying, is carried in open width by a tenter frame through a curing oven where it is subjected to temperatures of about C. to about 200 C. or higher for a period of time ranging from about one-half minute to about one-half hour or more, the shorter period being employed at the higher temperature and vice versa. Entirely satisfactory results are obtained by heating for 3 to 5 minutes at about C. This curing operation not only dries the impregnated fabric but apparently causes a reaction between the carbinol and the hydroxyl groups of the cellulose. The precise reaction is not known. The treatment generally increases the weight of the fabric, the increase in weight, or add-on of reagent, being from about 1% to 15% or more, as desired, and for optimum results usually being 5% to 13%. It is not intended, however, that the present invention be limited to this theory of operation.

The treated fabrics exhibit a high degree of crush resistance and crease recovery with little or no change in the hand or feel of the fabric. In addition, the treated fabrics have the important advantage that they do not retain chlorine, so that the use of bleaching agents containing chlorine does not cause deterioration either by way of discoloration or loss in tensile strength even when the treated fabrics which have been bleached are subjected to ironing temperatures. The treated fabrics are also resistant to shrinkage during laundering, and the treatment is very permanent towards laundering, drycleaning, and other procedures for cleaning textile fabrics. The treatment of the present invention using the carbinol as the sole cross-linking or crease-proofing agent provides a finish that is more stable to hydrolysis in acids and alkalies than the usual nitrogenous or amin0- plast finishes. Any color introduced by the treatment is readily removable by the usual bleaching agents, such as sodium hypochlorite.

The following examples illustrate the present invention, and the parts and percentages therein are by weight unless otherwise noted. The crease-recovery values given below were determined by the Shirley Institute stator-t that;

3 procedure (British Standards Handbook No. 11, 1949 ed., page 128) in the warp direction.

EXAMPLE A Preparation of 2,5-Furandimethanl S-hydroxymethylfurfural (63 g., 0.5 mole) was dissolved in 25 ml. of water and was slowly added to 95 g. (0.8 mole) of 33.3% aqueous sodium hydroxide. The reaction temperature maintained itself at 30-32 C. After stirring two hours, the mixture was saturated with carbon dioxide, cooling as needed. Filtration gave 88 g. of a dark solid which was extracted with 100 ml. of ethyl acetate. The aqueous filtrate was then extracted with the ethyl acetate in a continuous extraction at 50 C. for 48 hours. Evaporation gave 20 g. of a tan solid, and further extraction gave no more. The crude prodnot was recrystallized from 40 ml. of 1,2-dimethoxyethane, giving 15 g. of yellow crystals, M.P. 7879 C. The compound is very soluble in water, soluble in mineral oil, but insoluble in chlorinated solvents.

Analysis.Calcd. for C H O percent C, 56.24; percent H, 6.29. Found: percent C, 56.33; percent H, 6.40.

EXAMPLE 1 The carb'inol-treated fabric, which was 9.3% heavier after the treatment than before, was insoluble in cupram monium hydroxide while the control dissolved readily.

The durability of the treatment was shown by the following tests. Samples of the furfuryl alcohol-treated fabric were extracted (1) in boiling water for one hour, (2) in 0.1 N HCl at 80 C. for one hour, and (3) in 0.1 NaOH for 24 hour-s at 20 C. The extracted samples were still insoluble in cuprammonium hydroxide and still had good crease-recovery.

EXAMPLE 2 (a) A sample of cotton print cloth was saturated with an aqueous solution containing of 2,5-furandimethanol and 1.5% of zinc fluoborate. It was then put into an oven at 150 C. and baked for 15 minutes. A control treated with water was similarly prepared. After being conditioned, the samples had the following creaserecovery values:

Crease-recovery angle, degrees Water control 71 2,5-furandimethanol 133 The carbinol-treated fabric was 12.2% heavier than the initial fabric.

(b) The procedure of part (a) was repeated using rayon challis instead of cotton printclo-th. The treated fabric was insoluble in cuprammonium hydroxide and had similar crease-recovery.

(c) A solution containing 15% of 2,5-furandimethanol and 3.8% of citric acid was applied to cotton printcloth and the treated fabric was baked for 3.5 minutes 4 at 150 C. I-ts crease-recovery was improved by this treatment from 71 to 124.

EXAMPLE 3 A sample of cotton pr-intcloth was saturated with a 15 aqueous solution of 2,5 furandimethanol containing 0.5% NH Cl as the catalyst. It was cured in an oven at 150 C. for 3.5 minutes. After being conditloned, the sample had a crease-recovery angle of 139.

EXAMPLE 4 A sample of cotton printcloth was treated with a so lu-tion containing 10% of furfuryl alcohol, 1% of oxalic acid, and 4% of a partially condensed urea-formaldehyde resin. The treated fabric was cured for 10 minutes at 150 C. After being conditioned, it had a stiffer, firmer, more resilient hand and a crease-recovery of 137.

EXAMPLE 5 A sample of cotton printcloth was treated with a solution containing a mixture of 10% 2,5-furandimethanol and 5% dimethylol-N,N'-ethyleneurea with 4% citric acid as a catalyst. The application was made on a textile pad and the impregnated fabric was baked for 10 minutes at 150 C. After the fabric was conditioned, ltS crease-recovery angle was 139.

We claim:

1. The process comprising impregnating a cellulose fabric with an aqueous solution containing at least 2% by weight of at least one carbinol selected from the group consisting of 2,5-furandimethanol and furfuryl alcohol and at least about 0.1% by weight of an acidic catalyst and heating the impregnated fabric at a temperature of about to 200 C. for at least a period of half a minute to half an hour, whereby the crease resistance of the fabric is increased.

2. A process as defined in claim 1 in which the fabric 1s cotton. 3. A process as defined in claim 1 in which the fabric is rayon.

4. A cellulose fabric having improved crease resistance obtained by the process of claim 1.

5. A cotton fabric having improved crease resistance obtained by the process of claim 1.

6. The process comprising impregnating a cellulose fabric with an aqueous solution containing 2 to 25 by welght of at least one carbinol selected from the group consisting of 2,5-furandimethanol and furfuryl alcohol and 0.1 to 5% of an acidic catalyst and heating the impregnated fabric at a temperature of about 110 to 200 C. for at least a period of half a minute to half an hour.

7. The process comprising impregnating a cellulose fabric w1th an aqueous solution containing 2 to 25 by weight of 2,5-furandimethanol and 0.1 to 5% of citric acid as a catalyst, and heating the impregnated fabric at a temperature of about 110 to 200 C. for at least a period of half a minute to half an hour.

8. The process comprising impregnating a cellulose fabric with an aqueous solution containing 2 to 25 by weight of furfuryl alcohol and 0.1 to 5% of phenolborontrifiuoride complex as a catalyst, and heating the impregnated fabric at a temperature of about 110 to 200 C. for at least a period of half a minute to half an hour.

References Cited in the file of this patent UNITED STATES PATENTS 2,993,915 Luskin July 25, 1961

Claims

1. THE PROCESS COMPRISING IMPREGNATING A CELLULOSE FABRIC WITH AN AQUEOUS SOLUTION CONTAINING AT LEAST 2% BY WEIGHT OF AT LEAST ONE CARBINOL SELECTED FROM THE GROUP CONSISTING OF 2, 5-FURANDIMETHANOL AND FURFURYL ALCOHOL AND AT LEAST ABOUT 1.0% BY WEIGHT OF AN ACIDIC CATALYST AND HEALING THE IMPREGNATED FABRIC AT A TEMPERATURE OF ABOUT 110* TO 200* C. FOR AT LEAST A PERIOD OF HALF A MINUTE TO HALF AN HOUR, WHEREBY THE CREASE RESISTANCE OF THE FABRIC IS INCREASED.