US2203492A - Dyed cellulosic material - Google Patents

Description

Patented June 4,

DYED CELLULOSIC MATERIAL John Gwynant Evans, Henry Alfred Piggott, Reginald John William Reynolds; John Donald Rose, and Eric Everard Walker, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application June 23, 1938, Serial No. 215,494. g In Great Britain June 30, 1937 7 Claims.

The present invention relates to the dyeing of cellulosic material and in particular to a process of treatment whereby, by use of. certain dyestuffs, dyed cellulosic material is obtained with fastness properties superior to.those.hitherto possessed by dyeings made by use of the dyestuffs in question.

By cellulosic material we mean any materiai consisting of or containing natural cellulose fibre such as cotton, linen, jute, either spun, woven or in the formoi paper or cardboard; we include also regenerated cellulose in the form of fibre or film. i

It is an object of the invention to produce fast dyeings on cellulosic materials by use of direct cotton dyestuffs. n

The invention comprises the application to cellulosic material of a compound in the molecule of which there is at least'pne of each of two kinds of functional groups. These two functional groups are (A) an ammonium or similar group capable of sointeracting on the dyed material with a dyestuff of the kinddescribed so that, as is supposed, the material carries or encloses within its intermicellar or other interstices pigmentary substance which can be regarded asan organic salt of the dyestufi acid; and (B) a group originally such that the compound is water soluble but so adapted to self or conjoint reaction on application of heat that the heating treatment referred to results in the fixation on the material of a substance no longer containing group (B) but still containing group (A). Suitable groups classified under (B) are. such that the compound is a carboxylic amide, a substituted urea or a carbamate. l

In thesecompounds the functional groups (A) and- (B) may be linked together by arylene or alkylene radicals which may provide the entire link, or may be part of a link, e. g.,,alkylene links may themselves be linked by oxygen or nitrogen atoms According to the invention cellulosic material is dyed with dyestufisof the class known as direct dyestuffs and is then treated at a relatively low temperature with a solution of a compound constituted as described when necessary in presence of or subsequently with formaldehyde or a heated for a short time to a moderately elevated temperature, e. g., 5 to 30 minutes at a temperature of 100- 140 C.

As compounds coming under the above description as containing the groups (A) and (B) there formaldehyde yielding substance: finally it is spoken of, there come to be mentioned those of the general formula wherein the symbols used, so far as they do not carry their known and customary significance, are explained below.

R stands for hydrogen or an alkyl, aralkyl or aryi radical and R" and R' stand for the same or different alkyl or aralkyl radicals; or R'R" R"'N taken by itself may stand for a tertiary amine which is a heterocyclic compound, typified by pyridine of the one class, or the alkyl piperidines of another; or R"RNH taken by itself may stand for a heterocyclic secondary amine, e. g., piperidine.

L stands for the link spoken of above, 1. e., it stands for a divalent organic radical, for instance:

X stands for an acid radical.

Compounds suitable to be used in the process of the invention may conveniently be made by the processes described in British Patents Nos. 497,- 043; 497,368, and 497,485.

It is a further feature of the invention to use, instead of the compounds represented by the general formula given above the suitable products of their condensation with formaldehyde, for example, their methylol derivatives. As will be seen, here a preformed formaldehyde compound is used, but the treatment may nevertheless be carried out in presence of a further quantity of formaldehyde or a formaldehyde yielding substance.

As suitable formaldehyde yielding substances there may be mentioned, for example, dimethylol urea, the dimethyl ether of dimethylol urea and methylol urethane.

The invention iscarried into practical effect in a number of ways. For instance, (a) the dyed cellulosic material is impregnated with a solution, for example, an aqueous solution of one of the compounds mentioned, the solution containing also formaldehyde or a formaldehyde yielding substance. The impregnated material is then dried and subjected to a short heat treatment.

If desired, the drying and heating treatment may be carried out in one step.

(b) The dyed cellulosic material is impreg nated with a solution of one or more of the said compounds and exposed in the wet or dry state to formaldehyde vapour at atmospheric or higher pressure, preferably at elevated temperature.

(0) The dyed cellulosic material is impregnated with a solution of one or more of the compounds mentioned, then, preferably after drying, is treated in a bath containing formaldehyde or a formaldehyde yielding substance, dried, and finally subjected to a short heat treatment. Again, if necessary, the drying and heat treatment may be carried out as one step.

(d) When using pre-formed condensation products, such as the methylol compounds mentioned, the treatment is carried out by any of the foregoing methods, or the simultaneous or subsequent treatment with formaldehyde or a. form;

aldehyde-yielding substance may be omitted, as already explained.

The impregnation mentioned may be carried out with advantage by use of an acidified liquor containing, e. g., boric acid, acetic acid, tartaric acid, lactic acid, tannic acid, oxalic acid or an acid substance or compound which yields acid under the conditions of drying or heating, e. g., ammonium dihydrogen phosphate, ammonium thiocyanate, sodium bisulphite. The heat treat- 'ment may also be carried out in acid conditions by application of acid as vapouror in other ways. 4

'ent also in the impregnating liquor a small pro- In some cases it is advantageous to have presportion of borax.

The invention is illustrated but not limited by the following examples in which the parts are by weight.

Example 1 A linen material dyed to a 1% shade with Chlorazol Fast Red K (Colour Index No. 278) is soaked at room temperature in a bath containing 1 part of p-ureidoethyl-pyridinium chloride, of formula and 5 parts of formaldehyde in 94 parts of water. The material is squeezed to remove excess of liquor and is dried at 70 C. It is then heated for 10 minutes at C. The dyeing is now very fast in respect of washing and other aqueous treatments.

Example 2 A regenerated cellulose rayon woven fabric dyed to a 1% shade with Chlorazol Fast Hello BK (Colour Index No. 319) ispassed in. a continuous padding operation through a solution containing 2 parts of p-dimethylamino phenyl urea methosulphate of formula 5 parts of formaldehyde and 0.3 part of ammonium dihydrogen phosphate in 93 parts of water. The fabric is squeezed so that it contains its own weight of liquor and is then dried in a current of warm air at 4050 C. The dry material is heated for 5 minutes at C. The dyeing is now much faster in respect of washing and other aqueous treatments.

Example 3 Finely woven cotton fabric of the variety known as limbric dyed to a 1% shade with Chlorazol Fast Orange R (Colour Index No. 326) is soaked at 50C, in a solution containing 2 parts of p-dimethylaminophenylurea methosulphate, 6 parts of dimethylolurea and 0.3 part of oxalic acid in 92 parts of watei. The material is squeezed to remove the, excess of liquor and is dried at 50C. It is then heated for 5 minutes at 120 C. The dyeing is now much faster in respect of washing and other aqueous treatments.

Example 4 Cotton yarn dyed to a 1% shade with Chlorazol Fast Pink BK (Colour Index No. 353 is soaked at room temperature in a solution containing 1 part of p-ureidoethylpyridinium chloride of formula 'CsHsN(C1) CH2-CH2--NH-CONI-Iz, 2 parts of formaldehyde and 0.3 part of ammonium dihydrogen phosphate in 97 parts of water. The

yarn is wrung out-Ito remove excess of liquor, dried at 40 C.-50 C. and then heated for a few minutes at 120 C. The dyed yarn now possesses a greatly increased fastness in respect of washing and to aqueous treatments in general.

Example 5 Cotton sheeting which has been dyed to a 2% shade with Chlorazol Fast Red K (Colour Index No. 278) is soaked at room temperature in a solution of 2 parts of N-hydroxymethyl carbamyl methyl pyridinium chloride of formula CsHsN(Cl)-CH2CONHCH:OH

and 0.3 part of ammonium dihydrogen phosphate in 98 parts of water.- The fabric is squeezed to remove excess of solution and is dried at a temperature of 40 50 C. The dry fabric is heated for 15 minutes at a temperature of 120 C. The dye on the fabric now possesses a very considerably increased fastness to water and to washing treatments.

Example 6 Finely woven cotton fabric ,of the variety known as limbric, dyed to a 1% shade with Chlorazol Fast Hello BK (Colour Index No. 319) is soaked at room temperature in a solution of 2 parts of a syrupy condensation product obtained by. interaction of formaldehyde and p-ureidoethylpyridinium chloride of formula CsH5N(Cl)-.CHa-CH2-NHCONH2, 0.5 part of formaldehyde and 0.3 part of sodium hydrogen sulphite, in 97.2 parts of water. The material is squeezed until it contains its own weight of impregnating solution and is dried for 5 minutes at 120 C. The dyestuif on the fabric is now fast to water and washing treatments.

Example 7 Cotton sheeting dyed to a 1% shade with Chlorazol Sky Blue FF (Colour Index'No. 518) is soaked at room temperature in a solution containing 2 parts of the condensation product of formaldehyde and N-carbamylmethyl-N-benzylpiperidinium chloride of formula cmmmcm-mm) (ci --crn co m' and 0.3 part of ammonium dihydrogen phosphate in 98 parts 01' Water. The material is squeezed 75 dried. The dyeing now possesses improved fasta dried. The dyeing no to remove the excess of liquor and is dried in a or of ureidoethyl methyl piperidinium iodide of current of warm air at 40-50 C. The dry fabric is heated for 10 minutes at 120 C. The dyeing is now much faster in respect of aqueous treat-- ments.

Example 9 Cotton sheeting which has been dyed to a 2% shade with Chlorazol Fast Red K (Colour Index No. 278) is soaked at room temperature in a solution containing 2 parts of p-ureidoethylpyridinium chloride, 0.3 part of ammonium dihydrogen phosphate and 5 parts of dimethylol urea in 93 parts of water. The fabric is then squeezed to remove excess of solution and dried at 40-50 C. The dry fabric is then heated for 5 minutes at a temperature of 125 C. The dye on the fabric now possesses a very considerably increased fastness to water and to washing treatments.

If in the process of the above example there is used, instead of the dimethylol urea, an equal weight of dimethylol urea dlmethyl ether, the fastness of the dyeing to water and aqueous treatments is similarly increased.

Example 10 Finely woven cotton fabric of the kind known as limbric, which has been dyed to a 2% shade with Chlorazol Fast Red K (Colour Index No. 2'78) is soaked at room temperature in a solution containing 2 parts of p-ureidoethylpyridinium chloride, 0.3 part of ammonium dihydrogen phosphate, 0.35 part of borax and 5 parts of formaldehyde in 92 parts of water. The material is squeezed until it contains about its own weight of the solution and is then dried at about 40 C. It is then heated for 5 minutes at 120 C.,-rinsed in a solution containing 3 parts of concentrated ammonia solution (sp. gr. 0.880) in 1000 parts of water, rinsed again in water and ness to washing and other aqueous treatments.

Example 11 Finely woven cotton fabric of the kind known as limbric, which has been dyed to a 2% shade with Chlorazol Fast Red K (Colour Index No. 278) i is soaked at room temperature in a solution containing 2 parts of 'y-ureidopropylpyridinium chloride of the formula C5H5N(C1)CH-zCHz-CHzNH-COs-NH2,

0.3 part of ammonium dihydrogen phosphate and 5 parts of formaldehyde in 93 parts of water. The material is squeezed until it contains about its own weight of the solution and is then driedat about 40 C. It is then heated for 5 minutes at 120 C., rinsed in a solution containing 3 parts of concentrated ammonia solution (sp. gr. 0.880)

in 1000 parts of water, insed again in water and possesses improved fastness to washing and other aqueous treatments. If in this process there is used, instead of the 'y-ureidopropylpyridinium chloride, an equal weight of p-ureidoethylbenzylpiperidinium chloride of the formula CHz-CH:

CHr-CH:

the formula CHa' cal-cm NHg-CO-NE-OHr-Cflr-N CH:

- cHr-cm the fastness of the dyeing to washing and other 1 aqueous treatments is similarly increased.

If instead of the agents mentioned above there' is used an equal weight of carbamyl methyl pyridinium chloride of the formula and the final heat treatment iscarried out for 25 minutes at 125 C., a similar improvement in the fastness of the dyeing is obtained.

Example 12 Low plain cloth of warp ends per inch and weft 61 per inch, of width 28 inches, weight approximately 45 grams per yard, is dyed to a 2% shade with Chlorazol Blue 2R (Colour Index No. 472). The dyed cloth is then soaked in a solution containing'l part of fi-ureidoethylpyridinium chloride, 0.3 part of ammonium thiocyanate and 5 parts of formaldehyde in 94 parts of water. The material is squeezed until it contains approximately its own weight of impregnating liquor and is then dried at about 40 C. The cloth is then heated for 5 minutes at C., rinsed in a cold solution containing 3 parts of concentrated ammonia solution (sp. gr. 0.880), in 1000 parts of water, rinsed again in water and dried. The dyeing is now very fast to washing and other aqueous treatments.

We claim:

1. A proceess for improving the fastness to water and aqueous treatments of dyeings made on cellulosic material by theme of direct dyestuifs which comprises treating the dyed material with a solution of an organic compound selected from the class consisting of carboxylic amides,

substituted ureas and carbamates, said compound having the general formula wherein RR'R"N as a whole represents the entire molecular structure of an amine selected from the class consisting of aliphatic secondary amines, heterocyclic secondary amines, aliphatic tertiary amines, mixed tertiary amines, and heterocyclic tertiary amines, X stands for an acid radical, and L stands for a divalent organic radical selected from the group:

and -C6H4NH-; and the formaldehyde condensation products of said carboxylic amides, subimpregnating solution also containsa. small pro-' 7. A procws as set forth in clahii 1 wherein the portion of borax. substituted urea. which is employed is gamma 5. A process as set forth in claim 1 wherein the ureldopropylpyridinium chloride. substituted urea. which is employed is beta. JOHN GWYNANT EVANS.

ureidoethylpyridinium chloride, HENRY ALFRED PIGGO'I'I.

6. A process as set forth in claim 1 wherein the REGINALD JOHN WILLIAM REYNOLDS. substituted urea. which is employed is p-dimethyl- JOHN DONALD ROSE.

amlnophenyl urea methosulphate. ERIC EVERARD WALKER.