US2355265A - Textile materials - Google Patents

Description

A cicusly held gard to the The process may also be used for patterns on cloth-or sheets. thatthe afllnity of textile fibers,

cellulosic fibers truly become more wool-like in bothdyeing properties and physical properties."

,Patented Aug. 8, 1944 OFFICE TEXTILE MATERIALS Louis H. Bock, Hnntingdon Valley, and Alva L.

Honk, Philadelphia,

Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application April Serial No. 381,682-

12 Claims.

This invention relates to theimprovement of textile materials by treating them with condensates of formaldehyde and amides of malonic acid having at least one N-aminoalkyl substituent, the hydrocarboninterrupted by -NH- to form alkylene chains of at least two carbon atoms. each between niportion of which may be es of improving textile trogen atoms. In the preferred form this in e ntion deals with altering the, susceptibility of textile fibers to dyes by treating fibers with said'con- Resins have heretofore been used in finishing textile fabrics to impart increasedresilienceor stiffness, or to improve the wearingjqualities of dyed fabrics by protecting the dye witha deposit of resin. Prior methods OtTQSm flnishinghave not, however, markedlychangedthe-afilnity be- 15 tion leads to tween fiber and dye. Nor have such methods permitted the with the same dyeing of different typesqof fiber dye or the eflective dyeing of cel-.

lulose with acid dyes; .In this last respect. at-V i tempts have been made to increase the afllnity of'cellulose for acid dyes by chemicaltreatments' reacting a mixture of formaldehyde and an aminoalkyl malonamide having a reactive methylene group in juxtaposition to the amide car bonyl group in the presence orjabsence of a solvent while the temperature of the reacting mixture is held below about 100 C. The aminoalkyl amides are obtained by reaction between a malonic ester and an alkylene polyamine, such as bis(aminopropyl) ethylene diamine, tripropylene tetramine, tris(trimethylene)tetramine, etc. or mixtures of monoand di-amides which are soluble in aqueous systems.

ethyl malonamide, N,N'-bis(aminoethyl)malonamide, .N,N'-bis(aminoethylaminoethyl)malonamide. N-aminoethylaminoethylaminoethyl propyl malonamlde. N,N'-bis (aminoethylaminoethylannnoethylaminoethyl) malonamide: etc. These amides react with aqueous or solvent solutions of which, while' often attackingcellulose fibers seformaldehyde or with formaldehyde from a solid verely, have not been particularly effective. I In 35 polymer to yield condensates which resinii'y on general such methods have beentoo complicated further heating! To prevent prematuregelation and uneconomical to gain acceptance.

It ha been found that valuable improvements product of formforth. The treating is accomplished or impregnating the textile material with the said reaction product or with a solution thereof in water or organic solvent. The treated material is heated at a temperature general- It above about 100 C. but below the decomposition temperature of the material being treated.

Textile materials so processed have an increased ailinity for acid dyes and acquire full,

deep shades when treated therewith. Other dyes ordinarily effective only on wool or silk are tenaby thus treated fibers without reoriginal type of fiber. On the other hand, this treatment of textile materials'or fibers renders them resistant to various basic dyes. local efiects and yarns, or tabrics is'altered toward dyes, increased resilience is imparted withoutidevelopment Of a harsh or unpleasant handle 'ofethe textile material so that Thecondensates which areuseful in the procby treating and:

as ethylene diamine,

of these condensates it is often desirable to condense the aminoamide and-formaldehyde in the presence'of a primary or secondary amine such methylamine, dimethylamine, diethylamine. cap 'ylmethylamine, etc. Details of the preparation and nature of the aminoamides and theircondensates are given in applications having Serial N08. 387,679, 387,680,

387,681 (now Patent No. 2,325,567). filed on even C. Temperatures of 120 At the same time date. l

The formaldehyde-aminomalonamide con densates are applied to textile materials from neutral, acidic, or alkaline solutions by spraying, dipping, padding,,..printing, or other method of treatment. Excess solution is then desirably removed by a suitable means, such as a centrifugal extractor, vacuumslot extractor, or squeeze roll. The impregnated material is dried at room or higher temperature as a separate step or as part of the baking step. It'is then baked above up to C. for 5 to 30 minutes are particularly effective in fixing the condensate in the fibers, although temperatures as high as -160 C. may be used in some cases. lfdesired, after this curing step the materials may be washed or secured in a bath of a natural or synthetic soap or other detergent. The materials may nowbe dyed with wool andsilk dyes ll with highly satisfactory results. The process-is fibers are obtainable by.

ethylene diamine, dlethylene triamine, triethylene, tetramine, tetraethylene pentamine, N,N'-,

polyal'kylene polyamines. This reac- Typical of the amino- T amides which result are N-aminoethylaminoethyl applicable to all types of textile materials, including cotton, linen, regenerated cellulose fibers,

paper, straw, silk, fibers-or superlinear polymers,

Example 1 Ten parts of the reaction product obtained by heating together one mol of N,N-bis(aminoethylaminoethyl)malonamide, three mols of formaldehyde, and 3.5 mols of dimethylamine was taken up in water. Hydrochloric acid was added thereto until a pH of 6.8 was attained. The solution was then diluted with water to 100 parts. Bundles of rayon fiber (3 denier, 19/16" staple) were immersed in'the solution, which was-kept at the boil for five minutes. The bundles were removed from the treating solution and squeezed to remove excess liquor. They were then dried and heated for 30 minutes in an oven at 125 C. The fibers showed a definite increase in stiffness and were light tan in. color. The bundles of fibers were accordingly washed in warm soap solution, which removed most of the tan color. They were then placed for one-half hour in a simmering solution containing 1% Pontacyl Carmine 63 (Color Index No. 57) and 41% of acetic acid. The 11-- bers were dyed a deep purple color which was fast to washing and reasonably fast to light.

Example 2 Its greatest advantage is ob- Rayon taffeta was soaked for five minutes in this solution while it was maintained at '70 C. and stirred from time to time.

The taifeta was run through squeeze rolls to remove excess solution and dried. It was then baked for one-half hour in an oven at 130 C. and washed in a soap solution. The fabric was dyed in abath of Acid Brown EW #3 (Color Index No. 234) to a medium brown shade, which was fast.

Example 3 A 10% solution'of the reaction product of one mol of N,N-bis(aminoethylaminoethylaminoethyl) malonamide and 1.5 mols of formaldehyde was madeslightly acid with hydrochloric acid. The solution was then used for the im- Example 4 Cotton cloth waslsoaked at 70 C. for five minutes in a 20% solution of the reaction prod- 'uct from. one mol of N,N'-bis(aminoethyl) malonamide, two mols of ethylene diamine, and one mol of formaldehyde. The cloth was removed from the solution and immediately placed in an oven at 130 C. for a 40 minute period- It purple shade was then washed in soap solution anddyed in a bath of Pontacyl Carmine 63 to give a medium and two mols of formaldehyde-.- The fabric was;- :7 dried, heated in an oven' at- C:-for.one-half; hour, and washed in soap solution; It was'dyed in a bath of Brilliant W001 Blue (Prototype 40) The fabric was deep blueand retained this color. It was noticeably fuller and more resilient than untreated fabric and did not change dimensions: appreciably on being laundered. e

Example 6 A 10% aqueous solution of the reaction product, obtained by heating at 70-80". C. amixture of 27.4 parts of N,N'-bis(aminoethylamino-- ethyl)malonamide, 60 parts of dimethylamine, and 30 parts of 30% formaldehyde solution, was heated to 50 C. A hank of nylon yarn was immersed in this solution for fifteen minutes and squeezed free of excess solution. It was then dried and heated for 20 minutes in an oven at C. The yarn was dyed in a bath of Pontacyl Carmine 63. It retained a bright red color. Untreated nylon retained only a pale color.

Example 7 The solution used in Example 6 was similarly applied to silk yarn, which was likewise dyed with Pontacyl Carmine 6B. A full red color was obtained. Yarn dyed directly without process-.

fabrics and stabilize fabrics against changes in dimensions. These improvements appear due partly'to resinous deposits and partly to actual combination between fiber and condensate or resin. The formaldehyde-aminoalkyl malonamides may be applied to fibers as the sole finishing agent or they may be applied in conjunction with other resin-forming materials such as ureaformaldehyde, acrylic resins, etc. or in conjunction with finishing agents such as sulfonated oils, long-chained quaternary ammonium salts, etc.

We claim:

1. The process of improving textile materials which comprises treating said materials with the reaction product of formaldehyde and a malonamide having at least one N-aminoalkyl substituent, the hydrocarbon portion of which may be interrupted by --NH-- to form alkylene chains of at least two carbon atoms each between nitrogen atoms, and heating the treated materials above about 100 C. but below the decomposition temperature of said materials.

2., The process of improving the affinity of cellulosic textile fibers to acid dyes which comprises impregnating said fibers with an aqueous solution containing the reaction product of formaldehyde and a malonamide, having at least one N-polyamino polyalkylene substituent in which the alkylene chains consist of at least two carbon atoms each, and heating the impregnated fibers above about 100 C. but below the decomposition temperature of said fibers.

3. The process of improving textile fibers, yarns, and fabrics which comprises impregnating said textile materials with a solution containing the reaction product of formaldehyde and an N,N'-bis(polyaminopolyalkylene) malonamide, the alkylene chains of which contain at least two carbon atoms each, and heating the treated materials above about 100 C. but below the decomposition temperature of said materials.

4. The process of improving textile fibers, yarns, and fabrics which comprises impregnating said textile materials with a solution containing the reaction product of formaldehyde and a malonamide, having at least one N-aminoethylaminoethylaminoethylaminoethyl) group, and heating the impregnated materials between about 100 C. and about 150 C.

5. The process of improving textile fibers, yarns, and fabrics which comprises impregnating said textile materials with a solution containing the reaction product of formaldehyde and N,N'-bis(aminoethylaminoethylaminoethyl) malonamide, and heating the impregnated materials between about'100 C. and about 150 C.

6. The process of improving textile fibers which comprises impregnating said fibers with an aqueous solution of the reaction product of formaldehyde and N,N'--ibis(aminoethylaminoethyl)malonamide and heating the impregnated fibers between about 100" C. and about 150 C.

7. A textile material carrying the insolubilized reaction product offormaldehyde and a malonamide having at least' one N-amioalkyl substituent, the hydrocarbon portion of which may be interrupted by --NH to form alkylene chains of at least two carbon atoms each between nitrogen atoms.

8. A textile fabric carrying insolubilized thereon the reaction product of formaldehyde and an N,N-bis(polyaminopolyalkylene) malonamide,

the alkylene chains of which contain at least two carbon atoms each.

9. A textile material carrying insolubilized LOUIS H. BOCK. ALVA L. HOUK.