US3167384A - Process of rendering cellulosic textiles wrinkle resistant by reacting with bis(n-methylol carbamoylethyl)-methylamine - Google Patents

Description

United States Patent A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

Cellulosic textiles are known to have an inherently poor ability to recover from undesirable wrinkling and creas- 'ing." There is a large demand for a treatment that will ima part wrinkle resistance, and yet allow the textile to retain most of its original desirable characteristics. Some'of the existing treatments used are methylol derivatives of organic amides, formed from the reaction of formaldehyde with amides such as urea, melamine, and dicarboxylic acid diamides. After hypochlorite bleaching, however, textiles so treated often are susceptible to severe strength losses or suifer-discoloration. To prevent this, treatments have been devised utilizing alkyl substituents on the amido nitrogen of the compound. These substituents replace any amido hydrogens remaining after the reaction with formaldehyde and thereby remove the groups that react with hypochlorites. 1

All of these suffer some disadvantages. For example, N-N' dimethyldiamido derivatives of dicarboxylic acids have been used to prepare the dimethylol compounds. These have reduced effectiveness in producing desired wrinkle resistance.

Cyclic substituents such as inethyle'neurea have been used. The methylol derivative of this compound, dimethylol ethyleneurea, is highly effective in producing wrinkle resistance, and is initially resistant to damage from hypochlorite bleach. The finish, however, lacks durability to such acidic conditions assouring which is commonly encountered in many commercial laundries. The immunity to hypochlorite bleaching is also lost on repeated laundering, with or without souring. The dimethylol triazones, another widely known type'of agent, contain a tertiary amino group in the cyclic substituent. This tertiary' amino group is believed to neutralize the effects of hypochlorite bleaching. These compounds, however, produce a finish that is lacking in durabilityand is subject to discoloration on overheating, such as may occur on ironing. I p i It is the purpose of this invention to produce compounds of the organic amide class that can be used to impart durable wrinkle resistance finishes to cellulosic textiles.

The finish so produced will give a high degree of wrinkle resistance, withstand hypochlorite bleaching without damage to the treated textile, and be durable to laundering in which acidic or alkaline conditions are encountered.

The wrinkle resistance which is the subject of this invention is produced by the treatment of a .cellulosic textile with the polymethylol derivative of a new class of polyamides of polycarboxylic acids which are unsubstituted on the amido nitrogen, and which contain a tertiary amino group in the carboxylic acid moiety. This tertiary amino group may be part of the alkyl chain joining the carboxyl groups or may be attached as a substituent on the chain. Even though these agents contain incompletely ice substituted amido groups, hypochlorite resistance is obtained in the treated fabric, and the effectiveness of the agent remains high.

Examples of the polyamides of this invention are:

Bis carbamoylethyl methylamine HgN-4fi-0Hz-0 z-N-CHFOHZ-fi-NH, 0 H 0 Dimethylaminosuccinamide These compounds can be prepared by the reaction of the proper amine with the amide of a 1,2-unsaturated carboxylic acid. For example the first of the above mentioned compounds can be prepared by the reaction of methylamine with acrylamide:

These compounds canbe converted to methylol derivatives by the reaction in aqueous solution of one or more moles of formaldehyde, or a substance that liberates formaldehyde, with one mole of the polyamide at pH 9-10. At least two moles formaldehyde are required to prepare the dimethylol compound; however, less can be used to prepare a partially methylolated compound. The lower methylol substitution causes reduced etfe'ctiveness, but may be desired in some instances'where the highest wrinkle resistance is not required. The solution thus prepared is diluted to the padding concentration after standing at least four hours at the specified pH.

In accordance with the invention an aqueous solution is prepared as described above, containing from one to twenty percent of the reaction product containing two or more moles of formaldehyde in combination with one mole of the amide.

About 0.5 percent to 3 percent by weight of a catalyst, based on the total weight of the padding bath, is added to the padding bath to facilitate curing. Catalysts. which can be used to promote curinginclude mineral acids; various salts of strong acids such asv ammonium salts; alkanolamine salts; metallic salts of strong acids and Weak bases, such as zinc nitrate and magnesium chloride.

The treating solution of the methylol amide and catalyst, prepared as described above, is padded onto the cloth by passing through efiicient squeeze, rolls to give a wet pickup of sixty to one hundred percent. The curing step, the reaction of the methylol derivative of the polyamide wth the textile, is carried out by the usual procedure. The padded textile is dried at an elevated temperature, for example -70 C. for seven minutes, then further heated to effect the curing. Improved properties are obtained by curing at l20l60- C. from 0.5 to 10 minutes. The curing step is best followed by an afterwash with a detergent solution to remove any excess unreacted crease resistance agent, and to improve the hand of the textile. I

The process and compounds to which this invention relates can be used to treat any hydrophilic fibrous cellulosio textile such as cotton, linen, ramie, jute, regenerated cellulose, and others. a v

Textiles treated according to the process of this invention are wrinkle resistant, and have in addition wash-andwear properties, that is, textiles so treated require no ironing after washing to maintain a smooth appearance.

They can belaundered and bleached in the manner used on untreated textiles withoutlossof properties or dam age to the textile. t

The following examples are given as illustrations, and

arenot by any means intended to limitthe scope of this invention. All percentages given in the examples are percentages by weight'of the total solution. The fabrics were tested by thefolowingmethods: crease recovery angle, Monsanto method, American Society for Testing, Materials (ASTM), Standards. for Textile Materials,

D1295- 53T; damage caused by retained chlorine (scorch test), American Association of "Textile Chemists and Coloristsrtentative test'method 69-1952. The laundering procedure used to test the durability of the. finish was the 1 vigorous alkaline wash described in AATCC test method The crude produt, wl1ih separated from the solution melted at 1'l 3-120 C. Recrystallization from ethanol yielded 48 g. product melting at 114-116 -C.

EXAMPLE 2 I] Preparation of bis(carbamoyl e thyl) methylamine in water 7 v To -g. 40% aqueous methylaminewas-added 71.2

allowed to come slowly to roomitempera'ture, and to stand stoppered at room, temperature for gtwor hours, The solution was evaporated to'dryness under vacuum and the p g. acrylamide. f Thesolution was stirred and kept belowj 7 10." Cfthroughout the addition The solutionwas then V v V To 41 g.. anhydrous methylamine dissolved inl60 g j n'iethanolwas "added 19916 g. acrylamide' The solution was allowed to stand 'at'roomftemperature for sevendays;

14- 53 washes. The effects'of these washes on the physi- 7 Cal propefiiesfdf t-he fiiiish es ar e listedin T allele 1. i

' TABLET "Original After 5 AATOO 1453'Washes q r t g Brk.Str, H1 BrlnStr. Finishing AgentUsed -,Grease- RetAfter, Crease Ret.Aiter Rec; AAfIOO Rec. AATCC Angle 69-1952. Angle 69-1952 '(Deg.)= Scorch '(DegJ Scorch W+F Test, W+F- Test,

;Pereent Percent 3 Original 1 Original Untreated Fabric... 7 187. 91 172 H 106 10% bis (N-methylol carf bamoylethybmethylai e 269 102; s 114 73 Dimethylol dim'ethyl I suceinamide ,187 734% Dimethylol ethyleneurea 275' 1.08v 283' 50 7V %Dimethyl01ethy1tria'- v 7 zone -260. 95 250, 94

, The finish prsaucsa by'bis-(N-rnethylol r'banioy1ethy1),

- methylamine is ,durable through vthe 14-53 a washes. V The finish is 'far 'superior.inresistance to darnage dueto-i'etained chlorine after AATCC 14-53 alkaline' washes than is the dimethylol ethyleneu-rea; finish.

The bis(N-rnethylol carbamoylethyl)inethylamine'finish is nitrogensand a cyclic'subs tituent containing a tertiary product.recr'ystallized from a321,ac'etone-alcoholmix- T ture.

'(carbamoylethyl)methylamine was dissolved in 1L9 times its weight in water and sufiicient 36.3% formaldehyde solution added to afiord a mole ratio of formaldehyde 10 Yield, 70.0 g. M.'P.,- 115-1l7C. percent .yield,:'

equal to: or better than the. triazonefinish in durability, '&I1d dd$ :not discolor on-heating -as;does the triazone finish. The dimethylol dimethyl succinamide finish shows no improvement --in ,erea se resistance over thatof the untreated fabric; Table I shows thatall the other attempts, mentioned -earlier, to gimprove the resistance to damage due to retained ChlOIi-llCr-FE-Il alkyl substituent on the "arriido nitrogenfia eyclic substituent on the arnido amino group,-have "either failed to produce a wrinkle resistance finish at all, :produceda finish susceptible to discoloration from heating, or produced a. finish which, though initially acceptable, will break down after-launderings., Only, the finish containing a tertiary amine in the carboxylic aeid moiety, andY'no alkyl substituent on :the

bis'(carbamoylethyl-)methylamine of 221. This solution,

pH 9.1, or 33%% solids concentration was allowed-tot stand overnightat room-temperature. 'Afti rthis time c j'the'33V3% solution was dilutetlwith ,suificien't waterz'to give a 10%,3- solids concentration, and'1.5% byfweightd'f hydrated magnesium chloride (Mg'Cl -6H O) was added as catalyst,with sufiicient 6 N l-IClto makethe solution i to pH 4. The treating solution was padded onto a sample of 80 x 80 cotton print 'clo'th tozgive a 70-80% we"; pickup. The 'Wet'fabricwas drie d at:ofiginal din iensions-for seven, minutes at C., and, then cured at 7 original di- 1 mensions for three minutes at 160 1C; The 'cur ingstep amidq groups'is resistant to discoloration due to heat, and completely durable through the washes.

f.-EXAMPLE5- Y The vigorous 14-153 wasnesaranot'the only conditions Whichrnay encountered'i-n the use of arte'x- 'tile. A wrinkle-resistance :mu's' also be durable posure to solutions 6f thein'dica'ted pnsat 40 "CLfor thirty -minutes. The dinie'thylol "ethyleneurea "finish is re- 7 moved ap'pH sic-3.5, andfthe triaionefihish "removed was followed by an afterwash in warm water. with a nonionic detergent added, and then tumble dryingg The finished fabric possessed a crease recovery ahgleof 269 (Warp-'Ffill) while an untreated, afterwa'shed sample had a crease recovery angle of only l87 (w +'fi11) f 1 EXAM LE-4 -A sample of 80 x1 80 cotton 'print' cloth' w s treated a with a 10% bis(N-methylol carbamoylethyl) methylamine solution, and 1.5% magnesium chloride hexahy-tdrate as catalyst, as described in Example 3. This fabric;

samples finished with" 7 /2 -dimethylol lethyleneurea,

catalyzed by 0.5% zinc nitrate hexahydrate'-|+0.05%

acetic" acid; 7 /2% dimethylol ethyltriazone, 'catalyzed'by'g 0.5% zinc nitrate hexahydrate+ 005% acetic acid; and 7 /2% dimethylol dimethyl succinarnide, catalyzed by 0.5% nitrate hexahydrate, were'given S AATCC sistancej or nitrogen content of thefabric (96% 6f "the original nitrogencontefit retained) evens: pH

% of bis(N-methylol carbarnoylethyl)methylamine to a wet pickup of about from to drying the Wetted textile, curing the dried textile at a temperature of about from to C. for about from 0.5 to 10 minutes, the lower temperature being employed with the longer time intervals, to react said compound with the textile, and removing unreacted materials from the cured textile, thereby to produce a modified textile characterized in that it is wrinkle resistant, will withstand hypochlorite bleaching without damage to the textile, and is durable to laundering in which acidic or alkaline conditions are encountered.

r! 9 References Cited by the Examiner UNITED STATES PATENTS 2,203,493 6/40 Evans 8116.3

2,294,435 9/ 42 Wolf 8116.3

2,923,738 2/ 60 Williams 260--5 61 2,953,599 9/60 Welcher 260-561 FOREIGN PATENTS 1,072,082 12/59 Germany.

NORMAN G. TORCHIN, Primary Examiner.

JULIAN S. LEVITT, Examiner.