US2899263A

US2899263A - Eneurea

Info

Publication number: US2899263A
Authority: US
Priority date: 1949-08-15
Publication date: 1959-08-11
Anticipated expiration: 1976-08-11
Also published as: BE497571A; NL82933C; GB690237A; FR1023955A; DE878788C; CH306971A

Description

' possible. foregoing while at the same time affording much wider latitude with reference to conditions of treatment, and "especially the conditions during the mechanical treatment United States Patent PROCESS OF APPLYING DIMETHYLOL ETHYL- ENEUREA, PROPYLENEUREAS AND BUTYL- ENEUREAS TO CELLULOSE AND REGENER- ATED CELLULOSE FABRICS AND MECHANI- CALLY FINISHING THE FABRICS Albert C. Nuessle, Hatboro, and Peter J. McKone, Jr.,

Philadelphia, Pa., assignors, by mesne assignments, to

Joseph Bancroft & Sons Company, Wilmington, Del.,

a corporation of Delaware No Drawing. Application July 1, 1950 Serial N 0. 171,752

2 Claims. (Cl. S-116.3)

areas or in patterns.

Mechanical efiects on fabrics have been obtained with the aid of gums, starch, and other water-sensitivesubstances. These are not resistant to water or moisture and the effects are lost upon contact of fabric with water, as in washing. *This deficiency has in part been overcome by use of water-insoluble resins or formation of 'thermoset resins on or Within fabric. The application of resins to give mechanical effects is often not entirely satisfactory, however, as undesirable effects often result.

For example, resin-treated, mechanically-treated fabrics may be embrittled; they may have poor tear strength;

they have a hand which is objectionable for some uses. In addition the passage of the fabric through equipment for imparting mechanical effects must ordinarily be carried out under fairly closely controlled conditions, in order to avoid accumulation of deposits of polymerized resins on the equipment, for instance on glazing rolls. The accumulation of such deposits on finishing rolls is highly objectionable and troublesome, requiring shutdowns for cleaning.

It is an object of the present invention to provide mechanical effects which are highly durable, so that they will be retained after repeated launderings and dry cleanings of the fabrics, and to achieve this object while at the same time overcoming certain of the difficulties and objectionable characteristics of such finishes as obtained in accordance with prior practice. Thus, the invention not only provides the highly durable mechanical finish .but in'addition makes possible the retention of a soft hand, where that is desired, or the development of other types of hand where they are preferred, so that a wider variety of combinations of finish and hand are made The invention "still further accomplishes the to impart the desired mechanical finish. This greater According to the invention, instead of impregnating I the fabric with a relatively readily polymerizable resin,

'we have found that the use of certain dimethylol derivafives of the type mentioned below affords many striking ice advantages in the imparting of mechanical finishes to f abrics. In a typical treatment, a cotton fabric is impregnated with an aqueous solution of dimethylol ethylene urea and an acidic. catalyst- The impregnated fabrici's partially dried and mechanically treated or manipulated while in a moist or wet condition to impart the desired finish effect, then the mechanically treated fabric is heated at a temperature and for a time sufficient to react the cellulose of the farbic with the dimethylol ethyleneurea, The dimethylol ethyleneurea is Water solubleand we have found that this compound (and certain other related compounds mentioned hereinafter) readily reacts with the cellulose of the cotton fabric under the processing conditions substantially without polymerization and therefore without formation of an insoluble resin. Because of this, the tendency for this compound to form deposits on the mechanical treating equipment, for instance onja glazing roll, is greatly diminished, and this in turn makes possible greater latitude in the operating conditions used during the mechanical finishing, as compared with the practice where readily polymerizable resin forming materials are utilized. This greater latitude is manifested, for example, with reference to the quantity of moisture present during the mechanical'finishing operation. "In addition, greater latitude is permissible in the quantity of material applied to the fabric. Thus, on the one hand, much greater effect with reference to durability of is achieved according to the invention with a few or even a fractional percentage of the dimethylol derivative, than is possible with the same quantity of polymerizable resin forming impregnants. On the other hand, very large quantities of the "dimethylol derivative ranging even tip to 40% or 50% may be used for certain purposes, 'without encountering very stiff and boardlike handssuch as those resulting from similar quantities of resin forming materials heretofore used. 1

Still another general advantage of the treatment of the present invention is that a higher degree of durability with a lower degree of loss in strength is obtainable according to the present invention, as compared with the results where thermosetting resins are employed. Indeed, for certain mechanical effects a highly durable finish is obtainable according to the invention 'with little if any loss in strength of the fabric. This is especially true where relatively small percentages of the dimethylol derivative are utilized, but the improvement is pronounced even where substantial quantities are used, as will be pointed out more fully hereinafter. 1

The invention is applicable to a variety of fabrics formed from cellulose, especially to fabrics made of cotton, or rayon formed of regenerated cellulose such as viscose and cupro-ammonium rayons, or ramie, orv jute, or linen, or other cellulose fibers or cellulose derivatives which still contain hydroxyl grcups available for reaction with the dimethylol derivative. Mixtures of two or more such materials may, of course, also be treated. Cotton should be boiled off or at least free of waxes, and may, if desired, have been mercerized.

In addition to dimethylol ethyleneurea, certain other dimethylol derivatives may be employed, i. e., dimethylol 1,2-propyleneurea, dimethylol 1,3-propyleneurea (dimethylol trimethyleneurea), dimethylol 1,3-butyleneurea, dimethyl 2,3-butyleneurea. Mixtures of such compounds may also be utilized.

In considering the quantity of the dimethylol derivative to deposit on the fabric it is noted that this quantity will vary according to type of finish and hand desired, and according to the type of fabric being treated. For cotton fabrics the preferred range extends from about 3% to about 10% calculated on the basis of the weightof the bone dry fabric, i.e., the fabric with the natural free moisture content removed. However, even much smaller "phosphate, ammonium thiocyanate, or the like. monium salts develop acidity when theimpregnated fabricis heated. -When'free acid is used, it should be used percentages give appreciable eff ct, down to about .5% as is "shown in certain examples given hereinafter. On the other hand, the percentage inay also be increased above 1.0%, and may even be carried up to 20% or 30%. For most purposes goodiq'uality finishes are achieved up to aboutf20%, so that higher percentages are not ordinarily needed. U V V ,.f. .With regard to the quantity of the dimethylol derivative to be employed in the treatment of cotton fabric, the, strength-of the fabric should also be kept in mind, since the higher percentages tend to decrease the strength. Tlietextent, of 'loss instrength is not significant upto 1b0u t;.,12% or somewhat higher, but where strength is of "econdaryirnportance,quantities up to about 20% or 30% sa i.- b s as' b dica e V 111 In the treatment of rayon formed of regenerated cellulose; the quantity of the dimethylol derivative is preferably'somewhat higher than'that used for a corresponding 'cffiect on cotton fabric. Greater latitude is also permissihle in the case of rayon, For most purposes it is preferredto use at least 5% of the dimethylol derivative 'c'alculated on the weight of the bone dry fabric, and for most purposes this may be carried up to as high as 25%.

llioticeable effects are also achieved with rayon down to about 3.5%. On the other hand, very large quantities 'may be used in the treatmcntof rayon, even up to about 50%, without extensive loss in strength and also without producing a board-likehand, this result being very striking in comparison with use .of percentages of resin formi ng materials commonly employed in the prior art. Certain treatments evenwith as much as 30% to 40% of the dimethylol derivative have in some cases resulted in only very minor loss in strength. This is also in strikin'g contrast to the result where resins of the prior art a use -.7 I

, In connection with the mechanical finishing pressure it 'is' mentioned that in the caseof rayon the finishing machinery should not ordinarilyv apply as heavy pressure as can be used in treating cotton. This is especially true where embossing or other pattern effects are being imparted. ,V r p The concentration ofthe dimethylol derivative in the aqueous solution used to impregnate the fabric is not critical. Any concentration in the normal range conyenient for use with equipment for applying such solu- "'tions to cloth is acceptable. The solution may be applied either by immersion-and subsequent squeezing or by padding or other well known techniques in he textile finishing industry. a

An acidic catalyst should'be used for promoting the reaction between the dimethylol derivative and the' hydroxyl groups of the cellulose of the fabric being treated. The catalyst is conveniently applied inthe same solution as the dimethylol derivative; The acidic catalyst may be a freeacid, such asphosphoric, hydrochloric, acetic,

oxalic, tartaric,'p-toluenesulfonic, or the like; or an acid salt, such as sodium acid sulfate, or an ammonium salt of a strong acid, such as ammonium chloride, ammonium Arnat the lowest effective concentration. A range of 'concentration of acid of 0.1% to 2% of the total impregnating solution provides an effective amount of catalyst, al-

' though with strong acids the lower part of this range will 'be preferred and with weak acids best results are usually plied in the samesolution with the dimethylol derivative. Acidic solutions of these compounds are entirely stable This is one of the marked advantages for the use of thes dimethylol compounds as contrasted with solutions of ureaformaldehyde condensates and the like, which form resinous condensates in the presence of an acidic catalyst. In accordance with prior art technique using solutions of ureaformaldehyde condensates and the like, resort was frequently made to the use of delayed action catalysts and while these delayed action catalysts may alsorbe used according to the present invention, delayed action" not necessary because of the fact that the solutions are stable even in. the presence of substantial quantities of acidcatalysts which are active at room temperature. ,Thus, a wide selection ofcatalystsmay be employed, and this is another respect in which increase in'latitude of treatment conditions is permissible when following the technique of the present invention. 1.

The impregnating solution may contain in addition to the dimethylol derivative and catalyst a small amount of a wetting or penetrating agent. 'Such agent assists in the impregnation of fabrics, speeding up the process and ensuring uniformity of results.

The solution may still further contain materials acting as lubricants and/ or softeners some of such materials being mentioned shortly hereinafter. Onthis subjectit may be noted thatthe use oflubricants to facilitate the mechanical finishing operation, for instance glazing, is not of the same importance as in the prior art technique where various polymerizable resins are employed; and

hi s. a o r s in wh h Pr s nt nt o not being as critical as in the case of the polyriierizable resins heretofore used. his preferred that the moisture content be sutncient to; give a certain plasticity to the fabric which lends itself to realignment of fibers and molding of fibers and yarns to the desired shapes. n the case of cotton fabric the moisture content is preferably kept within from about 8% to 30% by weight of the bone dry fabric, and inthecase o f rayon made-from regenerated cellulose. the content is preferably kept from aboot 8% to about 20%. However, considerable leeway is permissible beyond either end of these two ranges. In the case'of either cotton or rayon the moisturemay even be taken downbelow the natural moisture content, for instance to about 5% of the bone dry fabric for cotton and to about 4% of the bone dry fabric for rayon, this being somewhat below the natural moisture content in each case. On'the other hand, the moisture content mayalso range upwardly even .to.60% in the cas'e .of cotton or about in the case of rayonJ. Even such hignpe r. centages do not adversely afiect the result of the treatment, althoughgreater times will be needed for drying and. heating the dimethylol derivative. with thefcelhilose after the mechanical treatment. .Heating the mechanical "to the fabric. {The fabric may be simultaneously dried,

i.e., may be dried in consequence of the heat and presing by other mechanical processes. chanical effect becomes substantially permanent after water-soluble. aldehyde condensate is insolubilized. Yet treatment of sure applied in the mechanical finishing, or it may be subsequently subjected to a drying operation. Moreover, since very small quantities of the dimethylol derivative may be used, and further since a very low moisture content may also be present during the mechanical finishing, the treatment in the mechanical finishing equipment may in some cases even completely effect reaction of the dimethylol derivative with the cellulose. This may for example occur by multiple passes through a heated friction calender. Thus, the heating to react the dimeth ylol derivative with the cellulose may be obtained either during the mechanical finishing; partly during the mechanical finishing and partly thereafter, or substantially all thereafter, as in an oven after passage of the fabric through the mechanical finishing equipment. In most cases, however, after the fabric is mechanically finished it is subjected to a separate heating treatment for the purpose of reacting the dimethylol derivative with the cellulose. This is ordinarily necessary in the case of use of a schreiner calender, or an embossing calender, where the fabric may be passed but once through the calender, subsequent oven treatment being required to complete the reaction of the impregnant with the cellulose of the fabric.

Where substantial moisture is still present in the fabric some drying should be effected prior to this final heat treatment.

Whether the heat treatment is effected either during the mechanical finishing or thereafter, the temperature of the fabric should be taken up to a point within the range from about 180 F. to about 400 F. in thecase of cotton and from 200 F. to 400 F. in the case of rayon. The time at such temperature will of course vary according to the temperature used, being from about 2 hours to 5 seconds in the case of cotton and from about 30 minutes to 5 seconds in the case of rayon. It is preferred to use a temperature for either cotton or rayon in the range from about 250 F. to 350 F. in which event the time should be from about minutes to 2 or 3 minutes.

The fabric may be further modified by use of known finishing agents. Thus, softeners, such as sulfonated oils, sulfonated tallow, or long-chained quaternary ammonium compounds may be used, being applied, if desired, in the impregnating bath or subsequent to the curing step. Similarly, if a harsher hand, increased body or stiifer fabric is required, the dimethylol derivative may be supplemented with sizing materials, such as starch, sodium polyaerylate, soluble cellulose ethers, ammonium salts or polymers of styrene-maleic anhydride, etc. In those cases where a stiff or papery finish is desired, there may even be used a small amount of a resinous finish, which is improved and supplemented by the reaction of cellulose and the dimethylol derivative. This process thus makes possible any hand from a very soft one up to harsh, wiry, or hard effects. Furthermore, quaternary ammonium salts which react with cellulose under heat, such as stearamidomethyl dimethyl benzyl ammonium chloride or cetyloxyrnethyl benzyl dimethyl ammonium chloride may be used to impart water-repellency to the fab- The mechanical efiects imparted to the impregnated fabric include embossing, development of a crepe-like finish, producing moire effects, continuous lusters, or other surface effects depending upon mechanical treatments. These effects may be obtained by pressing or stamping with plates, calendering, or chasing, or by treat- The particular me reaction of fabric and dimethylol compound.

It is an interesting consideration that when dimethylol ethyleneurea solution containing an acidic catalyst is dried on a glass plate for an hour at 300,.F., it remains Under the same conditions, a ureaformcellulose with dimethylol ethyleneurea gives a highly durable change in properties. Ureaformaldehyde can be used to stabilize and glaze, but the effect is gradually impaired on repeated alkaline washes. The differences between the two kinds of materials can be accounted for on the basis that dimethylol ethyleneurea reacts with cellulose whereas ureafonnaldehyde reacts primarily with itself. Furthermore, a much lower concentration of dimethylol ethyleneurea gives better dimensional stability to woven fabrics than is had by the use of ureaformaldehyde condensates.

Although we prefer. to use one of the five dimethylol derivatives hereinabove mentioned, it should be pointed out that corresponding dimethylol derivatives of certain thioureas may also be used, i.e., the dimethylol derivatives of ethylenethiourea,1,2-propylenethiourea, 1,3-propylenethiourea, 1,3-butylenethiourea, and 2,3- butylenethiourea. These thioure-a compounds also form stable solutions even where the solutions contain appreciable quantities of acidic catalysts and they also manifest a pronounced preference for reaction with the cellulose during the heat treatment, as compared with the tendency to polymerize to the insoluble state under the conditions of the treatment.

The following examples show typical procedures for finishing textiles according to the principles of this invention.

Example 1 A solution of dimethylol ethyleneurea was made in water and adjusted to 4% by weight. Ammonium chloride in an amount of 0.3% of the solution was added. A spun viscose rayon fabric was passed through this solution, squeezed free of excess solution, and dried to a 10% water content. The impregnated fabric was then embossed between plates at 260 F. for 30 seconds and cured at 300 F. for 10 minutes. A permanent embossed pattern was thus given the fabric". This pattern was well retained even after a 40' minute wash with a 0.1% soap solution, starting at 210 F. and dropping off to F.

Example 2 A dyed spun viscose rayon fabric was impregnated with a solution containing 12% of dimethylol ethyleneurea and 0.5% of ammonium chloride and squeezed free of excess solution. It was then partially dried and embossed between plates heated at 260 F. for 30 seconds. Curing followed at 300 F. for about 10 minutes. The embossed pattern was well retained on washing for 30 minutes at 160 F. with a solution containing 0.1% of soap and 0.1% of soda ash.

The embossed fabric was very soft and supple with a pleasant hand. It was changed less than one inch per yard in dimensions after being washed. Good dimensional stability is an important property provided by'the process of this invention.

Example 3 Spun viscose rayon fabric was padded through a. solution containing 4% of dimethylol ethyleneurea, 2% of a partially condensed, water soluble ureaformaldehyde resin, and 0.3% of ammonium chloride. The impregnated product was squeezed between rolls to remove excess solution and dried to a 10-12% water content. It was then embossed between patterned plates at 350 F. for 10 seconds and heated at 300 F. for 10 minutes.

The fabric then had a full, stilf hand and retained its embossed pattern after mechanical working and after being washed in a 0.1% soap solution at 180 F. for 40 minutes.

Example 4 Spun viscose rayon fabric was impregnated with an aqueousbath containing 4% of dimethylol ethyleneurea, fdispersed polyvinyl acetate, and 0.5% of am: meniurn' chloride. Excess solution was removed by pressure. The fabricwas then dried to a 12% water content, embossed between patterned plates at 300 F. for 20 seconds, and heated at 300 F. for 10 minutes.

The embossed fabric had a somewhat stiff, leathery hand which was retained after being washed in a 0.1% soapsolution at 180 F. for 40 minutes.

' Example 5 80 x 80 cottonfab'ric', which had been dyed, was impregnated in a solution containing 8% of dimethylol ethyleneurea, and- 0.5% of ammonium chloride. EX ce'ss solution wasrernoved by passage between rollers. The cloth'was dried to about an 8% water content, embossed between patterned plates at 260 F. for 30 secends, and heated at 300 F. for minutes. The resulting product was soft and full. The pattern was retained after a wash e210 F. to 160 F. in a 0.1% soap solution for 40 minutes. The product had good dimensional stability, shrinking less than one-third inch per yard.

Example 6 A piece of dyed cotton cloth was impregnated as in Example 5Qin a solution containing 2% of dimethylol ethyleneurea and 0.5% ammonium chloride. The impregnated fabric was partially dried to a still damp state and passed through a moire calendar at 300 F. The calendered fabric was heated at 340 F. for 2 minutes.

The fabric was soft with a well-developed moire effect. The effect was well retained after a 40 minute Wash-in 0.1 soap solution starting at the boil. Even after a second wash in 0.1% soap-0.1% soda ash solution at 180 F. no appreciable loss of the design was noticed.

Example 7 printed cottonfabric was impregnated with a solution containing 5% of dimethylol ethyleneurea and 0.5% of oxalic acid. Excess solution was removed by passage between squeeze rolls. The cloth was slightly dried, but while still damp was passed through a differential calender with a hot roll operating at 320 F. An excellent glaze was given to the fabric, yet it was soft with a pleasant handle. A wash at 210-l60 F. for 40 minutes in 0.1% soap solution did not dull the glaze.

Example 8 Example 9 A solution containing 6% of dimethylol ethyleneurea, of diammoniuin phosphate, and 0.3% of the ammonium salt of a soluble copolymer of styrene and maleic acid was applied to cotton cloth. Excess solution was removed by passage between squeeze rolls. The impreghated cloth was partially dried and given three passes through, a glazing calender at 360 F. No further cure was given. The product was a glossy, smooth fabric with a full, soft hand. The glaze was well retained when the cloth was washed in a 0.1% soap solution for 40 minutes, starting at the boil and dropping in temperature during the wash to about 160 F.

Example 10 A solutioncontaining 5% of dimethylol ethylenethiourea and 0.5 of ammonium chloride was used for impregnating cotton cloth. Excess solution was removed with-squeeze rolls and the cloth was allowed to dry partially. While still' somewhat damp, it was plain calendered with the rolls at 300 F. and then heated'at 300 F. for ten minutes. The fabric thus prepared had a smooth, lustrous finish, yet was soft and free of the usuallypap'ery hand associated with glazed cloth of the art. The finish was retained after the cloth waswashed in 0.1% soap solution at 180 F. for 40 minutes.

Example 11 An x 80 cotton perc'ale was padded through an 8% dimethylol'ethyleneurea solution containing 0;4% of ammonium chloride. The impregnated fabric was dried to 25% moisture content. Small areas of the fabric were then glazed by application of a discontinuous iron surface, i.e., having grooves therein so that portions only of the cloth were glazed. This was done at 400 F. for two seconds. The fabric was then dyed by boiling for 40 minutes in 1% Pontamine Fast Red 8BNL. The glazed areas were essentially undyed and retained their glaze un= changed, while the background not touched by the iron was dyed a bright red and had no luster.

Example 13 A paste comprising 4% of dimethylol ethyleneurea, 0.75% of Keltex (a refined algin), and 0.25% of ammonium chloride was printed onto a plain weave cotton fabric by means of an engraved roller. The fabric was partially dried and then given three passes through a glazing calender at 320 F. The resulting fabric was rinsed in water and then dyed in a 1% Pontamine Fast Red 8BNL solution. The printed area was pink with a glazed surface, while the background was dark red with no glaze. The effect was retained through several mild washings in soap solution.

Example 14 An 80 x 92, 3.50 cotton fabric was impregnated in a water solution containing 10% of dimethylol ethyleneurea, 2.5 of s-di [1-(2 stearoamidoethyl)] urea monoacetate and 1% of 2-amino-2-methyl-l-propanol hydrochloride by dip padding and squeezed between rolls with enough pressure to leave approximately 80% pickup on the fabric based on the dry weight of the fabric. The fabric was frame dried to approximately 10% moisture. The impregnated fabric while still damp was then passed three times through a glazing calender operating at 350 F. and cured 2 hours at 180 F. This was followed by washing in 1% soap and 1.6% soda ash at 180 F., rinsing, and frame drying.

The glaze was very durable to a boiling 1% soap, 2% soda ash solution.

Example 15 An 80 x 92, 3.50 cotton fabric was padded as in Example 14 and frame dried to 5.1% moisture based on the bone dry fabric, and glazed three times by being passed through a glazing calender at 350 F. The glazed fabric was then cured minutes at 300 F., washed in a solution of soda ash and sodium oleamidoethyl sulfonate at 180 F., rinsed and frame dried.

The glaze was found very durable to a boiling soap and soda ash solution.

Example 17 A dyed spun viscose rayon fuji fabric was padded through a solution containing 15% of dimethylol ethyleneurea, 3% of s-di [1-(2-stearoamidoethyl)] urea monoacetate and 1 A% of 2-amino-2-methyl-l-propanol hydrochloride. The impregnated product was squeezed between rolls to leave approximately 80% pickup on the cloth based on the dry weight of the cloth. The cloth was frame dried to approximately 4.4% moisture based on the bone dry fabric, embossed at 400 F. followed by curing for 5 seconds at 400 F., washing in soap and soda ash, rinsing and frame drying.

The mechanical effect was found very durable to washing and dry cleaning.

Example 18 A dyed spun viscose rayon fuji fabric was impregnated with a water solution containing 35% of dimethylol ethyleneurea, 3 of s-di [1-(2-stearoamidoethyl)] urea monoacetate and 3% of 2-amino-2-methy1-l-propanol hydrochloride and squeezed between two rolls with sufiicient pressure to give approximately 84% pickup based on the dry cloth. This gave about 30% of dimethylol ethyleneurea on the cloth. The cloth was frame dried to approximately moisture, embossed at 400 F., cured 3 minutes at 270 F., washed in soap and soda ash at 160 F., rinsed and dried.

A very durable pattern was obtained.

Example 19 A pure80 x 92, 3.50 cotton fabric was impregnated with a water solution containing 20% of dimethylol ethyleneurea, 236% of s-di [1-(2-stearoamidoethyl)] urea mono-acetate and 1 /z% of 2-amino-2-methyl-l-propanol hydrochloride, and squeezed between two rolls with sufficient pressure to give approximately 100% pickup'based on the dry cloth. This gave about 20% dimethylol ethyleneurea on the cloth. The cloth was frame dried to approximately 10% moisture, and passed three times through a glazing calender heated to 400 F. The glazed fabric was then cured 4 minutes at 300 F., washed, rinsed and dried.

A very satisfactory durable finish was obtained.

Example 20 Example 21 A dyed viscose rayon fuji fabric was impregnated with the mix of Example 17 squeezed to leave approximately 85% pickup on the cloth. This means that there was 71% moisture on the cloth. The cloth was not dried but passed immediately through a pattern calender at 400 F cured 3 minutes at 270 F., washed, rinsed, and dried.

A durable finish was obtained.

Example 22 A dyed spun viscose rayon fuji fabric was impregnated in a water solution containing 4% of dimethylol ethyleneurea and 2% of 2-amino-2-methyl-l-propanol hydrochloride by dip padding and squeezed between rolls with enough pressure to leave approximately 86% pickup on the cloth based on the dry weight of the cloth. This gave substantially 3.5% dimethylol ethyleneurea on the cloth. The fabric was frame dried to approximately 7% moisture. The impregnated fabric while still damp was then embossed at 400 F. followed by curing for 4 minutes at 300 F., washing in soap and soda ash, rinsing and frame drying.

The effect was well retained after a 1% soap, 2% soda ash boil.

Example 23 A pure, singed, bleached cotton fabric was impregnated with a water solution containing 7% of dimethylol trimethyleneurea and 2% of 2-amino-2-methyl-l-propanol hydrochloride on a mangle with enough pressure so that the pickup of the cloth was i.e., the cloth after padding shows an increase of 90% over the dry weight of the cloth before padding, frame dried on a tenter frame at 260 F., so that it contained about 10% moisture, glazed by being passed through a heated friction calender three times, and then baked 5 minutes at 300 F., followed by washing and drying.

The luster on the fabric is fast to washing and dry cleaning.

Example 24 A dyed 80 x 80, 4.00 fabric was presized in an aqueous solution of 2.5% HOCH (CH OCH ),CH OH [with molecular weight above 1000 (polymerized ethylene oxide)] by dip padding and squeezed between rolls with suflicient pressure to leave approximately 75% pickup on the fabric. The fabric was frame dried.

A paste comprising 12% of dimethylol ethyleneurea, 70% of locust bean gum (4%) (i.e. 2.8% locust bean gum was dispersed in 67.2% water), and 2% diammonium phosphate was printed onto the presized fabric by means of an engraved roller. The fabric was can dried to a moisture content of 1012% of the printed area and then given three passes through a glazing calender at 350375 F., cured 3 minutes at 310 F. This was followed by washing in soap and soda ash, rinsing and frame drying.

The printed portion had a durable glaze while the unprinted portion had no glaze.

Example 25 A printed cotton fabric was impregnated with a solution containing 8% dimethylol ethyleneurea, 2% dimethyl trimethylol melamine, and 2% ammonium thiocyanate, by dip padding and squeezed to approximately 90% pickup. The impregnated fabric was frame dried to approximately 8% moisture and while still damp passed three times through a glazing calender at 360 F., cured 5 minutes at 300 F., washed in open width, rinsed and dried to width.

The fabric then had a firm hand, and retained its lustrous surface after several washes in soap and soda ash at 180 F.

Example 26 An 80 x 92, 3.50 printed cotton fabric was impregnated in a Water solution containing 0.5% of dimethylol ethyleneurea and 2% 2-amino-2-methyl-l-propanol hydrochloride by dip padding and squeezed between rolls with sufiicient pressure to leave approximately pickup on the fabric based on the dry weight of the fabric. The fabric was frame dried to approximately 10% moisture and embossed at 400 F. followed by curing for 5 minutes at 300 F., washing, rinsing and drying.

The mechanical effect is very durable to washing in hot soap and soda ash.

From the foregoing examples it will be seen that highly advantageous results are obtained in securing mechaniv 11 cal effects by impregnation of the fabric the defined dimethylol alliyleneu reas or alkylene thiou'rea's, followed mechanical-tfeatment and by reaction between the cellulose of the fabric and the dimethylol compound. The process is readily 'carried'through without danger of fiber embrittlement or any untoward effects. Relatively low concentrations of finishing reagent can be used. There is no problem of migration of such reagent, The finish is outstandingly durable, even when using only very small quantities of the dimethylolderivative. Along with a desired niechanical'effect or finish, there is developed in the fabric a high degree of dimensional stability. The treated fabric does not yellow when subjected to chloiinebleaches, asdo most melamine-formaldehyde resins; nor does it char -on ironingfollowing chlorination and rinsing, as do most urea-formaldehyde resins. The change in the nature of the cellulose is also shown by an immunity against direct dyes.

' The process is advantageous in that the-treating baths are stable and do not form resinous condensates on standing. The treating agent is non-volatile. The reaction between treating agent and cellulosic fabric is easilycontrolled. .The reacted fabric can be obtained in a soft and pliable form. Where other characteristics are desired, such as greater stiffness, more body,.or even a papery hand, these effects can be imposed upon the fabric modified by reaction with the dimethylol derivative. Such modification can be had either concurrently ivvith or subsequently to the procedural steps of this invention; Where mechanical effects in limited areas of patterns are desired, the dimethylol derivative is applied to the cloth only in'such areas as by printing, and highly advantageous pattern effects are obtainable in this way. While the'amount of dimethylol derivative applied in the case of patterns will of course be relatively small 'compared to the total weight of the fabric, nevertheless "with respect to the actual area of the fabric to whichit is applied, the amount of "methylol 'derivative'should be er the order herein set forth, namely from .5 up to about 50%, by weight.

Following the treatment described herein, it is desirable to wash the fabric in most if not all instances;

-' The present application is a continuation-in-part of our copending application Serial No. 110,464, filed August 15, 1949 now abandoned.

Weclaim: a

1. In the art of imparting a durable finish to fabric selected from the group consisting of cellulose fabrics and regenerated cellulose fabrics 'by applying a solution of an impregnant thereto and heating the impregnated fabric, the steps of impregnating said fabric with an acidic catalyst and an impregnant'comprising a dimethylol derivative in solution in water,'said dimethylol derivative being reactive with the cellulose of the fabric to produce a water insoluble reaction product under the conditions of heating, and then imparting a mechanical finish to the impregnated fabric by passing the impregnated fabric 12 through the nip of the rolls of a pressure calender, the dimethylolderivative impregnant being selected from the cla s s consisting of dimethylol ethyleneurea, dimethylol 1,2 pr opyleneurea, dimethylol 1,3-propyleneurea, dimethylol 1,3-butyleneurea, dimethylol 2,3-butyleneurea, and the quantity thereof applied to the fabric being from .5 to 50% of the weight of the bone dry fabric, the impregnated and mechanically finished fabric being heated to a temperature between 180 F. and 400 F. for a-tirn'esuflicient to effect reaction between the dimethylol derivative impregnant and the cellulose of the fabric, and

said dimethylol derivative impregnant being incapable of polymerization to a water insoluble state even at the temperature of said heating and the mechanical finishing beingeflfect'ed while the fabric contains from 4% to 70% of water'calcula ted on the weight of the bone dry fabric to thereby reduce formation and accumulation of water insoluble deposits of impregnant on the surfaces of the mechanical finishing rolls. a

2. In the art of imparting a durable finish to fabric 4 selected from the group consisting of cellulose fabrics and regenerated cellulose fabrics by applying a solution of an impregnant thereto and heating the impregnated fabric, the steps of impregnating said fabric with an acidic catalystandan impregnant comprising a dimethylol derivative insolution in-water, said dimethylol derivative being reactive 'Withthe cellulose of the fabric to produce a waterinsoluble reaction product under the conditions of heating, and then imparting a mechanical finish to the impregnated fabric by passing the impregnated fabric through the nip of the rolls of a pressure calender, the dimethylol derivative impregnant comprising dimethylol ethyleneurea, and the quantity thereof applied to the fabric being from- ;5 to-50% of the weight of the bone dry fabric, the impregnated and mechanically finished fabric being heated to a temperature between 180 F. and 400 F. for a time suflicient to effect reaction between the dimethylol derivative impregnant and the cellulose :of the=fabric, and said dimethylol derivative impregnant being incapable of polymerization to a water insoluble state even at the temperature of said heating and the mechanical finishing being effected while the fabric contains from 4% to of water calculated on the weight ofthe bonedry fabric to thereby reduce formation and accumulation of water insoluble deposits of impregnant on the surfaces of the mechanical finishing rolls.

References Cited in the file of this patent UNITED STATES PATENTS 2,103,587 Lantz et al. Dec. ;28, 1937 2,119,150 Bowen et al. May 31, 1938 2,121,005 Bener June 21, 1938 2,142,623 Whinfield Ian. 3, 1939 2,238,839 Watkins Apr. 15, 1941 2,373,136 Hoover et al. Apr. 10, 1945