US3324062A - Textile treating composition comprising a mixture of a urea-formaldehyde condensate and a triazone-formaldehyde condensate - Google Patents

Description

June 1967 GEORGE SHIU YIM POON 3,324,062

TEXTILE TREATING COMPOSITION COMPRISING A MIXTURE OF A UREA-FORMALDEHYDE CONDENSATEIAND A TRIAZONE-FORMALDEHYDE CONDENSATE Filed June 25, 1957 4 Sheets-Sheetl EFFECT OF DEPRESSANT ON ACROLEIN MODIFIED UREA FORMALDEHYDE TREATED FABRIC 6G CURED A'T l30 c.

wrrnou'r DEPRESSANT 1 PERCENT 1.055 m STRENGTH. our: TO CHLORINE RETENTION 0zen;ssm-r ADDED TO GIVE A CONSTANT TOTAL CONCENTRATION OF I596 1! 0 9 l2 I5 1 PERCENT ACROLEIN moumzp UREA FORMALDEHYDE J=l.

EFFECT OF DEPRESSAN'I' ON ACROLEIN MODIFIED UREA FORMALDE HYDE TREATED FABRIC 8 CURE!) AT I50C.

/ WITHOUT ospaessm-r PERCENT LOSS m STRENGTH our: TO CHLORINE RETENTION I /r A DEPRESSANT ADDED TO cm: A

coNs'rAN'r TOTAL CONCENTRATION 0F|59a I! Ii I 12 I5 PERCENT ACROLEIN MODIFIED UREA FORMALDEHYDE L lNVENTOR GEORGE SH/U VIM POON ATTORNEYS J1me 1957 GEORGE sI-IIu YIM POON 3,3

TEXTILE TREATING COMPOSITION COMPRISING A MIXTURE OF A UREA-FORMALDEHYDE CONDENSATE AND A i TRIAZONE-FORMALDE'HYDE CONDENSATE Filed June 25, 1957 4 Sheets-Sheet 2 EFFEC OF DEPRESSANT ON ACROLEIN MODIFIED UREA FORMALDEHYDE TREATED FABRIC 0 6c .CURED AT I70 0.

r WIT'HOU'T DEPREssANT PERCENT LOSS IN STRENGTH 7 DuE To CHLORJNE RETENTION DEPREssANT ADDED m cm A CONSTANT ToTAI. coI -4cENTRATIoN OF I594 I l I .I I6 I: I: I5 PERCENT ACRDLEIN MODIFIED UREA FORMALDEHYDE .1.=:.&

EFFECT OF OEPFLESSANT ON DIMETHYLOL UREA 0c TREATED FABRIC CURED AT wITI-IouT DEPRESSANT e0 l /I so PERCENT L055 IN STRENGTH DuE To CHLORINE RETENTION l 4 DEPaEssANT ADDED TO GIVE A CONSTANT TOTAL CONCENTRATION OF [5% o o J I I I2 I5 PERCENT DIMETHYLOL UREA INVENTOR 4:2.4- GEORGE SH/U VIM POON ATTORNEYS June 1967 GEORGE SHIU YlM POCJN 3,3 ,062

TEXTILE TREATING COMPOSITION COMPRISING A MIXTURE OF UREA-FORMALDEHYDE CONDENSATE AND A TRIAZONE-FORMALDEHYDE CONDENSATE Filed June 25, 1957 4 Sheets-Sheet 5 EFFECT OF DEPRESSANT ON DIMETHYLOL UREA l0 TREATED FABRIC CUFLED AT J I I DE PRESSANT 8O FE RC ENT LOSS IN STRENGTH DUE TO CHLORINE RETENTION DEPRESSAN ADDED TO GIVE A CONSTANT TOTAL CONCENTRATION OF I59,

DUE TO CHLORINE RETENTION PERCENT 9 DIMETHYLOL UREA METHYLOL UREA LII DEFRESSANT ADDED TO GIVE A CONSTANT TOTAL CONCENTRATION OF I591,

3 6 PERCENT DIMETHYLOL UREA INVEN TOR GEORGE SH/U VIM POO/V ATTORNEYS June 6, 1967 TEXTILE TREATIN Filed June 25, 1957 PERCENT L055 IN STRENGTH ouz TO CHLORJNE RETENTION EFFECT OF DEPRESSANT ON DIM TREATED FABRIC CU EORGE SHIU YIM POON G COMPOSITION COMPRI UREA FORMALDEHYDE CONDE TR IAZONE-FORMALDEHYDE SING A MIXTURE OF A NSATE AND A CONDENSATE 4 Sheets-Sheet 4.

ETHYLOL ETHYLENE UREA RED AT I50C.

WITHOUT DEPRESSANT CONCEA DEPRESSANT ADDED CONSTANT TOTAL C TRATION OF I596 TO GIVE A IOG EFFECT OF DEPRESSANT O TREATE D FAB J PERCENT DIMETHYLOL ETHYLENE UREA N TETRAMETH FUC CURED AT YLOL ACETYLENE DIUREA WITHOUT DEPRESSANT PERCENT LOSS IN STRENGTH DUE TO CHLORJNE RETENTION DEPRESSANT ADDED TO GlVE AOCONSTANT TOTAL C NCENTRATIO J i la PERCENT TETRAMETHYLOL ACETYLENE DIUREA INVENTOR GEORGE SH/U VIM POON ATTORNEYS United States Patent TEXTHLE TREATING CGMPOSITION COMPRISING A MIXTURE OF A UREA-FORMALDEHYDE CON- DENSEATE AND A TRlAZONE-FORMALDEHYDE CONDENSATE George Shin Yim Poon, Danville, Va., assignor to Dan River Mills, incorporated, Danville, Va., a corporation of Virginia Filed June 25, 1957, Ser. No. 667,824 27 Claims. (Cl. 260-2944) This application is a continuation-in-part of the following applications: S.N. 584,443 filed May 14, 1956, SN. 632,434 filed January 4, 1957 and S.N. 655,956 filed April 30, 1957 all now abandoned.

This invention relates to the production of wrinkle-resistant cotton textile fabric. More specifically, it relates to an improved method of producing such fabrics and to improved compositions for use in such methods.

An important object of this invention is an improvement of the properties of wrinkle-resistant cotton fabrics, particularly with respect to chlorine retention. Another important object of the invention is the broadening of range of treating conditions which may be employed to produce the desired fabrics and thereby providing means for facilitating production of wrinkle-resistant fabrics possessing exceptionally desirable properties. Another object of the invention is the production of cotton fabrics having a high degree of resistance to wrinkling and a high resistance to damage from retained chlorine throughout the normal life of the fabric.

These and other objects of the invention are accomplished generally by treating cotton fabrics in accordance with conventional manipulative procedures for achieving wrinkle-resistance using novel and new impregnating compositions which produce unexpected advantages in several directions, particularly in the area of depressing the damage resulting from retained chlorine.

COEFFICIENT OF CHLORINE DAMAGE It has been found that, within practical working limits, the degree of damage from retained chlorine is a function of the particular resin being used and not of the amount of resin being used. This means that, for any given resin, low solids on the fabric will be just as damaging as high.

Thus, it may be stated that each resin has a coeflicient of chlorine damage. The art of testing materials is not sufficiently developed to assign absolute values to these coefficients, but it is safe to say that the more commonly used resins have a coefficient of chlorine damage well above the desired limit, and arbitrary values based on present testing methods may be assigned with reasonable relative accuracy.

For purposes of this invention, the coefficient of chlorine damage for any given material may be expressed as the percentage of strength loss when tested by the AATCC test method 6952, of an 80 square cotton fabric made wrinkle-resistant by being impregnated with that material and 1% of 23% 'monoethanolamine hydrochloride, dried and cured at 150 C. for 70 seconds. By this test, the coefficient of chlorine damage for several known materials may be expressed thus:

Tetramethylol acetylene diurea 100 Dimethylol urea 85 Urea acrolein formaldehyde 6O Dimethylol ethylene urea 50 It will be understood that these figures are somewhat arbitrary in that the testing procedure used for measuring the damage from retained chlorine is not always reproducible from one laboratory to another laboratory. However, it has been established through a long period of 3,324,062 Patented June 6, 1967 ice testing that the relative values are reliable as long as the coefficient of chlorine retention is below 100. It will be realized that the figures represent an actual measurement of the percentage of strength loss and represents a tot-a1 strength loss which may be relatively less than it should be in relation to a resin shown as 60 or 85.

HIGHLY CHLORINE RETENTIVE MATERIALS The highly chlorine retentive materials used as one component of this invention may be defined as those Water soluble, thermosetting-resin forming, materials, which, when cured on cellulose fabrics, will produce a substantially higher degree of wrinkle resistance than that produced by the same unit quantity of the depressant as defined below, which contains a plurality of reactive nitrogen groups reacted with formaldehyde, and which has a coefficient of chlorine retention as defined above at least as high as that of dimethylol ethylene urea.

Urea formaldehyde is probably the most important of these materials because it is inexpensive and it produces a high degree of wrinkle resistance per unit quantity. Urea formaldehyde is most commonly used in the form of dimethylol urea, but there are many other closely related urea formaldehydes which fall within the scope of this invention. Also within the scope of this invention are the following specific compounds:

tetramethylol acetylene diurea acrolein modified urea formaldehyde thiourea formaldehyde dimethylol ethylene urea dicyandiamide formaldehyde DEPRESSANT hyde. These same depressants may also be defined in terms of their method of manufacture. They may be prepared by the reaction of a dimethylol urea. with a primary amine and an appropriate amount of formaldehyde. A mono-amine produces one triazone ring and a diamine produces two triazone rings in a single molecule.

These same depressants may also be defined in terms of the following structural formula:

wherein R is selected from the group consisting of hydrogen, methylol and methoxymethyl; R is selected from the group consisting of hydrogen and an alkyl group having no more than three carbon atoms; R is selected from the group consisting of hydrogen, an alkyl group having from 1 to 4 carbon atoms, an alkanol group having from 1 to 4 carbon atoms and an aliphatic group having from 2 to 6 carbon atoms and being connected at its opposite end to the 5 position of a tetrahydro-2(1)-s-triazone group falling within this definition; and R is selected from the group consisting of hydrogen, methylol, methoxymethyl, an alkyl group having from 1 to 4 carbon atoms and an aliphatic group having from 2 to 6 carbon atoms and being linked at its opposite end with the 3 position of a tetrahydro-2(l)-s-triazone group falling within this definition and wherein the compound contains at least one group selected from the group of methylol and methoxymethyl.

The term triazone formaldehyde has been employed throughout the specification and claims as a simple term to designate the products included in the structural formula just defined and as further explained in the two preceding and the two following paragraphs.

These triazones are well known compounds. The triazones, per se, are described, for example, in Patent No. 2,016,521, issued in 1935 to Steindorfif and Paquin. Some of the triazone formaldehydes of this invention are disclosed in Martone Patent 2,641,584 of .1953. The corresponding formaldehyde derivatives of thiotriazones do not function satisfactorily in the process of this invention.

Thus, the three sub-species of triazone formaldehyde in this invention are defined by the following empirical formulas:

A mono triazone A bis triazone with a. 1,3 aliphatic linkage II ll O A bis triazone with a 5,5 aliphatic linkage I I I I N-CH CHN Certain advantages may be realized by using as the depressant 1,3-dimethylOl-S-ethyI-tetrahydro 2(1)-s triazone and much of the scope of this invention has been determined in terms of tests made with that product.

GENERAL DESCRIPTION The conventional procedure for producing wrinkle resistant fabrics is to impregnate the fabric with an aqueous solution containing an acid catalyst and a resin forming material after which the impregnated fabric is heated to dry the fabric and cure the resin. The most difficult problem in this process has been that the processes which produce high wrinkle resistance also produce high damage from retained chlorine, commonly referred to as the problem of chlorine retention.

Numerous suggestions have been made for eliminating chlorine retention. Some of these ideas have been meritorious and others have met with failure and yet even the most meritorious ones have not been entirely satisfactory.

The gist of this invention is the improvement of the conventional process of making textile fabrics wrinkle resistant by using at least two components in combination as the material for effecting wrinkle resistance. One component is a resin forming material which produces high wrinkle resistance but which also has a high coefiicient of chlorine retention. The other component is a chlorine damage depressant which has just been defined and which is also a resin forming material, but one which produces a relatively low degree of wrinkle resistance. The primary advantage of the invention is the securing of cellulose fabrics having high wrinkle resistance and low damage from retained chlorine retention.

An especially advantageous feature of this invention is that impregnating solutions containing triazone formaldehyde depressant may be applied by conventional procedures and the process remains responsive to other procedures for reducing chlorine retention damage, thereby enabling assurance of elimination of damage from retained chlorine.

The triazone formaldehydes of this invention also produce some wrinkle resistance and therefore are especially suited for this depressant purpose.

The important fact of this invention is not that these triazone formaldehydes are resistant to damage from retained chlorine, but that they also have the unexpected property of strongly depressing the coefficient of chlorine damage of other less expensive resin-forming materials.

Those resin-forming materials which have a lower coefficient of chlorine damage are easily converted to a safe coefficient of chlorine damage while those normally possessing a higher coefiicient of chlorine damage are more difficult to master and they require a much larger amount of triazone formaldehyde to accomplish the desired result.

Another outstanding advantage of the triazone formaldehydes is their ability to maintain the depression of the coefiicient of chlorine damage of resin treated fabrics on subsequent laundering. Fabrics treated in accordance with many prior procedures for obtaining resistance to damage from retained chlorine will produce satisfactory results on initial tests, but after 5-l0 commercial launderings will show a marked reduction of their resistance to this damage so that the splendid results which were initially obtained will be absent in the later stages of normal fabric usage. However, fabrics treated in accordance with the present invention retain their resistance to damage from retained chlorine even after repeated commercial launderings, thus protecting the fabric during its normal, useful life.

Other important features of this invention include new methods of manufacturing particular chemical products useful in fabric treatment as well as the chemical products themselves. These feat-ures are considered separately below.

FABRIC PROCESSING This invention has its greatest value in the treament of cotton fabrics where the sensitivity of the fabric to a hard cure makes the problem of eliminating damage from retained chlorine a severe one. At the same time, the beneficial results of the invention may also be realized in the treatment of other cellulose fibers such as rayon and linen.

Obviously, the preferred way of carrying out the invention is to impregnate the fabric with a single solution containing the two components of the invention, namely a depressant resin forming material and a resin forming material which has both a high wrinkle resistance value and a high coeflicient of damage from retained chlorine. However, it has been found that the advantages of the invention may still be realized if the fabric is first treated according to conventional procedure with first one of the components and later run through the same steps using only the other component as the resin forming material. The sequence in which the two materials are used appears to be immaterial.

In carrying out the present invention one may refer to the prior art for determination of the exact nature of the generally old processing steps. For example, it is conventional to apply resin forming materials to textile fabrics from aqueous solutions and such technique is used in this invention. It is conventional to use an acid catalyst. The range of satisfactory catalysts is well known. Among the satisfactory ones are zinc nitrate, calcium chloride, tartaric acid, monoethanolamine hydrochloride, 2-ethyl-2- amino-propanol-l-hydrochloride, magnesium chloride,

mixtures of these compounds and many others. Naturally some of these catalysts are better than others in specific applications of the invention, but in general, any of the known catalysts may be used successfully in the practice of this invention.

In the impregnation step, there has been considerable variation in prior art processing in that the fabrics being treated have been impregnated with from 50% to 150% of their weight of the aqueous treating solution. Such a range is entirely within the scope of this invention. How ever, as a practical matter it has been found desirable to impregnate the fabric with from about 65% to 75% of its weight of solution. In the step of heating the fabric to dry the fabric and cure the resin, there are also known variations. Some prefer to have a separate drying step followed by a curing step. Others combine the steps. This invention is susceptible of either mode of operation. The time and temperature of these steps are likewise the subject of much variation from plant to plant and often even within the same plant. In most plants, the time of treatment is arbitrarily fixed in accordance with the capabilities of the particular equipment being used and then the temperature of the cure is varied to achieve the desired degree of curing. These curing temperatures may vary anywhere from 120' C. to 200 C. and the time may vary from one minute to five minutes. It is well known that damage from retained chlorine is reduced by a hard cure, that is, that the longer the time and the higher the temperature of the cure, the lower the damage that will be caused by retained chlorine in wrinkle resistant fabrics. This is, of course, limited by the fact that a hard cure also degrades fabric. Thus, in the practice of the present invention it would appear desirable to use a relatively hard cure, but the advantages of the invention may be realized throughout the range of normal curing conditions. Sometimes the advantages of the invention are most strikingly revealed in operations at the lower temperatures. This is of extreme importance to production because this invention enables the curing conditions to be so regulated as to materially reduce the tendency to overcure and degrade fabrics. In other words, high production with low seconds may be directly attributable to this invention.

Still another variable is the amount of resin forming material deposited on the fabric. Some fabrics are treated to make them merely wrinkle resistant so that wrinkles will hang out of the fabrics overnight. Other fabrics are treated to produce the so-called wash and wear effect. In the latter case, the amount of resin forming material is much higher than in the former. In the latter case it is also common to use any of a large number of additives, such as thermoplastic resin emulsions, water repellents, softeners, lubricants and the like. This invention may be very successfully used in either of the above applications. In some instances, the amount of resin forming materials may be as low as 5% and in other instances it may be as high as 40%.

Yet another variable in the field is the quantity of catalyst to be used. Some base the quantity of catalyst on the amount of resin and others base it on the amount of fabric or the nature of the fabric. An alkaline fabric will require more catalyst than a neutral fabric. It is an outstanding feature of this invention that its benefits and advantages may be realized over an extremely wide range of catalyst concentrations. Ordinarily the amount of catalyst will be in the nature of from about 0.5% to 3% based on the total weight of the solution.

RATIO OF DEPRESSANT TO HIGHLY CHLORINE RETENTIVE MATERIAL There are no clearly defined limits which may be used to express the exact ratio of the resin forming components of this invention. The problem is somewhat complicated by the fact that there are no established standards of what is and what is not a commercially satisfactory level of damage from retained chlorine. It will be apparent that even minute quantities of the triazone formaldehydes of this invention do have a beneficial effect in the lowering of the damage from retained chlorine of the resin forming materials having a high coefficient of chlorine damage. By the same token, it will also be realized that there are no established standards of wrinkle resistance. This is especially a problem with the advent of wash and wear fabrics. However, it is well established that every textile finisher is seeking the highest possible wrinkle resistance he can economically obtain without placing goods on the market in such condition that they are apt to be returned because of fabric degradation. Thus, as a practical matter, each user of the present invention will want to regulate the ratio of the components of this invention to enable use of the largest possible relative amount of the resin forming component having a high wrinkle resistance value without risking fabric damage from retained chlorine below what is considered to be a safe level. It appears that a molar ratio of components in the nature of from about 1:10 to 10:1, respectively, defines the area of most desirable operation in accordance with the invention. It will be understood that this mol ratio is based on a monotriazone as distinguished from the his triazones which are theoretically twice as effective.

The molar ratio of 1:10 to 10:1 merely defines the broader limits of the invention and in practice, the actual ratio of compounds will be regulated within that range in accordance with the specific triazone formaldehyde used, the specific highly chlorine retentive material used and the arbitrarily established values being sought.

It has been found that the purity of the triazone has a definite relationship to its value as a depressant. Some of the triazones are not produced in anything like the theoretical quantities and yet they may be satisfactorily used in the impure state because it is cheaper to use an excessive quantity of the impure product than to practice the processes required for purification.

To illustrate the variations in satisfactory molar ratios, an impure 1,3 -dimethylol-S-ethyl-tetrahydro-Z(l)-s-triazone was prepared by heating one mole of dimethylol urea with one mol of ethylamine under alkaline aqueous conditions for about two hours and this product was thereafter reacted with two mols of formaldehyde as formalin and adjusted to about pH 5.5. Theoretically, this product contained one mol of triazone formaldehyde, This product was then used in varying quantities with dimethylol urea, dimethylol ethylene urea, *acrolein modified urea formaldehyde and tetramethylol acetylene diurea for the purpose of establishing the relative molar quantities required to be used in depositing 8% SOlids on a cotton fabric while retaining what is arbitrarily considered a safe level of damage from retained chlorine. Under these conditions, it was found that the minimum amount of triazone formaldehyde for each mol of resin was as follows:

Mols

Dimethylol urea 1.0 Dimethylol ethylene urea 0.1 Acrolein modified urea formaldehyde 0.5 Tetramethylol acetylene diurea 2.0

In contrast to these results, a mixture of dimethylol urea and 1,3-dimethylol-5 ethyl-tetrahydro-2(1)-s-triazone was prepared by reacting less than a stoichiometric amount of ethylamine with dimethylol urea under aqueous alkaline conditions and thereafter adding the theoretical amount of formaldehyde required to methylolate the newly formed triazone. Apparently this product resulted in a triazone of higher purity because a variation of the theoretical mol ratios of the triazone formaldehyde and unreacted dimethylol urea resulted in a finding that only 0.3 mol of triazone formaldehyde was required for each mol of dimethylol urea to produce the same satisfactory degree of damage from retained chlorine as in the previously listed illustrations.

The upper limit of 10 mols of triazone for each mol of resin is somewhat arbitrarily established, but it is believed that the most practical range of operation is with a maximum safe amount of the highly chlorine retentive material which produces a higher wrinkle resistance value.

Thus, it will be seen that the broader aspects of this invention have been described in terms of the means which may be used to depress the chlorine damage of wrinkle resistant fabrics and the products used in connection therewith.

There are also modifications or other aspects of the invention which are also important.

PRE-POLYMERIZED RESIN One such aspect of the invention relates to the manufacture of wrinkle resistant textile fabrics characterized by a relatively stiff hand or feel. It also relates to prepolymerized urea formaldehyde type resin forming materials which are water soluble and suitable for application to textile fabrics to impart stiffness and body while producing wrinkle resistance and dimensional stability. Such resin forming products may be used on cotton and rayon fabrics, as well as on nylon, acetate and other woven and knit textile fabrics.

A great disadvantage of the water soluble prepolymerized urea formaldehyde type resin forming materials which have heretofore been used for these purposes is their limited stability. Another distinct disadvantage of these materials is that on application to cellulosic fabrics, and particularly cotton fabrics, they retain chlorine which often damages the strength of the fabric on subsequent processing, particularly in chlorine bleaching.

One object of this aspect of the invention is the provision of a highly stable, water soluble, partially prepolymerized, urea formaldehyde type resin. Another object of this part of the invention is the provision of stiffened cellulosic fabrics having an excellent wrinkle resistance and dimensional stability which are retained even after commercial white washing. Still another object of this part of the invention is the provision of a cellulosic textile fabric having the aforementioned characteristics and at the same time having a high degree of resistance to chlorine yellowing and damage from retained chlorine which are also retained on commercial white Washing. It is also an object of this part of the invention to provide means for adjusting the stiffness of textile fabrics and it is still .a further object of the invention to accomplish the above-named objectives by a process of extreme simplicity, using materials of an inexpensive nature.

The advantages of that aspect of the invention described above are incorporated and preserved in the practice of this aspect of the invention. However, the gist of this part of the invention is the discovery that the combination of the triazone formaldehydes with urea formaldehyde may be pic-polymerized to produce stiffening agents of unexpected stability. It is also considered an important part that this added stability and stiffness can be attained without sacrificing the other benefits of my prior invention.

Generally, the objects of this part of the invention are accomplished by the preparation of a mixture of urea formaldehyde and a triazone formaldehyde which is then reacted by heating for a predetermined time at a predetermined temperature on the acid side, thereafter applying the thus formed product to a textile fabric from a water solution, preferably containing an acidic catalyst, after which the fabric is heated to effect drying and to cure the resin.

The formation of the mixture of the urea formaldehyde and the triazone formaldehyde may be effected in any of a number of ways. In some instances, the previously formed triazone formaldehyde and urea formaldehyde may be mixed together in the desired proportions or in other instances one may first form a triazone formaldehyde and thereafter add urea and formaldehyde separately. Still another technique for some triazone formaldehydes is to first add the desired amount of urea formaldehyde and add an amount of a primary lower alkyl amine sufficient to produce the desired mol ratio of urea formaldehyde and triazone formaldehyde. In any of these events, the desired mixture is subsequently heated and finished off on the acid side.

Still another and the preferred method of producing the pre-polymerized fabric treating product of this invention is to react a primary amine such as monoethylamine with urea and an urea formaldehyde concentrate in one portion, after which a second portion of urea formaldehyde concentrate and urea are added to the first portion (the urea formaldehyde concentrate contains an excess of formaldehyde and has a ratio of 60% formaldehyde to 25% urea and the balance water). This will produce a mixture of dimethylol urea and 1,3-dimethylol-5 ethyl-tetrahydro-ZU)-s-triazone. As in the prior instance, the mixture of urea formaldehyde and triazone formaldehyde will polymerize on the acid side.

It will be understood that the stiffening properties of the final product will necessarily be a function of the time and temperature of the pre-polymerization, as well as the pH at which the reaction is carried out and the mol ratio of the urea formaldehyde to the triazone formaldehyde.

The number of. variables which must be taken into account in carrying out stiffening in that part of the present invention are quite high and the permissive range of any one variable is dependent upon the conditions chosen for the other variables. For this reason it is almost impossible to set a specific pH range, a time range, or a temperature range. Further complicating the picture 15 the fact that the specific end use of the pre-polymerized resin product will require difierent conditions.

However, by arbitrarily choosing standard conditions for certain of the variables and varying one condition, such as time, one skilled in the art may readily obtain a Wide range of products having all the beneficial properties of this invention.

Despite the difiiculties attendant to the presentation of numerical values for the permissive ranges of the variable conditions, there are certain known relationships which may be used as guiding principles to enable one skilled n the art to accomplish the objectives of this invention in a large number of ways.

For example, for any given degree of polymerization and any given mol ratio of reactants, the shorter the time of condensation, the lower the pH and/ or the higher the temperature required. Or, stated another Way, the higher the pH, the longer the time and/or the higher the temperature required. Or, stated still another way, the lower the temperature, the longer the time and/or the lower the pH required. If one desires to increase the stiffening properties of the resin being produced this can be done by increasing the time or increasing the temperature of lowering the pH of the reaction.

The end product may also be varied by varying the mol ratio of the reactants, and the greater the amount of urea formaldehyde in relation to triazone formaldehyde the more stiffening will be obtained. However, if the amount of urea formaldehyde is increased, less strenuous conditions of pH, time and temperature are required for the same degree of polymerization.

Actually the permissive ranges of the reaction conditions and mol ratios permitted by the scope of the present invention can be varied to highly impractical limits. For example, it is theoretically possible to vary the time of reaction from an instantaneous time to an almost infinite time. Of course, as a practical matter, one would choose a relatively short time, say from 15 minutes to two hours. Similarly, the temperature of the reaction could theoretically be anywhere from room temperature to the boiling point of the reaction mixture but, again,

as a practical matter, the reaction temperature should be a moderate one to enable maximum flexibility and control.

The pH of the mixture during pre-polyrnerization may be extended over almost the entire range of acidity, provided the other conditions are suitably modified. Yet as a practical matter, the pI-l should be in a median range, preferably standardized to permit the end product to be varied by such easily controlled conditions as time and temperature.

There does not appear to be any sharp break point defining the limits of the mol ratios of reactants which may be used to obtain the benefits of this invention. If one chooses to obtain all the benefits of the broader aspects of this invention, the limits defined in the earlier portion of this application should be followed. However, for purposes of obtaining only the stability improvements of the stiffening part of this invention, it appears that there is a direct proportion between the amount of triazone used (based on the number of triazone nuclei) and the stability of the product.

The stability problem solved by this invention is really a dual problem. If the degree of polymerization of the product is too great, the solubility of the product is reduced, because if polymerization is carried to its extreme limits, the product will set up into a solid mass. On the other hand, if the degree of polymerization is too small, a water-soluble precipitate will form. The range of products intended to be covered by this invention is the entire range between the polymerized products which will be water-insoluble and the range of partially polymerized products which are subject to the formation of a watersoluble precipitate.

SPECIAL UREA FORMALDEHYDE-TRIAZONE FORMALDEHYDE PREPARATION In one preferred modification, useful only where a urea formaldehyde is one of the highly chlorine retentive materials, especially beneficial results are obtained by preparing the triazone formaldehyde by the reaction of either dimethylol urea or an appropriate quantity of formaldehyde and urea with less than an equimolar quantity of primary amine groups. The advantage of this process is that its product produces a higher wrinkle resistance per unit quantity when applied to cellulose fabric with less damage from retained chlorine. It is believed that the reason for the advantage is that a triazone of high purity is obtained. Quantitative tests against triazone formaldehydes prepared from 100% pure triazones support this view.

The depressant effects on several resins have been established by careful test examples as will be apparent from the following.

DEPRESSANT EFFECTS ON ACROLEIN-UREA-FORMALDEHYDE The resin-forming material used in this series oftest examples was a condensation product of acrolein, urea and formaldehyde prepared generally in accordance with the procedure of US. Patent 2,600,780 issued to Franz Kohler June 17, 1952 by using the following ingredients:

Parts Formaldehyde (37%) 1525 Urea 425 Water 220 Acrolein 150 Glacial acetic acid 4 A series of fabric samples 37 inches long and 8 inches wide were cut from asingle bleached, mercerized, scoured and dried piece of plain woven cotton check running about 4.5 yards per pound. These samples were divided into three equal groups, A, B and C, for testing the effects of the depressant at three separate curing temperatures, namely, A170 C., Bl50 C. and C130 C.

Each group A, B and C contained 20 samples, divided into two equal subgroups of 10. The first subgroup (1) of each of the groups A, B and C was impregnated with varying amounts of acrolein-urea-formaldehyde. The second subgroup (2) of each was impregnated with acrolein-urea-forrnaldehyde in the same varying amounts, but a commercial 1,3-dimethylol-5-ethyl-tetrahydro-2(1)-s triazone, a depressant, was added to each sample in an amount sufiicient to bring the total solids of the impregnating solution to a constant solids content equivalent to 15% of a solution of acrolein-urea-formaldehyde.

Each dry sample was individually impregnated with about 65% of its own weight of an aqueous solution containing its specified concentration of resin-forming materials with or without depressant and further containing 0.5% monoethanolamine hydrochloride catalyst. The impregnated samples were air dried and subsequently cured at the respective temperatures of groups A, B and C.

These treated samples were washed, centrifuged, pressed, conditioned and then tested at standard conditions to determine the wrinkle resistance, strength properties and chlorine damage as measured by the AATCC Tentative Test Method 6952, Damage Caused by Retained Chlorine.

The wrinkle resistance of all samples in groups A(2), B(2) and C(2) was satisfactory. There was, however, a definite distinction between the wrinkle resistances of the A, B and C groups as would be expected in view of the well-known fact that higher curing temperatures produce higher measurements of wrinkle resistance.

The Wrinkle resistance of the A(1), 13(1) and C(1) groups was entirely satisfactory at the normal concentrations of resin-forming materials, but naturally fell off in the lower and impractical concentrations.

The'strength properties of the treated samples were all considered satisfactory.

The unexpected effect of the depressant is graphically illustrated in graphs 1, 2 and 3.

DEPRESSANT EFFECTS ON DIMETHYLOL UREA The experimental procedure of the tests used on acrolein-urea-formaldehyde were repeated without change except for the substitution of dimethylol urea as the resinforming material. The test results generally duplicated the pattern of the previous series as to wrinkle resistance and strength properties. The depressant effects are illustrated graphically in graphs 4, 5 and 6.

Other depressants and other resin-forming materials have not been so thoroughly investigated, but the repetition of the pattern of depressant effects have been clearly demonstrated by following the B group of the experimental example outlined above for dimethylol ethylene urea and tetramethylol acetylene diurea with the results illustrated in graphs 7 and 8.

It will be noted that the resistance to damage caused by retained chlorine is not always completely eliminated in some of the tests, particularly when using such highly chlorine retentive materials as tetramethylol acetylene diurea. However, it is clearly shown that the coefficient of chlorine damage of each resin is greatly depressed by the triazone formaldehydes of this invention. Thus, it will be clear that the gist of this invention is the depressing of the coefiicient of chlorine damage of those resins which are subject to this difliculty.

It is believed that those skilled in the art will have no difliculty in carrying out this invention on the basis of the examples and graphs presented above, but the following typical examples illustrate prefenred procedures for carrying out the invention.

Example I 51.9 pounds of dry urea were added with stirring to 1059 pounds of a urea formaldehyde concentrate containing 25% urea and formaldehyde in water. To this, 290 pounds ofa monoethylamine solution (71% solution in water) was added slowly with cooling to keep the temperature below 140 F. After the addition was complete, reaction was continued for about two hours at 155 F. and the pH was adjusted to pH 5.5-6.0 after which the temperature was raised to 160 F. for 1 /2 hours. This product was cooled to 120 F. and the pH was adjusted to pH 4.4-4.8. This second heating stage was used to stabilize the product and assure uniformity of results.

This final product was a mixture of dimethylol urea and 1,3-dimethylol-S-ethyl-tetrahydro 2(1)-s-triazone in a molar ratio about 1:6.3 respectively, with a slight excess of formaldehyde.

An aqueous solution of 12% of this product (about 70% solids) and 1 /4% of a 50% solution of monoethanolamine hydrochloride was prepared and a plain woven, bleached, mercerized and soured 100% cotton gingham running about 4 /2 yards per pound was impregnated with about 65% of its own weight of this solution. The impregnated fabric was dried at 200 F. and cured at 300 F. for 70 seconds.

The chlorine retention damage of the fabric which would be expected to be high because of the urea formaldehyde, was tested and found to be about equal to an untreated fabric. The wrinkle resistance was tested and found excellent with little loss of strength properties. This procedure has been used commercially on approximately 1,000,000 yards of fabric with remarkable uniformity of low damage from retained chlorine.

Example II A condensation product of acrolein, urea and formaldehyde was prepared generally in accordance with the procedure of US. Patent 2,600,780 issued to Franz Kohler June 17, 1952, using the following ingredients:

Parts Formaldehyde (37%) 1525 Urea 425 Acrolein 150 Water 220 Acetic acid 4 One part by weight of this product (45% solids) was mixed with three par-ts by weight of 1,3 dimethylol-5- ethyl-tetrahydro-2(1)-s-triazone (50% solids).

A plain woven bleached mercerized and soured 100% cotton gingham fabric running about 4 /2 yards per pound was impregnated with about 65% of its own weight of an aqueous solution containing 1% of a 23% solution of monoethanolamine hydrochloride catalyst and 15% of the above described mixture. The thus impregnated fabric was dried at 200 F. and cured at 300 F. for 70 seconds.

The wrinkle resistance of the treated fabric was found to be high and the strength properties of the fabric were excellent. The damage from retained chlorine was uniformly low contrary to normal expectations.

Exmnple III A plain woven bleached mercerized and soured 100% cotton gingham fabric running about 4 /2 yards per pound was impregnated with about 65% of its own weight of an aqueous solution containing about 1% of the 50% solution of monoethanolamine hydrochloride catalyst, and about 15% of a mixture containing one part of a 50% solids solution of dimethylol ethylene urea and one part of 1,3 dimethylol 5 ethyl tetrahydro-2(1)-s-triaz0ne (50% solids).

The thus impregnated fabric was dried at 200 F. and cured for 70 seconds at 320 F. The treated fabric had excellent wrinkle resistance, strength properties and resistance to damage from retained chlorine. This procedure has been used commercially on both plaids and all whites with uniformly good results.

Thus it will be seen that the gist of the present invention is the depression of the damage caused by retained chlorine in resin treated fabrics by the addition of the specified triazones to the fabric impregnating solutions.

It will be obvious that the depressants of this invention are useful with mixtures of highly chlorine retentive resins as well as individual resins. This is illustrated in the following example:

Example IV The procedure of Example I was repeated using, in place of the final resin forming mixture alone, a mixture of 193 parts of that product and 307 parts of a 50% solution of dimethylol ethylene urea. The results of Example I were generally duplicated in an extended test of commercial production.

Good results were obtained with other 1,3-dimethyloltetrahydro-2(1)-s-triazones including the unsubstituted product, the 5 methyl product, the 5 propyl, the 5 isopropyl, the 5 ethanol and the 5 propanol. These results vary somewhat from product to product but the general pattern of results is always very similar.

Example V A mixture of dimethylol urea and 1,3 dimethylol-5- ethyl-tetrahydro-2(1)-s-triazone in a mol ratio of about 1 to 1 was prepared using the following ingredients:

Portion A: Parts Urea formaldehyde concentrate- (Allied Chemical) (60% formaldehyde, 25% urea and the balance water) 1000 Urea 40 Monoethylamine (71%) 320 Portion B:

Urea formaldehyde concentrate-85 (Allied Chemical) 540 Urea 185 The urea formaldehyde concentrate-85 and urea of portion A were mixed. The monoethylamine solution was added slowly, keeping the temperature 'below F. by cooling. This mixture was heated to F. and held at that temperature for one hour and 20 minutes, after which it was cooled slightly and a previously prepared mixture of the components of portion B were added. This mixture was heated to about 160 F. for 15 minutes, after which it was cooled to about 120 F.l30 F. and then adjusted to pH 5 plus or minus 0.1. At this stage the intermediate product was a mixture of dimethylol urea and dimethylol triazone ready for the pre-polymerization step.

Pre-polymerization was carried out as follows: This intermediate product was then heated to 160 F. for one and one-half hours after which it was cooled and adjusted to pH 5-pI-I 5.5. The final product was a viscous clear syrup Water soluble in any and all proportions. In other runs of this experiment the last heating cycle (on the acid side) was varied to obtain different degrees of stiffening properties on textile fabrics. It was found that the longer the heating cycle, the greater the degree of polymerization and accordingly the greater the stiffening effect of the product on a fabric treated therewith. Likewise, other experiments varying the pH of the final heating cycle and the time and temperature of the heating cycle also adjusted the stiffening properties of the final product in that a lower pH, a higher heating temperature, or a longer heating time would all increase the degree of polymerization and thus the stiffening of the final product.

The product prepared in accordance with the specified conditions of the above example was still water soluble in any and all proportions after more than five months storage at room temperature.

Example VI A pre-polymerized product containing the reaction product of dimethylol urea and 1,3, dimethylol-S-ethyl- '13 2(1)-s-tr'iazone in a molar ration of about 1 to l was prepared using the following ingredients:

. Parts Urea formaldehyde concentrate-85 (Allied Chemical) 1000 Urea 146 Monoethylarnine (71% 208 The urea formaldehyde concentrate-85 and urea were mixed and the monoethylamine was added slowly with cooling, keeping the temperature below 140 F. This mixture was then heated to 160 F. for one and one-half hours, after which it was cooled to 130 F. and adjusted to pH 5.5.

This mixture of urea formaldehyde and triazone formaldehyde was then pro-polymerized by being heated to 160 F.-1 65 F. for one hour. The final product was cooled and adjusted to pH 5. This product was also similar in appearance to the product of Example V, but it did not stiffen textile fabrics quite as much as that product. This product was stored at room temperature for five months and at the end of that time it was still water soluble in any and all proportions.

Perhaps the most unexpected result of the work forming the basis of the three examples above was the fact that the final products had a shelf life well above and beyond that of comparable products of the prior art. This is true not only of the specific triazone formaldehyde shown in the examples but also extends to the combinations of urea formaldehyde and the other triazone formaldehydes defined above.

The stability of the final product is somewhat responsive to its storage pH. It is almost infinitely stable when neutral or slightly alkaline. Of course, as the finished pH is lowered, there is a tendency for polymerization to continue, but for practical purposes this is negligible at no lower than pH 5. It is preferable to store the product in a slightly acid condition as alkaline products require excessive amounts of catalyst in application to textile fabrics.

Example VII The products of Examples V and VII were compared by application of each to a plain weave cotton gingham (about 4%. yards per pound) under identical conditions. The formula used in each instance was as follows:

% of the product of one of the above examples,

1% of a 23% solution of monoethanolamine, hydrochloride as a catalyst,

Balance water.

The fabric was impregnated with about 70% of its own weight of the abovesolution, dried to about 10% moisture content and cured at about 360 F. for seventy seconds in each instance. Each of the treated fabrics had a stiff and firm hand, a relatively high degree of wrinkle resistance, very low damage from retained chlorine and no tendency to yellow on treatment with hot Clorox. A comparison of the properties of the treated fabrics may be seen in Table I below:

linings of shirt collars Was treated with the following formula:

30% of the product of Example V,

4% corn starch (Hawk),

1% polyvinyl alcohol (Elvanol 72-60),

1% of a 23% solution of monoethanolamine hydrochloride as catalyst,

Balance water.

The fabric was impregnated with about 70% of its own weight of the above solution, dried to about 10% moisture and cured for seventy seconds at 360 F. Upon testing, this product was found to have an exceptionally high wrinkle resistance; namely, 3.6 x 3.6, according to the TBL test method. The fabric also had an exceptionally stiff hand which was permanent to washing. It also possesses the other desirable properties of the products of Example VII.

Example IX A plain weave rayon fabric (about 3 /2 yards per pound) was treated using the following formula:

15% of a product containing the product of Example I,

2% of a 23% solution of monoethanolamine hydrochloride,

0.5% of softener (Ahcovel G),

Balance water.

The prepared rayon was impregnated with about of its own weight of the above solution, framed and dried to about 8% moisture at a temperature of about 230 F. to 240 F. This fabric was then cured at 310 F. for six minutes, after which it was washed and framed according to the usual practice of the art. The thus treated fabric had an exceptionally firm hand similar to that of some finished linen fabrics. It had a TBL wrinkle resistance of 3.0 x 2.8, a trapezoid filling tear of 4.3 pounds, no damage from retained chlorine, no Clorox yellowing and ex tremely good dimensional stability. Dimensional stability was tested by AATCC standard test method 14-53 and after ten such washes the warp shrinkage was only 1.11% and the filling showed a gain of 1.39%.

The products of Examples V, and VI were also used as supplemental hand builders in fmishing rayon with other resin forming materials commercially used to provide dimensional stability and Wrinkle resistance, including acrolein-urea-formaldehyde resins and urea formaldehyde resins which had not been pre-polymerized. The products were exceptionally satisfactory in such uses.

With the combined properties of stiffening, wrinkle resistance producing, dimensional stabilization and low dam-age from retained chlorine, in addition to the good stability of the product, this textile treating product is distinctly different from the stiffening resins known in the prior art.

It should be noted that if the degree of polymerization is too great, the shelf life will be adversely effected, although the stiffening properties are increased and the assurance of low damage from retained chlorine is increased. There is a very wide range of satisfactory resin After ten commercial white washes the properties of forming materials which may be obtained in accordance the fabric had not changed significantly.

Example VIII A plain loose weave construction of cotton fabric with this part of the invention to meet the needs of specific uses.

Example X A resin-forming material suitable for treating textiles (about 4 yards per pound) intended to be used for inner was prepared by heating 0.37 mol of hexamethylene di- 15 amine with one mol of urea and four mols of formaldehyde as Formalin under alkaline conditions in water at about 180 F. A white solid product of undetermined constitution was found immediately. Heating at about 16 divided into two portions, one of which was cured for 70 seconds at 155 C. and the other of which was cured for 70 seconds at 180 C. The results of this example may be tabulated as follows:

Curing Wrinkle Chlorine Resin-Forming Material Tcmper- Resistance Tear Tensile Retention Reflectance ntnre (TBL) Strength Strength (Percent 111 0. Loss) P:oduct of Example X" 155 3.0 x 3. 2.15 30. 17 83.5 Product of Example X. 150 3.1 x 3.1 1.95 27. 5 5 81. 4 Product of Example XI. 155 3.1 x 3.1 1.90 27. 7 11 84. 2 Product of Example X1... 180 3.3 x 3. 3 1.70 24. 7 3 81. 5

1 Untreated.

180 F. was continued with stirring and the final product was formed after about seven hours. It will be seen that the final product was a mixture of dimethylol urea and triazone formaldehyde in a theoretical molar ratio of about 1 to 2.85 respectively. The particular triazone has the following formula:

The amount of water in the product was adjusted to bring the solids content to about 50% and the pH was adjusted to pH 5 with muriatic acid. The final product is a clear solution. If any solids remain, the product should be filtered.

Example XI A second product was prepared in the same manner with the exception that 0.25 mol of hexamethylene diamine was used in place of the 0.37 mol of the previous example. It will be seen that this changes the ultimate theoretical mol ratio to one to one.

Example XII A resin forming material suitable for treating textiles was prepared by heating 0.37 mol of hexamethylene diamine with one mol of urea and four mols of formaldehyde as Formalin at pH 6.06.9 in water at about 180 F.

A mixture of the reactants was formed in water without adjusting the pH. A white solid product of undetermined constitution was formed immediately. This mixture was heated at about 180 F. for about 30 minutes, after which the pH was adjusted to about pH 6.0 to 6.9 and heating was continued at the same temperature for another 1 /2 hours, to form the final product. This product was finished off as in Example X and the product was almost identical in appearance and reactivity to the product of Example XI.

Example XIII A resin forming material suitable for treating textiles was prepared by heating 0.50 mol of hexamethylene diamine with one mol of urea and four mols of formaldehyde reacted under the conditions specified in Example XII. The final product was a clear solution having the general appearance of the products of Examples X and XI.

Example XIV A series of comparative experiments were run to determine the effectiveness of the products produced in Examples X and XI as textile treating materials for the production of high wrinkle resistance with low damage from retained chlorine. In these experiments, a cotton After five severe cotton washes, these same samples still had almost identical physical properties, the only measured changes being in the nature of expected experimental error.

Example XV An aqueous solution was prepared containing 5% of the product of Example X111 (50% solids), 10% of a 50% solution of dimethylol ethylene urea and 1% of 23% solution of monoethanolamine hydrochloride as catalyst. A cotton gingham fabric was impregnated with about 75% of its own weight of the above solution. A second sample of the same fabric was impregnated with a solution prepared the same way except that the product of Example XIII was omitted. Both fabric samples were dried and cured at 170 C. for 70 seconds. The fabric containing the product of Example XIII was tested and found to have good wrinkle resistance, tear strength, tensile strength and low damage from retained chlorine. The similarly processed fabric without the product of Example XIII also had good wrinkle resistance, tear strength and tensile strength, but was found to have a considerably higher loss of strength from retained chlorine, with losses ranging up to 50%. On repeated laundering and retesting the good sample retained its'resistance to chlorine damage while the simple without the product of Example XIII became progressively more susceptible to chlorine damage.

Triazone formaldehydes similar to those described in Examples X-XV have been prepared and found satisfactory by replacing hexamethylene diamine with other aliphatic diamines including pentamethylene diamine and ethylene diamine.

Example XVI A triazone formaldehyde corresponding to the formula:

Fal s was prepared by adding 25 grams of methyl urea to 61 grams of 37% formaldehyde, adjusting the pH to about pH 89 and heating to F. for about 5 minutes and cooling to form as an intermediate, dimethylol methyl urea. This product was then reacted with 21 grams of 71% ethyl amine by heating at 160 F. to F. for two hours to form a triazone. Thirty and one-half grams of 37% formaldehyde were added to the thus formed product and the mixture was heated to 160 F.170 F. for ten minutes to form the triazone formaldehyde. Upon cooling, the product was adjusted to pH 5.0.

An aqueous solution containing 10% of the thus formed product, 5% (solids basis) dimethylol urea, and 0.5% zinc nitrate was prepared. A cotton fabric was then impregnated with about 75% of its weight of the aqueous solution, dried, and baked at 170 C. for 70 seconds.

:1 7 On testing the fabric was found to have lowdamage from retained chlorine and good wrinkle resistance.

Example XVII A triazone formaldehyde corresponding to the formula: oa s (F2115 l, l was prepared by refluxing for 3-4 hours, 2 mols of urea (360 grams) with one mol of ethylene diamine (189 grams of 91% product). The thus formed intermediate was crystallized with 95% ethanol and found to be ethylene diurea of the formula:

To this product 4 mols (324 grams) of 37% formaldehyde and 2 mols (126.6 grams) of 71% ethylamine were added. The mixture was heated to 160-170 F. for 1 /2 hours to form the triazone. Two mols (162 grams) of 37% formaldehyde were added to the triazone while the temperature was kept at 160-170 F. for five minutes to form the triazone formaldehyde. The final product was cooled and adjusted to pH 5.0-5.5.

A cotton fabric was then impregnated with about 75% of its weight of an aqueous solution containing 0.5% zinc nitrate, of the product prepared above in this example and 5% (solids 'basis) urea formaldehyde. The fabric was then dried and baked at 170 C. for 70 seconds. On testing the product was found to have good Wrinkle resistance and lower damage from retained chlorine than the product of Example XVII.

Similar satisfactory triazone formaldehydes were prepared by using equivalent molar quantities of hexamethylene diamine and pentamet'hylene diamine in place of ethylene diamine.

Many of the examples of the invention use amine hydrochloride catalysts which are satisfactory. However, minimum discoloration is obtained with metal salt catalysts such as magnesium chloride or zinc nitrate.

Thus, it will be seen that the present invention is primarily characterized by the depression of the damage caused by retained chlorine in resin treated fabrics by the addition of the triazone formaldehyde depressants of this invention. Improvements of the basic invention include especially the pre-polymerized mixtures of urea formal dehyde and triazone formaldehyde which are characterized by unexpected stability. A second important improvement is the process of preparing especially efficient mixtures of urea formaldehyde and triazone formaldehyde by reacting urea and formaldehyde with a primary alkyl amine in a quantity providing less than an equimolar quantity of primary amine groups.

What is claimed is:

1. In the process of treating cellulose textile fabrics to produce wrinkle resistance wherein said fabric is impregnated with an aqueous solution containing an acid catalyst and a resin forming material, the fabric is dried and the resin forming material is cured, that improvement which comprises using as the resin forming material two components including a first component having a high wrinkle resistance value and a high coeificient of chlorine damage and a second component being a chlorine damage depressant, the quantity of the two components being sufficient to produce high wrinkle resistance and said quantity being of from about 5% to 40% by weight of said aqueous solution, said first component being a watersoluble urea-formaldehyde condensate selected from the group consisting of urea formaldehyde, acrolein modified urea formaldehyde, and tetramethylol acetylene diurea and said second component being a triazone formaldehyde having the formula:

wherein n is a number from 2 to 6, R is selected from the group consisting of hydrogen, methylol, methoxymethyl, an alkyl group having from 1 to 4 carbon atoms and the triazone group:

and wherein said second component contains at least one group selected from the group consisting of methylol and methoxymethyl and wherein said second component has no more than two triazone rings, and the molar ratio of said components being regulated to substantially depress the coeflicient of chlorine retention of said first component while maintaining high wrinkle resistance, said molar ratio when said first component is urea formaldehyde being within the range of from about 1 to 6.3 mols of said second component for each mol of combined urea in said urea formaldehyde, said molar ratio when said first component is acrolein modified u-rea formaldehyde being within the range of from about 0.5 to 10 mols of said second component for each mol of combined urea in said acrolein modified urea formaldehyde, and said molar ratio when said first component is tetramethylol acetylene diurea being within the range of from about 2 to 10 mols of said second component for each mol of said tetramethylol acetylene diurea.

2. The process as set forth in claim 1 wherein the cellulose textile fabric contains cotton fibers, said first component is urea-formaldehyde, said second component is l,3-dimethylol-S-ethyI-tetrahydro-2( l )-s-triazone and the molar ratio is about 1 to 6.3 of urea formaldehyde to said second component, respectively.

3. The process as set forth in claim 1 wherein said second component is:

4. The process as set forth in claim 1 wherein said second component is:

CgH 1% C I: CHa

5. The process as set forth in claim 1 wherein said first component is acrolein modified urea formaldehyde, the cellulose textile fabric contains cotton fibers and said second component is 1,3-dimethylol-S-ethyl-tetrahydro- 2( 1 )-s-triazone.

6. The process as set forth in claim 1 wherein the cellulose textile fabric is cotton and said first component is tetramethylol acetylene diurea and said second component is a 1,3-dimethylol monotriazone.

7. A new composition of matter for treating textiles comprising a resin forming material including a first component having a high wrinkle resistance value and a high coefficient of chlorine damage and a second component which is a chlorine damage depressant, said first component being a water-soluble urea-formaldehyde condensate selected from the group consisting of urea formaldehyde, acrolein modified urea formaldehyde, and tetramethylol acetylene diurea and said second component being a triazone formaldehyde having the formula:

wherein R is selected from the group consisting of hydrogen, methylol, and methoxymethyl, R is selected from the group consisting of hydrogen and an alkyl group having from 1 to 3 carbon atoms, R is selected from the group consisting of hydrogen, methoxymethyl, an alkanol group having from 1 to 4 carbon atoms, an alkyl group having from 1 to 4 carbon atoms and the triazone group:

i /CHN 2)X.N =O

E R1 R4 wherein n is a number from 2 to 6, R is selected from the group consisting of hydrogen, methylol, methoxymethyl, an alkyl group having from 1 to 4 carbon atoms and the triazone group:

(C 2) u N and wherein said second component contains at least one group selected from the group consisting of methylol and methoxymethyl and wherein said second component has no more than two triazone rings, and the molar ratio of said components being regulated to substantially depress the coefiicient of chlorine retention of said first component while maintaining high wrinkle resistance, said molar ratio when said first component is urea formaldehyde being within the range of from about 1 to 6.3 mols of said second component for each mol of combined urea in said urea formaldehyde, said molar ratio when said first component is acrolein modified urea formaldehyde being within the range of from about 0.5 to 10 mols of said second component for each mol of combined urea in said acrolein modified urea formaldehyde, and said molar ratio when said first component is tetramethylol acetylene diurea being within the range of from about 2 to 10 mols of said second component for each mol of said tetramethylol acetylene diurea.

8. A composition as set forth in claim 7 in which said first component is urea formaldehyde.

9. A composition as set forth in claim 8 wherein said second component is 1,3-dimethylol-S-ethyl-tetrahydro- 2(1)-s-triazone and said molar ratio is about 1 to about 6.3.

10. A composition of matter as set forth in claim 7 wherein said first component is acrolein modified urea formaldehyde and said second component is a 1,3-dimethylol monotriazone.

11. A composition as set forth in claim 7 wherein said first component is tetramethylol acetylene diurea and said second component is a 1,3-dimethylol monotriazone.

12. A textile fabric characterized by low damage from retained chlorine and high wrinkle resistance, said fabric being formed predominantly of cellulose fibers impregnated with from about 5% to 20% of their weight of a composition of matter comprising a resin comprising a first component providing high wrinkle resistance and a second component which is a chlorine damage depressant, said first component being a water-soluble urea-formaldehyde condensate selected from the group consisting of urea formaldehyde, acrolein modified urea formaldehyde, and tetramethylol acetylene diurea and said second component being a triazone formaldehyde having the formula:

Ra I

wherein R is selected from the group consisting of hydrogen, methylol, and methoxymethyl, R is selected from the group consisting of hydrogen and an alkyl group having from 1 to 3 carbon atoms, R is selected from the group consisting of hydrogen, methoxymethyl, an alkanol group having from 1 to 4 carbon atoms, an alkyl group having from 1 to 4 carbon atoms and the triazone group:

CHN a)uN o=0 oH-N wherein n is a number from 2 to 6, R is selected from the group consisting of hydrogen, methylol, methoxymethyl, an alkyl group having from 1 to 4 carbon atoms and the triazone group:

and wherein said second component contains at least one group selected from the group consisting of methylol and methoxymethyl and wherein said second component has no more than two triazone rings, and the molar ratio of said components being regulated to substantially depress the coefficient of chlorine retention of said first component while maintaining high wrinkle resistance, said molar ratio when said first component is urea formaldehyde being within the range of from about 1 to 6.3 mols of said second component for each mol of combined urea in said urea formaldehyde, said molar ratio when said first component is acrolein modified urea formaldehyde being within the range of from about 0.5 to 10 mols of said second component for each mol of combined urea in said acrolein modified urea formaldehyde, and said molar ratio when said first component is tetramethylol acetylene diu-rea being within the range of from about 2 to 10 mols of said second component for each mol of said tetramethylol acetylene diurea.

13. A fabric as set forth in claim 12 wherein said fabric contains cotton fibers, said first component is urea formaldehyde and. said second component is a 1,3-dimethylol monotriazone, and the molar ratio of said components is about 1 to 6.3 of urea formaldehyde to said triazone, respectively.

14. A process for treating cellulose textiles comprising applying thereto an aqueous solution of a curable mixture of (a) a water soluble urea-formaldehyde condensate and (b) a compound of the formula:

wherein R is an alkyl group having 1-4 carbon atoms, the mole ratio of (b) to (a) being from about 1:1 to about 3:1, based on the amount of combined urea in said condensate (a) and thereafter heating to dry and cure the resin.

15. A composition as set forth in claim 8 wherein said second component is:

16. A fabric as set forth in claim 12 wherein said first component is urea formaldehyde and said second component is:

17. A process for treating cellulosic textiles comprising applying thereto an aqueous solution of a curable mixture of (a) a water-soluble urea-formaldehyde condensate and (b) a compound of the formula:

NCHrOR' wherein R is a member of the class consisting of hydrogen, methoxymethyl, an alkanol group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms, R is a member of the class consisting of hydrogen and methyl, the mol ratio of (b) to (a) being about 1:10 to about 10:1, based on the amount of combined urea in said condensate (a), drying the textile and curing the resin.

18. Process as claimed in claim 17 wherein said compound is 1,3 dimethylol -(2-hydroxyethyl)tetrahydro- 2(1)-triazone.

19. Process as claimed in claim 17 wherein said watersoluble urea-formaldehyde condensate is acyclic.

IIICHzO R wherein R is a member of the class consisting of hydrogen, methoxymethyl, an alkanol group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms, R is a member of the class consisting of hydrogen and methyl, and the mol ratio of (b) to (a) is from about 1:1 to about 10:1.

21. New composition as claimed in claim 20 wherein said urea-formaldehyde condensate consists of a methylol urea.

22. New composition as claimed in claim 21 wherein said urea-formaldehyde condensate is dimethylol urea.

23. New composition as claimed in claim 20 wherein said urea-formaldehyde condensate is acyclic.

24. New composition as claimed in claim 20 wherein said compound is 1,3-dimethylol-5-(2-hydroxyethyl)tetrahydro-2( 1 -triazone.

25. New composition as claimed in claim 7 wherein said compound is 1,3-dimethylol-5-(2-hydroxyethyl)tetrahydro-2( 1 triazone.

26. Process as claimed in claim 1 wherein the impregnated fabric is heated to dry the fabric and cure the resin in one operation.

27. Process of making an aqueous solution containing a bis triazone of the formula References Cited UNITED STATES PATENTS 2,370,839 3/1945 Burke et al. 260-675 2,373,135 4/1945 Maxwell 260-72 2,373,136 4/ 1945 Hoover et al. 260-675 2,641,584 6/1953 Martone 260-173 2,690,404 9/1954 Spangler et a1. 117-139.4 2,755,198 7/1956 Stewart 117-1394 2,804,402 8/ 1957 Williams 260-849 2,826,500 3/1958 Keim 260-70 X 2,884,407 4/ 1959 Keim 260-70 2,901,463 8/1959 Hurwitz 260-70 MURRAY TILLMAN, Primary Examiner.

MILTON STERMAN, R. D. NEVTUS, Examiners.

G. B. DUNAWAY, T. L. TULLY, W. D. MARTIN,

I. C. BLEUTGE, Assistant Examiners.

Claims (1)

1. IN THE PROCESS OF TREATING CELLULOSE TEXTILE FABRICS TO PRODUCE WRINKLE RESISTANCE WHEREIN SAID FABRIC IS IMPREGNATED WITH AN AQUEOUS SOLUTION CONTAINING AN ACID CATALYST AND A RESIN FORMING MATERIAL, THE FABRIC IS DRIED AND THE RESIN FORMING MATERIAL IS CURED, THAT IMPROVEMENT WHICH COMPRISES USING AS THE RESIN FORMING MATERIAL TWO COMPONENTS INCLUDING A FIRST COMPONENT HAVING A HIGH WRINKLE RESISTANCE VALUE AND A HIGH COEFFICIENT OF CHLORINE DAMAGE AND A SECOND COMPONENT BEING A CHLORINE DAMAGE DEPRESSANT, THE QUANTITY OF THE TWO COMPONENTS BEING SUFFICIENT TO PRODUCE HIGH WRINKLE RESISTANCE AND SAID QUANTITY BEING OF FROM ABOUT 5% TO 40% BY WEIGHT OF SAID AQUEOUS SOLUTION, SAID FIRST COMPONENT BEING A WATERSOLUBLE UREA-FORMALDEHYDE CONDENSATE SELECTED FROM THE GROUP CONSISTING OF UREA FORMALDEHYDE, ACROLEIN MODIFIED UREA FORMALDEHYDE, AND TETRAMETHYLOL ACETYLENE DIUREA AND SAID SECOND COMPONENT BEING A TRIAZONE FORMALDEHYDE HAVING THE FORMULA:

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