US3822995A - Process for modifying keratin fibers to reduce relaxation and felting shrinkage and product produced thereby - Google Patents

Abstract

SHRINKAGE IS REDUCES IN TEXTILE FABRIC CONTAINING KERATIN FIBERS BY IMPREGNATING THE FABRIC WITH AN ORGANIC SOLVENT WHICH IS NONREACTIVE WITH ISOCYANATES. THE PROCESS REDUCES RELAXATION AND FELTING SHRINKAGE AND MAY SET THE FIBERS IN A GIVEN CONFIGURATION.

Description

"United States Patent Office 3,822,995 Patented July 9, 1974 3,822,995 PROCESS FOR MODIFYING KERATIN FIBERS TO REDUCE RELAXATION AND FELTlNG SHRINK- AGE AND PRODUCT PRODUCED THEREBY Emile E. Habib, Spartanburg, S.C., assignor to Deering Milliken Research Corporation, Spartanburg, 8.0. No Drawing. Continuation of application Ser. No.

292,769, July 3, 1963, which is a continuation-inpart of application Ser. No. 230,731, Oct. 15, 1962, now abandoned. This application Sept. 25, 1972, Ser. No. 292,048

' Int. Cl. A61k 7/10; D06m 3/02, 13/00 US. Cl. 8127.5 23 Claims ABSTRACT OF THE DISCLOSURE Shrinkage is reduced in textile fabric containing keratin fibers by impregnating the fabric with an organic solvent which is nonreactive with isocyanates. The process reduces relaxation and felting shripkage and may set the fibers in a given configuration.

This invention relates to a process for modifying the characteristics of structures containing keratin fibers and more particularly, to processes for reducing the relaxation and felting shrinkage of a structure containing keratin fibers and for setting said fibers in a given configuration if desired, and to the structures so improved.

This application is a Continuation of my copending US. patent application, Ser. No. 292,769, filed July 3, 1963, which is a Continuation-in-Part of my copending US. patent application, Ser. No. 230,731, filed Oct. 15, 1962, now abandoned.

The relaxation and felting shrinkages of structures containing keratin fibers have been a serious problem in the textile industry. The considerable amount of research and development has resulted in several methods that will inhibit the felting shrinkage of these structures. No method, however, has been developed prior to this invention for the control of relaxation shrinkage. The most widely used process to date involves digestion of the fiber scales by chlorigation. A similar effect is obtained by use of acid/permgnganate. Both of these methods, however, are objectionable because of the loss of tensile strength and abrasion resistance which results from degradation of the fib'ers. Furthermore, fabrics treated by these methods must be made to higher Weights so that after the degradative action, sufiicient strength remains in the structure to meet minimum wear requirements. The combination of degradation plus weight loss during the processing results in the necessity for using more wool and, therefore, a higher cost of product.

A considerable awunt of research has been conducted to circumvent the degradative action of chlorination and other oxidative methods. This research has produced several procedures which are not as widely used at the present time. One method consists of depositing on the surface of the keratin fiber a polymeric material as, for example, a polyamide-type polymer. In this method, the fabric is passed through a solution of a diamine and then treated with a salt of a dibasic acid; the polyamide is thus formed at the interface between the diamine and the salt of the dibasic acid to form a coating affected. The relaxation shrinkage is not adequately inhibited.

Other polymeric resins designed to form a film on the keratin fibers have also been developed. Combinations of polyamides with epoxys and/or acrylates have been used; also polyesters which have been made to high molecular weight to obtain flexibility have been used in conjunction with peroxide curing agents. These processes also produce fabrics which have a harsh hand and poor drape when the amounts of these modifying materials are such as to inhibit the shrinkage to the required amount. The relaxation shrinkage is also not adequately inhibited.

Another process has been developed for inhibiting the shrinkage of structures containing keratin fibers by use of isocyanates. To obtain sufficient reaction, using isocyanates alone, to render the fabric being treated resistant to shrinkage, long refluxing conditions are required, which makes this process commercially impracticable. Furthermore, to obtain thedesired resistance to shrinkage, large amounts of the isocyanate compounds must be added to the fibers which results in a fabric that is both harsh and stiff, having a hand more like horsehair than wool.

Relaxation and felting shrinkage propensities are not the only problems associated with fabrics containing keratin fibers. Such fabrics, particularly those containing at least a major proportion of keratin fibers, are also characterized by a low degree of configurational stability. For example, the crease in a pair of wool trousers is virtually eliminated by wetting. The same is true of the lustrous finish applied to wool fabrics in a typical textile finishing operation.

To overcome these difliculties, durable configurations have been imparted to such fabrics through the use of reducing agents. According to these prior art processes, the fabric is impregnated with a reducing agent, hereupon some of the cystine disulfide linkages of the keratin fiber molecule are ruptured. The resulting fabric, in its reduced condition, can be heat-pressed, generally in the presence of large quantities of moisture, into configurations which are durable to subsequent wetting. These procedures, particularly as improved by the addition of certain compounds which obviate the use of large quantities of moisture during pressing, have been highly successful because of the desirable properties imparted to fabrics so treated. These processes, however, are degradative processes and, therefle, the physical properties of the resulting fabrics are diminished. Furthermore, the reduced keratin fibers have a characteristic, unpleasant odor regardless of the reducing agent utilized. Additives have been developed for eliminating this odor, but such techniques invariably increase the cost of the process.

Although present processes for setting keratin fibers in durable configurations have been developed to practicable levels, it would be highly desirable if a process could be developed which enhanced, rather than degraded, physical properties and which avoided the unpleasant odor of reduced keratin fibers without the use of costly additives. Even more desirable would be a process which resolved these problems while providing a fabric, treated at the mill level, which is presensitized for subsequent durable setting, by the garment manufacturer, in the absence of large quantities of water.

The difficulties associated with the above prior art processes are overcome in accordance with the process of this invention which comprises reacting the keratin fibers with polyfunctional isocyanates in combination with polymeric polyfunctional compounds selected from polyesters, polyamides, polyepoxides, reaction products of phenols and alkylene oxides, formaldehyde resins, hydrogenation products of olefine-carbon monoxide copolymers, and polyepihalohydrins. To set the fibers in a given configuration, it is required only that the fibers be maintained in the desired configuration during this reaction.

The process of this invention requires the use of relatively small amounts of material to obtain the required stabilization and/or setting. The process of application is a simple one involving impregnating the keratin fibers with the various components from a single solution, as a pre-polymer, or separately (as when the polymeric polyfunctional compound is particularly reactive with isocyanates, e.g., some polyamides) by any conventional technique such as padding, immersing, spraying or the like, followed by drying and curing of the components on the fibers. These steps may be run in tandem on equipment that is available in textile plants.

The products of this invention not only are superior in almost every instance to those treated by other known methods but also are superior to the same fabric prior to treatment. In the process of this invention there is no degradative action on the wool fiber; on the contrary, improvements in strengths and abrasion resistance are obtained over the untreated controls. It has also been found that more uniform dyeing may be accomplished on keratin fibers treated in accordance with this invention than those treated by the degradative processes of the prior art.

A particular advantage in the practice of this invention is the virtual elimination of the relaxation shrinkage of the fabric, which is a highly desirable property in that it is not necessary that the fabric be preshrunk prior to cutting into garments as is required in the processes of the prior art. This results in savings of both labor and material since yardage is always lost when the fabric is relaxed prior to cutting into garments.

The process also allows the manufacture of lighter weight garments which are washable without felting shrinkage which has not been possible in processes of prior art. Besides the savings in wool, it is often highly desirable to have lighter weight fabrics available for the production of more comfortable garments.

The hand of fabrics treated in accordance with this invention may be varied by balancing construction of the fabric with the amount of pickup of treating compound used in the system.

One embodiment of this invention comprises forming a prepolymer from the polyfunctional isocyanate and the various polymeric polyfunctional compounds, applying the pre-polymer to the structure containing keratin fibers (with or without coreactant and unblocked or blocked as lebreinafter set forth) and curing the pre-polymer on the ers.

By pre-polymer as used herein is meant the reaction product of the polyfunctional isocyanate and polymeric polyfunctional compound carried to an extent below which a gel is produced which is insoluble in one of the organic solvents, particularly the chlorinated hydrocarbons, hereinafter set forth.

In preparing the pre-polymers of this invention, at least equimolar amounts of the polyfunctional isocyanate and polymeric polyfunctional compound are reacted, although a small excess is preferably utilized. Generally, an excess of about 1.1 to 1.0 of N=C=X groups of the polyfunctional isocyanate to total active hydrogen atoms is present.

It is generally preferred to have a small amount of water present during formation of the pre-polymer. The amount of water added should be less than that amount which would cause gelation of the pro-polymer. Generally, no more than about 0.5% of water based on the weight of polymeric polyfunctional compound is required to provide the desired effect.

In a more preferred practice of this embodiment of the invention, an additional amount of polyfunctional isocyanate is added to the pre-polymer system after polymerization. This additional isocyanate increases the stability of the pre-polymer, reacts with regain water in the wool and thereby enhances the reaction of the pre-polymer with keratin fibers. It has been found, however, that shrinkage inhibition is obtained with the pre-polymers of this invention even though there is present an excess of active hydrogen atoms from extraneous water, water in the structures containing keratin fibers, and from the added coreactants which will be described hereinafter. For example, a ratio of N=C=X groups to total active hydrogen atoms as low as about 0.6 provides some improvement in inhibiting shrinkage in structures containing keratin fibers or enabling one to set such fibers. While improvement is noted at ratios of N=C=X to total active hydrogen atoms below about 1, substantially more pre-polymer is required to obtain sufficiently low shrinkage values or sufficiently high degree of settability. When this ratio exceeds about 1, however, reduced amounts, for example, as low as a few percent (2-5% depending on the particular fabric) of the pre-polymer may be utilized to produce commercially acceptable levels of low shrinkage and/or settability.

In another embodiment of this invention, the polyfunctional isocyanate and polymeric polyfunctional compound, preferably along With one of the well-known catalysts for the reaction of active hydrogen atoms with isocyanates, may be applied to the structure containing keratin fibers from a solution in a non-reactive solvent directly, i.e., without first preparing a pro-polymer as set forth above. In obviating the production of a pre-polymer, the expense and control problems associated therewith are eliminated.

Although some improvement is noted when the polyfunctional isocyanate (unblocked or blocked as hereinafter set forth), polymeric polyfunctional compound, coreactant if added, and catalyst are present in amount sufficient to provide a ratio of -N=C=X to total active hydrogen atoms of at least about 0.4, best results are obtained at higher ratios, for example, greater than about 1. As in the prepolymer embodiment of this invention, shrinkage inhibition at commercial levels is obtained with less reactants at higher ratios of N-=C=X to total active hydrogen atoms.

In the practice of this embodiment of the invention, it is preferred to react the polyfunctional isocyanate and polymeric polyfunctional compound, with or without a coreactant and unblocked or blocked as hereinafter set forth, with the keratin fibers in the presence of catalyst. Any of the well-known catalysts for the reaction of active hydrogen atoms with isocyanates may be used. Of these catalysts, which are used in the production of polyurethanes, the organo-tin compounds are preferred, particularly stannous octoate.

Among the classes of catalysts which can be used, there are included the inorganic and organic bases such as sodium hydroxide, sodium methylate, sodium phenolate, tertiary amines and phosphines. Particularly suitable amine catalysts include 2,2,l-diazabicyclo-octane, trimethylamine, 1,2-dimethylimidazole, triethylamine, diethyl cyclohexylamine, dimethyl long-chain C to C amines, dimethylaminoethanol, diethylaminoethanol, N methyl morpholine, N-ethyl morpholine, triethanolamine and the like. Other suitable catalysts include arsenic trichloride, antimony trichloride, antimony pentachloride, antimony tributoxide, bismuth trichloride, titanium tetrachloride, bis(cyclopentadienyl) titanium difiuoride, titanium chelates such as octylene glycol titanate, dioctyl lead dichloride, dioctyl lead diacetate, dioctyl lead oxide, trioctyl lead chloride, trioctyl lead hydroxide, trioctyl lead acetate, copper chelates such as copper acetylacetonate, and mercury salts.

Organo-tin compounds characterized by at least one direct carbon to tin valence bond are also suitable as catalysts.

Among the many types of tin compounds having carbon to tin bonds, of which specific representative compounds have been tested and shown to be active, are tin compounds having the general formulae as follows:

(a) R SnX (c) RSnX (e) R'SnOOR' (f) R(SnOR') in which the Rs represent hydrocarbon or substituted hydrocarbon radicals such as alkyl, aralkyl, aryl, alkaryl, alkoxy, cycloalkyl, alkenyl, cycloalkenyl, and analogous substituted hydrocarbon radicals, the Rs represent hydrocarbon or substituted hydrocarbon radicals such as those designated by the R's or hydrogen or metal ions, the Xs represent hydrogen, halogen, hydroxyl, amino, alkoxy, substituted alkoxy, acyloxy, substituted acyloxy, acyl radicals or organic residues connected to tin through a sulfide link, and the Ys represents chalcogens including oxygen and sulfur.

Among the compounds of group (a) that deserve special mention are trimethyltin hydroxide, tributyltin hydroxide, trimethyltin chloride, trimethyltin bromide, tributyltin chloride, tn'octyltin chloride, triphenyltin chloride, tributyltin hydride, triphenyltin hydride, triallyltin chloride, and tributyltin fluoride.

The compounds in group (b) that deserve particular mention and are representative of the group include dimethyltin diacetate, diethyltin diacetate, dibutyltin diacetate, dioctyltin diacetate, dilauryltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dimethyltin dichloride, dibutyltin dichloride, dioctyltin dichloride, diphenyltin dichloride, diallyltin dibromide, diallyltin diiodide, bis(carboethxymethyl)-tin diiodide, dibutyltin dimethoxide, di butyltin dibutoxide,

(in which x is a positive integer), dibutyl-bis[O-acetylacetonyl]-tin, dibutyltin-bis(thiododecoxide), and

all readily prepared by hydrolysis of the corresponding dihalides. Many commercially available compounds used as stabilizers for vinyl resins are also included in this group.

Among the compounds that are representative of group (0) are butyltin trichloride, octyltin trichloride, butyltin triacetate and octyltin tris(thiobutoxide).

Typical among the compounds of group (d) are dimethyltin oxide, diethyltin oxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, diallyltin oxide, diphenyltin oxide, dibutyltin sulfide,

[HOOC (CH 1 5110,

and

[CH 0CH (CH2oCH2) 1CHg0 5] 28110 (in which the xs are positive integers).

Mcthylstannonic acid, ethylstannonic acid, butylstannonic acid, octylstannonic acid,

63 HO 0 C (CHM-S110 0H, (O s):N(GHa)sSnO OH CHaO OHKCHIO CHl)x-1CH2SI1O OH are examples of group (e) catalysts and group (f) catalysts are represented by HOOSn(CH SnOOH HOOSnCH (CH OCH CH- SnOOH and the xs being positive integers.

Typical compounds in group (g) include compounds as poly (dialkyltin oxides) such as dibutyltin basic laurate and dibutyltin basic hexoxide.

Qther compounds that are eflicient catalysts are those of group (h), of which the organo-tin compounds used as heat and light stabilizers for chlorinated polymers and available under the trade names Advastab 17-M (a dibutyl tin compound believed to contain two sulfur-containing ester groups), Advastab T-SO-LT (a dibutyl tin compound believed to contain two ester groups), are typical, as well as many other organo-tin compounds available under such trade names as Advastab, Nuostabe, and Thermolite.

In another embodiment of this invention, the reaction between the isocyanate/polymeric polyfunctional compound system or the pre-polymers thereof and the keratin fibers is considerably enhanced when conducted in the presence of a coreactant having at least two groups containing at least one active hydrogen atom, as determined by the Zerewitinoif method. (Zerewitinofi', Ben, 40, 2023 (1907); Ben, 41, 223'6( 1908); Kohler, J. Am. Chem. Soc., 49, 3181(1927). These materials contain at least two groups, or combinations thereof, such as -OH, NH -NRH, -COOH, -SH or groups which react similarly under reaction conditions.

Suitable polyol coreactants for use in accordance with this invention include the polymeric polyfunctional compounds noted below, as well as polyols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butane diol, 1,4-butanediol, 1,5-pentane diol, 1,2 hexylene glycol, 1,10-decane diol, 1,2-cyclohexane diol, 2-butene-1,4 diol, 3-cyclohexene-1,l-dimethanol, 4- methyl-3-cyclohexene-1,l-dimethanol, 3 methylene-1,5- pentanediol, 3,2 hydroxyethyl cyclohexanol, 2,9-paramenthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,5-dimethyl-2,5-hexane diol and the like; alkylene oxide modified diols such as diethylene glycol, (2-hydroxyethoxy)-1-propanol, 4-(Z-hydroxyethoxy)-1-butanol, 5-(2-hydroxyethoxy)-l-pentanol, 3-(2-hydroxypropoxy)-1-pr0panol, 4-(2- hydroxypropoxy) 1 butanol, 5-(2-hydroxypropoxy)-1- pentanol, I-(Z-hydroxyethoxy)-2-butanol, 1-(2-hydroxyethoxy)-2-pentanol, 1-(2-hydroxymethoxy)-2-hexanol, 1- (2-hydroxyethoxy)-2-octanol, and the like.

Representative examples of ethylenically unsaturated low molecular weight diols include 3-allyloxy-l,5-pentanediol; 3-allyloxy 1,2 propanediol; 2-allyloxymethyl-2- methyl-1,3-propanediol; Z-methyl 2 [(4-pentenyloxy) methyl]-1,3-propanediol; and 3-(o-propenylphenoxy)- 1,2-propanediol.

Representative examples of low molecular weight polyols having at least 3 hydroxyl groups include: glycerol; 1,2,6-hexanetriol; 1,1,1-trimethylolpropane; 1,1,1- trimethylolethane; pentaerythritol; 3-(2-hydroxyethoxy)- 1,2-propanediol; 3-(2-hydroxypropoxy)-1,2-propanediol; 6-(2-hydroxypropoxy) 1,2 propanediol; 2-(2-hydroxyethoxy)-l,2-hexanediol; 6-(2-hydroxyropoxy)-l,2-hexanediol; 2,4 dimethyl-2-(2-hydroxyethoxy)methylpentanediol-1,5; mannitol; galactitol; talitol; iditol; allitol; altritol; guilitrol; arabitol; ribitol; xylitol; lyxitol; erythritol; threitol; 1,2,5,6 tetrahydroxyhexane; meso inositol; sucrose; glucose; galactose; mannose; fructose; xylose; arabinose; dihydroxyacetone; glucose-a-methylglucoside; 1,1,1 tris[(2 hydroxyethoxy)methyl] ethane and 1,1,1- tris (Z-hydroxypropoxy) methyl] propane.

There may also be utilized low molecular weight polyalkyleneether glycols such as tetraethyleneether glycol, triethyleneether glycol, tritetramethyleneether glycol, ditetramethyleneether glycol and the like.

Exemplary diphenylol compounds include 2,2-bis (p-hydroxyphenyl) propane; bis(p-hydroxyphenyl)methane and the various diphenols and diphenylol methanes disclosed in U.S. Pats. 2,506,486 and 2,744,882, respectively.

Exemplary triphenylol compounds which can be employed include the alpha, alpha, omega, tris(hydroxyphenyl)alkanes such as 1, 1 ,3-tris (hydroxyphenyl ethane;

1, l ,3-tris (hydroxyphenyl propane;

1, 1,3-tris(hydroxy-S-methylphenyl) propane;

1, 1 ,3-tris (dihydroxy-3-methylphenyl propane;

, 1 ,3-tris (hydroxy-2,4-dimethylphenyl propane;

, 1 ,3-tris (hydroxy-2,S-dimethylphenyl propane;

, 1 ,3-tris (hydroxy-2,6-dimethylphenyl propane;

, 1 ,4-tris (hydroxyphenyl butane;

,1,4-tris(hydroxyphenyl) -2-ethylbutane;

,1,4-tris (dihydroxyphenyl) butane;

,1,5-tris(hydroxyphenyl) -3-methylpentane;

,1, 8-tris (hydroxyphenyl) -octane;

1-10-tris(hydroxyphenyl)decane;

and such corresponding compounds which contain substituent groups in the hydrocarbon chain, such as 1,1,3-tris(hydroxyphenyl)-2-chloropropane;

,1,3-tris(hydroxy-3-propylphenyl)-2-nitropropane; l,1,4-tris(hydroxy-3-decylphenyl)-2,3-dibromobutane;

and the like.

Tetraphenylol compounds which can be used in this invention include the alpha, alpha, omega, omega, tetralris (hydroxyphenyl) alkanes such as 1,1,2,2,-tetrakis(hydroxy-phenyl) ethane;

, ,3,3-tetrakis(hydroxy-3-methylphenyl)propane; ,3,3-tetrakis(dihydroxy-3-methylphenyl) propane; ,4,4-tetrakis(hydroxyphenyl)butane;

,4,4-tetrakis(hydroxyphenyl)-2-ethylbutane;

1 1 l 1 1 1 1,1 1,1, ,S-tetrakis(hydroxyphenyl)pentane;

1,1 ,5,5-tetrakis(hydroxyphenyl) -3-methylpentane; 1,l,5,5-tetrakis-(dihydroxyphenyl) pentane; 1,1,8,8-tetrakis(hydroxy-3-butyl-phenyl) octane; 1,1,8,8-tetrakis(dihydroxy-3-butylphenyl) octane; 1,1,8,8-tetrakis(hydroxy-2,S-dimethylphenyl) octane; 1,1,10, IO-tetrakis (hydroxyphenyl) -decane,

and the corresponding compounds which contain substituent groups in the hydrocarbon chain such as 1,1,6,6-tetrakis(hydroxyphenyl) -2-hydroxyhexane;

1,1,6,6-tetrakis(hydroxyphenyl)-2-hydroXy-5-methylhexane;

, l ,7,7-tetrakis (hydroxyphenyl -3-hydroxyheptane;

,1,3,3-tetrakis(hydroxyphenyl)-2-nitropropane;

,1,3 ,3-tetrakis(hydroxyphenyl -2-chloropropane;

,1,4,4-tetrakis(hydroxyphenyl) -2,3-dibromobutane;

4,4-methylenebis (2-chloroaniline), 4,4-methylenebis (2-bromoaniline), 4,4-methylenebis(2-iodoaniline),

4,4-methylenebis (Z-fiuoro aniline) 4,4-methylenebis(Z-methoxyaniline), 4,4-methylenebis 2-ethoxyaniline 4,4-methylenebis(Z-methylaniline), 4,4'-methylenebis(2-ethylaniline), 4,4-methylenebis (2-isopropylanilinc 4,4-methylenebis (Z-n-butylaniline) and 4,4-methylenebis(Z-n-octylaniline) and the like.

Other arylene diamines which maybe used include compounds such as:

his (4-aminophenyl) sulfone,

bis (4-aminophenyl) disulfide, toluene-2,4-cliamine,

1 ,S-naphthalenediamine, cumene-2,4-diamine, 4-methoxy-1,3-phenylenediamine, 1,3-phenylenediamine, 4-chloro-1,3-phenylenediamine, 4-bromo-1,3-phenylenediamine, 4-ethoxy-1,3-phenylenediamine, 2,4-diaminodiphenylether, 5,6-dimethyl-l,3-phenylenediamine, 2,4-dimethyl-1,3-phenylenediamine, 4,4-diaminodiphenylether, benzidine, 4,6-dimethyl-1,3-phenylenediamine, 4,4'-methylenebisaniline, 9,10-anthracenediamine, 4,4-diaminodibenzyl, 2,4-diaminostilbene, 1,4-anthradiamine, 2,5-fluorenediamine, 1,8-naphthalenediamine, 2,6-diaminobenzfuran, 3,3'-biphenyldiamine, Z-methylbenzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2'-dichloro-3,3'-dimethylbenzidine, 5,5'-dibromo-3,3'-dimethylbenzidine, 2,2-dichlorobenzidine, 2,2'-dimethoxybenzidine, 3,3'-dimethoxybenzidine, 2,2',5,5-tetramethylbenzidine, 2,2'-dichloro-5,5-diethoxybenzidine, 2,2'-difluorobenzidine, 3,3'-difluorobenzidine, 3-ethoxybenzidine, 3-ethyl-3'-methylbenzidine, 2,2',6,6'-tetrachlorobenzidine, 3,3',5,5'-tetraiodobenzidine, 3-trifluoromethylbenzidine, 2-iodobenzidine, 1,4-phenylenediamine and the like.

Aliphatic diamines are also suitable, for example: di- (u methylbenzyl)ethylene diamine, hexamethylene diamine, 2,6 diaminopyridine, 2,4-diaminopyridine, ethylenediamine, 1,4 diaminobutane, 1,3-diaminobutane, 1,3- diaminopropane, 1,10 diaminodecane, 3,3-diaminodipropyl ether and the like, as are amines with greater than 2 amino groups; such as 3,3-diaminodipropylamine, triethylenetetramine, diethylenetriamine, tetraethylene pentamine, 3-(N isopropylamino)-propylene diamine, 4,4 diaminodiphenylamine, 3,3-dimethyl-4,4'-diaminodiphenylamine, 4,4 diamino-dibutylamine, melamine and the like.

Suitable acids include the aliphatic acids, such as malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, p-methyladipic, 1,2-cyclohexane dicarboxylic, teraconic acid, isatropic acid, citric acid, tartaric acid and the like.

Aromatic acids are also suitable, for example isophthalic, terephthalic, uvitic (5,1,3), uvitonic (2,4,6), salicylacetic, 1,4-naphthalene dicarboxylic, 1,8-naphthalenedicarboxylic, 1,10-diphenic acid, 2,9-diphenic acid, benzophenone dicarboxylic acid, pyromellitic, mellophanic, trimellitic, trimesic and the like, as are heteroaromatic acids such as pyridine tricarboxylic acid, pyridine dicarboxylic acid and the like.

Suitable sulfhydryl compounds include 1,4-butanedithiol, 1,5-pentanedithiol, 1,2-hexanedithiol, ethylene thioglycol, propylene thioglycol, trimethylene thioglycol, 1,10 decane dithiol, 1,2-cyclohexanedithiol, 2-butene-l,4-dithiol, 2,9-para-menthanedithiol ethylcyclohexyl dimercaptan, 2,2,4-trimethyl-1,3-pentanedithiol, and the like. In this regard, the keratin fibers can be treated with reducing agents to provide reactive sulfhydryl groups in situ.

In most instances, the isocyanate/polymeric polyfunctional compound system, either as such or in pre-polymeric form, and the coreactant containing at least two groups having at least one active hydrogen atom may be applied to the fabric or other structure from a single solution. In some cases, however, where the coreactant and/or polymeric polyfunctional compound is highly reactive with the residual N=C=X groups, such as when certain amines or polyamides are utilized as the coreactant, it is preferred that the coreactant and/or polymeric polyfunctional compound be applied to the fabric or other structure from a separate system. This may be accomplished by padding the amine and/or polymeric polyfunctional compound, preferably drying and then applying the remaining components onto the fibers or vice versa.

In selecting an organic solvent to prepare solutions for the application of the various systems described above, care should be taken to provide a non-reactive solvent.

By non-reactive as used herein is meant a solvent in which reactivity between the isocyanate and active-hydrogen containing components, even in the presence of catalyst, is substantially inhibited. Small amounts of reactive solvents may be present provided the amount present is sufficiently low as not to precipitate a substantial amount of the components with which it is reactive. In other words, sufiicient components remain reactive with the keratin fibers to provide adequate inhibition of shrinkage and/or settability in the fabric or other structure being treated.

Suitable organic solvents include halogenated hydrocarbons, such as trichloroethylene, methylene chloride, perchloroethylene, ethylene dichloride, chloroform and the like; aromatic solvents such as toluene, xylene, benzene, mixed aromatics, such as the Solvesso types and the like, n-butyl acetate, n-butyl ether, n-butyl phosphate, p-dioxane, ethyl oxalate, methyl isobutyl ketone, pyridine, quinolene, N,N-dimethylfrmamide, N,N-dimethylacetamide, 2,2,4-trimethylpentane and the like. Mixtures of solvents may be used.

The use of a non-reactive organic solvent enables the practitioner to combine all desired components in a single solution while substantially inhibiting reaction between them, thereby greatly facilitating application of all components, even catalyst, uniformly onto the desired structure in controllable amotmts. In the absence of a nonreactive solvent, the combined components and catalysts would react, often quite readily, to produce an insoluble polymer which cannot be conveniently applied to the fabric or other structure uniformly in the amounts desired. This reaction, however, is inhibited when a nonreactive solvent is used and the inhibiting influence substantially continues in the fabric until the solvent is removed by any conventional drying technique. After the solvent is removed, the various components are free to cure on the keratin fibers.

By cure as used herein is meant the reaction of the various components, such as the isocyanate/polymeric polyfunctional compound system, or pre-polymers therefrom, unblocked or blocked as hereinafter set forth and with or without a coreactant, with the keratin fibers. It is believed that the components react with the fibers, in

that extraction methods fail to remove the components after curing. The mechanism of the reaction with the keratin fibers, however, is not completely understood.

When a pre-polymer is applied, it is probable that the terminal -N=C=X groups thereof react with the various groups in the wool molecule which contain active hydrogen atoms, for example, the amino, hydroxy, thiols, amide, guanidine, carboxyl and imido groups.

When the isocyanate, polymeric polyfunctional compound and catalysts are mixed without apparent reaction therebetween and applied directly to the keratin fibers, it is not at all understood just how the various components combine with the keratin fibers to inhibit the shrinkage thereof or to set the fibers in a given configuration. It is not known, for example, whether the components first combine to form an N==C=X terminated prepolymer which then reacts with the keratin fiber or wether the components react individually or sequentially with the keratin fibers.

It is believed, however, that the isocyanate-terminated compounds utilized in the process of this invention whether in pie-polymeric form or as available polyfunctional isocyanates per se or derived from blocked compounds, as in a mixture thereof with polymeric polyfunctional compounds in a non-reactive solvent, react with active hydrogen atoms in the wool molecule as follows:

wherein X is as before and R is the residue from the above isocyanate-terminated compounds.

While the coreactant utilized in accordance with a preferred embodiment of this invention very likely induces some cross-linking in the reaction product of the above systems and the keratin fibers, the mechanism of the crosslinking is similarly not understood.

The presence of regain amounts of water in the structure of keratin fibers will consume free isocyanate groups to lower the -N=C=X to active hydrogen atom ratio of the total system with a consequent increase in felting shrinkage and decrease in settability where the initial ratio is low. This problem may be readily solved by either drying and maintaining dry the said structure during treatment or by compensating for this regain moisture by addition of equivalent amounts of the diisocyanate to react with this water.

Even though the mechanism of curing is not completely known, it is most apparent in the practice of this invention that a very high level of shrinkage inhibition and/or setting is produced with only 'very small amounts of isocyanates, either unblocked or blocked as hereinafter set forth, when there is combined therewith a polymeric polyfunctional compound, either as such or when a pre-polymer is formed therefrom, and with or without a coreactant present. Furthermore, the handle of fabrics so treated is superior tofabrics similaly treated but in the absence of these additional components.

Exposure of the impregnated fabric or other structure to temperatures above ordinary room temperatures increases the rate of curing. Temperatures of about 220 to about 260 F. are preferred, while temperatures above about 300 F. are considered higher than necessary. Such higher temperatures, however, may be utilized provided care is taken not to expose the keratin fiber to these higher temperatures for so long a time that undue degradation takes place.

The time of'curing varies inversely with the temperature utilized. Optimum balance of time and temperature may readily be determined by the practitioner of this invention through shrinkage tests or crease ratings.

In the shrinkage inhibition embodiment of this invention, it has been found that the properties of fabrics and other structures treated in accordance with this invention are improved by mechanically working the fibers of the fabric after curnig. This is most efficaciously accomplished during a scouring operation, during which the fabric is passed repeatedly in and out of an aqueous solution containing small amounts of a wetting agent, with periodic squeezing between rolls. Similar effects are noted during normal dyeing after treatment. This subsequent immersion in aqueous media may cause hydrolysis of the reaction product of the keratin fibers with the isocyanate/polymeric polyfunctional compound system, or pre-polymers therefrom, but whatever the reason, sufiicient improvement is noted that a scouring or equivalent operation or other mechanical working of the fabric after curing is a highly preferred technique.

Improved shrinkage control is obtained in many instances if an aging period is interposed between the curing and scouring operations. Aging is similarly pre ferred in the durable setting of keratin fibers, although the scouring operation, for a garment manufacturer, is generally not feasible or necessary in this particular embodiment of the invention. This aging believed to be an extenuation of the curing mechanism, may be conducted for any desired period of time based upon degree of shrinkage inhiibtion obtained. Aging periods of from about 12 to about 24 hours, or more or less are quite satisfacory.

While any amount of the various systems of this invention may be applied to structures containing keratin fibers to modify the characteristics thereof, excellent relaxation and felting shrinkage inhibition and/or settability has been obtained at levels as low as about 2% total pickup of all components added. If it is desired to obtain relaxation shrinkage inhibition only, or a lesser degree of settability, then lesser amounts may be used. Generally, no more than about 6% by weight of the components is required in any instance. Greater amount, e.g., up to about 10% or more may be utilized, if desired, for specific end uses where soft handle is not required.

The desired amount of the components may be applied by any of the conventional techniques for applying liquids to fabrics, for example, by padding, immersing, spraying, from applicator rolls or other techniques whereby all fibers are treated substantially uniformly.

It has been found that better results are obtained if the pH of the fabric or treating solution is maintained substantially neutral. Strongly basic solutions, for example, those above a pH of about nine, may cause excessive damage to keratin fibers if the pH thereof is raised to this level for too long a period of time, while some difiiculty may be experienced in obtaining good results when the fabric or treating solution is maintained below a pH of about three. The fabric or other structure, which is often quite acidic, because of the carbonizing procedure which entails treatment with strong acid, is preferably washed or neutralized prior to treatment in accordance with this invention, to raise the pH level thereof.

The process of this invention may be utilized to improve the properties of any structure containing keratin fibers, either woven, non-woven, or knitted, dyed or undyed. Dyeing may be conducted after these structures have been treated in accordance with this invention without deleterious effects on the dyestuffs. For that matter, it has been found that pretreatment of keratin fibers with the systems of this invention greatly enhances the dyeability of such fibers with conventional dyestuffs. The keratin fibers accept the dyestuffs more readily and to a greater degree after reaction with the systems of this invention so that less dyestulf is required for a given shade of dyeing. For example, after treatment of keratin fibers in accordance with this invention, up to about 12 20% less dyestulf is required to obtain the same shade when dyeing keratin fibers with premetalized and acid milling dyestufis used conventionally to dye keratin fibers particularly wool.

The structure may be composed entirely of wool fibers or be produced from blends thereof with synthetic, natural or other keratin fibers. Preferred synthetic fibers include polyamides, such as poly(hexamethylene adipamide) and those derived from caprolactam; polyesters, such as poly(ethylene terephthalate); and acrylic fibers, such as acrylonitrile homopolymers or copolymers containing at least about combined acrylonitrile, e.g., acrylonitrile/methylacrylate (85/ 15) and cellulosics, such as cellulose acetate and viscose rayon. Of the natural fibers which may be blended with the keratin fibers, cotton is preferred. Other keratin fibers include mohair, alpaca, cashmere, vicuna, guanaco, camel hair, silk, llama, and the like.

Among the suitable isocyanates that may be used in accordance with this invention there are included aryldiisocyanates, such as 2,4-toluylene diisocyanate, 2,6- toluylene diisocyanate, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthylene diisocyanate, m-phenylene diisocyanate, diphenyl-4,4-diisocyanate, azobenzene-4,4' diisocyanate, diphenylsulphone-4,4-diisocyanate, l-isopropylbenzene-Ia,S-diisocyanate, l-methyl-phenylene-2,4 diisocyanate, naphthylene-1,4-diisocyanate, diphenyl-4,4-diisothiocyanate and diisocyanate, benzene-1,2,4-triisothiocyanate, 5-nitro-1,3-phenylene diisocyanate, xylylene-1,4-diisocyanate, xylylene-l,3-diisocyanate, 4,4-diphenylenemethane diisocyanate, 4,4'-diphenylenepropane diisocyanate and xylylene-1,4-diisothiocyanate and the like; alicyclic diisocyanates, such as dicyclohexamethane-4,4'-diisocyanate and the like; alkylene diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate and the like, as well as mixtures thereof and including the equivalent isothiocyanates. Of these compounds, the aryldiisocyanates are preferred because of their solubility and availability.

Additional isocyanates include polymethylene diisocyanates and diisothiocyanates, such as ethylene diisocyanate, dimethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, and the corresponding diisothiocyanates; alkylene diisocyanates and diisothiocyanates such as propylene-1,2-diisocyanate, 2,3- dimethyltetramethylene diisocyanate and diisothiocyanate, butylene-1,Z-diisocyanate, butylene 1,3-diisothiocyanate, and butylene-1,3-diisocyanate; alkylidene diisocyanates and diisothiocyanates such as ethylidene diisocyanate (CH CH(NCO) and heptylidene diisothiocyanate cycloalkylene diisocyanates and diisothiocyanates such as 1,4-diisocyanatocyclohexane, cyclopentylene-1,3-diisocyanate, and cyclohexylene 1,2 diisothiocyanate; aromatic polyisocyanates and polyisothiocyanates such as aliphaticaromatic diisocyanates and diisothiocyanates such as phenylethylene diisocyanate (C H CH(NCO CHZNCO) diisocyanates and diisothiocyanates containing heteroatoms such as SCNCH 'OCH NSC, SCNCH CH OCH CH NSC and SCNCCH 'S-(CH NSC;

1,2,3,4 tetraisocyanatobutane, butane-1,2,2-triisocyanate, toluylene 2,4,6 triisocyanate, toluylene-2,3,4-triisocyanate, benzene-1,3,5-triisocyanate, benzene 1,2,3 triisocyanate, l-isocyanato 4 isothiocyanatohexane, and 2- chloro-l,3-diisocyanatopropane.

The preferred diisocyanates, diisothiocyanates and mixed isocyanate-isothiocyanates have the general formula 13 in which R is a divalent hydrocarbon radical, preferably aryl, and Z is a chalcogen of atomic weight less than 33. For availability, toluylene-Z,4-diisocyanate is preferred.

The isocyanates or isocyanate-terminated pre-polymers utilized in accordance with this invention may be derived from the corresponding blocked isocyanate compound to produce essentially the same effect. Blocked isocyanate compounds contain little or no free isocyanate groups, as the result of the addition onto these groups by active hydrogen compounds (as determined by the Zerewitinoli method). These addition products are relatively inert at room temperatures, but have only limited thermal stability, so that upon heating beyond a certain temperature called the unblocking temperature, the addition product is activated, or freed, to form the same type product with keratin fibers as would the unblocked compound.

Preferred adduct-forming compounds produce adducts which may be activated, or unblocked, by heat alone. Typical active hydrogen compounds which provide heatreversible adducts include the following:

1. Tertiary alcohols, such as tertiary butyl alcohol, tertiary amyl alcohol, dimethyl ethinyl carbinol, dimethyl phenyl carbinol, methyl diphenyl carbinol, triphenyl carbinol, l-nitro tertiar butyl carbinol, l-chloro tertiary butyl carbinol, and triphenyl silinol and the like;

2. Secondary aromatic amines which contain only one group having a hydrogen reactive with an isocyanate group, such as the diaryl compounds including diphenyl amine, o-ditolyl amine, m-ditolyl amine, p-ditolyl amine, N-phenyl toluidine, N-phenyl xylidine, phenyl-alphanaphthyl amine, phenyl-beta-naphthyl amine, carbazole, and the nuclear substituted aromatic compounds such as 2,2'-dinitro diphenyl amine and 2,2'-dichloro diphenyl amine and the like;

3. Mercaptans, such as 2-mercaptobenzothiazo1e, 2- mercapto thiazoline, dodecyl mercaptan, ethyl-Z-mercapto thiazole, dimethyl-Z-mercapto thiazole, beta-naphthyl mercaptan, alpha-naphthyl mercaptan, phenyl-Z-mercapto thiazole, Z-mercapto-5-chloro-benzothiazole, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, and ethinyl dimethyl thiocarbinol and the like;

4. Lactams, such as epsilon-caprolactam, delta-valerolactam, gamma-butyrolactam, and beta-propiolactam;

5. Imides, such as carbimide, succinimide, phthalimide, naphthalimide, and glutarimide;

6. Monohydric phenols in which the hydroxyl group is the only group containing hydrogen reactive with the isocyanate group, such as the phenols, cresols, xylenols, trimethyl phenols, ethyl phenols, propyl phenols, chloro phenols, nitro phenols, thymols, carvacrols, mono alpha ethyl phenol, di alpha phenyl ethyl phenol, tri alpha phenyl ethyl phenol, and tertiary butyl phenol and the like;

7. Compounds containing enolizable hydrogen, such as acetoacetic esters, diethyl malonate, ethyl n-butyl malonate, ethyl benzyl malonate, acetyl acetone, acetonyl acetone, benzimidazole, and 1-phenyl-3 methyl 5-pyrazolon and the like.

The adduct forming compounds should, preferably, possess only one group containing a reactive hydrogen atom. The presence of more than one such group would permit polymerization reactions with the polyisocyanate, which are not desired in most instances.

Among the more preferable adduct-forming compounds are included diphenyl amine, phenyl beta naphthylamine, succinimide, phthalimide, tertiary butyl alcohol, tertiary amyl alcohol, dimethyl ethinyl carbinol, acetoacetic ester, diethyl malonate, mono alphaphenyl ethyl phenol, epsiloncaprolactam, and Z-mercaptobenzothiazole and others shown in the Examples.

It is believed that the adducts formed by reacting a polyisocyanate or pre-polymer therefrom with a compound from the groups listed above will become activated and dissociate into the original components upon application of heat to the system, so that such adducts may be mixed with reactants having a plurality of groups containing reactive hydrogen with the result that there is a reduction in the rate of reaction forming the polymeric materials until the mixture is subjected to heat.

In the preparation of the mono-adducts in general, the polyisocyanate and the adduct-forming compound are usually dissolved in a suitable inert solvent such as toluene, methyl ethyl ketone, or o-dichlorobenzene. The solutions are stirred together and permitted to stand. The reaction should be caused to take place at a temperature below the decomposition temperature of the desired product and preferably at a temperature not exceeding approximately C. In most instances, the reaction will proceed satisfactorily at room temperature. When the solvent used for the isocyanate compound and blocking agent is not also a solvent for the adduct formed, the adduct formed separates from the solution and is removed therefrom by filtration or evaporation of the solvent. The time required for the adduct to form will vary from a few minutes to several hours depending upon the particular reactants used. If a mono-adduct of a polyisocyanate is desired, usually an excess of the polyisocyanate is provided so that the product which separates will be substantially pure mono-adduct. The precipitated product will probably contain small amounts of unreacted material which, if necessary, can be removed by recrystallization or extraction procedures known to those skilled in the art.

In one embodiment of this invention, a blocked isocyanate is applied to keratin fibers in combination with the desired polymeric polyfunctional compound. Upon heating beyond the unblocking temperature, e.g. during curing, the blocked isocyanate compound is believed to dissociate into the corresponding isocyanate terminated compound and blocking agent, the isocyanate terminated compound then being free to react with the polymeric polyfunctional compound and keratin fibers in the presence of the blocking agent. The mechanism of this partic ular reaction is no more fully understood thtan the reaction using unblocked isocyanates, but the result is essentially the same whether the isocyanate is blocked or unblocked, indicating that the reaction mechanisms for the respective reactions, whatever they are, are essentially similar.

When a blocked pre-polymer is utilized, the same situation occurs, namely, upon heating beyond the unblocking temperature, the blocked pre-polymer is activated and freed to react with the keratin fibers to form the same reaction product with keratin fibers as if the pre-polymer had not been blocked.

When a blocked isocyanate compound is utilized the ratio of -N=C=X groups to active hydrogen atoms is computed from the number of --N=C=X groups theoretically available after unblocking.

Catalysts and or coreactants may be utilized in these embodiments of the invention just as if the isocyanate compound were not blocked.

Since these blocked isocyanate compounds are not free to react with other reactants or the keratin fibers except upon thermal activation, they are quite stable, so that the use of a nonreactive organic solvent is not necessary. Consequently, the blocked isocyanate compounds may be applied to keratin fibers from aqueous systems, for example, in the form of an aqueous emulsion or dispersion. For better penetration and uniformity of application of the blocked isocyanate compound into the keratin fibers, however, it is still preferred to apply these compounds from an organic solution.

The blocked isocyanate compounds are stable during storage and would be preferred in some instances where stability is a problem. It should be noted, however, that the use of nonreactive solvents substantially eliminates stability problems with the unblocked isocyanate compounds utilized herein, so that these systems are generally preferred for the improved results obtained in their use.

By polymeric polyfunctional compound is meant a long-chain polymer of the types described containing at least two groups having at least one active hydrogen atom as determined by the Zerewitinolf method. In the process of this invention, there may be utilized such compounds as polyesters, polyamides, polyepoxides, reaction products of phenols and alkylene oxides, formaldehyde resins, hydrogenation products of olefine-carbon monoxide copolymers, and polyepihalohydrins.

The polyesters suitable for use in accordance with this invention are well known and are generally prepared by conducting a condensation reaction between an excess of a monomeric or polymeric polyhydroxy compound and a polyacid or by esterifying a hydroxy substituted acid and a polyhydroxy alcohol.

Among the suitable acids there are included the alkane dibasic acids, alkene dibasic acids, cycloalkene dibasic acids, cycloalkane dibasic acids, aryl dibasic acids, or any of the foregoing types wherein the hydrocarbon radical is substituted with an alkyl, alkenyl, cycloalkyl, cycloalkenyl or aryl radical.

Representative dibasic carboxylic acids which can be employed for reaction with polyols in preparation of polyesters for use in accordance with this invention include the following: succinic; monomethyl succinic; glutaric; adipic; pimelic; suberic; azelaic; sebacic; brassylic; thapsic; 6-oxoundecanedioic; octadecanedioic acid; 8-octadecenedioic acid; eicosanedioic acid; 6,8-octadecadienedioic acid; malic; and the like. Other acids include: unsaturated acids such as maleic, fumaric, glutaconic, and itaconic; the cycloalkane dicarboxylic acids such as cyclopentane-1,2- dicarboxylic and cyclopentane-1,3-dicarboxylic; aromatic dicarboxylic acids such as phthalic, isophthalic, terephthalic, naphthalene 1,2-dicarboxylic, naphthalene-lj'dicarboxylic, naphthalene-1,4-dicarboxylic, naphthalene-1,5-dicarboxylic, naphthalene-1,S-dicarboxylic, diphenyl-2,2-dicarboxylic, diphenyl-4,4'-dicarboxylic and diphenyl-2,4'- dicarboxylic; and aliphatic-aromatic dicarboxylic acids such as 2,6 dimethylbenzene-1,4-dicarboxylic acid, and 4,5 dimethylbenzene-1,2-dicarboxylic acid; and the like. Natural products which are particularly useful include castor oil, which comprises a glyceride of ricinoleic acid, and ricinoleyl alcohol, and mixtures thereof.

Representative monomeric polyols for reaction with the above acids for the production of polyesters for use in accordance with this invention include the polyalkyleneether glycols represented by the formula HO(RO),,H, wherein R is an alkylene radical which need not necessarily be the same in each instance and n is a integer. Representative glycols include polyethyleneether glycol, polypropyleneether glycol, polytrimethyleneether glycol, polytetramethyleneether glycol, polypentamethyleneether glycol, polydecamethyleneether glycol, polytetramethyleneformal glycol and poly-1,2-dimethylethyleneether glycol. Mixtures of two or more polyalkyleneether glycols may be employed if desired.

Representative polyalkyleneether triols are made by reacting one or more alkylene oxides with one or more low molecular weight aliphatic triols. The alkylene oxides most commonly used have molecular weights between about 44 and 250. Examples include: ethylene oxide; propylene oxide; butylene oxide; 1,2-epoxybutane; 1,2-epoxyhexane; 1,2-epoxyoctane; 1,2-epoxyhexadecane; 2,3-epoxybutane; 3,4-epoxyhexane; 1,2-epoxy--hexene; and 1,2- epoxy-S-butane, and the like. Ethylene, propylene, and butylene oxides are preferred. In addition to mixtures of these oxides, minor proportions of alkylene oxides having cyclic substituents may be present, such as styrene oxide, cyclohexene oxide, 1,2-epoxy-2-cyclohexylpropane, and amethyl styrene oxide. The aliphatic triols most commonly used have molecular weights between about 92 and 250. Examples include glycerol; 1,2,6-hexanetriol; 1,1,1-trimethylolpropane; l,1,1-trimethy1o1ethane; 2,4-dimethylol- 2 methylol-pentanediol-1,5 and the trimethylether of sorbitol.

Representative examples of the polyalkyleneether triols include: polypropyleneether triol (M.W. 700) made by reacting 608 parts of 1,2-propyleneoxide with 92 parts of glycerine; polypropyleneether triol (M.W. 1535) made by reacting 1401 parts of 1,2-propyleneoxide with 134 parts of trimethylolpropane; polypropyleneether triol (M.W. 2500) made by reacting 2366 parts of 1,2-propyleneoxide with 134 parts of 1,2,6 hexanetriol; and polypropyleneether triol (M.W. 6000) made by reacting 5866 parts of 1,2-propyleneoxide with 134 parts of 1,2,6-hexanetriol.

Additional suitable polytriols include polyoxypropylene triols, polyoxybutylene triols, Union Carbides Niax triols LG56, LG42, LG112 and the like; Jefferson Chemicals Triol G-4000 and the like; Actol 32-160 from National Aniline and the like.

The polyalkylene-aryleneether glycols are similar to the polyalkyleneether glycols except that some arylene radicals are present. Representative arylene radicals include phenylene, naphthalene and anthracene radicals which may be substituted with various substituents, such as alkyl groups. In general, in these glycols there should be at least one alkyleneether radical having a molecular weight of about 500 for each arylene radical which is present.

The polyalkyleneether-thioether glycols and the polyalkylene-arylenether glycols are similar to the above-described polyether glycols, except that some of the etheroxygen atoms are replaced by sulfur atoms. These glycols may be conveniently prepared by condensing together various glycols, such as thiodiglycol, in the presence of a catalylst, such as p-toluene-sulfonic acid.

Additional polyesters include those obtained by reacting one or more of the above acids with a mixture of polyhydric alcohols comprising (1) polyhydric alcohols of the general formula:

N-alkylene-N wherein alkylene means a divalent saturated aliphatic radical having at least 2 carbon atoms, preferably not more than 5 carbon atoms, x, y and z are whole numbers and the sum of x, y and z is from 3 to 10, preferably from 3 to 6, at least two of the talkylene-Ol H groups contain primary alcoholic hydroxyl groups and R is a large alkyl group containing from 10 to 25 carbon atoms, and (2) polyhydric alcohols containing only carbon, hydrogen and oxygen, and the polyhydric alcohols from (1) and (2) are employed in such proportions that from 1 to 15 alcoholic OH groups are contributed by (1) for every 10 alcoholic OH groups contributed by (2).

The polyepoxides used in accordance with the invention are organic compounds having at least two epoxy groups per molecule and may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted with non-interfering substituents such as hydroxyl groups, ether radicals, and the like. Polyepoxides containing ether groups, generally designated as polyepoxide polyethers, may be prepared as well known in the art by reacting a polyol with a halogen-containing epoxide employing at least 2 moles of the halogen-containing epoxide per mole of polyol. Thus, for example, epichlorhydrin may be reacted with a polyhydric phenol in an alkaline medium. In another technique the halogen-containing epoxide is reacted with a polyhydric alcohol in the presence of an acid-acting catalyst such as hydrofiuoric acid or boron trifluoride and the product is then reacted with an alkaline compound to effect a dehydro- 1,4-bis(2,3-epoxypropoxy)benzene;

1,3-bis(2,3-epoxypropoxy)benzene;

4,4'-bis(2,3-epoxypropoxy) diphenyl ether;

1,8-bis(2,3-epoxypropoxy)octane;

1,4-bis(2,3-epoxypropoxy)cyclohexane;

4,4'-bis(2-hydroxy-2,4-epoxybutoxy) diphenyl dimethylmethane;

1,3-bis(4,5-epoxypentoxy)--chlorobenzene;

1,4-bis 3,4-epoxybutoxy-Z-chlorohexane;

diglycidyl thioether;

diglycidyl ether;

ethylene glycol diglycidyl ether;

propylene glycol diglycidyl ether;

diethylene glycol diglycidyl ether;

resorcinol diglycidyl ether;

1,2,3,4-tetrakis(2-hydroxy-3,4-epoxybutoxy)butane;

2,2-bis(2,3-epoxypropoxyphenyl)propane;

glycerol triglycidyl ether;

mannitol tetraglycidyl ether;

pentaerythritol tetraglycidyl ether;

sorbitol tetraglycidyl ether;

glycerol di-glycidyl ether; etc.

It is evident that the polyepoxide polyethers may or may not contain hydroxy groups, depending primarily on the proportions of halogen-containing epoxide and polyol employed. Polyepoxide polyethers containing polyhydroxyl groups may also be prepared by reacting, in known manner, a polyhydric alcohol or polyhydric phenol with a polyepoxide in an alkaline medium. Illustrative examples are the reaction product of glycerol and di-glycidyl ether, the reaction product of sorbitol and bis(2,3-epoxy 2-methylpropyl)ether, the reaction product of pentaerythritol and 1,2,3,5-diepoxy pentane, the reaction product of 2,2-bis(parahydroxyphenyl)propane and bis(2,3-epoxy- 2-methylpropyl)ether, the reaction product of resorcinol and diglycidyl ether, the reaction product of catechol and diglycidyl ether, and the reaction product of 1,4-dihydroxy-cyclohexane and diglycidyl ether.

Polyepoxides which do not contain ether groups may be employed as for example 1,2,5,6-diepoxyhexane; butadiene dioxide (that is, l,2,3,4-diepoxybutane); isoprene dioxide; limonene dioxide.

For use in accordance with the invention, we prefer the polyepoxides whic hcontain ether groups, that is, polyepoxide polyethers. More particularly we prefer to use the polyepoxide polyethers of the class of glycidyl polyethers of polyhydric alcohols or glycidyl polyethers of polyhydric phenols. These compounds may be considered as being derived from a polyhydric alcohol or polyhydric phenol by etherification with at least two glycidyl groups- The alcohol or phenol moiety may be completely etherified or may contain residual hydroxy groups. Typical examples of compounds in this category are the glycidyl polyethers of glycerol, glycol, diethylene glycol, 2,2-bis- (parahydroxyphenyl)propane, or any of the other polyols listed hereinabove as useful for reaction with halogencontaining epoxides. Many of the specific glycidyl polyethers derived from such polyols are set forth hereinabove. Particularly preferred among the glycidyl polyethers are those derived from 2,2-bis (parahydroxyphenyl)propane and those derived from glycerol. The compounds derived from the first-named of these polyols have the structurewherein n varies between zero and about 10, corresponding to a molecular Weight about from 350 to 8,000. Of this class of polyepoxides it is preferred to employ those compounds wherein n has a low value, i.e., less than 5, most preferably where n is zero.

In commerce, the polyepoxide polyethers are conventionally termed as epoxy resins even though the compounds are not technically resins in the state in which they are sold and employed because they are of relatively low molecular weight and thus do not have resinous properties as such. It is only when the compounds are cured that true resins are formed. Thus it will be found that manufacturers catalogs conventionally list as epoxy resins such relatively low-molecular weight products as the diglycidyl ether of 2,2-bis(parahydroxyphenyl)propane, the diglycidyl ether of glycerol, and similar polyepoxide polyethers having molecular weights substantially less than 1,000.

It is within the purview of the invention to employ mixtures of different polyepoxides. Indeed, it has been found that especially desirable results are attained by employing mixtures of two commercially-available polyepoxides, one being essentially a diglycidyl ether of glycerol, the other being essentially a diglycidyl ether of 2, 2-bis(parahydroxyphenyl)propane. Particularly preferred to attain such results are mixtures containing more than 1 and less than 10 parts by weight of the glycerol diglycidyl ether per part by weight of the diglycidyl ether of 2,2-bis (parahydroxyphenyl) propane.

The polyamides used in accordance with the invention are those derived from polyamines and polybasic acids. Methods of preparing these polyamides by condensation of polyamines and polycarboxylic acids are well known in the art. One may prepare polyamides containing free amino groups or free carboxylic acid groups or both free amino and free carboxylic acid groups. The polyamides may be derived from such polyamines as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, l,4diaminobutane, 1,3-diaminobutane, hexamethylene diamine, 3-(N-isopropylamino)propylamine, 3,3'-imino-bispropylamine, and the like. Typical polycarboxylic acids which may be condensed with the polyamines to form polyamides are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, betamethyl adipic acid, 1,2-cyclohexane dicarboxylic acid, malonic acid, polymerized fat acids, and the like. Depending on the amine and acid constituents and the conditions of condensation, the polyamides may have molecular weights varying about from 1,000 to 10,000 and melting points about from 20-200 C. Particularly preferred for the purpose of the invention are the polyamides derived from aliphatic polyamines and polymeric fat acids. Such products are disclosed for example by Cowan et al., Pat. No. 2,450,940. Typical of these polyamides are those made by condensing ethylene diamine or diethylene triamine with polymeric fat acids produced from the polymerization of drying or semi-drying oils, or the free acids, or simple aliphatic alcohol esters of such acids. The polymeric fat acids may typically be derived from such oils as soybean, linseed, tung, perilla, oiticica, cottonseed, corn, tall, sunflower, safflower, and the like. As well known in the art, in the polymerization the unsaturated fat acids combine to produce a mixture of dibasic and higher polymeric acids. Usually the mixture contains a preponderant proportion of dimeric acids with lesser amounts of trimeric and higher polymeric acids, and some residual monomeric acid. Particularly preferred are the polyamides of low melting point (about 20-90 C.) which may be produced by heating together an aliphatic polyamine, such as diethylenetriamine, triethylene tetramine, 1,4-diaminobutane, 1,3-diaminobutane, and the like with the polymerized fat acids. Typical among these is a polyamide derived from diethylene triamine and dimerized soybean fatty acids. The polyamides derived from aliphatic polyamides and polymerized fat acids, like the polyepoxides, are often referred to in the trade as resins even though not actually resins in the state in which they are sold and applied. Particularly good results are obtained in the use of low molecular weight, non-fiber forming polyamides sold under the trade name of Versamids.

Any suitable condensation product of a phenol and an alkylene oxide may be used such as, for example, the condensation product of cresol or 4,4'-isopropylidenediphenol with one of the aforementioned alkylene oxides.

Any suitable formaldehyde resin may be used such as, for example, the condensation product of formaldehyde per se or a compound capable of yielding formaldehyde such as, for example, paraformaldehyde or reaction products thereof with the condensation products of alkylene oxides to prepare polyoxymethylene compounds having terminal hydroxyl groups.

Any suitable hydrogenation product of olefine-carbon monoxide copolymers may be used such as, for example, the hydrogenation product of an ethylene-propylene-carbon monoxide copolymer and others disclosed in US. Pat. 2,839,478, issued to Wilms et al. June 17, 1958, and US. Pat. 2,495,292, issued to Scott, Jan. 24, 1950.

As noted above, keratin fibers can be durably set in any given configuration by applying one of the various systems of this invention to the fibers and curing while holding the fibers in the desired configuration. The keratin fibers, particularly fabrics containing them, are most conveniently held in the desired configuration during at least the initial stages of curing by pressing elements, preferably heated to initiate and facilitate curing. For example, there may be utilized such pressing elements as hand irons, pleating papers, rotary presses, decating machines, paper presses, calender rolls, Hoffman presses and the like.

It is also possible, in accordance with this invention, to set crimp in keratin fibers either in fabric form or prefabric form, e.g., roving, sliver, yarn and the like.

In pre-fabric form, the fibers can be set by curing while maintaining the fibers in a crimped or otherwise distorted configuration. The distorted configuration is most readily achieved in this embodiment of the invention by mechanical means, such as gear crimping apparatus, stuifer boxes and the like.

One of the systems of this invention can be applied to the fibers prior to distortion thereof, or afterwards, as desired, although it is generally preferred for control purposes to impregnate the fibers with one of the systems of this invention prior to distortion.

Permanently crimped yarn can also be obtained by knitting the yarn into fabric form and setting the fabric by impregnating the fabric with one of the systems of this invention and curing. The cured, and thereby set, knitted fabric is then unravelled. The resulting yarn is permanently set in the configuration in which it was set while in knitted form.

The setting of crimp in keratin fibers in fabric form has its greatest applicability in the field of stretch fabrics.

In the production of all-wool stretch fabrics, or fabrics containing at least a major proportion of wool fibers, a base fabric is shrunk by immersion in a treating solution, with or without reducing agents, so as to increase the crimp amplitude in either or both warp and filling yarns thereof. This increased crimp amplitude is substantially recoverable as stretch in the fabric. When such a fabric is treated with one of the systems of this invention and cured while in its shrunken condition, the rate of the fabrics return from a stretched condition, i.e., the fabric's elastic recovery rate, is greatly increased, thereby providing a livelier stretch fabric.

Once again, one of the systems of this invention may be applied to the fabric before or after shrinking, but, in this embodiment, it is generally preferred to impregnate the fabric with one of the systems of this invention after shrinking in order to avoid any effects that the shrinking bath may have on the compound systems of this invention. The impregnated fabric is then dried and cured to set the fabric in its shrunken condition.

Crimp in the yarns of a fabric may also be induced by mechanical means, such as compacting wherein a fabric is mechanically shrunken in a given direction, e.g., the warp direction. One apparatus for accomplishing this efiect is the Compactor, trade name for equipment developed by Fabric Research Laboratories. In this embodiment of the invention, the fabric is preferably impregnated with one of the compound systems, dried, compacted and cured to permanently set the fabric in its compacted form to obtain stretch in the direction of compacting. This technique is particularly useful for obtaining fabrics having stretch in the warp direction.

Fabrics having enhanced stretch in the filling direction only can be obtained by impregnating the fabric with one of the systems of this invention and exerting tension forces thereon in the warp direction during either or both drying and heating wherein curing is initiated. By this procedure, the crimp amplitude in the filling yarns is increased. The fabric is maintained in this condition throughout drying and curing, which as noted above, generally extends through an aging period to provide a fabric having enhanced stretch properties in the filling direction.

Fabrics treated with the various systems of this invention can have durable configurations imparted thereto in the textile mill, e.g., by pressing to impart a durable lustrous finish, or presensitized in the mill for subsequent durable setting by the garment manufacturer.

Durable luster or other effects wherein surface fibers of the fabric are set in a given configuration can be imparted to fabrics in the mill by impregnating the fabric with the systems of this invention and then at least partially curing the impregnated fabric while pressing at least one surface, for example, by passing the impregnated fabric between heated rolls at a temperature sufficient to initiate the cure. For embossed effects, batch or continuous molding procedures involving longer curing times under pressure are preferred.

Alternatively, the impregnated fabric can be pressed into the desired configuration and, in a separate operation, cured while substantially maintaining the configuration, whereupon this configuration will be retained even during subsequent wetting. In other words, it is essential only that the fabric be maintained in the desired configuration during curing.

The desired configuration is most conveniently imparted to the fabric during the early stages of curing, but the curing step can follow the pressing step if desired. In many instances, in fact, curing continues during an aging period following the normal curing operations. In that event, improved results are obtained if care is taken to maintain the fabric in its desired configuration during aging also. For that matter, some permanent setting of the fabric can be achieved during the aging period if desired.

Calendering techniques are preferred for imparting finishes in the mill. Calendering pressures from about /2 ton to about 2 tons per linear inch, preferably from about 1 ton to about 1 /2 tons per linear inch, are preferred. The upper limit for calendering pressures may be higher; the only real limitation being the equipment utilized and the properties desired.

Fabrics may be presensitized in the mill for subsequent durable setting by garment manufacturers by impregnating the fabric with one of the systems of this invention and maintaining the dried, impregnated fabric in a substantially uncured state until after garments have been produced from the fabric. The fabric can then be pressed into the desired configuration and cured, whereupon the configuration is durably set into the fabric.

As when lustrous finishes or other configurations are imparted at the mill level, the pressing and curing operations, through preferably simultaneous, may be performed in sequence, provided the fabric is maintained in the desired configuration, e.g., in a creased state, during curing. For example, an impermanent crease can be imparted to the fabric on a conventional Hoffman press utilized by the majority of garment manufacturers, particularly trouser manufacturers, and the creased fabric aged in this configuration to permanently set the crease.

In the presensitizing field, it is preferred to use either a blocked polyfunctional isocyanate or a blocked pre-polymer since the blocked isocyanate compounds have greater stability by themselves and on the fabric during shipment and storage than the equivalent unblocked compounds. Storage periods for presensitized fabrics vary considerably so that the blocked compounds provide a margin of safety without effecting performance.

In this embodiment of the invention, the blocked compound on the fabric is activated for reaction with the keratin fibers and other active hydrogen compounds available on the fabric by means of a heat-setting operation, for example, by Hoffman pressing, steaming in an autoclave, and the like, during which curing is at least initiated. Curing can then be completed during the aging period following the heat-pressing operation. For optimum results, as pointed out above, the fabric is maintained in the desired configuration throughout the aging period or until curing has been completed to a substantial degree.

A further advantage of this embodiment of the invention is that the blocked systems of this invention can be applied to the fabric from a water based system such as a dispersion or emulsion. Emulsions of these systems are normally produced from organic solutions of the blocked isocyanate compound by the addition of water and well known emulsifying agents thereto. This procedure obviously is less costly than when organic solutions per se are utilized, although improved penetration and hand are obtained when the isocyanate compound is applied to the keratin fibers from an organic solution.

As in the other embodiments of this invention, improved results are generally obtained when a catalyst and/ or coreactant are present during curing. The same amounts of reactants are utilized for durable setting in a given configuration as are utilized for stabilization of fabrics.

Durable configurations are imparted in accordance with this invention to fabrics containing keratin fibers while obtaining many desirable properties in the fabric. For example, the fabric is substantially stabilized toward both relaxation and felting shrinkage and, furthermore, has enhanced physical properties, such as tensile strength and abrasion resistance, rather than diminished physical properties as results from prior art processes which utilize reducing agents. In addition, fabrics so treated have no unpleasant odor such as characterizes the products of these other processes. Furthermore, these durable configurations are obtained in the absence of the large quantities of water required by many prior art processes.

Stabilization of a fabric depends to a great extent on its density, e.g., at lower densities, higher levels of treatment are usually utilized for best results.

The process of this invention may be varied to provide various levels of control of both relaxation and felting shrinkage and/or setting. For example, in some fabrics it may be desired to reduce relaxation shrinkage only, in that washability by reduction of felting shrinkage may not be required. For washable fabrics, both relaxation and felting shrinkage should be reduced to an acceptable level. Techniques for providing both type effects are illustrated in the following Examples.

In many of the following Examples, particularly where the level of shrinkage is above about 5%, the shrinkage values obtained may be lowered even further merely by increasing the level of pickup of the components. In the Examples, the effect of varying certain of the components is shown by lowering the level of pickup, so that differences in effect will be more apparent.

Parts are given on a dry basis in the Examples, as percent pickup on the wool sample being treated, unless otherwise indicated.

In preparing the solutions of the following Examples, the polymeric compound is first diluted below about 20% in trichloroethylene. The polyfunctional isocyanate is similarly diluted below this level, as are the coreactants and catalysts where utilized. These solutions are then mixed to provide the desired proportion of the various components. The resulting solution is diluted further with trichloroethylene, depending upon the wet pickup obtained on application of the various solutions to the fabric, to obtain the desired amount of pickup (on a dry basis) of the various components on the fabric.

EXAMPLE I Various solutions in trichloroethylene containing toluylene-2,4-diisocyanate, Quadrol [trade name for =N,N,N', N'tetrakis(Z-hydroxy propyl) ethylene diamine], varying amounts of various polyesters and a low molecular weight non-fiber forming polyarnide sold under the trade name of Versamid and a catalyst system composed of N- methyl morpholine (NMM), trimethylbutanediamine (TMBDA), and stannous octoate (SO) are padded onto swatches of a plain weave, all wool, piece-dyed fabric having 35 ends and 24 picks per inch of 3.875 run yarn to the pickup levels shown in Table I. The impregnated swatches are then placed in an oven at 160 F. for 5 minutes for drying and then placed in a second oven at 250 F. for curing.

Unless otherwise indicated, all shrinkage tests are run on unscoured samples. Where the samples are scoured prior to testing, the procedure is as follows:

The fabric is scoured in a dolly washer for 40 passes using water at 100-110 F. and 0.25% on the weight of wool of the wetting agent Surfonic N-95, followed by 20 passes in plain water to rinse and 20 more passes in a solution of Ampitol GIL softener. The fabric is then dried on a tenterframe to return the fabric to its initial dimensions (before scouring dimensions) and the shrinkage tests are conducted. The samples designated by the letter A in Table I are not scoured prior to testing, whereas the samples designated by the letter B are scoured in accordance with the above procedure.

Shrinkage tests are determined after aging for about 18 hours. The swatches are immersed in water containing 0.1% of Surfonic N-95, a non-ionic wetting agent, at 140 F. for 30 minutes, after which they are dried in a relaxed state on racks, pressed and measured to determine the extent of relaxation shrinkage. The swatches (3 lb. load) are then washed in a Kenmore Washer at 140 F. for 12 minutes, rinsed at F. and spun-dried for a total cycle of 20 minutes. The above wash cycle is repeated 9 times, after which the felting shrinkage is measured. The relaxation and felting shrinkage values are given in Table I.

TABLE I Area shrinkage Pickup (percent) dry basis (percent) Diiso- Poly- Cure Age Relax- Designation Polymer cyanate mer Catalyst Quadrol (min.) (hrs ation Felting Control 16.1 46.3 Nopcofoam 3914.-. 0. 97 2. 06 0.147 NMM, 0.0145 'IMBDA, 0.03 SO 0. 22 24 0. 8 11. 4 0. 97 2. 06 0.147 NMM, 0.0145 TMBDA, 0.03 SO 0. 22 15 18 1. 7 29. 8 0. 92 2. 10 0.147 NMM, 0.0145 TMBDA 0.03 SO 0. 22 5 24 1. 2 10. 4 0. 92 2. 10 0.147 NMM, 0.0145 'IMBDA, 0.03 SO 0. 22 18 1. 5 25. 7 C. 88 2. 14 0.174 NMM, 0.0145 TMBDA 0.03 50 0. 22 5 24 1. 7 15. 5 0. 88 2. 14 0.147 NMM, 0.0145 TMBDA, 0.03 SO 0. 22 1E 18 2. 2 30. 1 1. 05 1. 98 0.147 NMM, 0.0145 'IMBDA, 0.03 SO 0. 22 5 24 1. 6 10. 1. 1. 05 1. 98 0.147 NMM, 0.0145 TMBDA, 0.03 SO 0. 22 15 24 1. 6 9. 8

EXAMPLE II room conditions and 9.08 grams of Union Carbides L45 The procedure of Example I is utilized to impregnate a fabric swatch with a trichloroethylene solution containing the isocyanate, catalyst and coreactant of Example I, as well as a polyester prepared from 16 mols of adlpic acid, 16 mols of diethylene glycol and 1.0 mol of trimethylol propane. This polyester has an OH number of 56 and an acid number of about 1. The pickup on the fabric is 1.05% isocyanate, 2.76% polyester, 0.22% coreactant and the same level of catalyst as in Example I. After drying for 5 minutes at 160 F., curing for 15 minutes at 250 F., and aging for 48 hours, the relaxation and felting shrinkage values are found to have been decreased to essentially the same level as with Nopcofoam 3730.

EXAMPLE III The procedure of Example II is repeated except that equivalent amounts of 1,4 butanediol, methyldiethanolamine, trimethylol propane, triethanolamine, azelaic acid, pimelic acid, citric acid, 1,6 hexamethylene diamine, 2,6- diaminopyridine, 3,3'-diaminodipropylamine, triethylene tetramine and MOCA, trade name for 4,4'-methylene-bis- (2-chloroaniline), are substituted for the Quadrol coreactant. Substantially similar reduction of relaxation and felting shrinkage values is obtained.

EXAMPLE IV The procedure of Example 11 is repeated except that there is substituted for the polyester equivalent amounts of the following polymers:

( 1) the condensation product of cresol and ethylene oxide (2) a polyoxymethylene compound prepared from formaldehyde and butylene oxide having a hydroxyl number of about 5 6 (3) a hydrogenation product of an ethylene-propylenecarbon monoxide copolyrner having a hydroxyl number of about 33 (4) an epoxy resin made by condensing epichlorohydrin with 1,3-propylene glycol (5) and polyepichlorohydrin.

Once, again, the relaxation and felting shrinkage values are substantially reduced.

EXAMPLE V Formation of a Pre-Polymer Into a jacketed stainless steel reactor are poured 108 lbs. of the polyester of Example II. The reactor is then closed and the pressure therein reduced to about 10 mm. mercury after which the reactor is flushed with dry nitrogen. The pressure regulation and flushing operation is repeated for 3 cycles, after which 23 lbs. of dry toluene are poured into the reactor. A blanket of nitrogen gas is maintained in the vessel throughout the reaction. The pressure is again reduced to 10 mm. mercury and the reactor is heated to 140 C. to distill off the toluene, after which it is cooled to room temperature using cold water in the jacket around the reactor. The pressure is returned to silicone resin and 181.6 grams of distilled water are poured into the reactor. After stirring for 15 minutes to thoroughly mix the components, 14.3 lbs. of toluylene-2,4- diisocyanate are added rapidly and stirred until the heat of reaction ceases and the temperature has risen slowly up to 40-45 C. from room temperature of about 28 C. This occurs in about 20 minutes. The reaction mix is then heated at a rate of about 2 C. per minute to a temperature of 146 C., where it is held for 18 minutes and then cooled at a rate of about 2 C. per minute to a maximum temperature of E. Additional toluylene-2,4-diisocyanate (27.0 lbs.) is then added to the reactor and stirred for 30 minutes, after which 72 lbs. of trichloroethylene are added, thereby providing a solution containing about 70% of the resulting pre-polymer. The prepolymer solution is then transferred from the reactor to a pre-dried drum under a dry nitrogen atmosphere to avoid water contamination. At the time of the transfer, the pro-polymer solution is a pale straw color. The viscosity of the pre-polymer at this time is about 900 cps. (Brookfield viscosimeter spindle #2).

A treating solution is prepared from the 70% solution of the pre-polymer by dilution with additional trichloroethylene to below 20% solids to inhibit destabilization, after which are added Dow Cornings 1172 silicone resin and the coreactant Quadrol. The resulting solution is then diluted further with trichloroethylene and padded onto a swatch of the fabric of Example I to provide a pickup of 3.49% pre-polymer, 0.26% Quadrol and 0.4% silicone. After drying, curing and aging as in Example II, the relaxation and felting shrinkage values are measured and found to be considerably reduced.

EXAMPLE VI The procedure of Example V is repeated, except that aditional toluylene-Z,4-diisocyanate is added to various pre-polymer solutions to provide an N=C=O to OH ratio of 0.4, 0.7, 1.0, 2.0, 2.3, 3.4, 6.1 and 33.0, respectively. More effective reduction of relaxation and felting shrinkage values is obtained at ratios above 0.7, with best overall results at a ratio of 2.3. Felting shrinkage values are at their lowest levels at the higher ratios.

EXAMPLE VII A mixture of diisocyanate isomers containing 80% toluylene-2,4diisocyanate and 20% toluylene-2,6-diisocyanate are blocked by the addition thereto in stoichiometric amounts, of the various active hydrogen compounds dissolved in the various solvents containing certain catalysts as set forth in Table II.

After the heat of reaction subsides, the resulting solutions are heated at 80 C. for three hours. The resulting hot solutions are diluted to 10% solids with additional solvent heated to the same temperature, after which 10% trichloroethylene solutions of Nopcofoam 3914 containing Quadrol, trimethylbutanediamine and tin octoate are added thereto. The resulting systems are diluted further with a 1/1 solution of trichloroethylene and the particular solvent used during blocking, so that at wet pick-up during padding onto samples of the all-wool fabric of Example I the following pick-ups on a dry basis are obtained: 2.0% polyester, 0.20% Quadrol, 0.015% trimethylbutanediamine, 0.03% tin octoate and sufficient blocked diisocyanate to provide 1.0% active diisocyanate.

26 while still creased, is padded to 145 wet pickup with the solution of Example IX dried for 5 minutes at 160 F. and cured for 5 minutes at 25 F. All operations are conducted while maintaining the fabric in its creased condition.

The impregnated fabric is then dried for minutes at After g l f testmg as set forth above the 160 F. and cured at the temperature given in Table II. crease mung agam Very hlgh' In each instance, the relaxation and felting shrinkage of EXAMPLE XI the fabflc Samples are greatly lnhlblted Over the control Substantially durable creases are obtained when allvalues. Wool fabrlcs samples are treated in accordance with Ex- TABLE II Curing tempera ure Blocking agent Solvent Catalyst C.)

Ethannl Ethanol Nona 160 2-methyl-2-propannl Toluene Triethylamine 150 m-Crpq fl Bomene (lo 95 O-Nitrophenol Toluene 'Iriethylenediamine 85 o-Ghlorophenol Chlorofrom-.- o 65 Gnaiannl n Triethylamine 100 Resoreinol. D oxano d o 90 Phloroglucinol do do 120 l-dodecanethiol. Toluene 120 Benzenetbiol Chloroform Triethylenediamine 100 Ethyl nontnaoptafa nlnann Sodium methoxide 100 Diethyl malnnate (in do Y 95 Ca,pm1actam l Triethylenediamine 150 Ethyl carbamate Carbon tetrachloride Triethylamine 135 Boric acid Tetrahydrnfuran None 5 Substantially similar results are obtained when these active hydrogen compounds are utilized to block the prepolymer of Example V and this blocked pre-polymer is applied to the fabric and cured under the same conditions.

EXAMPLE VIII The relaxation and felting shrinkage values of the fabric of Example I are diminished considerably when the procedures of Examples II, III and IV are repeated except that the blocked isocyanates of Example VII are substituted for the isocyanates of those Examples and the curing temperatures of Example VII are utilized.

Dry crease performance data are obtained in the following Examples from presensitized fabric samples having dimensions of 4 inches in the filling direction by 6 inches in the warp direction. These samples are folded in half with the fold parallel to the warp yarns. The samples are then placed on a Hoffman press, the cover is closed and locked and the samples are pressed for periods of time indicated in the Example, generally with seconds top steam and 30 seconds baking, followed by 10 seconds vacuurning.

The creased samples are then opened and placed in a standing water bath, which contains a wetting agent and is heated to 170 F. After 30 minutes, the samples are removed, folded along their original crease line and allowed to air dry. After drying, the creases remaining in the samples are rated subjectively by at least three observers, the crease ratings running from 1 (no appreciable crease) to 5 (very sharp crease).

EXAMPLE IX A trichloroethylene solution containing 8.9 grams of the pre-polymer of Example V, 0.9 grams Quadrol and 0.62 grams of silicone resin 1172 is padded onto a sample of Deering Milliken woolen fabric Style No. 477 to 145% wet pickup. After drying for 5 minutes at 160 F., the fabric is folded and creased on a Hoffman press, using a pressing cycle of 30 seconds steam, 30 seconds bake, followed by 10 seconds of vacuum. The creased fabric is removed and, while maintained in a creased configuration, is cured for 5 minutes at 250 F. After aging overnight while maintained in a creased configuration, the fabric is tested as set forth above. The crease rating of this fabric is very high.

EXAMPLE X A sample of the fabric of Example I is creased on a Hoffman press as set forth in Example IX. The fabric,

ample VII but creased and cured at the temperatures given in Table II. In the procedure of Example VII the creases imparted to the fabric are substantially durable after creasing on the Hoffman press for those embodiments wherein the blocking agent comprises m-Cresol, o-nitrophenol, o-chlorophenol, benzenethiol, ethyl acetoacetate, guaiacol, resorcinol, boric acid, and diethyl malonate. Improved results are obtained, however, when the fabric is subjected to the heating operation at 250 F. for 5 minutes, since this temperature exceeds the unblocking temperatures for these compounds and assures release of active isocyanate groups. For the blocked compounds that are activated at higher temperatures, e.g., wherein the blocking agent comprises ethanol, 2-methyl-2-propanol, phloroglucinol, l-dodecanethiol, benzenethiol, ethyl acetoacetate, epsilon-caprolactam, and ethyl carbamate, the heating operation is conducted at the unblocking temperature shown in Table II for the individual compound.

EXAMPLE XII An all-Wool flannel fabric is padded with a trichloroethylene solution containing toluylene-2,4-diisocyanate, the polyester of Example II and silicone resin 1172 to provide a pickup of 2.0%, 0.25% and 0.2% of these components, respectively. The fabric is then dried by heating for 5 minutes at F., after which it is folded and pressed on a Hoffman press under a cycle of 30 seconds steam and 30 seconds bake, followed by 10 seconds vacuum. The fabric is then tested for crease retention both after aging for 15 minutes and after aging overnight in a creased configuration. The crease rating of both samples is excellent, the crease rating of the sample which was aged overnight being slightly higher.

Both crease ratings are increased slightly when the fabrics are baked for 3 minutes on the Hoffman press. The best crease ratings are obtained when the samples are heated for 15 minutes at 250 F. after Hoflman pressing, the crease rating being still higher after aging overnight, although the increase in rating after aging overnight is not as marked as when no subsequent heating step is used.

EXAMPLE XIII Various fabric swatches are padded as in Example XII to the same level of pickup of the various components. All swatches are dried for 5 minutes at 160 F., after which one swatch is creased as in Example XII on a cycle of 30 seconds steam, 30 seconds bake and 10 seconds vacuum. After creasing, this swatch is heated for minutes at 250 F. while held in a creased configuration.

The remaining samples are similarly heated for 10 minutes at 250 F. and are not creased as above until after a time lag of minutes, 1, 3, 6 and 18 hours, respectively.

The fabric sample which is creased and then heat-cured exhibits excellent crease retention properties. The remaining samples exhibit decreasingly sharp creases. For example, the fabric swatch which is creased after a time lag of 15 minutes is characterized by a good crease rating. After a time lag of 6 hours, good crease ratings still are ob tained. After an 18 hour time lag, however, a crease rating of 1.0 or no crease is obtained.

EXAMPLE XIV An all-wool fabric is impregnated with the solution of Example XII to the same level of pickup. After drying at 160 F., the fabric is pressed by passing through a 3 roll calender having a fiber filled roll set between two steel rolls in a vertical arrangement. The fiber filled roll is a 55/45, corn husk/cotton filled roll. Temperatures of about 350 F. and pressures of about 80 tons, which correspond to 3200 lbs. per square inch at the nip, are employed. The fabric is then full decated by forcing steam through the fabric at 60 p.s.i.g. and holding for 10 minutes after breakthrough. The fabric so treated is found to have a high luster which is durable to steam sponging and wetting.

What is claimed is:

1. A process for reducing the shrinkage in a textile fabric containing keratin fibers comprising impregnating said fabric with an organic solvent, said solvent being non-reactive with isocyanates, containing (1) the reaction product of a molar excess of a monomeric polyfunctional isocyanate and a polymeric polyfunctional compound selected from the group consisting of hydroxy terminated polyesters, synthetic polyamides having a molecular weight of from about 1,000 to about 10,000, and polyepoxides having terminal epoxy groups, (2) a different material having at least two groups containing at least one active hydrogen atom selected from diamines, diand tricarboxylic acids, aliphatic dithiols, and polyols containing 2-4 hydroxyl groups and (3) a monomeric polyisocyanate and drying and curing said fabric whereby the fabric is rendered less susceptible to shrinkage, the ratio of isocyanate groups to active hydrogen atoms in said solvent being greater than 1.0.

2. The process of Claim 1 wherein the reaction product of the polyfunctional isocyanate and polymeric polyfunctional compound is blocked.

3. The process of Claim 1 wherein the isocyanate is an aryl diisocyanate.

4. The process of Claim 1 wherein the polyfunctional compound comprises a hydroxy terminated polyester.

5. The process of Claim 1 wherein the polyfunctional compound comprises a synthetic polyamide having a molecular weight range of from about 1,000 to about 10,000.

6. The process of Claim 1 wherein the polyfunctional compound comprises a polyepoxide having terminal epoxy rou s. g 7. The process of Claim 1 wherein the material having at least two groups containing at least one active hydrogen atom is a diamine.

8. The process of Claim 1 wherein the material having at least two groups containing at least one active hydrogen atom is a dior tricarboxylic acid.

9. The process of Claim 1 wherein the material having at least two groups containing at least one active hydrogen atom is a polyol containing 2-4 hydroxyl groups.

10. A process for shrinkproofing a fabric containing keratin fibers comprising:

(a) impregnating said fabric with a non-reactive organic solvent solution containing (i) a monomeric polyisocyanate and (ii) a polymeric polyfunctional compound selected from the group consisting of synthetic polyamides other than polyesteramides and having 28 a molecular weight of from about 1,000 to about 10,000 and polyepoxides having terminal epoxy groups.

(b) drying said fabric to remove substantially all of any water present, and

(c) curing said fabric at a temperature sufficient to effect a reaction between the keratin fibers and the components of the organic solution.

11. The process of Claim 10 wherein the solution also contains a catalyst.

12. The process of Claim 10 wherein the isocyanate is an aryl diisocyanate.

13. A process for shrinkproofing a textile fabric containing keratin fibers comprising:

(a) impregnating said fabric with an aqueous composition comprising (i) a monomeric polyisocyanate blocked by reaction with an organic compound having an active hydrogen atom and which is activated by heating at an elevated temperature, and

(ii) a polymeric polyfunctional compound selected from the groups consisting of synthetic polyamides having a molecular weight of from about 1,000 to about 10,000 and polyepoxides having terminal epoxy groups, and

(b) drying to remove substantially all of any water present, and curing said fabric at a temperature sufficient to activate the blocked isocyanate and effect a reaction between the keratin fibers and the components of the aqueous composition.

-14. The process of Claim 13 wherein the ratio of isocyanate groups to activate the hydrogen atoms is greater than 1.

15. A process for shrinkproofing a textile fabric containing keratin fibers comprising:

(a) impregnating said fabric with a non-reactive organic solvent solution comprising (i) a monomeric polyisocyanate, and (ii) a hydroxy terminated polyester other than polyesteramides, the ratio of isocyanate groups to active hydrogen atoms in the polyester being greater than 1.0; and

(b) drying the fabric to remove substantially all of any water, and curing said fabric at a temperature sufficient to effect a reaction between the keratin fibers and the components of the organic solution.

16. A process for shrinkproofing fabrics containing keratin fibers comprising:

(a) impregnating said fibers with an aqueous composi tion containing a pre-polymer blocked by reaction with an organic compound having an active hydrogen atom and obtained by reacting an excess of a monomeric polyisocyanate with a polymeric polyfunctional compound selected from the class consisting of synthetic polyamides having a molecular weight of from about 1,000 to about 10,000 and polyepoxides having terminal epoxy groups,

(b) drying the treated fabric to remove substantially all of the water; and

(c) curing said fabric at a temperature sufficient to activate said blocked isocyanate terminated prepolymer whereby a reaction occurs between the keratin fibers and the pre-polymer.

17. The process of Claim 16 wherein the aqueous composition also contains a catalyst.

18. The process of Claim 16 wherein the aqueous composition also contains a co-reactant having at least two groups containing at least one active hydrogen atom selected from diamines, diand tricarboxylic acids, aliphatic dithiols, and polyols containing 2-4 hydroxyl groups.

19. A process for shrinkproofing fabrics containing keratin fibers comprising:

(a) impregnating said fabric with an aqueous composition comprising (i) a monomeric polyisocyanate blocked by reaction with an organic compound having an active hydrogen atom and which is activated by heating to an elevated temperature, and

(ii) a hydroxy terminated polyester, the ratio of isocyanate groups to active hydrogen atoms in the polyester being greater than 1.0; and

(b) drying to remove substantially all of any water present, and curing said fabric at a temperature sufficient to activate the blocked isocyanate and eifect a reaction between the keratin fibers and the components of the aqueous composition.

20. A process for durably setting a fabric containing keratin fibers in a desired configuration comprising:

(a) impregnating said fibers with a non-reactive organic solvent solution comprising (i) a monomeric polyisocyanate, and

(ii) a polymeric polyfunctional compound selected from the class consisting of synthetic polyamides other than polyesteramides and having a molecular weight of fromabout 1,000 to about 10,000 and polyepoxides having terminal epoxy groups,

(b) fixing said impregnated fabric in the desired configuration;

(c) drying to remove substantially all of any water; and heating said fabric, while maintaining it in the desired configuration, to a temperature suflicient to set the fabric.

21. The process of Claim 20 wherein the isocyanate is toluylene-2,4-diisocyanate.

22. A process for shrinkproofing a fabric containing keratin fibers comprising:

(a) impregnating said fabric with a non-reactive organic solvent solution containing (i) a monomeric polyisocyanate,

(ii) a co-reactant having at least two groups containing at least one active hydrogen atom selected from diamines, diand tricarboxylic acids, aliphatic dithiols and polyols containing 2-4 hydroxyl groups, and

(iii) a polymeric polyfunctional compound selected from the group consisting of synthetic polyamides other than polyesteramides having molecular weights of from about 1,000 to about 10,000 and polyepoxides having terminal epoxy groups,

30 (b) drying said fabric to remove substantially all of any water present; and (c) curing said fabric at a temperature sufficient to elfect a reaction between the keratin fibers and the components of the organic solution. 23. The fabric prepared by the process of Claim 1.

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FOREIGN PATENTS 767,287 1/ 1957 Great Britain.

890,228 2/ 1962 Great Britain.

573,932 12/1945 Great Britain 8-116 220,077 2/ 1959 Australia 8-128 696,029 8/1953 Great Britain 117-150 579,340 7/1946 Great Britain 117-150 BENJAMIN R. PADGETT, Primary Examiner R. S. GAITI-IER, Assistant Examiner US. Cl. X.R. 8-128 R; 128 A