US3832132A

US3832132A - Process for improving the dimensional stability of wool-containing fabrics

Info

Publication number: US3832132A
Application number: US00774499A
Authority: US
Inventors: G Tesoro; S Sello; R Wurster
Original assignee: JP Stevens and Co Inc
Current assignee: JP Stevens and Co Inc
Priority date: 1968-11-08
Filing date: 1968-11-08
Publication date: 1974-08-27
Anticipated expiration: 1991-08-27
Also published as: FR2030069A1; GB1254243A; DE1956153A1; FR2030069B1

Abstract

THIS INVENTION CONCERNS A NOVEL PROCESS FOR MODIFYING PROTEINACEOUS SUBSTRATES COMPRISING TREATING SAID SUBSTRATES WITH POLYFUNCTIONAL REAGENTS DERIVED FROM UREA AND HEATING THE TREATED SUBSTRATE UNTIL THE DESIRED MODIFICATION TAKES PLACE.

Description

7 3,832,132 Patented Aug. 27, 1974 United States Patent Oflice ABSTRACT OF THE DISCLOSURE This invention concerns a novel process for modifying proteinaceous substrates comprising treating said substrates with polyfunctional reagents derived from urea and heating the treated substrate until the desired modification takes place.

The present invention relates to novel processes for treatment of proteinaceous materials and more particularly processes for enhancing the properties and characteristics of textiles containing wool fibers and improved products obtained thereby.

Various methods have been devised for the treatment of textile fabrics containing wool in order to improve certain properties thereof. Particularly important to the wool industry are methods and compositions to bring about improvements in the dimensional stability and the felting characteristics of textiles containing wool fibers. Although many methods have been developed for W001 treatment, relatively few give satisfactory results from the standpoint of improvement in dimensional stability and felting. Moreover, prior known methods frequently may deleteriously and adversely affect the appearance, handle, strength and other properties of the woolen textiles.

Accordingly, it is the object of the present invention to provide novel processes for imparting improved properties to proteinaceous materials, particularly wool-containing textile materials, which overcome the shortcomings and disadvantages associated with prior methods and compositions.

It is a further object of the present invention to provide novel processes for imparting excellent properties and characteristics to wool-containing textiles which avoid the drawbacks of prior methods and compositions.

It is a further object of the present invention to provide novel processes for imparting to wool-containing textile material excellent properties of dimensional stability and resistance to felting.

It is a further object of the present invention to provide woolen textiles having improved properties, particularly dimensional stability.

'- It is a further object of the present invention to provide processes for treating wool-containing textile materials without adversely atfecting the appearance, handle, strength and other desirable properties of the textile.

J It is a further object of the present invention to provide processes for treating wool-containing fabrics which have desirable surface appearance after laundering, particularly minimal fuzziness.

In attaining the above objects, one feature of the present invention resides in imparting excellent properties and characteristics to proteinaceous materials by treating textile materials containing wool fibers with a selected group of polyfunctional compounds of a specified structure whereby the improvements in dimensional stability and other physical properties are achieved without adversely affecting the appearance, hand, strength and other desirable properties of the textile.

More particularly, a proteinaceous textile substrate such as wool and its blends is treated with a solution of poly functional composition represented by the structural formula:

[ lt-i it] R d H H d m wherein A is selected from the group consisting of epoxyalkoxy, particularly wherein the alkoxy moiety has from 3 to 6 carbon atoms, Az, NHC,,H ,,Az, and O-C,,H Az, where a is an integer from 1 to 4, and m is an integer from 2 to 3, Az is where R R and R are independently selected from the group consisting of H and alkyl having from 1 to 4 carbon atoms,

R is selected from the group consisting of H and alkyl having 1 to 5 carbon atoms,

J is a divalent or trivalent organic radical, and

Q is selected from the group consisting of divalent aromatic and alkyl-substituted aromatic groups having 6 to 18 carbon atoms,

to deposit an amount sufficient to obtain the enhancement A is selected from the group consisting of epoxypropoxy, Az, NH-C H ,,Az, and OC,,H ,,Az, where a is a number from 1 to 4, m is a number from 2 to 3, AZ is wherein where R and R are independently selected from the group consisting of H and alkyl having from 1 to carbon atoms;

R is H or alkyl having 1 to 5 carbon atoms;

I is a divalent aliphatic or alicyclic radical, and

Q is methylphenylene.

In the preferred process embodiment, a woolen or,

wool blend substrate is contacted with an amount of one or more of the preferred treating agents, in the form of a liquid solution, suflicien't to deposit a modifying or enhancing amount of agent and cured until the desired coricentration of treating'agent required varies" between" about 0.25 to by weight with the true upper limit determined primarily by economics. The mode of application is not critical; padding, spraying,dipping or the. like being applicable. Depending upon the initial concentration of agent utilized, the pickup varies between about to about 300%. Normally the treated substrate is dried and cured at about 100 C. to 200 C. for about 3 to 6 minutes, longer times being acceptable.

A further feature of the present invention resides in treating wool-containing textile materials with a group of polyaziridinyl compounds and with selected co-reactants in order to further enhance and improve the dimensional stability and other physical properties of the textile without adversely affecting the appearance, hand, strength and other desirable properties thereof.

A more specific feature of the present invention resides in treating wool-containing textile materials according to a process hereinafter defined with a certain group of relatively high molecular weight polyaziridinyl compounds in the presence of selected polybasic acids of polyamino compounds whereby excellent properties are imparted to the textile.

The above, as well as other objects, features and advantages of the present invention will become apparent from the following detailed description thereof.

According to the present invention, novel processes are provided whereby wool-containing textile materials, particularly woven and knitted fabrics containing wool fibers, are treated with selected polyfunctional compounds to impart dimensional stability and other desirable properties to the textile product Without substantially adversely affecting the appearance, handle, strength and other mechanical properties thereof.

It has been observed that the dimensional properties of Wool-containing textile materials are considerably enhanced as a result of the novel processes of the present invention and further that the desired properties are obtained Without causing undesirable discoloration, harshening or other undesirable side effects. Moreover, in accordance with a further aspect of the present invention, novel processes are provided whereby an enhancement in the physical properties of wool-containing textile materials, particularly dimensional stability, are obtained when the above-defined aziridine compounds are used in conjunction with co-reac-tants to be defined hereinafter which bring about an even greater improvement than was heretofore possible.

A detailed description of the substituents included within the formulae defining the polyfunctional compounds of this invention follows:

The compounds that are preferred for the present invention are polyfunctional compounds defined by Formula (I), supra.

Aziridinyl and oxiranyl compounds as defined by the symbol A in the various formulas which are suitable for purposes of the present invention may be obtained by several methods described in the chemical and patent literature. Briefly described, the class of compound defined by Formula (I), supra, may be prepared by reacting an organic polyisocyanate with, preferably, an organic compound containing at least two amino groups to produce an intermediate having at least two isocyanate groups. Then the intermediate compound is reacted with a hydroxy-terminated 1,2-alkylenimine or hydroxyterminated oxirane to obtain the desired product. It has been determined that compounds falling within the scope of the Formula (I), supra are exceptionally suitable for the treatment of wool-containing textile materials. It will 'be apparent from a consideration of the compounds encompassed by, the present invention that the average molecular weight of the preferred compounds will range fromabout 1000 to about 6000. Such compounds are commercially available or can be prepared by known methods from commercially 'available rWniatrialsf The following descriptivematter illustrates specific aspects of the various moieties that are used to produce the polyfunctional compounds of this-invention.

GROUPS REPRESENTATIVE- bale Name:

Phenylene (0, m, or p) Methylphenylene (various isomers such as 4-methylm-phenylene) (0, m, or p)-Pheny lenedi- The residue I can be (a) divalent, or (b) trivalent. (a) Illustrative of the residue J in the'form of a divalent radical are the following: Y (II) (CH where x is a number from 1 to 100. (III) (C H ,O) C,-,H where a is a number from'l to 4, and x is a number from about 1 to about 100, pre'ferably from about 5 to about 40. (IV) (CH CH=CHCH which is d erived from polybutadiene, wherein the average degree of polymeri zation, u is between about 6 and aboutlOO.

( a 2a( a Za )x O a 2a "T) yCa 2aT: where I p a is 1 to 4; x and y independently are 1 to and g Y L is a divalent alicyclic radical of to 20 carbon;

atoms, C to C alkylene, or C to C alkylene having the chain interrupted by 1 to 10 groups in which R is alkyl having 1-to=5 carbon.

atoms. 1

In all instances, J is connected directly to nitrogen atoms, that is, the general formula is wherein the molecular weight of J ranges from about 14 to about 5,500, and A, R, and Q have thedefinitions ascribed to them above. r For instance, suitable divalent radicals ofthe type represented by Formula (V) are provided'by condensation. products of the alkoxylate type which can be formed from any of the following starting compounds 'HOLOH- which are given by way of example by (A) ethoxylation with approximately 10 parts of ethylene oxide, (B) propoxylation with approximately 8 to 95 mole-parts I of propylene oxide, or v v (C) alkoxylation with a proportionate mole ratio of higher or mixed alkylene oxides.

to" ntole- When I represents a trivalent radical, glycerin or similar. triols can be used as starting materials. 7 l The starting materials which can be used when I represents a divalent radical are listed as follows:

STARTING COMPOUNDS HO-LOH PRIOR TO ALKOXYLATION Ethylene glycol BIO-CHgCEk-OH Propylene glycol H0OH(CH:)CH=OH Trimethylene glycol HO-CHgCHgGHr-OH H Decamethyleue glycol HO-(CHgM-OH V v Diethylene glycol HO-CHzCHzOCHzCH1-OH i 2-butene-1,4-diol.--- H0OH3CH=CHCH20H GHjCHZ 1,4-cyclohexanedimethanol Ho-cmcim cHcm-on CHICH;

2,2'-thiodiethanol HO-CH;CH1SCH1CH OH Diethanolamines (HO-CHflHg-hN-R, wherein R is H or alkyl having 1 to 5 carbon atoms, andg is -CH1CHgN(R)CHzCHr-.

Typical of the methods whereby the aziridinyl com- P Y Y compounds as defined y the Symbol in the various Roman numeral formulas including (I) pounds may be made 15 the procedure shown m Examp 1e 1 which are suitable for the purposes of the present invenand the subsequent reaction with the reaction aziridine. tion are illustrated by the f l below and by the Illustrative of the above compounds are: 5 fen-ed preparation of Example 3.

I L i HN 0 0 pet tag p Hl I'm H O i (CH CH=CHCH:)enNCN@'Cl-h o o N ll LN l H111 1 H3O NON-(MEMO cmmo-cmcm-o(clmomclm-ncn cm a a a 11 .H H H cmonmcnucmnolmcnamcarom-@411, in I 8 I'm O= =0 ocmcmW -cm)= (cmnmcmcmo I H H H H HN@-@NCN(CIhCHzOMCHaCHzNCN-WNH a a Y o= -ocmcnn'I oih(-cm), (cmhoon ncmomo- =0 H H H H I O :43-0 CHzHCHi-Z) In carrying out the present invention, the wool-containing textile material which may be in any suitable form such as fiber, yarn or fabric may be treated with the polyfunctional compounds defined by Formula (I), generally by impregnation with a solution thereof.

The solvent vehicle may be aqueous or non-aqueous. The treating mixture of solvent and polyfunctional compound may be in the form of a solution, suspension, emulsion or the like. The textile material may be sprayed, padded, immersed, dipped, brushed or similarly contacted with the polyfunctional compound, thereafter dried and cured. Exposure to elevated temperature may be used to insolubilize the polyfunctional compound. Alternatively, the textile, after being contacted with the polyfunctional compound, may be permitted to stand for a brief period so as to achieve insolubilization.

If desired, the treated wool-containing textile material may thereafter be washed to remove residual soluble chemicals which may interfere or adversely afiect the properties of the final product. Excellent dimensional stability is imparted to woolen textiles treated in the aforementioned manner. When laundered by conventional procedures commonly used for cotton or hydrophobic fibers, the woolen textile materials treated in accordance with the present invention as well as garments made from such woolen textile materials do not exhibit noticeable felting, fuzzy appearance, shrinkage or other undesirable properties which would deleteriously affect the final quality of the garment.

The present invention constitutes a considerable advance over what has gone heretofore inasmuch as the treatment with the selected polyfunctional compounds does not deleteriously alter the color, hand or other aesthetic properties of the woolen textile and, moreover, does not substantially adversely impair the tensile strength, tear strength, abrasion resistance and other important properties of the textile material.

In accordance with a further preferred aspect of the present invention, textile materials containing wool are treated with the aziridine compounds represented by the Formula (I) supra in combination with the coreactants as defined hereinafter to achieve even greater enhancement of the dimensional stability and other desirable properties of the textile products. Suitable co-reactants are polybasic acids and polyamine compounds particularly saturated aliphatic dicarboxylic acids containing from 2 to 12 carbon atoms and polyalkylenepolyamines containing, for example, from 4 to 20 carbon atoms and 2 to 5 nitrogen atoms. Representative examples of acids include succinic acid, adipic acid, sebacic acid, citric acid, tartaric acid, polyacrylic acid, and the like. Examples of poly-" amines include diethylenetriamine, tetraethylenepentamine, hydroxyethylethylenediamine, polyethylenimines of wide molecular weight range, 1,3-diaminopropane, 1,6-diaminohexane, and the like.

In general, it has been observed that the co-reactants will accelerate insolubilization of the polyfunctional compound in or on wool and will drive the polymerization reaction to completion in a shorter period of time. In addition, it has been observed that in certain respects the resulting properties of the textile are superior to that treated with the polyfunctional compound alone. It is, however, to be noted that the invention does not require the presence of co-reactants in order to achieve satisfactory dimensional stability or other desirableproperties in the Wool-containing textile. i v

The treating mixture containing .the polyfunctional compounds as defined by the structural Formula (I) and a vehicle therefor may take the form of a solution in organic solvents or water when feasible. The compounds may also be applied from aqueous emulsion which can be rapidly prepared by suitable choice of solvents an'demulsifying agents. Because of their stability at room temperature over relatively long periods of time, solutions and emulsions of the treating agents of the present invention may normally be stored without special precautions being necessary.

According to a further more detailed aspectof the present invention, the wool-containing textile material may be treated with the above-defined polyfunctional compounds, either before or after dyeing because the treatment with aziridines does not alter or deleteriously affect the dyeing properties of the woolen textiles. No adverse effects on the rate and evenness of the dyeing have been observed, even if the treatment with the polyfunctional compound is carried out before the dyeing operation. Moreover, there is no change of shade or-adverse effect on color-fastness if the treatment with the polyfunctional compound is applied to the textile after the dyeing operation. This aspect of the invention is particularly important from a commercial standpoint inasmuch as it allows a wider range of operating conditions and greater flexibility in carrying out the modification of the woolen textile product.

When carrying out the process of the invention utilizing aziridinyl compounds in combination with selected co-reactants as defined above, the treatment may be cartied out in a single step or in several separate steps. Because of their nature, it is possible to use the polyfunctional compounds as defined herein in a single step in conjunction with other functional finishes such as water and stain repellents, soil release agents and the like. The latter include the acrylics and their salts as well as the fluorocarbons. The ease of formulation and application of the polyfunctional compounds makes them particularly suitable for use in combination with other finishes to impart permanent creasing properties to woolen fabrics.

No special precautions need be taken when carrying out the process of the present invention'inasmuch as the insolubilization reaction of the polyfunctionafcompound on the wool textile can take place at moderate temperatures. It is therefore possible to obtain the desired insolubilization reaction even by tumble-drying procedures which are especially desirable when the objective is the stabilization of manufactured woven or knitted garments which cannot be conveniently processed in curing ovens at elevated temperature. Thus, the present "invention provides a commercially feasible means for applying shrink- 9 proofing finishes to manufactured garments in a convenient or simple method without requiring the use of complex equipment and procedures.

-Applicable to wool textile materials in any form or shape, the present invention may be used to impart dimensional stability and other desired properties to wool fibers, woolen and worsted yarn, woven or knitted fabrics and garments. In general, for optimum effects to be realized, the fabric customarily contains appreciable proportion of wool fiber, generally 30% or more, 60 to 100% being the preferred range.

It will be apparent from the foregoing that the wool present in the textile can be by itself or present in a blend or admixture with other natural fibers such as cotton or with synthetic fibers such as polyamides, polyesters, polyolefins and acrylic fibers.- The examples which appear hereinafter generally show the reaction condition suitable for obtaining satisfactory results. It will be noted, however, that the optimum conditions for processing any given fiber blend or mixture will be determined by many factors such as concentration of reagent, time of impregnation, temperature, atmospheric conditions, configuration, as well as other parameters. Conditions within the ranges discussed hereinafter will generally give satisfactory results on the textile materials indicated although these ranges are not to be construed as limiting the invention in any way.

For most purposes, the polyfunctional compounds employed in this invention are used in amount sufficient to keep shrinkagebelow 6% based upon the original dimensions of the substrate. Generally between about 0.5 and 10% by weight add-on based upon the weight of the dry substrate is suflicient to keep shrinkage below the desired level. This add-on is referred to as a modifying amount of polyfunctional composition throughout this application. For example, in a typical embodiment where a 100% wool substrate is treated, add-n amounts of about 2% to about 5% based on the weight of the wool treated are, preferred, although amounts outside these ranges may be used.

In accordance with the aspect of this invention relating to the combination of the aziridine compound and coreactant, when the co-reactant is used, the amount thereof employed should be sufficient to provide approximately 0.5 to about 2.0 reactive groups of the co-reactant which is in the form of amino groups or carboxyl groups for each aziridinyl group of the aziridinyl compound defined by Formula (I). In other words, approximately 0.5 to about 2.0 equivalents of the co-reactant, polyamine or polycarboxylic acid, should be present for each aziridinyl equivalent present. It has been determined that the coreactant may be added to the treating solution which contains the aziridinyl compound of Formula (I) or can be applied in a separate step either before or after application of the-aziridinyl compound. Properties and characteristics may vary somewhat depending upon the sequence of reaction; however, it has been observed that generally the order of reactants can be varied with equally satisfactory results.

As mentioned above, the aziridinyl compound can be applied to the wool-containing textile material in any convenient manner. Generally, the aziridinyl compound is dissolved at the desired concentration in an anhydrous organic solvent such as a hydrocarbon including toluene, xylene, petroleum fractions and similar materials, halogenated solvent such as carbon tetrachloride and perchloroethylene or any other convenient inert solvent in which the aziridinyl compound is soluble and which in itself will not adversely affect the woolen textile material or deleteriously interfere with the insolubilization of the aziridinyl compound or interfere with the functioning of the co-reactant if any is used.

The aziridinyl compound may be applied to the woolen textile substrate in the form of a self-emulsifiable concentrate which is diluted with water to the desired concentration prior to using same. In'any event, the co-reactant polyamine or polycarboxylic acid may be added to the treating solution or emulsion containing the aziridinyl compound or the co-reactant may be applied in a separate step from a solution prepared from the same solvent as that used in connection with the aziridine compound, or a different organic solvent or water. When the co-reactant is applied in a separate step either before or after the treatment with the aziridinyl compound, the solvent from which it is deposited on the woolen textile material may be mis cible or immiscible with the solvent system from which the aziridinyl compound is applied. It has been observed that the pH of the treating solution may be varied within a considerable range. Generally, very high and very low pH ranges should be avoided since degradation of the wool can occur under extreme conditions. A pH range in general of 3.0 to about 9.0 is suitable with the range of 4.0 to 8.0 being preferred for most applications.

Methods of application of the polyfunctional compounds to the woolen textile not being critical, the treating solution can be applied by any suitable means including padding, spraying, dipping or the like. Excess solution is generally removed by wringing, squeezing, centrifuging or spinning. Thereafter, the woolen textile material is dried at a temperature ranging from ambient temperature to about C., the range of 50 C. to 70 C. being particularly convenient. It is to be noted that the drying step is not essential to the overall efficiency of the process. After drying, the treated textile is cured by allowing it to stand at ambient temperature for several hours or preferably by heating for a few' minutes at C. to about 170 C. to complete the insolubilization reaction. The time required for the curing step varies with the particular reagent and the concentrations employed. It will be noted that the curing duration will be dependent upon the temperature, the higher temperatures requiring less curing time. Curing cycles of 3 to 15 minutes at C. to 150 C. have been found to give excellent results in the majority of situations. The above ranges are indicative of suitable reaction conditions and are by no means considered limiting of the present invention.

Although the textile may be used without further treatment, it is generally preferred to wash the textile after the curing step with suitable detergent solutions, solvent scours or by any other desirable means in order to remove residual soluble unreacted chemicals. The textile material can thereafter be dyed by conventional procedures or subjected to other conventional chemical or mechanical finishing operations such as shearing, topping with softeners and other textile treatments designed to impart specific properties or behavior characteristics.

The following examples are illustrative of the process of the invention. Parts are by weight unless otherwise specified. The methods used in obtaining the test data given in the examples are as follows:

Shrinkage: Measurement after laundering according to the following procedure: Samples ca. 18 x 18 inches with 10 x 10-inch markings laundered in an automatic home-type agitator washing machine at 41 C., using a 5-lb. load, detergent (Fab or Tide) and 15 minutes suds time. Washed samples were rinsed, extracted in the washer for the full cycle, dried flat on a horizontal screen and fiat-bed pressed for 5 seconds at -150 C. and conditioned for a minimum of 12 hours at 63 to 67% RH. and 20-22 C. The samples were then measured for shrinkage in the warp and filling directions. Results reported in percent. The number of laundering-drying cycles is indicated by 5L or 10L, respectively.

Flex abrasion resistance: ASTM D-1175-61T (Stoll Flex Abrader, lb. head, 2 lbs. toggle). Results reported in cycles to break.

Stiffness: Cantilever procedure. ASTM D-1388-55T. Re

sults reported in milligram-centimeters.

1 1 Reflectance: ASTM E97-5 5 Photovolt 610 .and

' 6104, using the green tristumulus filter.

H ABBREVIATIONS I'NTABLES. When used individually:

Search EXAMPLE 1 Preparation of a polyfunctional compound having 1) a backbone derived from a polyetherdiamine, and (2) was charged with 200 grams .of the polyetherdiamine dissolved in. 200 gramssof dichloromethane and cooledt to l5i5 C. Then, 4-methyl-m-phenylene.-,diiso.cyanate (24.5grams, 0.141 mole) dissolved in 50 gramsoinichloromethane was added. The temperature-was allowed to rise to.25 C. during-one hour.

Next; the second stage of adding terminal 2-(1-aziridinyl)ethoxy radicals was carried out. (l-Aziridine),ethanol (8.8 grams, 0.101 mole) was added dropwise to 19/20 of the original solution obtained fromthe, first stage.=The addition was completed in 0.5- hours, all at 2612 C. The solution was stirred for 2 hours longer, afterwhich time the infrared spectrum was devoid of the isocyanate band at 4.3 to 4.5 microns. The aziridinyl content of'the product was 0.034 equivalent per 100 grams of solid (0.047 eq./100 -g., calculated). The solution was miscible with dimethylformamide. l

EXAMPLE 2 i For the chemical equation applying to the first stage; see Example 1, x=about 33 on the average. 3

Second stage:

terminal 2-(1-aziridinyl)ethoxy groups F z'rst stage:

CHCHaNHz HzN H-CH: O)

ICTID, and isocyanate-terminated intermediate having a backbone derived from a polyetherdiamine.

O=JJNCH2CHT In the first stage, the isocyanate-terminated intermediate (ICTID) having a backbone derived from a polyetherdiamine was prepared in a manner similar to that of Example 1. The polyetherdiamine had an' average equivalent Weight of approximately 1000. T In the second stage, 0127 equivalent of the i'socyanateterminated intermediate was allowed to react with 5.6 grams (0.13 mole) of ethylenirnine dissolved in 50 grams of dichloromethane. The conditionswere similar to those described in Example 1. The aziridinyl content was found to be 0.06 equivalent per 100 grams of solid (0.061 'eq./

100 g. calculated).

EXAMPLE 3 A preparation similar to Example 1 but with 2,3-epoxypropyl in place of 2-(1-aziridinyl)ethoxy as the terminal groups v v For the chemical equation applying to the first see Example 1, x=about 33 on the average.

Second stage:

stage,

Second stage:

In the first stage, the isocyanate-terminated intermediate (ICTID) having a backbone derived from a polyetherdiamine was prepared in a manner similar to that of Ex.- ample 1, from the polyetherdiamine having anaverage equivalent weight of approximately 1000..

In the second stage, 0.109 equivalent of the isocyanateterminated intermediate (calculated isocyanate content, 0.129 equivalent) was allowed to react with'8.06 grams (0.109 mole) of 2,3-epoxy-1-propanol. (The 2,3 -epoxyl-propanol in 50 grams of dichloromethane was added gradually over the period of an hour to the isocyanateterminated intermediate.) After stirring for one week at room temperature, the epoxy content was found 'to be 0.031 equivalent per grams of solid (calculated: 0.050 eq./ 100 g.). The infrared spectrum was devoid of the band characteristic of isoc yanate at the end of t hepreaction period.

13 EXAMPLE 4 A preparation similar to Example 2 but of lower molecular weight I For the chemical equations'applying, see Example" 2,

14 of Example 1. A 38% solution of the product in dichloromethane was diluted with dimethylformamide to give the percentages OWB shown in the accompanying table. S- lutions were applied by 'rneans'of a laboratory padder. After padding, the samples were framed at the original grams (0.244 mole) of ethylenimine dissolved in 50 grams of dichloromethane. Conditions were similar to those described in Example 1. The aziridinyl content was found to be 0.11 equivalent'per 100 grams of solid (0.13 eq./ 100 g., calculated). The infrared spectrum of the product was devoid of the isocyanate band.

' EXAMPLE A preparation similar to Example 1 but of lower molecular weight wherein x=about 16 on the average. 5 dimensions and dried at approximately C. All sam In the first stage, the isocyanate-terminated intermediples were cured for 5 minutes at 135 C. The cured-fabate (ICTID) having a backbone derived from a poly- 'ric was rinsed in dimethylformamide, then in water, again ether-diamine was prepared in a manner similar to that of framed to the original dimensions, and dried. Very ef- Example 1. The polyetherdiamine had an average molec- 10 fective shrinkproofing was achieved on the wool, as the ular weight of approximately 1000. It was marketed under results in the accompanying table bear out.

EXAMPLE 0 Warp flex Green Shrinkage, percent Product of Example Actual abrasion filter 6, percent weight resistance Warp reflec- 1L 5L gain, 0.5 x 2 stiffness, tence, Sample OWB WPU OWF percent lbs.,cycles mgJcm. percent W F W F 5.0 5.75 cos 1. 250 349 63 1.0 (0.5) 1.5 (0.5) 3.3 119 5.93 5. 24 1.050 334 63 2.0 (0.5; 2.5 (1. 0) 1.7 124 2.11 ass 1.050 202 as 2.5 0.5 4.0 1. 5) 0.2 121 0.97 3.19 850 20a 02 3.5 (0.5) 5.5 (1. 0)

Percentages in parentheses are the opposite of shrinkage.

the trade name Polyetherdiamm' e L-1000 by Union Car- 25 EXAMPLE 7 bide Corp. In the second stage, 0.223 equivalent of the isocyanate- 'Dlmenslonal Stablhzatlon 15mg the Product of terminated intermediate was allowed to react with 10.5 Example 2 Samples of the 100% woolen fabric weighing 6.15 oz./sq. yd. were treated according to the general procedure of Example 6 with the following variations: The reagent was the product of Example 2. A 40% solution of it in dichloromethane was diluted with dimethylformamide to give the percentages OWB shown in the accompanying table. For the preparation of the E and *F series of samples, the pad bath also contained tetraethylenepentamine '(TEPA). The concentration of TEPA was approximately 9% of the concentration of the product of Example 2 OWB. Adter padding, samples were dried at approximately 65 C. Quantitative details and curing conditions are in the accompanying table, as are the evaluation results of the use of the reactive polymer having a backbone made up of repeating propyleneoxy units and having terminal amide-type l-azir-idinyl groups.

TABLE T0 EXAMPLE 7 Warp flex abrasion resist- Shrinkage, percent Product of Actual ance Warp Example 2, percent TEPA, Cure, weight 0.5 x 2 stifi- 1L 5L Wool fabric OW 5 min gain, lbs ness, sample OWB WPU OWF percent at 0. percent cycles mg. cm W F W F 5.2 123 6.4 None 135 1. 6 800 140 9.0 (1.5) 13.5 3. 0 2 129 6.7 None 163 3.0 825 220 2.0 None 3.0 0. 5 .4 125 4.2 None 1.8 950 7.0 None 11.5 3.0 4 118 4. 1 None 163 l. 5 900 128 7. 0 0. 5 11. 0 3. 5 .2 132 6.8 0. 0 135 3. 2 975 178 5. 5 None 7. 0 None .2 122 6.3 0.6 163 3.5 1,000 198 4.5 (0.5) 6.5 None .4 123 4.2 0.4 135 2.8 1,000 128 5.0 (1.0) 8.0 None 4 119 4. 1 0. 4 168 2. 5 750 120 7. 0 0. 5 8. 0 0. 5 Control 725 114 15.0 3.5 27.5 15. 0

Percentages in parentheses are the opposite of shrinkage.

mole of (1-aziridine)ethanol in a manner similar to that EXAMPLE 8 used in Example 1. The aziridinyl content of the product was 0.09 equivalent per 100 grams of solid (0.10 eq./100 65 Dlmenslonal Sta lhzatlonl 2 the P Oduct g., calculated). The infrared spectrum of the product was of 'EXamP e 3 devoid of the isocyanate band. The product was very soluble in dimethylformamide.

EXAMPLE 6 Dimensional stabilization of woolen fabric by treatment with the product of Example 1 Samples of the 100% woolen fabric weighing 6.15 oz./sq. yd. were treated according to quantitative details in the accompanying table with solutions of the product 75 evaluation results, improved dimensional stabilization resulted from the. use of the productof Example'3,-. espeall features which would be treated as equivalents thereof cially when tetraethylenepentarmne also was used. by those skilled in the art to which the invention pertains. I I TABLE TO EXAMPLES 1 i I Warp flex Shrink e, erccnt Product of Example 3, Actual abrasion ag p r A. percent TEPA weight resistance Warp 1L 5L 7 OWF, gain, 0.5x2lbs., stiffness, Wool fabric sample OWB WPU OWE percent percent cycles mg. cm. W F W F 3.6 125 4.5 None 2.9 1, 050 145 6.5 None 11.5 4.0

2.7 124 3.3 None 2.5 1,025 146 8.0 None 12.0 255- 0. 9 121 1. 1 None 2. 5 870 171 6. 5v None 11. 3. 3.6 129 4.6 0.9 5.7 1, 050 537 2.0 None 3.0 None 2.7 125 3.4 0.6 4.1 1,015 440 1.5 (0. 5) 2.0 None 0.9 129 1.1 0.2 2.3 1,025 308 2.0 None 3.5 None Control untreated 725 114 15. O 3. 5 27. 5 15. 0

The opposite of shrinkage. v v EXAMPLE 9 What is claimed is:

1. A process for improving the dimensional stability of Wool-containing fabrics comprisingapplying to said fabric a polyfunctional compound of theformula A procedure similar to that of Example 8 was fol- J lowed, using the product of Example 4, a polymer whose l: I I5 I I 1 central moiety had repeating ethyleneoxy groups (fewer R H H Dimensional stabilization using the product of Example 4 than the product of Example 2), and whose terminal whelfiin groups were amide-type l-aziridinyl groups. A 41% A 15 an epoxyalkoxy group; solution of the product in dichloromethane was diluted in all t g r fr m 2 o 3; with dimethylformamide to give the percentages OWB hydrogen alkyl 0f fwm 1 to 5 carbcnatomsl shown in the accompanying table. All samples Were cured J 15 a member selected from the group Co sis g f. for 5 minutes at 135 C. Excellent dimensional stabiliza- (--OH where x is an integer from 1- to 100; tion was obtained, whether in the presence of tetraethyla 2a )xC H2 Where ,a is an integer of ene-pentamine or without it. from 1 to 4 and x has the'meaning given above;

TABLE TO EXAMPLE 9 Warp flex Shrinkage, percent Product of Example 4, Actual abrasion percent TEPA weight resistance Warp 1L 5L OWF, gain, O.5x2lbs., stiffness, Wool fabn'c sample OWB WPU OWF percent percent cycles mg. cm. W F W F A..- 5.2 123 6.4 None 5.5 1,325 711 0.1 1.0 1.0 1.0 B 3.4 127 4.3 None 3.2 1,050 398 1.5 1.0 2.0 1. 0.85 129 1. 1 None 2 5 1,250 602 2.5 None 4.5 0.5 5.2 125 6.5 1.3 4 3 1,200 610 1.5 None 2.0 None 3.4 125 4.2 0.8 6 7 1,550 475 0.5 None 1.0 0.5 H 0.85 125 1.1 0.3 4.5 700 509 3.0 g 0.5 4.5 0.5 Control untreated 725 114 15.0 3.5 27.5 15.0

EXAMPLE 10 (CH CH=CHCH where u is an integer of Dimensional stabilization using the product of from to 100; V

1 x m 1e E a P 5 2.(o 2.- 1 A procedure similar to that of Example 9 was followed, C H O (j H using the product of Example 5, a polymer whose central moiety had repeating propylcneoxy groups (fewer than where the product of Example 1), and whose terminal groups a and 1' have the meanings given above; were 2-(l-aziridinyl)ethoxy groups. A 20% solution of y 13 an integer of from 1 to 100; and the product in dichloromethane was diluted with dimethyl- L is alkylene of 2 to 20 carbon atoms or alkylformamide to give the percentages OWB shown in the one of 2 to 20 carbon atoms having the accompanying table. All samples were cured for 5 minchain lnterrupted by l'to 10 utes at 135 C. Evaluation results in the accompanying or table indicate that the reactive derivative of a polyether- I diamine is a very effective shrinkproofing agent.

TABLE To EXAMPLE 10 Warp flex Shrinkage, percent Product of Example 5, Actual abrasion Warp percent weight resistance stift- 1L 5L gain, 0.5 x2 lbsi, ness, Wool fabric sample OWB WPU OWF percent cycles mg. em- 'W F w F 5.2 126 6.6 7.3 1,375 715 0.5 0.5 1.0 0.5 3.4 127 4.3 6.9 1,125 705 0.5 0.5 1.0 0.5 1.7 133 2.2 5.8 075 483 1.5 None 3.0 0.5 0.85 130 1.1 4.5 700 253 3.5 None 5.5 None 725 114 15.0 27.5 15 0 It is understood that various other modifications will be I Where R is alkyl 0f l Carbon m i i apparent to and can readily be made by those skilled in 11 011 0119, the art without departing from the scope and spirit of this HO (0 01120133) 1Ij1EV6lll1tlOIll..ACCOfd1I1ily 1: 18:10:;1Iil6l1ii? tthalt Z scope H20 (0 CEO-Hm? I p p c 1 1 t e c alms app e ere e nm e r p and Q 1s a member selected from the group consisting tion set forth herem but rather that the claims e conof phenylene methylphenylene, phenylenedimethyb strued as encompassing all the features of patentable we, bi henylylene, methylenediphenyl'ene, "b p novelty which reside in the present invention, including phenylene and naphthy lene, p

1 7 said polyfunctional compound being applied from a liquid medium, and insolubilizing said polyfunctional compound on said fabric.

2. A process as claimed in Claim 1 wherein said polyfunctional compound is applied to said fabric in the form of a solution in an anhydrous solvent.

3. A process as claimed in Claim 1 wherein said polyfimctional compound is applied to said fabric in the form of an aqueous solution.

4. A process as claimed in Claim 1 wherein said polyfunetional compound is applied to said fabric in the form of an aqueous emulsion.

5. A process as claimed in Claim 1 wherein A is an epoxypropoxy group of the formula 6. A process as claimed in Claim 1 wherein said polyfunctional compound is insolubilized by curing at a temperature of about 100 C. to 200 C.

References Cited UNITED STATES PATENTS 2,327,760 8/1943 Bestian 8Oxirane 3,165,375 1/1965 Tesoro 8--127.6 3,248,280 4/1966 Hyland 8Oxirane 3,279,882 10/ 1966 Tesoro 8127.6

LEON D. ROSDOL, Primary Examiner H. WOLMAN, Assistant Examiner US. Cl. X.R.

8-1l5.7, 128 R, 128 A, Digest 8; 260-348 mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,832,132 Dated August 27, 1974 Giuliana C.Tesoro, Stephen B.Sello and Rudolf F.Wurster It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

C B olumn 4, line 39, should read L is a divalent alicyclic radical of 3 to 20 carbon Column 5, under "Starting Compounds, etc. (the 7th compound) l,4-cyclohexanedimethanol in the formula should read CH CH HO-CH 'CH 'CHCH -OH cH of Column 5, formula at the bottom of the page, at the right side should read Column 8, line 55, "tied" should read ried Column 11, line 66, Second stage Formula, last ring, should read I Columns 13 and 14, Example 6 Table, under "Green filter reflectance percent" the sample "Control untreated" "62" should read 65 Signed and sealed this 15th day of April-12 75.

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