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Publication numberUS3645781 A
Publication typeGrant
Publication dateFeb 29, 1972
Filing dateJul 14, 1969
Priority dateJul 15, 1968
Also published asDE1934678A1, DE1934678B2
Publication numberUS 3645781 A, US 3645781A, US-A-3645781, US3645781 A, US3645781A
InventorsThomas D Brown, Bryan Dobinson, Michael Rushforth, Walter Wilson, Kenneth Winterbottom
Original AssigneeCiba Geigy Ag, Iws Nominee Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Treatment of keratinous fibers and fabrics
US 3645781 A
Abstract
The present invention relates to a process for rendering keratinous material, particularly wool, resistant to shrinkage and for imparting durable press characteristics to the material. The products used therefor are polythiol compounds containing in the molecule (a) a radical of a polyhydric alcohol, (b) poly(oxyalkylene) chains, and (c) radicals of mercapto-ethers or mercapto-esters.
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United States Patent Brown et al.

[ Feb. 29, 1972 TREATMENT OF KERATINOUS FIBERS AND FABRICS lnventors: Thomas D. Brown, Keighley; Michael Rushiorth, Brighouse; Bryan Dohinson, Duxford; Walter Wilson, Cambridge; Kenneth Winterbottom, Whittlesford, all of England Assignees: l.W.S. Nominee Company Limited, London, England; Ciba-Geigy AG, Basel, Switzerland Filed: July 14, 1969 Appl, No.: 841,557

Foreign Application Priority Data July 15, 1968 Great Britain .33,687/68 U.S.Cl ..ll7/14l,ll7/10,117/11,

117/1394, 117/1355 A, 8/127.5 Int. Cl. ..D06m 15/16 Field of Search ..117/141,l39.4,10,139.5 R,

117/11; 8/l27.5;260/2 EP, 79, 609 A Primary ExaminerWil1iam D. Martin Assistant Examiner-Theodore G. Davis Att0rney-Harry Goldsmith, Joseph G. Kolodny and Mario A. Monaco [57] ABSTRACT The present invention relates to a process for rendering keratinous material, particularly wool, resistant to shrinkage and for imparting durable press characteristics to the material. The products used therefor are polythiol compounds containing in the molecule (a) a radical of a polyhydric alcohol, (b) poly(oxyalkylene) chains, and (c) radicals of mercapto-ethers or mercapto-esters.

27 Claims, No Drawings TREATMENT OF KERATINOUS FIBERS AND FABRICS The present invention relates to a process for modifying keratinous material, and, in particular, to a process for rendering the material resistant to shrinkage and to a process for imparting durable press characteristics to the material.

A number of shrink-resist processes for keratinous material are known, some of which comprise the application of a resin to the material which may be in fabric or fiber form. Shrinkresist processes stabilize the dimensions of keratinous materials against shrinkage due to felting.

Durable press processes for keratinous material are also known and many of them employ resins the same or similar to those used in shrink-resist processes. In some durable press processes the desired shape is imparted to the keratinous material before the resin is cured and then curing is allowed to take place while the material is maintained in the desired shape, e.g., in form of creases or pleats. In others the resin is applied after the desired shape is imparted to the material. Durable press processes stabilize the shape and surface smoothness of the material against agitation in the presence of aqueous solutions. The desired shape may be imparted to the material before or after resin treatment by well-known methods involving the use of setting agents such as water, reducing agents, and bases.

A desirable, though not essential, feature of shrink-resist and durable press processes is that the keratinous material so treated should be washable in domestic washing machines. To be machine washable the finish on the treated material should withstand vigorous agitation in warm or hot water containing detergents, and this requirement sets a severe test for the durable press and shrink-resist treatments.

One of the attractions of keratinous fibers and particularly wool is their excellent handle, and an important disadvantage associated with many of the resins used in shrink-resist and durable press processes is the harsh handle imparted to the fiber and fabric containing the fibers. Attempts to overcome this harsh handle have been made by the use of softeners, but these have been unsuccessful in that they reduce the effectiveness of the resin.

We have now found a class of resins, comprising certain thiol-terminated poly(oxyalkylene) resins, which can be used in durable press and shrink-resist processes successfully and which does not impart an unattractive handle to the treated material. These resins cure, i.e., undergo reaction, on the keratinous fiber and we have further found that the rate of curing may be largely controlled by selection of the appropriate catalyst.

Accordingly, the present invention provides a process for modifying keratinous material which comprises treating the material with a polythiol resin having at least two thiol groups per molecule and containing a. a radical of a polyhydric alcohol,

b. bound to this radical, at least two poly(oxyalkylene) chains,

c. bound through oxygen atoms to carbon atoms in the said poly(oxyalkylene) chains, at least two residues selected from the group comprising an acyl residue of a thiol-containing aliphatic carboxylic acid or a residue, after removal of a hydroxyl group, of a thiol-containing aliphatic alcohol, and curing the resin on the material.

The treatment according to the invention, whether to achieve shrink-resist or durable press results,'provides fibers or garments which will withstand washing in machines and still retain their original dimension and shape. In addition to the excellent handle obtained from material treated in accordance with the invention, the treated material also has good recovery from wrinkling, which is an important attribute in fabrics employed in trousers where there is a strong tendency to wrinkles in the areas of the knee and back of the knee. Of course, wrinkle resistance is an important advantage in many garments.

The resins used in the process according to the invention, as well as inhibiting or preventing felting shrinkage, also inhibit or prevent relaxation shrinkage, which is an important problem associated with knitted goods, and thus the present process finds particular application in the shrink-resist treatment of knitted goods.

The term "keratinous material as used throughout this specification includes all forms of keratinous fibers or fabrics and garments made therefrom, e.g., fleeces, tops, card sliver, noils, yarns, threads, pile fabrics, nonwoven fabrics, woven fabrics and knitted goods. In most cases the treatment will be applied to fabrics or made-up garments though it is quite feasible, and may be desirable in some circumstances, to shrink-resist fibers, e.g., in the form of tops. The material to be treated can consist either wholly of keratinous fibers or of blends of these fibers with synthetic fibrous and filamentary material such as polyamides, polyesters, and poly(acrylonitrile), and with cellulosic and regenerated cellulosic material. In general, however, the material should contain at least 30 percent by weight of keratinous fibers and better results are obtained with percent keratinous fiber-containing material.

The keratinous material may be virgin or reclaimed: preferably, though not exclusively, it is sheeps wool. It may also be derived from alpaca, cashmere, mohair, vicuna, guanaco, camel hair, silk, and llama, or blends of these materials with sheeps wool.

The polythiol resin used in the process of the invention preferably contains three to six thiol groups per molecule. Especially good results have been obtained with resins containing three or four thiol groups per molecule.

Preferred polythiols are those having a molecular weight between 400 and 10,000, particularly those of formula [R [(0-alky1erre)m0H]u-i I [(0a1kylene)mO (C O )nIX]D in which p, and q each represent positive integers,

m is an integer of at least 1 and may have different values in each of the p and (q-l) chains,

n is at most 2,

p is at least 2,

(p+q) equals at least 3 and at most 7, each alkylene group contains a chain of at least two and at most six carbon atoms between consecutive oxygen atoms,

R represents an aliphatic radical containing at least two carbon atoms,

and X represents an aliphatic radical containing at least one thiol group.

The oxyalkylene units in individual poly(oxyalkylene) chains may be different. They may be substituted, if desired, by e.g., phenyl or chloromethyl groups.

There may thus be used the partially or fully esterified compounds of the formula in which R, alkylene," m, p, and q have the meanings previously assigned, and r is a positive integer which may be as high as 18 or even 24.

Further preferred are esters of the formula in which "alkylene," signed,

p is an integer of at least 3 and at most 6,

and R represents an aliphatic hydrocarbon radical having at least three and at most six carbon atoms.

Still further preferred are esters based on glycerol, hexanel,2,5-triol, or hexane-1,2,6-triol, and ethylene oxide and/or propylene oxide, i.e., those of the formulas m, and u have the meanings previously asand CHn-(O ctHzomo-oo-cumu SH in which m and u have the meanings previously assigned, and t is an integer of at least 2 and at most 3.

These thiol-terminated poly( alkylene oxide) ester resins are readily prepared by the reaction of a polyhydric alcohol with an alkylene oxide followed by esterification of the terminal hydroxyl groups with a mercaptocarboxylic acid.

Suitable polyhydric alcohols include ethylene glycol, poly(oxyethylene) glycols, propylene glycol, poly(oxypropylene) glycols, propane-1,3-diol, poly(epichlorohydrin)s, butane-1,2-diol, butane-1,3-diol, butane-l ,4-diol, butane-2,3-diol, poly(oxy-l,1- dimethylethylene) glycols, poly(tetrahydrofuran)s, glycerol, 1,] ,l-trimethylolethane, l,l,1-trimethylolpropane, hexanel,2,5-triol, hexane-1,2,6-triol, pentaerythritol, dipentaerythritol, mannitol, sorbitol, and adducts of alkylene oxides with ammonia or amines, such as diethanolamine and tetrakis(2-hydroxyethyl)ethylenediamine. Suitable alkylene oxides include ethylene oxide, propylene oxide, and, less preferably, the butylene oxides, epichlorohydrin or tetrahydrofuran. If desired, the polyhydric alcohol may be treated with one alkylene oxide, say propylene oxide, and then tipped with a different alkylene oxide, such as ethylene oxide.

The preferred mercaptocarboxylic acids for the esterification are thioglycollic acid (Z-mercaptoacetic acid), and 2- mercaptopropionic acid, but other mercaptomonocarboxylic acids which may be used include mercaptoundecylic acid and mercaptostearic acid.

Polythiol esters most preferred for the purposes of the present invention are those obtained from glycerol, propylene oxide, and thioglycollic acid, i.e., of formula where m has the meaning previously assigned, having a molecular weight within the range 1,000 to 5,000. Such resins are commercially available.

The second class of thiol-terminated poly(alkylene oxides) includes those ethers of formula R [(Oalkylene) O OHgCfHCHgSH] in which R denotes OH, (O-alkylene),OH, -O-CO-C,,H, SH,

R, alkylene, m, p, q, and u have the meanings previously assigned,

and v is an integer of at least l and may have different values in each of the p chains.

The oxyalkylene units in the individual poly(oxyalkylene) chains may likewise be different, but are preferably the same, and may be substituted if desired by e.g., phenyl or chloromethyl groups.

Preferred among such ethers are those which are also of formula in which alkylene, R,, m, R;,, p,, and q have the meanings previously assigned, and further preferred are those of the formula in which R 2, m, and p have the meanings previously assigned, are commercially available. The ethers of Formula II in which R denotes OH may be prepared in a known manner by reaction of an alkylene oxide with a polyhydric alcohol, etherification of the hydroxyl groups of the product with epichlorohydrin, and treatment with sodium hydrosulphide to replace the chlorine by a sulphhydryl group (see US. Pat. No. 3,258,495, and United Kingdom Specifications 1,076,725 and 1,144,761). In many cases the average number of thiol groups per molecule is not an integer but, for example, may be 2.6. This is attributable partly to the replacement of the chlorine atom by the -SH group not going to completion, and partly to side reactions: for example, the chlorohydrin ether obtained by reaction with epichlorohydrin may also react with epichlorohydrin, so forming an ether which contains two replaceable chlorine atoms per hydroxyl group originally present in the polyhydric alcohol.

III

in which R,, t, m, v, and p have the meanings previously assigned, are likewise particularly preferred. Ethers of Formula ll in which R denotes --(O-alkylene),OH may be prepared by treating the product which is obtained from epichlorohydrin, the alkylene oxide and the polyhydric alcohol, first with an alkylene oxide, and then with sodium hydrosulphide (see United Kingdom Specification 1,144,761).

The most preferred ethers are those of formula especially such ethers having a molecular weight within the range 700 to 3,500.

The ether-esters of Formula II in which R denotes O-CO- C H SH or -(O-alkylene),.O-CO-C,,H ,,SH are obtainable by esterification of the corresponding alcohol with a mercaptocarboxylic acid HOOCC H Sl-l.

The polythiol resins may be used alone or in association with other resins or resin-forming materials, such as aminoplasts and preferably epoxy resins (i.e., substances containing on average more than one 1,2-epoxide group per molecule) or polyisocyanates. Particularly good results have been obtained with mixtures of the polythiol resins and prepolymers of a polymeric polyhydroxy compound and a polyisocyanate. Examples of these latter type of resins are prepolymers of a polyoxyalkylene glycol and an aromatic diisocyanate or of a poly(oxyalkylene)triol and an aliphatic diisocyanate. Especially good results have been obtained with a mixture of a. Thiol resin A, which is described in detail below, and

b. Synthappret LKF, obtainable from Farbenfabriken Bayer and described as a polyisocyanate prepolymer.

Many of these polythiol resins are insoluble in water but can be applied as aqueous dispersions or emulsions. Preferably the resins are applied to fabrics and garments from organic solvents, for example, lower alkanols such as ethyl alcohol, lower ketones such as ethyl methyl ketone, benzene, and halogenated hydrocarbon solvents, especially chlorinated and/or fiuorinated hydrocarbons containing not more than three carbon atoms such as the dry cleaning solvents, carbon tetrachloride, trichloroethylene, and perchloroethylene.

The amount of the polythiol resin used depends on the effect desired. For most purposes, from 0.5 to 15 percent by weight based on the material treated is preferred. Stabilization of knitted fabrics usually requires from 1 to percent by weight of the resin. A high level of shrink resistance, crease setting and substantial resistance to wrinkling can be achieved on woven fabrics with rather smaller quantities, especially from 1 to 5 percent by weight. The hand or handle of the treated material will, of course, depend on the amount of resin employed and by simple experiment the least amount of resin required to give the desired effect may readily be determined. Further, the construction of fabrics also influences the amount of resin required.

The desired effects are not fully obtainable until substantially all the polythiol resin on the material has cured. At ordinary temperatures this may take from 5 to 10 days or even longer. The-curing reaction can, however, be accelerated greatly by the use of a catalyst, and generally it is preferred to add the catalyst to the material to be treated at the same time as the resin is applied although it may be added before or afterwards if desired. The curing time can-be controlled by selecting an appropriate catalyst and the choice of curing time will depend on the particular application of the process according to the invention. The catalysts may be organic or inorganic bases, siccatives, oxidative curing agents, and free-radical catalysts such as azodi-isobutyronitrile, peroxides and hydroperoxides, or combinations of these. As organic bases there may be used primary or secondary amines such as the lower alkanolamines, e.g., monoand diethanolamine, and polyamines, e.g., ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and hexamethylenediamine. As inorganic bases there may be used the water-soluble oxides and hydroxides, e.g., sodium hydroxide and ammonia. Examples of siccatives are calcium, copper, iron, lead, cerium, and cobalt naphthenates. Examples of suitable peroxides and hydroperoxides are cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, dilauryl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, and chlorobenzoyl peroxide.

The fibers and fabrics are preferably treated at a pH greater than 7, typically 7.5 to 12: under acid conditions the resins tend to cure more slowly.

The amount of catalyst used can vary widely. However, in general from 0.1 to 20 percent, preferably 1 to 10 percent, by weight based on the weight of resin used is required, although much larger quantities can be used.

Curing of the polythiol resin is also assisted by using elevated temperatures and if especially fast results are required then temperatures in the range 30 to C. may be used. High humidities also tend to accelerate curing in the presence of catalysts.

The resin, and the catalyst if desired, can be applied to the keratinous material in conventional ways. For example, where wool tops or where fabric is tobe treated, impregnation by padding the resin onto the material or by immersing the material in a resin bath may be used. If garments or garment pieces are to be treated then it is convenient to spray them with the resin, and more convenient still to tumble the garments in the presence of the resin dissolved in an organic solvent. For the latter method a drycleaning machine using a drycleaning solvent is a particularly useful apparatus for carrying out the process of the invention.

If a shrink-resist treatment is required, then it is usually convenient to apply the resin to the fabric although as previously stated it may be applied to the fibers in the form of tops or card sliver. The fabric may be flat-set" before or after resin treatment and by this means the fabric will, in addition to retaining substantially its original dimensions, also retain its flat smooth appearance during wear and after washing. It should be stated, however, that fiat-setting may not be necessary or even desirable with certain types of cloth. Flat-setting is normally carried out either by treating the cloth with steam at superatmospheric pressure, or by treating the cloth with steam at atmospheric pressure in the presence of a setting agent and moisture and maintaining the cloth in a flat state. Flat-setting may also be achieved by applying high concentrations of a reducing agent and a swelling agent, and maintaining the cloth in a flat state during washing off the excess reagents. In another method fiat-setting may be achieved by impregnating the material with a swelling agent and an alkanolamine carbonate, e.g., urea and diethanolamine carbonate, drying the material and semidecatizing the dried material.

If a durable press treatment is required, there are a number of ways this may be achieved. One method is to treat the material with polythiol resin, make the material up into garments or garment pieces and insert therein pleats or creases, using reducing agents, bases, or superheated steam as setting agents. The resin may be applied to the fibers at any stage during the manufacture of the fabric, e.g., in top form, in yarn, or in fabric form. If desired, agents which block the thiol groups of the wool, e.g., formaldehyde or higher aldehydes, may be applied to the creased or pleated garments after curing the polythiol resin.

A preferred method of applying the polythiol resin to obtain a durable press effect comprises treating the made-up garment or garment piece, which already has the desired creases or pleats imparted thereto, with the polythiol resin dissolved in an organic solvent. in this method it is essential that the resin is applied in an organic solvent because treatment with aqueous systems would only serve to remove the creases or pleats already set in the fabric.

An alternative method, which is primarily concerned with the production of durable press pleats or creases only, comprises impregnating the fabric in the area where a crease or pleat is to be inserted with the resin, imparting the crease or pleat, and maintaining it in this position while heat and pressure are applied.

The setting of the fabric, whether carried out before or after resin treatment, may be effected using any of the known methods, for example, by means of setting agents e.g., reducing, agents, bases, water, and superheated steam. Monoethanolarnine sesquisulphite is the mostfrequently used and may be used in association with a swelling agent, e.g.,

urea.

The invention will now be illustrated by reference to the following examples. Unless otherwise specified, parts and percentages are by weight. References to various standard tests are made: the nature of these tests is as follows.

TEST PROCEDURES EMPLOYED IN THE EXAMPLES Standard Wash Prior to measurement of surface smoothness and crease retention, all garment samples unless otherwise stated were washed for 1 hour in a Bendix MRE rotating drum, domestic washing machine in a phosphate buffer of pH 7 and at 40 C. using a liquor/sample ratio of 22:1 by weight. The samples were removed and hydroextracted in a domestic spin dryer for 1 minute. After removal from the spin dryer the samples were sharply shaken three times and then allowed to hang until dry at room temperature. Greased and pleated garments were allowed to hang vertically.

Shrinkage Shrinkage was measured as the difference in dimensions of the fabric before and after washing. Area shrinkage was calculated from linear shrinkage measurements.

Smooth Drying Index Surface smoothness of the garment after the standard wash procedure was assessed by comparison with Monsanto threedimensional plastic Wash-n-Wear" standards. This comprises a series of five graded plastic panels having surface smoothness characteristics varying on a scale between one and five. The test panels are illuminated under oblique overhead lighting conditions (angle of incidence of lighting 16). A sample of material for assessment is illuminated under the same conditions, and its surface smoothness assessed by comparison with the test panels. The grade numbered five corresponds to negligible or no change in the appearance of the sample after washing.

Degree of Set The crease retention of the garment after the standard wash procedure is measured on an apparatus described in the Journal of the Textile Institute, 1962, 53, 143. In this equipment, the creased sample is mounted at the center of the rotation of a light source which is in the form of a slit, the plane of rotation being at right angles to the crease, and the slit being parallel to the crease. The light source is rotated until the shadow formed by the crease just disappears, and the angle of incident light under this condition is measured. The fabric is then rotated until the shadow formed at the other side of the crease also just disappears, and the incident angle measured. The degree of crease set is then calculated as:

percentage set mean incident angle/90Xl00 on this basis, the sharper the crease measured, the higher is the value of the set obtained.

The polythiol resins used were prepared as follows.

7 eq uiv./kg. and contained five to si x thiol groups per molecule.

JEIPLiE--- A mixture of 800 g. (0.2 'g.-mol.) of a triol of average molecular weight 4,000 made from glycerol and propylene oxide, 55.2 g. (0.6 g.-mol.) of thioglycollic acid, 5 g. oftoluenep-sulphonic acid, and 350 ml. of toluene was heated to reflux with stirring in an atmosphere of nitrogen. Water 10.8 ml. 0.6 g.-mol.) formed during the reaction was removed as its azeotrope with toluene. The mixture was cooled and washed with water, and the organic layer was separated. On removal under vacuum of the solvent from the organic layer there remained 793 g. (94 percent of the theoretical yield) of the desired tris(thioglycollate) (Thiol Resin A"), having a mersaet n 99-, 92 !:2.

Thiol Resins B and C These denote poly(2-hydroxy-3-mercaptopropyl) ethers prepared from glycerol-propylene oxide adducts having an average molecular weight of 600 and 4,800 respectively epichlorohydrin, and sodium sulphide. The products had a mercaptan content of I 3.7 equiv./kg. and 0.32 equiv.lkg.

Thiol Resins T and U These denote poly(2-hydroxy-3-mercaptopropyl) ethers similar to Thiol Resins B and C.

Thiol Resin T contained two to three SH groups per molecule; its thiol content was 1.4 equiv./kg. and its molecular weight in the range l,5002,000. Thiol Resin U contained approximately three Sl-I groups per molecule; its thiol content was 0.54 equiv./kg.- and its average molecular weight was about 3,000. (Compare general Formula 11).

-miesg g Thiol Resin V A mixture of Thiol Resin B (500 g.), thioglycollic acid (218 g., 2.37 equiv.), toluene-p-sulphonic. acid (1.5 g.) and perchloroethylene (500 ml.) was heated to reflux for 8 hours under nitrogen with entrainment of water formed (44 ml.) during the reaction. After themixture had been washed with water until its pH was 5 to 6, the solvent was stripped off in vacuo. The residue (640 g.) had a thiol content of 5.7

Thiol Resin W A mixture of Thiol Resin C (529 g.), thioglycollic acid (19.5 g., 0.212 equiv.), toluene-p-sulphonic acid (1 g.) and perchloroethylene (350 ml.) was heated as before, 4 ml. of water being evolved. The mixture was stirred with a slurry of sodium bicarbonate (5 g.) and water (2.5'ml.), filtered, and stripped in vacuo. The residue (532 g.) had a thiol content of 0.58 equiv./kg. and contained five to six thiol groups per Thiol Resin X This was prepared as described for Thiol Resin V from Thiol Resin T" (500 g.), 89 g. of thioglycollic acid, 4 g. of toluene-p-sulphonic acid, and 500 ml. of perchloroethylene: 23 ml. of water was entrained. The residue had a thiol content of 1.78 equiv./kg. and contained five to six thiol groups per Thiol Resin Y This was prepared as described for Thiol Resin X but using Thiol Resin U (500 g.) and 36.4 g. of thioglycollic acid. The residue had a thiol content of 0.75 equiv./kg. and contained five to six thiol groups per molecule.

TABLE I Polyol adduot Average Prepared frommol. wt

Polythiol Manufacturer's designation Alkylene oxide Alcohol or amine Esterifying acid D Carado13000 3,000 GlyceroL 'Ihloglyoolic. E. Caradol 5001... 5,000 Do. F Polyurax G 1000 1,000 Do. G Polyurax G 3000 3,000 Do. H Polyurax G 3521 3,000-4,000 Do. I... Polyurax G 1000 1,000 2 mercaptoproplonic. J. Caradol 5001 5,000 Thioglycollc. K Polyurax G 1000 1,000 Do. L Voranol CP 700 700 D0. M Caradol 3000 3, 000 Do. N. Niax LHI 112 1, 500 Do. Polyurax G 4000." 4,000 2-mereaptopropionic P Pluracol EDP 500 500 Thioglycolic. Q 2,200 Do. R Pluraeol TP 4040 4,040 PO Tr1methylolpropane Do. S .i. Ploymeg 1000 1,000 Tetrahydrofuran Butane-1,4-diol Do.

E0 Ethylene oxide EXAMPLE 2 P0 Propylene oxide CARADOL, POLYURAX, VORANOL, NIAX, PLU- RACOL and POLYMEG are trademarks, the CARADOL products being available from Shell Chemical Co., the POLYURAX products from B.P. Chemicals Ltd., the VORANOL product from Dow Chemical Co., the NIAX product from Union Carbide, the PLURACOL products from Wyandotte Chemical Corp., and the POLYMEG from The Quaker Oats Co. The polyol used toprepare Thiol resin Q was obtained in a known manner by reaction in the presence of sodium hydroxide.

EXAMPLE 1 This example illustrates the superior results achieved by using an uncatalyzed thiol-terminated poly(oxyalkylene) resin for shrinkproofing of wool textiles.

Solutions containing 2 percent, 5 percent and 8 percent of Thiol Resin A were made up in perchloroethylene. Knitted fabric samples made from 2/28s botany yarn to a cover factor of 1.1 were impregnated with these solutions using a pad mangle at 100 percent pickup in each case. They were then dried at 50 C. After 12 days storage at room temperature, these samples were washed in a washing machine at a :1 liquor ratio for minutes and the percentage area felting shrinkage was measured.

The results obtained were as follows:

% Thiol Resin A Area Felting Shrinkage A much more severe test was also carried out using a 12.5:1 liquor-to-goods ratio for 60 minutes, and the following results were obtained:

% Thiol Resin A Area Felting Shrinkage This example illustrates how a combination of a thiol-terminated poly(oxyalkylene) resin with a resin having reactive groups capable of reacting with thiols, such as anepoxy resin, can produce an excellent shrink-resistant finish on woolen fabrics.

Thiol Resin B (20 g.) was dissolved in trichloroethylene (300 ml. A liquid epoxy resin, a diglycidyl ether of 2,2-bis(4- hydroxyphenyl)propane which had a 1,2-epoxide content of about 5.2 equiv./kg. (10 g.), was also dissolved in 363 ml. of trichloroethylene, and the two solutions were mixed; the total resin concentration was 3 percent. The knitted fabric described in Example 1 was impregnated with this solution using a pad mangle at 143 percent pickup, and the sample was dried at 50 C. and then left for 24 hours at room temperature for the resin to cure. The sample was then washed in a washing machine at a liquor-to-goods ratio of 25:1 for 30 minutes.

The untreated knitted fabric was found to shrink by 40 percent under these washing conditions whereas the sample treated with 4.3 percent of the resin mixture did not shrink at all.

EXAMPLE 3 A piece of grey wool worsted flannel was treated in a drycleaning machine with a solution of Thiol Resin A in perchloroethylene, the fabric being tumbled in this solution for 5 minutes. The fabric was then spun to give a liquid reten tion of approximately 30 percent, which is equivalent to 3 percent of resin on the weight of the fabric. The fabric was then tumble dried and cured by storing for 10 days at 20 C. and

EXAMPLE 4 A piece of wool grey worsted serge was flat set by padding through a solution of monoethanolamine sesquisulphite (MEAS) containing 1 g. per liter of a nonionic wetting agent such that the fabric retained 2 percent of its own weight of MEAS and 60 percent of water. The fabric was semidecatized (i.e., treated when rolled up with steam at atmospheric pressure) while wet for 5 minutes, and finally dried without tension. The fabric was made up into apair of trousers and the trouser creases were set by spraying the trousers with a percent solution of MEAS in the region of the creases so that, in that region, the fabric retained approximately 2 percent of its own weight of MEAS and 40 percent of water. The trouser legs were then pressed on a Hoffman press using the pressing cycle seconds steam (head locked), 20 seconds press without steam (head locked), vacuum until cool (head open). The trousers were then treated in a drycleaning machine with a solution of Thiol resin A in perchloroethylene containing 2 percent (on weight of resin) of diethylenetriamine such that they retained 2.5 percent of their own weight of resin.

Six days later the trousers were washed by the standard procedure; they displayed excellent crease retention and smooth drying characteristics and did not shrink.

EXAMPLE 5 A piece of woolen fabric with a check design was impregnated with monoethanolamine sesquisulphite (MEAS) solution by padding so that the fabric retained 3 percent of its own weight of MEAS. The impregnated fabric was tenter dried without tension and cut' into panels for making a pleated skirt. The panels were sprayed with water to percent of their own weight, pleated between paper pleating formers and set by steaming in an autoclave for 10 minutes at 8 pounds per sq. inch (0.56 kg. per sq. cm.) steam pressure. After drying and removing from the formers, the skirt panels were made into a skirt. The skirt was then treated with Thiol resin A in a drycleaning machine by the following means.

A solution in perchloroethylene containing 4 percent Thiol Resin A, 0.08 percent diethylenetriamine, and 0.20 percent cumene hydroperoxide (Trigonox l(-70, obtainable from Novadel Limited) was made in the drycleaning machine. The skirt was immersed and tumbled in this solution, allowed to drain, and excess resin solution removed by centrifuging until the skirt retained 60 percent of its own weight of resin solution, i.e., 2.4 percent resin and other ingredients pro rata. The skirt was then tumble dried in the drycleaning machine. After removal from the machine the skirt required no repressing.

The resin on the skirt was allowed to cure, and, 7 days later, after being washed for 1 hour by the standard procedure, the skirt had shrunk 1 percent in the length and not at all in the width; the pleats displayed an average set of 89 percent and the Smooth Drying Index of flat parts of the skirt was found to be 4-5.

EXAMPLES 6l4 These examples indicate the shrink-resist and durable press effects achieved with other polythiol resins according to the invention.

The fabric used in these examples was a grey melange wool worsted serge of 270 g. per square meter and the pH of the aqueous extract was 7.8. The fabric was flat set using 1.5 percent of monoethanolamine sesquisulphite (MEAS) on the weight of the fabric, and was semidecatized for 4 minutes. The fabric was cut into swatches, and creases were set in these swatches by spraying in the region of the crease line with 5 percent MEAS solution to percent pickup, folding and pressing in a Hoffman press using the pressing cycle: 30 seconds steam (head locked), 30 seconds press without steam (head locked), vacuum to cool (head open).

To these creased flat-set swatches were applied polythiol resins by padding them from a perchlorethylene solution using a concentration and a pad expression to give 3 percent of resin on the weight of the fabric. The catalysts were diethylenetriamine (DETA) or calcium naphthenate (CaN), used at levels of 1 percent or 5 percent on the weight of the resin used. The treated swatches were allowed to cure at 65 percent relative humidity and 20 C., and were submitted to the standard wash procedure. The area shrinkage, Smooth Drying Index and percentage crease set were then measured, and the results are given in Table I1.

TABLE 11 Area Smooth Crease Catalyst Time shrinkage drying set Example Resin system (days) (percent) index (percent) D 5% DETA..... 8 0.0 4-5 99 1% DETA..... 28 4.0 3 75 5%DETA..... 8 1.0 4 96 F.... 1%CaN 28 0.0 4-5 87 F.... 5%CaN.. 8 1.0 4 100 G... 1%CaN.. 14 0.0 4 97 1d 5%CaN.. 14 5.5 3 77 H... 1%CaN.. 2| 0.0 4 86 1 5%CaN 14 1.5 4 75 Untreated swatch 14.0 1 17 It will be seen from these results that treatment of the fabric with the resins gave excellent shrink resistance. Further, the crease setting was of a goodorder, all the results showing a percentage set of 75 percent or more, and most of them showing a set of percent or more. These results indicate that full machine washability of garments can be realized by using the resins according to the invention in that the resin-treated garments do not shrink, they retain their surface smoothness as evidenced by the Smooth Drying Index, and they retain their creases after severe washing and drying cycles. The handle of the treated fabrics was very good, having a fuller feeling but no increased harshening of the fabric. The draping qualities of the fabric were virtually unimpaired.

Curing of the resins took varying times and it was found that by selecting particular catalysts for particular resins, the

desired curing time could in most cases be obtained. The times quoted in the examples are not necessarily those taken for the resin to cure: they indicate the intervals between application of the resin and carrying out of the standard wash procedures, and in many cases the actual curing time will be less than the interval quoted.

EXAMPLES 15-25 TABLE III Area Smooth Crease Thiol Time shrinkage drying set Example resin Catalyst (days) (percent) index r) 15 1% DETA/5% DP... 14 1.5 4 89 16.. 1% CaN/5% DP 14 0.5 45 100 17.. 1% CaN 14 0.5 4-5 a 88 18.. 1% CaN/5% DP. 14 1.5 4-5 89 19.. 1% CaN 14 0.0 4-5 75 1% CaN/5% DP. 14 3.0 4-5 80 1% DETA 0.0 4-5 951 1% DETA/5% DP... 7 0.5 4-5 I 88 1% CaN ,21 0.0 3-4 76 1% DETA. 21 1.0 4-5 90 25 N 1% CaN 21 0.5 5 81 Untreated sample 14.5 1 l5 These results again show that treatment according to the invention enables garments having satisfactory machine washability properties to be produced. Furthermore, the handle was remarkably good, particularly with the fabrics treated with Thiol Resin A.

EXAMPLES 26-37 These examples illustrate the application of other thiol resins under different conditions.

The cloth used was a wool flannel of approximately 170 g. per square meter; the pH of the aqueous extract was 3.1. The flannel was padded with a solution of the thiol resin in perchloroethylene, containing 10 percent by weight of monoethanolamine based on the weight of the thiol resin, such that the uptake of the thiol resin was 8 percent. Then the flannel was dried to its original dimensions for 2% minutes at 50 C. in a fanned oven, and stored at room temperature for the times indicated in Table IV. The treated samples were washed in a Hoovermatic washing machine at 50 C. in an aqueous solution containing 5 g. per liter of soap flakes and 2 g. per liter of anhydrous sodium carbonate, rinsed in cold water, spun in a domestic spin dryer, and finally dried at 50 C. The results obtained are shown in Table IV.

Similar results were obtained when the flannel was prereduced or preoxidized. To reduce the flannel, it was padded to 50 percent uptake with an aqueous solution containing, per liter, g. of sodium metabisulphite (Na S O and 4 g. of Emulsifierl (an adduct of nonylphenol and 9 molar proportions of ethylene oxide) and dried at 50 C. in a fanned oven for 2% minutes. To oxidize the flannel it was padded to 140 percent uptake with an aqueous solution containing, per liter, ml. of hydrogen peroxide (30 percent "/v), 1.2 ml. of formic acid (85 percent), and 1 g. of Emulsifier I, and which had been adjusted to pH 3.7 with aqueous sodium carbonate, kept for 4 hours in a polyethylene bag, then dried as before TABLE IV Example Thiol Time Area resin (days) shrinkage 26 B 1 12.3 9 8.7 27 C 1 12.2 9 5.5' 28 P 1 11.7 5 10.5 29 Q l ll.3 8 7.0 30 R 8 12.5 31 S 6 12.3 32 T 1 12.5

5 11.5 33 U 9 8.7 34 V l 7 8 7 35 W l 9.3 5 8.5 18 5.5 36 X l 6.5

Untreated 23.5

EXAMPLES 38-46 This set of examples illustrates how the resins of the invenhas been proposed to wash the goods in liters of wash liquor for minutes in a CUBEX washing machine then for 60 minutes in 12.5 liters of wash liquor in the same machine. Accordingly the treated samples were submitted to this washing test which was carried out after full curing ofthe resin. The

catalyst used was diethylenetriamine at 2 percent by weight on v the weight of the resin used.

The results obtained are given in Table V.

The CUBEX washing machine is an internationally available machine for carrying out machine washability tests and comprises a cube container of 50 liters internal capacity supported at the diagonally opposite corners and revolving at 60 revolutions per minute, the direction of rotation being reversed every 5 minutes with 5 seconds pause during the change in direction of rotation.

EXAMPLE 47 An emulsion of Thiol Resin A was made containing the following ingredients:

Thiol resin A 3.00% Emulsifier l 0.30% Monoethanolamine 015% Water to 100% The emulsion was applied by padding to a piece of grey serge fabric which had previously been flat set by the procedure described in Example 4 except that a solution of monoethanolamine was used as the setting agent. The fabric retained 100 percent of its own weight of emulsion. The impregnated fabric was dried without tension and the resin was allowed to cure. A pair of trousers was constructed from the fabric and the trouser creases were set as described in Example 4. After being washed 7 days later by the standard procedure, the trousers shrank 0.7 percent in the width and 0.8 percent in the length, had a Smooth Drying index of 5, and a crease set of percent.

In other experiments an aqueous emulsion of Thiol Resin A was prepared by mixing 320 g. of this polythiol with 144 g. of water and 16 g. of Emulsifier 11 (an adduct from a mixture of primary aliphatic amines (1 mol), containing 16-18 carbon atoms in the molecule, and ethylene oxide (70 mols)). A l 10- g. portion of this emulsion was mixed with 7.5 g. of monoethanolamine and 882.5 g. of water; wool flannel was impregnated with the resulting solution to a l 10 percent takeup, dried at 50 C. in a fanned oven, and then left for 16 days at 20 C. Flannel so treated was washed for 1 hour in a Hoovermatic washing machine at 50 C. with a scouring liquor containing 5 g. of soap flakes and 2 g. of anhydrous sodium carbonate per liter. The shrinkage in area was 6.5 percent, whereas untreated flannel shrunk 29.7 percent under the same conditions of washing.

EXAMPLE 48 A piece of shirting fabric containing 50 percent wool and 50 percent cotton was flat set with monoethanolamine sesquisulphite as described in Example 4. Half of this piece of fabric and a piece of previously untreated fabric were treated in a drycleaning machine with Thiol Resin A catalyzed by the addition of 2 percent diethylenetriamine (based on the weight of resin) such that the fabric retained 2.5 percent of its own weight of resin. After the resin had been allowed to cure over 7 days, two shirts were made from these two pieces of resintreated fabric, a further shirt from the fabric which had been flat set only, and a fourth shirt from untreated fabric.

The four shirts were washed and spin dri edbylhestandard method'and, after drying, displayed the following smooth drying characteristics:

The results show the improved smooth drying of the wool/cotton fabric when Thiol Resin A is used both with and without a flat-setting step.

EXAMPLES 49-50 These examples illustrate the machine washability of lambswool and Shetland sweaters.

The sweaters were first solvent scoured and then impregnated with a mixture of Thiol Resin A (4,425 g.), diethylenetriamine (88.5 g.), and perchloroethylene (54.6 liters). After being impregnated for 3 minutes the goods were spun to 60 percent pickup, cold tumbled for 3 minutes and then dried at 65-70 C. for 10 minutes. The treated sweaters were found to have excellent antifelt properties on washing 3 days later in a domestic washing machine; the results are as follows.

Wash Test:

Two 10-minute washes in a Hoovermatic washing machine 50 Shetland 2.85

EXAMPLES 51 and 52 These examples demonstrate the use of Thiol Resin A in the stabilization of wool double jersey on washing and the prevention of shrinkage due to felting.

Wool double jersey was impregnated in a drycleaning machine with a solution of Thiol Resin A (9.65 kg.) and diethylenetriamine (195 g.) in perchloroethylene (159 liters). The piece of double jersey was tumbled in the resin solution for 3 minutes, the liquor was allowed to drain to the tank, the piece was centrifuged at high speed for 7 seconds to give a pickup of 84.5 percent, and then dried at 50 C. for 12 minutes. The treated jersey was found to have a pleasant soft handle and to show good stabilization to relaxation shrinkage and excellent antifelt properties on being washed 3 days later. Wash Test:

a. Relaxation- 1 minutes static soak followed by 5 minutes in the Cubex b. Washing-l hour in the Cubex with 12.5 liters of wash liquor This example demonstrates the aqueous application of Thiol Resin A to knitwear to produce shrink-resistant goods.

Thiol Resin A (150 g.) and Emulsifier I (22.5 g.) were blended by a high-speed stirrer and then 327.5 g. of water was slowly added to make a stable emulsion. This 30 percent emulsion was then diluted to 3 percent, and 5 percent of diethylenetriamine on the weight of resin was added as catalyst. Botany fabric (cover factor 1.1) was padded through the emulsion and tumble dried at 60 C. The treated fabric was allowed to cure at room temperature, and the wash tests per- 5 formed 14 days later showed that the treatment gave an excellent shrink-resistant finish.

911 Area Felling Shrinkage 30 min., Cubex 30 min.. Cubex (25 liters wash (25 liters wash liquor) liquor) +.l hr.,

Cubex (12.5 liters wash liquor) Example Resin 5 3 Untreated EXAMPLE 54 A piece of grey worsted serge fabric which had been flat set with monoethanolamine sesquisulphite (MEAS) as described in Example 4 was creased in the warp direction by spraying .the fabric with a 5 percent solution of MEAS so that it retained 40 percent of the solution in the region of the intended crease, folding and pressing in a Hoffman press using the cycle: seconds steam (head locked), 20 seconds press without steam (head locked), 10 seconds vacuum to cool (head open).

The sample was treated with a solution in perchloroethylene of equal quantities of Thiol Resin A and Synthappret LKF." The sample was treated such that 0.75 percent of Thiol Resin A and 0.75 percent of Synthappret LKF was retained on the fabric. Immediately after the solvent had been evaporated off, the fabric was washed under standard conditions and the fabric was subjected to the standard tests. The results were area shrinkage 0.5 percent; Smooth Drying Index 5; set 100 percent.

The handle of the treated fabric was better than that of the fabric treated to retain 1.5 percent Synthappret LKF" alone.

The resin cured rapidly and yet 7 days later the resin bath was still usable and gave similar results.

We claim:

1. Process for modifying, keratinous material which comprises treating the material with 0.5 to 15 percent by weight based on the material of a polythiol resin in the form of a solution in an organic medium or in the form of an aqueous emulsion and having three to six thiol groups per molecule, a I

molecular weight between 400 and 10,000 and containing a. a radical of a polyhydric alcohol,

b. bound to this radical, at least two poly(oxyalkylene) chains,

0. bound through oxygen atoms to carbon atoms in the said poly(oxyalkylene) chains, three to six radicals selected from the group consisting of an acyl radical of a thiol containing aliphatic carboxylic acid and a radical, after removal of a hydroxyl group, of a thiol containing aliphatic alcohol and curing the resin on the material.

2. A process according to claim 1 which comprises treating the keratinous material with a polythiol resin of the formula X represents an aliphatic radical containing at least one thiol group.

3. A process according to claim 1, which comprises treating the keratinous material with a polythiol prepared by the reaction of a polyhydric alcohol with an alkylene oxide followed by esterification of the terminal hydroxy groups with a mercaptocarboxylic acid.

4. A process according to claim 1, which comprises treating the keratinous material with the polythiol in the presence of a catalyst selected from the group consisting of a base, a free radical catalyst and a siccative.

5, A process according to claim I, which comprises curing the polythiol resin on the keratinous material at a temperature ranging from 30 to l80C.

6. A process according to claim 1, which comprises treating the keratinous material with the polythiol resin in the form of a solution in a solvent containing at most three carbon atoms and selected from the group consisting of a chlorinated hydrocarbon, a fluorinated hydrocarbon and chlorofluorinated hydrocarbon.

7. A process according to claim 1, which comprises treating with the polythiol a wool fabric which has been previously flat set.

8; A process according to claim 2, which comprises treating the keratinous material with a polythiol resin of the formula in which R, represents an aliphatic hydrocarbon radical, each alkylene group contains a chain of at least two and at the most six carbon atoms between consecutive oxygen atoms, m, p, q and u each represents a positive integer m is at least 1 p is at least 2 and at most 6 (p,+q) equals at least 3 and at most 7, and u is at most 2. 9. A process according to claim 2, which comprises treating the keratinous material with a polythiol resin of the formula -\H--- 5 m Ra W W w in which R represents an aliphatic radical containing at least two carbon atoms,

each alkylene group contains a chain of at least two and at the most six carbon atoms between consecutive oxygen? atoms,

R denotes a member selected from the group consisting ofl -OH, (O-alkylene),.-OH, -OCO-C,,H ,,Sl-l[ and -(O-alkylene) -O-COC,,l-l ,,Sl-l, v being anl integer of at least 1 and u being an integer of at most 2,

m, p, and q are integers,

m is at least 1,

p is at least 2, and

(p-l-q) equals at least 3 and at most 7.

10. A process according to claim 4, which comprises employing the catalyst in a quantity of 0.1 to percent, based on the weight of the polythiol employed.

11. A process according to claim 8, which comprises treating the keratinous material with a polythiol resin of the formu-' la in which R represents an aliphatic hydrocarbon radical having at least three and at most six carbon atoms,

each alkylene group contains a chain of at least two and at the most six carbon atoms between consecutive oxygen atoms,

m, p; and u each represents a positive integer,

m is at least 1,

p, is at least 3 and at most 6, and

u is at most 2.

12. A process according to claim 9, which comprises treating the keratinous material with a polythiol resin of the formu- [R] Ct MmO CH2$HCHQSH1 in which R represents an aliphatic hydrocarbon radical having at least three and at the most six carbon atoms,

m, p and t each represents a positive integer,

m is at least 1,

p is at least 3 and at most 6, and

t is at least 2 and at most 3. I 13. A process according to claim 9, which comprises treating the keratinous material with a polythiol resin of the formuin which CzH2t)m0CHzCHCHgsH OCOCHgSH p:

t is at least 2 and at the most 3, and

u is at most 2. 15. A process according to claim 12, which comprises treat- ;ing the keratinous material with a polythiol resin of the formu- ;la

orno (1,110.0 cmcH o fiTs H H on 0 0311. ,0 CHICHCH, s11

in which m is a positive integer. material is essentially 100 percent keratinous fiber-containing 16. A process according to claim 13, which comprises treatmaterial. ing the keratinous material with a polythiol resin of the formu- The materials of claim 18 wherein the kel'atinolls material comprises at least 30 percent by weight of keratinous fibers. o o gmgncm H 22. Keratinous materials as defined in claim 18 wherein the materials are garments or garment pieces.

C0 H 23. Keratinous materials as defined in claim 18 wherein the H(0 (l fi)mO CHZCHCHZS H Qpolythiol resin contains three to six thiol groups per molecule.

0 00 cms H i 24. Keratinous materials as defined in claim 18 wherein the ol thiol resin has a molecular wei ht between 400 CHz-(OC;Ha)mOCHzCHCHzSH g g and 0 G 0 CHzSH 25. Keratinous materials as defined in claim 18 wherein the polythiol resin has the formula in which m is a positive integer. 17. A process according to cla1m 14, which comprises treat- OH, (O CaHQmO CHCHCHSH mg the keratinous material with a polythrol resin of the formu- H la a .m, H-(OCaH9) 0CH1CHCH1SH 20 a H CH (O 0311650 (:0 cmsn 1 CHr-(O CBHOEO 011113303153 CH (OC3Hs)mOCOCHgSH OH I in which m is a positive integer. 26. Keratinous materials as defined in claim 18 wherein the in which m represents a positive integer. polythiol resin has the formula 18. Keratinous materials bearing thereon from 0.5 to 15 k percent by weight of a cured polythiol resin having three to six CH2 (O CSHOEO CHZCH CH2 S H thiol groups per molecule a molecular weight between 400 and 10,000 and containing OCOCHZSH a. a radical of a polyhydric alcohol, H-(O 03H6)m0 CHzCI-ICHzS H b. at least two poly(oxyalkylene) chains bound to the O C 0 CH2 8 H polyhydric alcohol radical, and c. three to six radicals selected from the group consisting of acyl radicals of thiol-containing aliphatic carboxylic acids H V g g Qggfi SH and a radical after removal of a hydroxyl group, of thiolcontaining aliphatic alcohols. 19. Keratinous materials of claim 18 wherein the materials are wool or wool fabrics.

in which m is a positive integer. 27. Keratinous materials of claim 18 wherein the weight of the cured polythiol is from 1 to 10 percent.

20. The materials of claim 18 whereiri tl e lter tingt s 22 2 3 UN TED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 33 517 Dated February 29, 1972 Inventor(s) THOMAS DESMOND BROWN ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 9, column 17, line 58, delete "-(O-alky1ene) ,-OH," and substitute -(O-alkylene) -OH, v

Claim 9,. column 17, line 59, delete "-(O-alkylene) -O-CO-- c n sn," and substitute -.(O-alkylene -o-rio- Signed'and' sealed this 11th day of July 1972.

Attes t: 4

EDWARD M.FLEICHER,JR. ROBBED GOTTSCHALK Attes ting Officer Commissioner of Patents

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2780567 *Mar 22, 1954Feb 5, 1957Rohm & HaasStabilization of protein-containing textiles
US2831830 *May 24, 1954Apr 22, 1958Shell DevSulfur-containing resinous products from polyepoxides
US2974432 *Feb 20, 1956Mar 14, 1961Koret Of CaliforniaPress-free crease retained garments and method of manufacture thereof
US3258495 *May 27, 1963Jun 28, 1966Diamond Alkali CoThiol terminated polyoxyalkylene glycols
US3278496 *Mar 1, 1961Oct 11, 1966Diamond Alkali CoThiol terminated liquid polymers
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3881047 *Jul 2, 1973Apr 29, 1975Ciba Geigy AgTreatment of fibres
US4066392 *Sep 15, 1975Jan 3, 1978I.W.S. Nominee Company LimitedProcess for modifying keratinous materials
US5362486 *Apr 10, 1992Nov 8, 1994Helene Curtis, Inc.In-situ polymerization of oligomers onto hair
Classifications
U.S. Classification442/106, 428/474.4, 442/152, 442/107, 427/389, 8/127.5
International ClassificationD06M101/00, C08G65/334, D06M15/53, D06M15/63, D06M13/148, D06M23/00, D06M15/71, C08G65/26, D06M101/02, D06M101/10, D06M13/02, D06M13/244, D06M13/224
Cooperative ClassificationC07C323/00, C08G65/3342, D06M15/63, C08G65/26, D06M23/00
European ClassificationC07C323/00, D06M15/63, D06M23/00, C08G65/26, C08G65/334B