US3832131A

US3832131A - Treatment of fibres

Info

Publication number: US3832131A
Authority: US
Inventors: D Massy; K Winterbottom
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1971-04-19
Filing date: 1972-03-15
Publication date: 1974-08-27
Anticipated expiration: 1991-08-27
Also published as: FR2133898B1; CH416472A4; ES401866A1; CH549686A; DE2217268A1; BE782302A; CA973664A; FR2133898A1; GB1376606A; IT952689B; ZA721799B

Abstract

CELLULOSIC TEXTILES ARE TREATED WITH AN ESTER WHICH CONTAINS, ON AVERAGE, AT LEAST TWO MERCAPTAN GROUPS PER MOLECULE, AND WITH AN AMINOPLAST WHICH IS FREE FROM ETHYLENIC UNSATURATION, AND THE AMINOPLAST IS CURED. THE TREATED TEXTILES HAVE ENHANCED DIMENSIONAL STABILITY, RESISTANCE OF CREASING, AND MAY HAVE PERMANENT CREASES IMPARTED, WHILST HAVING A FULLER, SOFTER HANDLE AND INCREASED TEAR STRENGTH COMPARED TO CELLULOSIC TEXTILES TREATED WITH THE AMINOPLAST ALONE. TYPICALLY, THE ESTER IS PREPARED BY THE REACTION OF (A) A COMPOUND CONTAINING AT LEAST TWO CARBOXYLIC ACID GROUPS, (B) A COMPOUND CONTAINING AT LEAST TWO ALCOHOLIC HYDROXYL GROUPS AND, OPTIONALLY, (C) A COMPOUND CONTAINING NOT MORE THAN ONE CARBOXYLIC ACID GROUP OR ALCOHOLIC HYDROXYL GROUP, ESPECIALLY A MONOMERCAPTOMONOCARBOXYLIC ACID OR A MONOMERCAPTOMONOHYDRIC ALCOHOL.

Description

3,832,131 TREATMENT OF FIBRES Derek James Rowland Massy, and Kenneth Winter-bottom, Cambridge, England, assignors to Ciba-Geigy AG, Basel, Switzerland No Drawing. Filed Mar. 15, 1972, Ser. No. 235,036 Claims priority, application Great Britain, Apr. 19, 1971, 9,767/71 Int. Cl. D06m 15/54, 15/36 US. Cl. 8115.6 8 Claims ABSTRACT OF THE DISCLOSURE (a) a compound containing at least two carboxylic acid groups,

(b) a compound containing at least two alcoholic hydroxyl groups and, optionally,

(c) a compound containing not more than one carboxylic acid group or alcoholic hydroxyl group, especially a monomercaptomonocarboxylic acid or a monomercaptomonohydric alcohol.

This invention relates to a process for modifying cellulosic materials in fibrous form, and to materials so treated.

It is Well known to treat cellulosic materials with aminoplasts. Cellulosic textiles are often treated with these substances to impart dimensional stability, resistance to creasing, or permanent mechanical effects such as seersucker effects and pleats. One drawback is that the tear-strength of the treated textile is often lowered, another is that the treated textile is often harsher to the touch. These drawbacks have, to a certain extent, been overcome by incorporating softening agents such as polyethylene emulsions or adducts of ethylene oxide with phenols or amines, but for many purposes these agents are insufficiently eflfective, and give rise to an impairment of the water-absorption properties of the treated textile.

It has now been found that, by the use of specified esters containing mercaptan (-SH) groups in conjunction with certain aminoplasts, cellulosic materials having improved properties, in particular textiles having a fuller, softer handle, can be obtained. Textiles treated in this manner have, at most, only a slight impairment of their water-absorption properties.

Accordingly, the present invention provides a process for modifying cellulosic fibres which comprises treating the fibres, in the absence of ketratinous material with, in any desired sequence or simultaneously,

(i) An ester which contains on average at least two mercaptan groups per molecule and is obtainable by the reaction of (a) a compound containing at least two carboxylic acid groups,

(b) a compound containing at least two alcoholic hydroxyl groups, and optionally,

(c) a compound containing not more than one carboxylic acid group or alcoholic hydroxyl group,

at least one of (a), (b), and (c) if used, having one or more mercaptan groups, and

United States Patent Patented Aug. 27, 1974 (ii) An aminoplast which is free from ethylenic unsaturation, and curing the aminoplast on the fibres.

It is believed, although the usefulness of the invention does not depend on the truth of this belief, that the mercaptain-containing esters which are employed also undergo curing on the fibres.

The present invention further provides cellulosic fibrous materials bearing thereon an ester and an aminoplast as aforesaid in the cured or still curable, state.

As already indicated, treatment of the fibres with the aminoplast and the ester can take place in any desired sequence. For example, the fibres may be impregnated with a mixture of the aminoplast and the ester, and then the aminoplast is cured. Or the fibres may be impregnated first with the ester and then with the aminoplast, or vice versa, and then the aminoplast is cured. Or the fibres are first impregnated with the aminoplast which is then cured, and the fibres are subsequently treated with the ester.

Cellulosic fibres which may be subjected to the process of this invention include cotton, regenerated cellulose (including viscose and cuprammonium rayons), jute, linen, hemp, ramie, sisal, and paper. The term cellulosic fibres" includes fibres comprised of a substance derived from a cellulose in which some, but not all, of the three available hydroxyl groups per anhydrogluco unit have been chemically modified, e.g., by acylation, etherification, or cyanoethylation. Thus methylcellulose and cellulose monoacetate are included but not, for example, cellulose triacetate. The cellulosic materials are preferably textiles, including yarns, threads, woven, nonwoven and knitted fabrics, and garments.

Mixtures of two or more cellulosic fibrous materials, or blends with synthetic fibres, may also be treated but it should be understood that blends with keratinous fibres are not included within the scope of the present invention.

Preferred esters for use in the process according to this invention are those estters containing on average not more than six mercaptan groups per molecule, and they usually have an average molecular weight of between 400 and 10,000 but, if desired, esters having an average molecular weight of up to 20,000 or even 40,000 may be used.

Such esters may be those obtainable by the reaction, in any desired sequence, of

(d) a monomercaptomonocarboxylic acid ora monomercaptomonohydric alcohol,

(e) a compound containing two, but not more than two,

alcoholic hydroxyl groups, and

(f) a compound containing at least three carboxylic acid groups.

If desired, components (e) and (f) may be caused to react to form a hydroxyl or carboxyl-terminated ester which is then esterified with (d).

Such esters may also be those obtainable by the esterification of (g) a monomercaptodicarboxylic acid with,

(h) a compound containing at least two but not more than six alcoholic hydroxyl groups and, optionally,

(i) a dicarboxylic acid containing no mercaptan group, or

an anhydride of such an acid, or

(j) a monocarboxylic acid, preferably a monomercaptomonocarboxylic acid, or

(k) a monohydric alcohol, preferably a monomercaptomonohydric alcohol.

Similarly, there may be employed esters obtainable by the reaction, in any desired sequence, of (d) a monomercaptomonocarboxylic acid, or a monomercaptomonohydric alcohol,

(1) a compound containing'at least three alcoholic hydroxyl groups per molecule, and

(m) a compound containing two, but not more than two carboxylicacid groups per molecule.

3 As those skilled in the art of makingpolyesters will appreciate, a carboxylic anhydride may be used in place of the corresponding carboxylic acid while a 1,2-epoxide may be substituted for an alcohol, one epoxide group corresponding to two alcoholic hydroxyl groups.

The esters are prepared in a known manner, preferably by heating the reactants together in the presence of a catalyst such as a strong acid (especially an anion exchange resin, toluene-p-sulphonic acid, or 50% sulphuric acid) and of an inert solvent, such as toluene, xylene, trichloroethylene, or perchloroethylene, with which water formed in the reaction can be removed as an azeotrope.

Substances containing at least two carboxylic acid groups, or anhydrides thereof, which may be used as compound (a) include succinic, adipic, phthalic, hexahydrophthalic, sebacic, malic, citric, tricarballylic, pyromellitic and dimerised or trimerised fatty acids, and their anhydrides (where existing), and thiomalic acid,

HO OCCH CH (SH) COOH otherwise known as mercaptosuccinic acid.

Monomercaptomonocarboxylic acids used as component (d) are usually of formula HOOC-RSH, where 1 to as high as 18 or even 24. There may thus be used mercaptoundecylic acid, mercaptostearic acid, and especially thioglycollic acid and 2- and 3-mercaptopropionic acid, i.e. r in the above formula is 1 or 2. Mercaptancontaining aromatic acids may also be used, such as and p-mercaptobenzoic acids.

Monomercaptomonohydric alcohols used as component (cl) commonly have the general formula HORSH, where R denotes a divalent organic radical, the HO group and the SH group being directly bound to carbon atoms of the radical R. Preferably they are also of formula HOC H -SH, where t is a positive integer of from 2 to 18 and especially preferred are those of the foregoing formula where r is 2 or 3, such as Z-mercaptoethanol, 1-mercaptopropan-2-ol, and Z-mercaptopropan-l- 01, but substances such as l-chloro-3rnercaptopropan-Z- 01 may also be used.

Compounds containing at least three carboxylic acid groups, or anhydrides thereof, which may be used as component (f) include citric acid, tricarballylic acid, pyromellitic acid, and trimerised linoleic acid, and their anhydrides (where existing).

The monomercaptodicarboxylic acid (g) is usually of formula HOOCRCOOH,

sorbitol, and adducts of ethylene oxide'or propylene oxide with such alcohols, including mixed polyhydric polyethers obtained by treating an initiator containing active hydrogen, such as ethylene glycol, with say, propylene oxide, and then tipping the adduct with a second alkylene oxide, say, ethylene oxide.

Mono'l,2-epoxides which may be used in place of a dihydric alcohol include: ethylene oxide, propylene oxide, butylene oxide, 1,1-dirnethylethylene oxide, epichlorohydrin, glycidyl ethers of alcohols (such as n-butyl and isooctyl glycidyl ethers) or of phenols (such as phenyl and p-tolyl glycidyl ethers), N-glycidyl compounds (such as N-glycidyl-N-methylaniline or N-glycidyl-n-butylamine), and glycidyl esters of carboxylic acids (such as glycidyl acetate).

In place of trihydric and higher alcohols there may be used monoepoxymonohydric alcohols such as glycidol, or a diepoxide such as a diglycidyl ether of an alcohol or a phenol.

The dicarboxylic acids containing no mercaptan group (i) which may be used are generally of the formula HOOC-R COOH, where R represents a divalent aliphatic, aromatic, or alicyclic residue, and include succinic, adipic, phthalic, hexahydrophthalic, sebacic, and malic acids, and dimerised fatty acids or their anhydrides. Although they can be used, ethylenically-unsaturated dicarboxylic acids are not preferred.

The dicarboxylic acids (m) and their anhydrides may be selected from those listed above for (i) and also the mercaptan-containing dicarboxylic acids (g) and their anhydrides.

It is often desirable, when preparing a polymercaptan ester for use in the present invention, to incorporate a monofunctional compound such as a monocarboxylic acid (j) or a monohydric alcohol (k) as a chain-terminator. Examples of these are aliphatic alcohols such as methanol, ethanol, Z-ethylhexanol, Z-methoxyethanol, and monomethyl ethers of poly(oxyethylene) glycols and poly(oxypropylene) glycols; cycloaliphatic alcohols such as cyclohexanol; aliphatic carboxylic acids such as acetic acid, Z-ethylhexanoic acid, stearic acid, and oleic acid; and aromatic acids such as benzoic acid. As already indicated, it is especially advantageous to use as the chainterminator a compound which contains a mercaptan group, examples being monomercaptomonocarboxylic acids and monomercaptomonohydric alcohols and, more specifically, thioglycollic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptoethanol, and Z-mercaptopropan-l-ol.

The polymercaptan esters are, in general, known substances (see US. Patent Specifications Nos. 2,456,314, 2,461,920, 2,914,585 and 3,138,573, French Patent Specification No. 1,503,633 and British Patent Specification No. 941,829).

The preferred polymercaptan esters used in the process of the present invention contain, directly attached to carbon atoms, on average 11 groups of formula where a and b are each zero or 1 but are not the same, n is an integer of at least 1 and at most 6, Y and Z each represent a divalent organic radical, and X represents a divalent organic radical which must contain an SH group when n is 1. More specifically, the average structures of the preferred esters can be represented by one of the formulae and especially by one of the formulae L (XI) D (XIII) (XIV) SH (XVI) R denotes the residue of an aliphatic, cycloaliphatic, or aromatic dicarboxylic acid after removal of the COOH groups,

R denotes the residue of an aliphatic, araliphatie, or cycloaliphatic diol after removal of the two hydroxyl p R denotes an organic radical containing at least two carbon atoms and directly linked through carbon atoms thereof to the indicated mercaptan-terminated ester chains,

R denotes the residue of an aliphatic, eycloaliphatic, or aromatic dicarboxylic acid containing a mercaptan group, after removal of the COOH groups,

m is an integer of at least 1,

p is an integer of at least 2, and

R, R, r, and t have the meanings previously assigned.

It will be understood that formulae II to XVII represent the average structure of the esters. Because of incomplete esterification, other substances may also be present. Further, as already indicated, not all units designated R, R and R to R need be the same.

Many of these esters are insoluble in water but can be applied as aqueous dispersions or emulsions. They may also be applied 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 ester to be used depends on the effect desired. For most purposes, a pick-up of from 0.1 to 5% by weight based on the material to be treated is suitable. Usually, woven fabrics require from 0.2 to 3% by weight of the ester but rather smaller quantities are needed on knitted fabrics, say from 0.1 up to 1.5% by weight. The handle of the treated material will, of course, depend on the amount of ester employed, and by simple experiment the least amount required to give the desired effect may readily be determined. Further, the composition and the construction of fabrics composed of the fibres also influence the amount of ester required.

The preferred aminoplasts contain, per molecule, at least two groups, of formula CH OR directly attached to an amidic nitrogen atom or atoms, where R denotes a hydrogen atom, an alkyl group of from one to four carbon atoms, or an acetyl group. Examples of such aminoplasts are the N-hydroxymethyl, N-al-koxymethyl, and N- acetoxymethyl derivatives of the following amides and amide-like substances.

(I) Urea, thiourea, and the cyclic ureas having the formula in which Q denotes oxygen or sulphur, and Y denotes either a group of formula or a divalent group containting from 2 to- 4 carbon atoms in the chain, which may be substituted by methyl, methoxy, and hydroxy groups, and which may be interrupted by '00-, -o-, or 1 lIR where R denotes an alkyl or hydroxyalkyl group containing up to 4 carbon atoms.

Examples of such cyclic ureas are ethyleneurea (imidazolidin-Z-one), dihydroxyethyleneurea (4,5 dihydroxyimidazolidin-Z-one), hydantoin, uron (tetrahydro-oxadiazin-4-one), 1,2-propyleneurea (4-methylimidazolidin-2- one), 1,3-propyleneurea (hexahydro-2H-pyrimid-2-one), hydroxypropyleneurea (5hydroxyhexahydro-ZH-pyrimid- 2-one), dimethylpropyleneurea (5,5-dimethylhexahydro- 2H-pyrimidone), dimethylhydroxypropyleneurea and dirnethylmethoxypropyleneurea (4-hydroxyand 4'me thoxy-S,5-dimethylhexahydro2H-pyrimid 2 one), 5- ethyltriazin-Z-one and 5-(2-hydroxyethyl)triazin-Z-one.

(II) Carbamates and diearbamates of aliphatic monohydrie and dihydrie alcohols containing up to four carbon atoms, e.g. methyl, ethyl, isopropyl, 2-hydroxyethyl, 2-methoxyethyl, 2-hydroxy-n-propyl, and 3-hydroxy-npropyl carbamates, and ethylene and 1,4-butylene dicarbamates.

(III) Melamine, and other p-olyamino-l,3,5-triazines.

If desired, aminoplasts containing both N-hydroxymethyl and N-alkoxymethyl, or N-hydroxymethyl and N- acetoxymethyl groups, may be used (for example, a hexamethylol melamine in which from 1 to 5 of the methylol groups have been so etherified or esterified) The aminoplast is usually applied as such but when a urea-formaldehyde or melamine-formaldehyde product is to be used, it may, if desired, be formed in situ in a conventional manner from a urea-formaldehyde concentrate or melamine-formaldehyde concentrate and the requisite additional urea or melamine.

The aminoplasts employed are, in general, soluble in water and may be applied from aqueous solution; or they may be applied from aqueous emulsions, from solutions in the dry-cleaning solvents, or from solutions in mixtures of water and a suitable co-solvent, such as methanol.

The proportions of the ester and the aminoplast can vary widely; there may be employed, per thiol group equivalent of the ester, from 2 to 50 or even 75, but usually from 5 to 40, N-methylol, N-alkoxymethyl or N- acetoxymethyl group equivalents of the aminoplast.

The desired effects may not be fully obtainable until substantially all the ester has cured. At room temperatures (say, 20 C.) this may take from five to ten days or even longer. When the ester has been applied before, or with, the aminoplast, and heat is used to promote curing of the aminoplast, the ester cures rapidly. The curing reaction can also 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 ester 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 bases, siccatives, oxidative curing agents, sulphur, sulphur-containing organic compounds, salts and chelates of heavy metals, and free-radical catalysts such as azodiisobutyronitrile, peroxides and hydroperoxides, or combination of these. As organic bases there may be used primary or secondary amines such as the lower alkanolamines, e.g., monoand di-ethanolamine, 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, water-soluble strongly basic salts such as trisodium phosphate, and also ammonia. As sulphur-containing organic compounds there may be used compounds in which the sulphur atoms are not exclusively present as mercaptan groups and which are mercaptobenzothiazoles and their derivatives, dithiocarbamates, thiuram sulphides, thioureas, disulphides, alkyl xanthogen sulphides and alkyl xanthates. 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, di-isopropyl peroxydicarbonate, and chlorobenzoyl peroxide.

Yet other catalysts are salts of a heavy metal with an acid having an acid strength (-log pK) below 5, or chelates of a heavy metal, including chelates which are also salts. By heavy metal is meant one classified as heavy in Langes Handbook of Chemistry, revised th Edition, McGraw-Hill Book Co., at pp. 6061, that is, a metal of group IB, IIB, IIIB, IVB, VB, VIB, VIIB, or VIII, a metal of group IIIA having an atomic number of at least 13, a metal of group IVA having an atomic number of at least 32, or a metal of group VA having an atomic number of at least .51. Preferably the metal is a member of group IB, IIB, IVB, VB, VIB, VIIB, or VIII, particularly the first series of such metals, i.e., titanium, vanadium, chromium, manganese, nickel, and especially iron, cobalt, and copper. Suitable salt-forming, non-drying acids are mineral acids, especially hydrochloric, hydrobromic, nitric, sulphuric, phosphorous, and phosphoric acids, and organic acids such as chloracetic, fumaric, maleic, oxalic, salicylic and, more especially, citric acid. Suitable chelating agents include those in which the chelating atoms are oxygen and/or nitrogen, for example, 1,2- and 1,3-diketones such as acetylacetone, alkylenediamines such as ethylenediamine and, more particularly, ethylenediaminetetra-acetic acid.

The amount of catalyst used can vary widely. In general from 0.1 to 20%, and preferably from 1 to 10%, by weight based on the weight of the ester used is required, although much larger quantities can be used.

Curing of the ester is also assisted by using elevated temperatures and if especially rapid results are required then temperatures in the range 30 to 180 C. may be used. High humidities also tend to accelerate curing in the presence of catalysts.

The aminoplast may be cured at room temperature, or as already indicated, at elevated temperatures. The mechanism by which the ester exerts its effect in conjunction with the aminoplast is not known. It is believed that either the -SH groups of the ester react with the N-methylol groups (present as such or formed in situ from esterified or etherified N-methylol groups), or oxidation of the -SH groups occur, molecules of the ester being coupled by means of disulphide bridges. The utility of this invention, however, does not depend on the truth of this belief.

In many cases it is desirable to include a catalyst for curing the aminoplast. Catalysts which may be used include latent acid compounds (which may be metal salts), or mixtures thereof, or certain basic substances. Ammonium salts which are latent acids, developing acidity in the mixture on heating, include ammonium chloride, ammonium dihydrogen phosphate, ammonium sulphate, and ammonium thiocyanate. These ammonium salts may be used admixed with metal salts which have a similar catalytic effect. Amine salts may also be used, e.g., Z-amino- Z-methylpropanol hydrochloride. Among suitable latent acid metal salts are zinc nitrate, zinc fiuoroborate, zinc chloride, zirconium oxychloride, magnesium chloride, magnesium fiuoroborate, and magnesium dihydrogen orthophosphate. These catalysts are generally used at concentrations of 0.3% to 5% by weight, calculated on the weight of resin-forming materials of the aminoplast. There may also be used stronger acids, such as hydrochloric and sulphuric acids, which may be used as aqueous solutions (say, as 4- to 8-normal solutions) or which may be dissolved in a mixture of water and a solvent which is immiscible or partly miscible with water, and also acidic gases. Basic substances which may be used include sodium bicarbonate and sodium carbonate.

When strong acid catalysts are used, in liquid or gaseous form, heating may not be required. In other cases it may be necessary to heat the treated material, e.g., at a temperature of to 200 C. for 30 seconds to 10 minutes, and preferably to 180 C. for 2 to 7 minutes.

To impregnate the fibres it is particularly convenient to use an aqueous emulsion comprising (i) an ester as aforesaid,

(ii) an emulsifying agent which is preferably nonionic or anionic (for example, compounds containing polyoxyethylene chains),

(iii) a protective colloid (such as sodium carboxymethylcellulose, hydroxyethylcellulose, methoxyethylcellulose, and a methyl vinyl ether-maleic anhydride copolymer in the form of an alkali metal or ammonium salt).

The ester, the aminoplast, and the catalyst if used, can be applied to the material in conventional Ways. For example, where fabric or yarn is to be treated, they may be padded on, or the material may be immersed in a bath. If garments or garment pieces are to be treated then it is convenient to spray them on, and more convenient still to tumble the garments with the solution, emulsion, or suspension.

A crease-resistant finish may be applied to cellulosic textiles by impregnating with the ester, an aminoplast, and a catalyst for the aminoplast, drying, and curing the fabric in a fiat state at a high temperature. Compared to that treated with aminoplast only, fabric treated in the above manner is considerably softer and has either substantially improved dry crease-resistance with no further loss in tear strength or substantially improved tear strength with no loss in dry crease-recovery.

Alternatively, a celulosic textile fabric having good wet crease-recovery may be obtained by impregnating the material with an aqueous solution of an aminoplast (such as methylolated dihydroxyethylene urea) and with a strong acid catalyst (e.g., hydrochloric acid) and maintaining the Wet fabric in a flat state, usually for 16 to 24 hours, rinsing, neutralising and drying the fabric, and then treating it with the ester (usually as an aqueous emulsion, and preferably containing a catalyst). Material so aftertreated with the ester has much better wet crease-recovery than, and tear strength as good as that of, that treated with the aminoplast alone.

A durably pressed cellulosic garment may be made by treating fabrics in piece form with the ester (preferably as an aqueous emulsion), an aminoplast, and a catalyst for the aminoplast, and drying the impregnated fabric, fashioning the sensitised fabric into garments, inserting creases or pleats, and curing the aminoplast, preferably at an elevated temperature. Compared to a garment treated with the aminoplast only, the garment is much softer to the touch and has a much better balance of crease-recovery and strength.

Unlike other softeners currently used, the esters used in the process of this invention do not impair the water absorption properties of the treated cellulosic materials.

The compositions used in the process of this invention may contain antisoiling, antistatic, bacteriostatic, rotproofing, fiarneproofing, and wetting agents. They may also contain water-repellents, such as parffin wax, and fluoroescent whitening agents.

The following examples illustrate the invention. Unless otherwise specified, parts and percentages are by weight. The esters used were prepared as follows.

Thiol A A mixture of 1,1,1-trimethylolpropane (26.8 g.), polyoxypropylene glycol of average molecular weight 425 (170 g.), adipic acid (58.4 g.), thioglycollic acid (55.2 g.), toluene-p-sulphonic acid (3 g.), and perchloroethylene (350 ml.) was heated under reflux in an atmosphere of nitrogen. Water formed during the reaction (25 ml.) was removed as its azeotrope with perchloroethylene. The mixture was cooled and washed with water, the organic layer was separated and the solvent was evaporated oif to leave Thiol A (278.9 g.) having a thiol content of 1.88 equiv./ kg.

Other esters listed in Table I were prepared in a similar manner except that, in making Thiol U, the toluene-psulphonic acid was replaced by 1 ml. of 50% aqueous sulpuric acid.

TABLE I Components Thiol content (equiv./

Molar Substance ratio Glycerol Adipic acid- Butane-1 ,4-diol. Thioglycollic acid Trimer acid Empol 1043 Pilgygoxypropylene glycol, average mol. wt.

Thioglycollic acid Pggaxypropylene triol, average mol. wt.

Mercaptosuccinic acid n-pentanol Pcltygxypropylene triol, average mol. wt.

Adipic acid Q-mercaptoethanol P il(%%xypropylene glycol, average mol.

Thiol H Butane-1 .4-diol 1. 64

Thioglycollic acid TABLE IContinued Components Molar Thiol Substance ratio {Polyoxypropylene triol average mol. wt. 700. 1 I

Hexane-1,2,6-triol.

J Ptllggoxypropylene glycol, average mol. wt.

Thioglycollic acid Glycerol Adipic acid Polyoxyethylene glycol, average mol. wt. 400. Thioglycollic acid 1,1,1-trirnethylo1propane Succinic acid Comerginol 65. Thioglycollic acid M lrimer acid Empol 1043 Butane-1,4-diol 3-mercaptopropionic acid 1,1 ,l-trimethylolpropane- Adipic acid Pillzygoxypropylene glycol, average mol. wt.

3-mer captopropionic acid {1,1,1-trimethylolpropane adipic acid 0 Adipic acid 2,2-bis(p-(2-hydroxypropoxy) phenyDpropane. Thioglycollic acid Glycerol Adipic acid Poilggoxypropylene glycol, average mol. wt.

Thioglycollic acid Polyoxypropylene triol, average mol. wt. 700.

Adipic acid Thioglycollic acid Polyoxyethylene glycol, average mol. wt. 300: Thioglycollic acid Pgloylgxypropylene triol, average mol. wt.

Succinic anhydride 48 Z-mercaptoethanol Pentaerythritol-propylene oxide tetrol adduct average mol. wt. 650. "Dimer acid Empol 1022 Z-mercaptoethanol lycerol Phthalic anhydride- Butane-1,4-diol. Thioglycollic acid v {P(il(]}6t())xypl0l)l6ll8 glycol average mol. wt.

Mercaptosuccinic acid w {Pgloygxypropylene glycol average mol. wt.

. 0.40 Mercaptosuccinic acid Polyoxypropylene glycol average mol. wt.

Mercaptosuccinic acid Y {Butane-IA-diol Mercaptosuccinic acid Z {Comerginol 65...

Mercaptosuccinic acid. Thioglycollic acid Pilggoxypropylene glycol average mol. wt.

Mercaptosuccinic acid Adipic ac" [Acetic acid H H p-n- H reu e: F-INFNDUIOIO Ho Hm clwbhyhifi lh Hose Hutchw man-w: unl t-wretch d: remweeeawwmmrwrorowee term-meow:

"Trimer acid Empol 1043 is available from Unilever-Emery N.V., Gouda, Holland. It is a trimerised unsaturated 0 fatty acid, having an average molecular Weight of about 800 and a carboxyl content oi about 3.4 equiv./kg. Dimer acid Empol 1022 was obtained from the same source: it is a dimerised unsaturated 0" fatty acid, having an average molecular weight of about 570 and a carboxyl content of about 3.4 equiv.

Comerginol 65 was obtained from Bibby Chemicals Ltd., Liverpool. It has an average molecular weight of about 700, and a hydros yl value of -165. It consists essentially of diprlmary alcohols, prepared by catalytic hydrogenation of the methyl esters of long chain aromatic-aliphatic fatty acids, together with, as by-products, small amounts of monohydric and tr hydric alcohols.

Emulsions of the polythiols were prepared by mixing the following components at room temperature with a Silverson mixer until a uniform emulsion resulted Emulsifying agent 1 denotes an adduct of a mixture of Cm and C18 aliphatic primary amines (1 mol) and ethylene oxide (70 mols).

11 1 Emulsifying agent 1 denotes an adduct of a mixture of C1 and C aliphatic primary amines (1 mol) and ethylene oxide (70 mols).

EXAMPLE 1 Samples of bleached cotton poplin (108 g. per square metre) were padded with a liquor (Liquors l7) so that the uptake was 70%. The samples were dried for minutes at 70 C. on tenter frames to their original dimensions, and then they were cured by heating for 5 minutes at 150 C. The crease angles and tear strength properties of the treated cloth were measured and are given in Table II.

Liquor 1 Aminoplast A 60 MgCl -6H O 18 per litre of water Liquors 2-7 Liquors 2-7 were the same as Liquor 1 but contained 20 g. of Thiol Resins A, B, C, D, E, or F respectively, in emulsion form, per litre of water.

Aminoplast A is a co-condensate of a methylated hexamethylolmelamine containing 4.5 methoxymethyl groups per molecule with N,N'-dimethylolethyleneurea.

In this and the following examples, the dry crease angles of the treated samples were measured by the Monsanto method. Twelve specimens (six folded warpwise, six folded weftwise) were used in each test and the specimens were creased under a 2 kg. load for 3 minutes and allowed to recover, suspended over a wire, for 3 minutes before the crease angles were measured. The values given in the tables are the average of the six obtained by adding the warpwise value to the corresponding weftwise value and dividing by two. Tear strengths were determined by the Elrnendorf method according to TAPPI Standard T 414n49. Three samples, each 63 mm. X 63 mm., were used, and the tear strengths were measured in the warp direction. All measurements of crease angle and tear strengths were determined on cloth which had been conditioned in an atmosphere of 66% relative humidity and a temperature of 25 C. for at least 8 hours.

TAB LE I I Crease Tear angle strength Liquor (deg) 03-) 1 (control) 91 336 7 Untreated Inclusion of the thiol did not impair the chlorine-resistant properties of fabric treated with the above liquors.

Similar results could be achieved by using any of Polythiols G to Z and A in place of the Polythiols A to F.

EXAMPLE 2 Example 1 was repeated, using the following liquors.

Liquor 8 Aminoplat B 100 MgCly per litre of water Liquors 9-12 The sample treated with Liquor 11 had a particularly soft handle.

EXAMPLE 3 Samples of the cotton poplin described in Example 1 were padded with Liquors .1 or 8 so that the uptake was and dried for 10 minutes at 70 C. on tenter frames to their original dimensions, then they were heated for 5 minutes at 150 C. to cure the resin. Next, some of the patterns were padded with solutions of a thiol in perchloroethylene so that the uptake of solution was 150% and that of thiol was 2%. They were dried as before and then allowed to cure by being kept at room temperature for 1 day. The crease angles and tear strengths are shown in Table IV.

Liquor 8 plus Thiol F EXAMPLE 4 Cotton poplin was padded with a solution of a thiol in perchloroethylene so that the uptake of the solution was 150% and that of the thiol was 2%. The samples Were dried for 10 minutes at 70 C. on tenter frames to their original dimensions and then kept at room temperature for 24 hours. Next, they were treated with either Liquor 1 or Liquor 8, dried as above, and finally cured for 5 minutes at 150 C. Results obtained are shown in Table V.

TABLE V Crease Tear angle strength Treated with (deg) (g.)

Untreated 43 1, 016 Liquor 1 only. 91 336 Thiol A plus Liquor 1- 106 384 Thiol B plus Liquor 1 112 384 Thiol 0 plus Liquor 1 108 368 Thiol D plus Liquor 1. 115 400 Thiol E plus Liquor 1. 112 368 Thiol F plus Liquor 1 116 416 Liquor 8 only 98 416 Thiol A plus Liquor 8. 112 352 Thiol B plus Liquor 8 126 384 Thiol 0 plus Liquor 8--.. 116 320 Thiol D plus Liquor 8 116 384 Tluol E plus Liquor 8-... 114 384 Thiol F plus Liquor 8 117 352 The sample treated with Thiol E and Liquor 1 had a particularly soft handle.

EXAMPLE 5 Samples of a bleached viscose fabric (177 g. per square metre) were padded with a liquor (Liquors 13-19) such that the uptake of liquor was 80%. The samples were dried at 70 C. for 10 minutes on tenter frames to their original dimensions, then cured by heating for 5 minutes at C. Table VI shows the crease recovery and tear strength properties of the treated materials.

13 Liquor 13 G. Aminoplast C 200 NH H PO 12 per litre of water Aminoplast C is a 50% aqueous solution of a methylated urea-formaldehyde resin in which the U:F molar ratio is 121.8.

Liquors 14-19 Liquors 14-19 were the same as Liquor 13 but contained in addition 20 g. of Thiols A-F respectively, in emulsion form.

TABLE VI Crease Tear Treated with angle strengt liquor (deg) (g.)

EXAMPLE 6 Samples of the viscose cloth which was described in Example were padded to 80% pick-up with Liquor 13, dried for 10 minutes at 70 C. on tenter frames to their original dimensions, and then heated for 5 minutes at 150 C. to cure the aminoplast. Next, some of the patterns were padded with a solution of a thiol in perchloroethylene so that uptake of the thiol was 2% The samples were dried as before and then allowed to stand for 24 hours at room temperature before the crease recovery properties and tear strengths of the treated fabric were assessed.

Liquor 13 plus Thiol F..'

EXAMPLE 7 The viscose fabric described in Example 5 was treated with a solution of a thiol in perchloroethylene so that the EXAMPLE 8 Samples of a cotton poplin similar to that described in Example 1 were padded with a liquor (Liquors 20-28) so that the uptake was and dried for 10 minutes at 60 C. on tenter frames to their original dimensions. They were then cured by heating for 5 minutes at C. The crease angles and tear strength properties of the treated cloth were measured. The handle of the treated cloth was assessed by a panel, and the absorption of the materials was determined by the American Association of Textile Chemists and Colorists Test Method 39-1952. The results are given in Table IX. The treated materials were washed in a solution of 2 g./l. soap and 0.8 g./l. soda ash in an English Electric Reversomatic washing machine set on programme 5, dried for 10 minutes in a Parnall Tumble Drier on a full heat, and their crease recovery and tear strength properties measured.

Liquor 20 Aminoplast D 120 MgCl -6H O 20 per litre of water Liquors 21-26 Liquors 21-26 were the same as Liquor 20 but contained in addition 20 g. of Thiol Resin A, B, C, D, E, or F respectively, in emulsion form per litre of water.

Liquors 27 and 28 TABLE IX Crease angle (deg.) Tear strength (g.) Water absorption Liquor Unwashed Washed Unwashed Washed Handle (secs) 107 105 156 156 Harsh 3.9 111 102 164 156 Fairly soft.--" 4.0 114 103 172 Fairly harsh--- 4.7 127 117 172 240 Fairly soft 8.7 122 112 220 200 t 6. 2 120 107 196 Fairly soft 3.8 121 108 204 180 it 7.0 113 104 208 192 Fairly hars 7.2 117 99 276 232 t 1,700 42 45 520 364 .--..do 5.2

EXAMPLE 9 per litre of water. The patterns were placed on a roller, covered with a film of polyethylene and held wet for 18 hours whilst the roller was rotated slowly. The patterns were then well rinsed with water, a solution of 5 -g./l. of sodium carbonate, water again and finally dried on tenter frames at their original dimensions.

Some of the patterns were then treated with Liquors 29- 33 to 70% expression, dried for 10 minutes at 70 C. and then allowed to cure for 5 days at room temperature. The wet and dry crease recovery angles and the tear strength of the treated cottons were measured and are recorded in Table X.

Liquors 29-33 Liquors 29-33 contained g. of Thiol Resin C per litre of water; Liquors 30-33 contained in addition 2 g. of monoethanolamine, 2 g. of sodium dimethyl dithiocarbamate, 0.1 g. of copper sulphate, or 10 g. of 100 vol. hydrogen peroxide per litre of water respectively.

TABLE X Crease angle (deg) Tear strength Liquor Wet Dry (g.)

Aminoplast D only 112 61 272 29 127 70 320 30.. 126 70 312 31 118 68 308 32- 136 66 312 33 128 70 328 Untreated 59 48 560 where R denotes the residue of an acid of 4 to 36 carbon atoms selected from aliphatic, cycloaliphatic, and aromatic dicarboxylic acids after removal of the two carboxylic groups,

R denotes the residue of a diol of at least 4 carbon atoms selected from aliphatic, araliphatic, and cycloaliphatic diols after removal of the two hydroxyl groups,

R denotes an organic radical containing at least 2 carbon atoms and directly linked through carbon atoms thereof to the indicated mercaptan-terminated ester chains.

R denotes the residue of an acid of three to four carbon atoms selected from aliphatic, dicarboxylic acids containing a mercaptan group, after removal of the two carboxyl groups,

In is an integer of at least 1,

p is an integer of at least 2 and no more than 6, and R is a divalent hydrocarbon radical of 1 to 24 carbon atoms. y

2. The process of claim 1, wherein the polyester material is selected from the formulae:

(I), (IV), and (V) Where is C H (II), (III), (IV), and (VIII) Where R is C,H and (VII) and (VIII) where R is -CHTCH;

wherein r is an integer of 1 to 24, t is an integer of 2 to 18, and the average molecular weight of the polyester material is 400 to 10,000.

3. Process according to claim 1, in which there is used from 0.1 to 5% by weight of the polyester material, calculated on the weight of the cellulosic fibres treated.

4. Process according to claim 1, in which there is employed from 5 to 40 group equivalents of a group selected from the class consisting of N-methylol, N-alkoxymethyl, and N-acetoxymethyl, per thiol group equivalent of the polyester material.

5. Process according to claim 1 wherein a catalyst for curing the polythiol is also applied which is selected from the group consisting of bases, siccatives, oxidising agents, sulfur, sulfur-containing organic compounds, free-radical catalysts, salts of a heavy metal with an acid having an acid strength (log pK) below 5, and chelates of a heavy metal.

6. Process according to claim 1 wherein a catalyst for curing the aminoplast is also applied which is selected from the group consisting of acids, latent acid compounds, and bases.

7. Process according to claim 1 in which the treated cellulosic fibres are heated at a temperature of from to 200 C. for from 30 seconds to 10 minutes to cure the aminoplast.

8. Cellulosic fibrous materials, free from keratinous material, bearing thereon a polyester material and an aminoplast as specified in claim 1.

3,476,697 11/1969 Clements 117-1395 X 3,706,527 12/1972 Dobinson et al 8-115.6 X 2,461,920 2/1949 Pratt 260-828 X 3,498,821 3/1970 Hanson 8-115.6 X 3,526,474 9/1970 Reeves et al. 8-185 X 3,576,591 4/1971 Cusano et a1 8-185 3,350,162 10/1967 Beck 8185 X 3,690,942 9/ 1972 Vandermaas et a1. 117139.5 X 3,703,352 11/1972 Dobinson et a1. 117141 X 3,706,528 12/1972 Dobinson et a1. 117-128 HERBERT B. GUYNN, Primary Examiner US. Cl. X.R.

UNITED s'rAirrfa FATsN'r OFFICE CER'IIFICATE ()F CORRECTION Patent No. I 3, 832,;31 Dated August 27, 1974 Inventor(s) Derek James Rowland Massy et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 16, claim 2, lines 1 4-19, delete the structural formula which now reads (I), (IV), and (V') where is -C H (II), (III), (IV), and (VIII) where R is -C H and (VII) and (VIII) where R is -CH -(l3H-;

and substitute the following structural formula I, IV, and V where R is -C H VII and VIII where R is CH2-CH l SH Signed and sealed this 1st day of July 1975.

(SEAL) Attest:

, C. MARSHALL DANDY RUTH C. MASON Commissioner of Patents attesting Oificer and Trademark