US3617194A - Textile finishing process using chlorinated hydrocarbon solvents and sulfohalide reaction catalysts - Google Patents

Abstract

Crease-resistance and easy-care properties of textile materials containing at least 20 percent by weight of cellulosic material are improved by impregnating the textile material with a solution or dispersion in a halogenated hydrocarbon solvent of a resin precondensate and an acid catalyst therefor, then subjecting the impregnated material to the action of hot water or steam and finally heating.

Description

0 United States Patent I 3,617,194

[72] Inventors Michael Bannister; [56] Referenc Ci d James Albert Moyse; Alexander Parkinson; James William Roberts, Manchester; Brian 3 I83 282 zg g STATES PATENTS Crosbie Fielding, Rumor, a of England urwitz 260/335 [21] Appl. No. 739,209 FOREIGN PATENTS [22] Filed June 24, 1968 1,174,859 3/1959 France 8/116.3 [45] Patented Nov. 2, 1971 OTHER REFERENCES [73] Assgnee lmler'alchemmnndustr'es Hofstetter, Melliand Textilberichte, March, 1969, pp. 321- London, England 3 3 4 [32] Priority May 10,1968 [33] Great Britain Primary ExaminerGeorge F. Lesmes 3 331 Assistant ExaminerJ. Cannon Attorney-Cushman, Darby and Cushman [54] TEXTILE FINISHING PROCESS USING CHLORINATED HYDROCARBON SOLVENTS AND SULFOHALIDE REACTION CATALYSTS 13 Claims, No Drawings [52] US. Cl 8/l16.3, ABSTRACT: Crease-resistance and easy-care properties of 8/115.7,8/116.2,8/115.6,260/33.8, 117/1394, textile materials containing at least 20 percent by weight of 117/161, 2/243, 38/144 cellulosic material are improved by impregnating the textile [51] Int. Cl D06m 13/08, material with a solution or dispersion in a halogenated D06m13/14,C08g51/30 hydrocarbon solvent of a resin precondensate and an acid [50] Field of Search .1 8/1 16.3, catalyst therefor, then subjecting the impregnated material to the action of hot water or steam and finally heating.

TEXTILE FINISHING PROCESS USING CI-ILORINATED IIYDROCARBON SOLVENTS AND SULFOI'IALID REACTION CATALYSTS This invention relates to a process for the finishing of textile materials, and more particularly toa process for applying-resin precondensates from a halogenated hydrocarbon solvent to halogenated or dispersion in a; halogenated hydrocarbon sol- .vent of a resin precondensate as hereinafter defined which reacts under acid conditions, together with a catalyst which is an aeid or "an acid-generating substance, immediately thereafter subjecting the' textile material so impregnated to the action of hot water or steam and thereafter heatin'g'the textile material.

By a resin precondensate is meant an initial stage condensa tion product of formaldehyde with a nitrogen-containingcompound, which is capable of reacting with itself under acid conditions to give a fully cured resin and/or is also capable ofreacting with thehydroxyl groups present in'the ctrllulosio textile material. Resin precondensates suit'able for use in'theprocess of the invention include theinitial stage condensation products of formaldehyde with urea, thiourea, dicyandiamide, amides carbamates, aminotriazines, urons,f ureins, ureides, imidazolidinones, pyrimidinones and 'triazinones, especially.

the methylolfderivatives of such compoundsand their loweralkyl ethers. Preferred resin ,precondensates are the .alkyl ethers of the aforesaid methylol compounds in which the alkyl.

groups contain from one to four carbon atoms.'-Particular eit =amples of such preferred resin precondensates' include metho'xymethylurea, polymet'hoxymethylmelaminc, 1,3- dimethoxymethyl-4,5-dihydroxy-imida2olidin-2-one and 1,3

. dimethoxymethyl-hexahydropyrimidin-2-one.

Halogenated hydrocarbon'solvents whichmay be employed inthe process of the invention include any of the commer' cially available halogenated hydrocarbons; it is preferable that the solvent should'be sufficiently volatile tobe capable of being rapidly removed from 'the'textile material ontreatm'eht with hot water or steam. Particularly suitable solvents are chlorinated and chlorofluorinated hydrocarbon solvents, for example trichloroethylene, perchloroethylene and l:l:ltrichloroethane. t o v As catalysts there are used'in the process of the invention substances which are themselves'acidor which-generateacid under the conditions of the proess,,the said'substances'being water is employed, the water is conveniently maintained at a temperature offrom 80 C. to; 100C. and the textile-material is allowed to remain in contact with the hot water for a period of from S'secs. to'60 secs. It is,however,- preferred to subject the textile material to which thesolution has beenapplied to the 'action of a steamatmosphere.The steam is preferably at atmospheric pressure, sov that the-textile material attains-a temperature of from 80 C. to 100 C., but superheated steam under pressure may be-employed if higher temperatures are desired-Thetextilematerial is preferably maintained in contact with'the steam atmosphere for a period of from 5 secs. to 60 secs The; steam treatment may conveniently be carried out in a steam chamber such as -,that described in British Pat. Specification'No. 916,338 or-thatdescribediin our copending ApplicationN'o. 42620/66.

After the treatment with hot water onsteam, the textile material is heated in order to bring about thenecessary curingof the resinprecondensate under the influence of the acid catalyst. The heating operation maybe carried out withina shorter is theh'eating time necessary. The heating operation may if-desired be'preceded-by a dryingstep in which-thetextile materialis-heated at'a lower temperature, for example in the range 50C. to 120 0. Alternatively, the-heating operation may optionally be deferred until after the textile material has been made up' into a garment. The resin-treated'textile material may optionally also be subjectedt o a mild washing treatmentto-remove-residualformaldehyde-and/or aid. v

The treatrnentgoflthe textile-material with hot water or steam immediately following the application of the solution of theresinpreconden'sate and the acid catalyst is'an essential soluble in the'halogenated hydrocarbon solvent. Suitable solvent-soluble acids include, for example, monochloracetic acid, dodecylbenzene sulfonie acid and 2,3-bis( hydrox"- ymethyl) butylphosphonic acid. Suitable solvent-soliible'acidgenerating compounds include, for example, esters: such' as methyl p-toluene-sulphonate, quaternary ammonium salts such as cetyl pyridinium bromide and stearamidometh'ylpyridinium chloride, and in particular; aliphatic, aromatic or araliphaticsulphohalides such asmethane-sulphonyl'chloride, methanesulphonyl fluoride, benzene'sulphonyl chloride, ptoluenesulphonyl chloride, p-toluenes'ulphonyl' fluoride and m-benzenedisulphonylchloride. Such sulphohalides' are the preferred catalysts for use in the processof the invention.

The reactive componentswhich are to be applied to the cellulosic textile materialaecord'ing' toe the process of the invention7 that is to say, the resin precondensate and the acid catalyst, are initially dissolved or dispersed in the halogenated hydrocarbon solvent, and the resulting solution or dispersion is applied to the textile material by any of the known methods, such as impregnating, coating or spraying. The textile material may then be squeezed, if desired, to remove any excess of the solution. The textile material so treated is then immediately conducted either into a vessel of hot water or into a chamber containing an atmosphere of steam. In the case where hot part of the-process of the invention. Not only does thisti'eatment serv'etoremo ve-the halogenated hydrocarbon solvent by volatilization,-but it also brings about an'unexpected enhancement'of the desirableproperties of the textile material which are conferred by the process. If the'halogenated hydrocarbonsolvent isremoved from the textile material by the application The amount of the -resinprecondensate which is applied to thetextile material bythe process of the invention=may be varied according-to the magnitude of the treatment effect which it is desired to achieve, but in general anamount of from 2,5 percentto- 15 percent of thedry weight of the textile material is preferred.

The process" of'the invention may with advantage be carried out ins'u'cha way'that' the halogenated hydrocarbon solvent is re'cove're'd'fbr reuse after its removal from the textile material by hot wateror steam. in the case where hot water is employed for removal of the solvent, a solvent recovery system such as that described in British Pat. Specification No. 812,89 may be" used. When the solvent is removed by the preferred method of treating with steam, the solvent may conveniently Be recovered in conventional manner, for example by condensation of the vapors by means of a condenser positioned inside or outside the flash-off vessel, the condensate being passed to a water separator to remove water from the liquid solvent, as described, for example, in our copending Application No.42620/66. In this way loss of solvent vapor to the atmosphere can be obviated, and the resultingliquid solvent an be reused in the treatment of further textile material.

Cellulosic process materials which may be treated according to the process of the invention include fibers, yarns and fabrics containing at least percent by weight of cellulosic material. It is preferred to treat such textile materials which are composed wholly of cellulose, for example, cotton, viscose rayon (including rayon made from polynosic fibers) and linen. The process may, however, be applied to textile materials which are blends of cellulosic material with a noncellulosic material, for example a synthetic polymeric material such as a polyester, such blends containing at least 20 percent by weight, and desirably 50 percent by weight, of cellulosic material. Treatment of such textile materials by the process of the invention results in a substantial improvement in the crease-resistance and easy-care properties of the materials.

There may be added to the solution in the halogenated hydrocarbon solvent of the resin precondensate and the acid catalyst as hereinbefore defined other textile treatment agents of known type which are soluble in the said solvent. Such other treatment agents include lubricants and softeners, for example low molecular weight polyethylene waxes, water repellent agents, for example silicones, methylolstearamide and stearamidomethyl pyridinium chloride, stiffening agents, for example polyvinyl acetate, and antisoil and soil-release agents such as the alkylene glycol/polyalkylene glycol terephthalic acid polyester resins described in Specification No. 1,088,984 and in our copending Application No. 47166/66.

The invention is illustrated but not limited by the following examples, in which parts and percentages are by weight:

EXAMPLE 1 A mercerised cotton poplin fabric is impregnated in a solution of 6.2 parts of polymethoxymethylmelamine, prepared as described below, and 0.6 part of monochloracetic acid in 93 parts of trichloroethylene. The fabric is then passed through squeeze rollers at such a pressure that the amount of trichloroethylene solution retained by the fabric is 65 percent of its dry weight. It is attached to a frame and immersed in a steam chamber at 95 C. for 30 seconds in order to remove the solvent. The fabric is then heated at 150 -l55 C. for 3 minutes.

The resulting fabric is found to possess good crease resistance (when measured by British Standard Method of Test B.S. 3086:1959) and superior smooth-drying performance to the untreated cotton. This improvement is illustrated by the following crease recovery figures:

Untreated Treated fabric fabric Crease recovery angle 174 268 (warp weft) 1f the process is carried out by removing the Untreated Treated fabric fabric Crease recovery angle 171 265 (warp -1- weft) The finish is therefore durable to the above washing treatment.

The solvent-soluble polymethoxymethylmelamine used in the above treatment is prepared as follows:

126 Parts of melamine are added to 412 parts of a 51 percent w/w methanolic formaldehyde solution which have been basified by the addition of 7.2 parts of 47 percent w/w aqueous soda solution. The mixture is stirred and heated to reflux temperature, the mixture then being reluxed for V2 hour. The mixture is cooled to room temperature, 191 parts of methanol and 52 parts of concentrated hydrochloric acid are added, and the mixture is stirred at 2530 C. during 1% hours. The solution is basified to pH 7.8 by the addition of 40 parts of anhydrous sodium carbonate and the mixture is filtered from precipitated salts. The clear filtrate is evaporated under reduced pressure, the final conditions being 1 hour at C and 15 mm. mercury pressure. The product is filtered hot from a further small amount of precipitated salts, yielding a clear viscous liquid product which is readily soluble in halogenated hydrocarbon solvents.

EXAMPLE 2 A mercerised cotton poplin fabric is impregnated with a solution containing 6.2 parts of methoxymethylurea, prepared as described below, and 0.77 part of stearamidomethyl pyridinium chloride in 93 parts of trichloroethylene. The fabric is squeezed through a pad mangle so that the amount of solution it retains is 65 percent of its own weight. The solvent is then removed from the fabric by attaching the fabric to a frame and immersing the frame in a steam chamber at 95 C. for 30 seconds. The fabric is finally heated at C., for 3 minutes.

The treated cotton is found to possess a crease recovery angle (warp weft) of 223, while that of the untreated is 136. The solvent-soluble methoxymethylurea used in the above treatment is prepared as follows:

180 Parts of urea are added to 794 parts of 51 percent w/w methanolic formaldehyde solution which have been basified by the addition of 10.8 parts of 47 percent w/w aqueous caustic soda solution. The solution is stirred at 60-65 C. during 3 hours and cooled to room temperature. The solution is acidified to pH 2 by the addition of about 10 parts of concentrated hydrochloric acid, the solution then being stirred at 25-30 C. during 2 hours. The solution is basified to pH 9.5 by the addition of about 9 parts of 47 percent aqueous caustic soda solution and is then evaporated under reduced pressure, the final conditions being 1 hour at 90 C. and 15 mm. mercury pressure. The product is filtered from a small amount of precipitated salts, yielding a clear liquid product which is readily soluble in halogenated hydrocarbon solvents.

EXAMPLE 3 A mercerised cotton poplin is impregnated with a solution of 5 parts of polymethoxymethylmelamine prepared as described in example 1 of our copending application No. 29424/67 and 0.5 parts of p-toluene sulfonyl chloride in 94.5 pans of trichloroethylene. The fabric is then passed through squeeze rollers at such a pressure that the amount of trichloroethylene solution retained by the fabric is 80 percent of its dry weight. The fabric is passed into a steam chamber at 95 C. where it is steamed for 30 seconds in order to remove the solvent. The fabric is dried by heating at 100 C. for 1 minute and is then heated at -1 60 C. for 3 minutes.

The resulting fabric is found to possess improved crease resistance (when measured by British Standard Method of Test 85. 3086:1959) and superior smooth-drying performance to the untreated cotton. This improvement is illustrated by the following crease recovery figures:

(warp 1- weft) After washing the treated and untreated cotton for 1 hour at 95 C. in a solution of 0.1 percent soap and 0.1 percent soda ash, the crease recovery figures obtained are as follows:

A polyester/cotton blend fabric comprising 65 parts of polyester and 35 parts of cotton is impregnated in a solution of 6.7 parts of methoxymethylurea prepared as described in example 2 of the copending application No. 29424/67, /67 part of p-toluene sulfonyl chloride and 0.67 part of a copolymer made by the reaction of dimethyl terephthalate, polyethylene glycol mol.wt. 1540 and ethylene glycol as described in example 2 of our copending application No. 47 l 66/66, in 92.6 parts of trichloroethylene. The fabric is then passed through squeeze rollers at such a pressure that the amount of trichloroethylene solution retained by the fabric is 75 percent of its dry weight. The fabric is passed into a steam chamber at 95 C. where it is steamed for 30 seconds in order to remove the solvent. The fabric is dried by heating at l00 C. for 1 minute and is then heated at 160 C-l65 C. for 2 /2minutes.

The resulting fabric is found to possess good crease resistance (when measured by British Standard Method of Test BS. 3086:1959) and superior smooth-drying performance to that of the untreated fabric. The improvement in crease resistance is illustrated by the following crease recovery figures:

Untreated Treated Fabric Fabric Crease recovery angle 2l4 284 (warp weft) After washing the treated and untreated polyester/cotton fabric for 1 hour at 95 C. in a solution of 0.1 percent soap and 0.1 percent soda ash, the crease recovery figures obtained are as follows:

Untreated Treated Fabric Fabric Crease recovery angle 225 286 (warp weft) EXAMPLE A mercerised cotton poplin fabric is impregnated with a solution of 5 parts of polymethoxymethylmelamine, prepared as described in example 2 of our copending application No. 29424/67, 0.63 parts of p-toluene sulfonyl chloride and 0.32 parts of a low molecular weight polyethylene lubricant in 94 parts of trichloro-ethylene. The fabric is then passed through squeeze rollers at such a pressure that the amount of trichloroethylene solution retained by the fabric is 80 percent of its dry weight. The fabric is passed into a steam chamber at 95 C. where it is steamed for 30 sees. in order to remove the solvent. The fabric is dried by heating at 100 C. for 1 minute and is than heated at 155-160C. for 3 minutes.

The resulting fabric is found to possess improved crease resistance (when measured by British Standard Method of Test Bs 3086:1959) to the untreated cotton. This improvement is illustrated by the following crease recovery figures:

Untreated Fabric Treated Fabric Crease recovery angle (warp weft) After washing the treated and untreated cotton for 1 hour at C. in a solution of 0.1 percent soap and 0.1 percent soda ash, the crease recovery figures obtained are as follows:

Untreated Treated Fabric Fabric Crease recovery angle l 52 222 where X is oxygen, sulfur or an amino group, and which is capable of reacting with itself under acid conditions to give a fully cured resin and/or is capable of reacting with the hydroxyl groups present in the said cellulosic material, and (iii) a catalyst for the said resin precondensate selected from acids and acid-generating substances, (b) immediately after the said impregnation treating the textile material with an aqueous agent selected from hot water and steam, and (c) thereafter heating the textile material at a temperature of 120 C. to 200 C. for a period of from ten seconds to thirty minutes, the improvement which comprises utilizing as the catalyst an acidgenerating substance selected from aliphatic, aromatic and araliphatic sulphohalides.

2. A process as claimed in claim 1, wherein the resin precondensate is an alkyl ether of a methylol derivative selected from the methylol derivatives of urea, thiourea, dicyandiamide, an amide, a carbamate, an aminotriazine, a uron, a urein, a ureide, an imidazolidinone, a pyrimidinone and a triazinone, the alkyl group of the alkyl either containing from 1 to 4 carbon atoms.

3. A process as claimed in claim 2, wherein the resin precondensate is selected from methoxymethylurea, polymethoxy-methylmelamine, l,3-dimethoxymethyl-4,5- dihydroxy-imidazolidin-2-one and 1,3-dimethoxymethyl-hexahydropyrimidin-Z-one.

4. A process as claimed in claim 1, wherein the halogenated hydrocarbon solvent is selected from trichloroethylene, perchloroethylene and 1:l:l-trichloroethane.

5. A process as claimed in claim 1, wherein the sulphohalide is selected from methanesulphonyl chloride, methanesulphonyl fluoride, benzenesulphonyl chloride, methanesulphonyl fluoride, benzenesulphonyl chloride, p-toluenesulphonyl chloride, p-toluenesulphonyl fluoride and mbenzenedisulphonyl chloride.

6. A process as claimed in claim 1, wherein the textile material, after impregnation, is treated with water at a temperature of from 80 to l00 C. for a period of from 5 secs. to 60 secs.

7. A process as claimed in claim 1, wherein the textile material, after impregnation, is treated with steam at atmospheric pressure, so that the textile material attains a temperature of from 80 to C. for a period of from 5 secs. to 60 secs.

8. A process as claimed in claim 1, wherein the textile material is heated for a period of from 1 to 5 minutes.

9. A process as claimed in claim 1, wherein the concentration of the resin precondensate in the treatment liquor which is applied to the textile material is from 3 percent to 20 percent by weight of liquor.

10. A process as claimed in claim 1, wherein the amount of catalyst present in the treatment liquor is from percent to 20 percent of the weight of the resin precondensate.

11. A process as claimed in claim 1, wherein the amount of the resin precondensate which is applied to the textile material is from 2.5 percent to percent of the dry weight of the textile material.

Claims (12)

1. 2. A process as claimed in claim 1, wherein the resin precondensate is an alkyl ether of a methylol derivative selected from the methylol derivatives of urea, thiourea, dicyandiamide, an amide, a carbamate, an aminotriazine, a uron, a urein, a ureide, an imidazolidinone, a pyrimidinone and a triazinone, the alkyl group of the alkyl either containing from 1 to 4 carbon atoms.
2. 3. A process as claimed in claim 2, wherein the resin precondensate is selected from methoxymethylurea, polymethoxy-methylmelamine, 1,3-dimethoxymethyl-4,5-dihydroxy-imidazolidin-2-one and 1,3-dimethoxymethyl-hexahydropyrimidin-2-one.
3. 4. A process as claimed in claim 1, wherein the halogenated hydrocarbon solvent is selected from trichloroethylene, perchloroethylene and 1:1:1-trichloroethane.
4. 5. A process as claimed in claim 1, wherein the sulphohalide is selected from methanesulphonyl chloride, methanesulphonyl fluoride, benzenesulphonyl chloride, methanesulphonyl fluoride, benzenesulphonyl chloride, p-toluenesulphonyl chloride, p-toluenesulphonyl fluoride and m-benzenedisulphonyl chloride.
5. 6. A process as claimed in claim 1, wherein the textile material, after impregnation, is treated with water at a temperature of from 80* to 100* C. for a period of from 5 secs. to 60 secs.
6. 7. A process as claimed in claim 1, wherein the textile material, after impregnation, is treated with steam at atmospheric pressure, so that the textile material attains a temperature of from 80* to 100* C. for a period of from 5 secs. to 60 secs.
7. 8. A process as claimed in claim 1, wherein the textile material is heated for a period of from 1 to 5 minutes.
8. 9. A process as claimed in claim 1, wherein the concentration of the resin precondensate in the treatment liquor which is applied to the textile material is from 3 percent to 20 percent by weight of liquor.
9. 10. A process as claimed in claim 1, wherein the amount of catalyst present in the treatment liquor is from 5 percent to 20 percent of the weight of the resin precondensate.
10. 11. A process as claimed in claim 1, wherein the amount of the resin precondensate which is applied to the textile material is from 2.5 percent to 15 percent of the dry weight of the textile material.
11. 12. A process as claimed in claim 1, wherein there is also present in the treatment liquor which is applied to the textile material a soil release alkylene glycol/polyalkylene glycol terephthalate polyester resin.
12. 13. A textile material treated by a process as claimed in claim