Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
  • D06M15/423—Amino-aldehyde resins
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
  • D06M13/252—Mercaptans, thiophenols, sulfides or polysulfides, e.g. mercapto acetic acid; Sulfonium compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2369—Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
  • Y10T442/2393—Coating or impregnation provides crease-resistance or wash and wear characteristics

Definitions

• This invention relates to a process for modifying cellulosic materials in fibrous form, and to materials so treated.
• 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,
• the present invention further provides cellulosic fibrous materials bearing thereon an ester and an aminoplast as aforesaid in the cured or still curable, state.
• treatment of the fibres with the aminoplast and the ester can take place in any desired sequence.
• the fibres may be impregnated with a mixture of the aminoplast and the ester, and then the aminoplast is cured.
• the fibres may be impregnated first with the ester and then with the aminoplast, or vice versa, and then the aminoplast is cured.
• 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.
• 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.
• esters may be those obtainable by the reaction, in any desired sequence, of
• components (e) and (f) may be caused to react to form a hydroxyl or carboxyl-terminated ester which is then esterified with (d).
• esters may also be those obtainable by the esterification of (g) a monomercaptodicarboxylic acid with,
• a monocarboxylic acid preferably a monomercaptomonocarboxylic acid, or
• (k) a monohydric alcohol, preferably a monomercaptomonohydric alcohol.
• esters obtainable by the reaction, in any desired sequence, of (d) a monomercaptomonocarboxylic acid, or a monomercaptomonohydric alcohol,
• 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.
• 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,
• 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.
• R denotes a divalent organic radical
• the HO group and the SH group being directly bound to carbon atoms of the radical R.
• 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).
• glycidyl ethers of alcohols such as n-butyl and isooctyl glycidyl ethers
• phenols such as phenyl and p-tolyl glycidy
• 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.
• a monofunctional compound such as a monocarboxylic acid (j) or a monohydric alcohol (k) as a chain-terminator.
• 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.
• 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.
• 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,
• n 1
• p is an integer of at least 2
• R, R, r, and t have the meanings previously assigned.
• 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.
• 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 perchlor
• 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.
• 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.
• cyclic ureas examples include 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.
• 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.
• 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.
• room temperatures say, 20 C.
• 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.
• 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.
• 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.
• 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.
• siccatives are calcium, copper, iron, lead, cerium, and cobalt naphthenates.
• 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.
• 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.
• 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 does not depend on the truth of this belief.
• 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.
• 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.
• 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.
• 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.
• an aqueous emulsion comprising (i) an ester as aforesaid,
• an emulsifying agent which is preferably nonionic or anionic (for example, compounds containing polyoxyethylene chains),
• 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.
• fabrics or yarn 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.
• 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.
• a cellularosic 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.
• an aminoplast such as methylolated dihydroxyethylene urea
• a strong acid catalyst e.g., hydrochloric acid
• 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.
• the garment is much softer to the touch and has a much better balance of crease-recovery and strength.
• esters used in the process of this invention do not impair the water absorption properties of the treated cellulosic materials.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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).
• Emulsifying agent 1 denotes an adduct of a mixture of C1 and C aliphatic primary amines (1 mol) and ethylene oxide (70 mols).
• Liquor 1 Aminoplast A 60 MgCl -6H O 18 per litre of water
• 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.
• 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.
• 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.
• 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 were the same as Liquor 13 but contained in addition 20 g. of Thiols A-F respectively, in emulsion form.
• 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.
• 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 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.
• 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.
• 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.
• 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,
• 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.
• polyester material is selected from the formulae:
• 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.
• 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.
• a catalyst for curing the aminoplast is also applied which is selected from the group consisting of acids, latent acid compounds, and bases.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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Publications (1)

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Country Status (10)

• 1971
  • 1971-04-19 GB GB976771A patent/GB1376606A/en not_active Expired
• 1972
  • 1972-03-15 US US23503672 patent/US3832131A/en not_active Expired - Lifetime
  • 1972-03-16 ZA ZA721799A patent/ZA721799B/xx unknown
  • 1972-03-21 CH CH416472D patent/CH416472A4/xx unknown
  • 1972-03-21 CA CA137,608A patent/CA973664A/en not_active Expired
  • 1972-03-21 CH CH416472A patent/CH549686A/xx unknown
  • 1972-04-11 DE DE19722217268 patent/DE2217268A1/de active Pending
  • 1972-04-17 IT IT4967872A patent/IT952689B/it active
  • 1972-04-18 ES ES401866A patent/ES401866A1/es not_active Expired
  • 1972-04-19 FR FR7213807A patent/FR2133898B1/fr not_active Expired
  • 1972-04-19 BE BE782302A patent/BE782302A/xx unknown

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