US2903381A - Treatment of synthetic textiles with a polyepoxide having a plurality of 1,2 epoxy groups - Google Patents

Treatment of synthetic textiles with a polyepoxide having a plurality of 1,2 epoxy groups Download PDF

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US2903381A
US2903381A US454193A US45419354A US2903381A US 2903381 A US2903381 A US 2903381A US 454193 A US454193 A US 454193A US 45419354 A US45419354 A US 45419354A US 2903381 A US2903381 A US 2903381A
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fabric
parts
treated
polyepoxide
polyether
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Carl W Schroeder
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Shell Development Co
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Shell Development Co
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Priority to FR1136341D priority patent/FR1136341A/fr
Priority to BE540980A priority patent/BE540980A/nl
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79—Polyolefins
    • 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
    • D06M15/55—Epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6131—Addition products of hydroxyl groups-containing compounds with oxiranes
    • D06P1/6133—Addition products of hydroxyl groups-containing compounds with oxiranes from araliphatic or aliphatic alcohols
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65131—Compounds containing ether or acetal groups
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/04—Polyester fibers
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/08—Oxirane
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/10—Polyvinyl halide esters or alcohol fiber modification
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/21—Nylon
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/927—Polyacrylonitrile fiber

Definitions

  • the invention further provides a method for coloring the synthetic fibers and fabrics treated in the above-described manner.
  • the polyepoxides to be used in the process of the invention comprise those compounds possessing a plurality groups). These polyepoxides may be saturated or unsatured, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted if desired with various substituents, such as halogen atoms, hydroxyl groups, ether radicals, and the like. They may also be monomeric or polymeric.
  • the epoxy equivalency will be integers, such as 2,3,4, and the like.
  • many of the materials may contain some of the monorneric monoepoxides or have some of their epoxy groups hydrated or otherwise reacted and/ or contain macromolecules of somewhat different molecular weight so the epoxy equivalency may be quite low and contain fractional values.
  • the polymeric material may, for example, have an epoxy equivalency of 1.5, 1.8, 2.5, and the like.
  • Polyepoxides to be used in the process of the invention may be exemplified by 1,4-bis(2,3-epoxypropoxy)benzene, 1,3-bis(2,3-epoxypropoxy)benzene, 4,4-bis(2,3- epoxypropoxy)diphenyl ether, 1,3-bis(2,3-epoxypropoxy) octane, 1,4-bis(2,3-epoxypropoxy)cyclohexane, 4,4-bis- (2-hydroxy3,4-epoxy butoxy) diphenyldimethylmethane, l,3-bis(4,5-epoxypentoxy)-5-chlorobenzene, 1,4-bis(3,4- epoxybutoxy)Zmhlorocyclohexane, diglycidyl ether, ethylene glycol diglycidyl ether, resorcinol diglycidyl ether,
  • polyether D which is substantially 2,2-his(2,3-epoxypropoxyphenyl)-propane, is obtained by reacting bis-phenol-AE2,2-bis(4-hydroxyphenyl)] with an excess of epichlorohydrin in an alkaline medium.
  • polyhydric phenols that can be used for this purpose include resorcinol, catechol, hydroquinone, methyl resorcinol, or polynuclear phenols, such as 2,2-bis(4-hydroxphenyl)-butane, 4,4-dihydroxybenzophenone, bis(4-hydroxyphenyl)ethane, and 1,5-dihydronaphthalene.
  • polyepoxides comprises the polyepoxy polyethers obtained by reacting, preferably in the presence of an acid-acting compound, such as hydrofluoric acid, one of the aforedescribed halogen-containing epoxides with a polyhydric alcohol, and subsequently treating the resulting product with an alkaline component.
  • an acid-acting compound such as hydrofluoric acid
  • polyhydric alcohol is meant to include those compounds having at least two free alcoholic OH groups and includes the polyhydric alcohols and their ethers and esters, hydroxy-aldehydes, hydroxyketones, halogenated polyhydric alcohols, and the like.
  • Polyhydric alcohols that may be used for this purpose may be exemplified by glycerol, propylene glycol, ethylene glycol, diethylene glycol, butylene glycol, hexanetriol, sorbitol, mannitol, pentaerythritol, polyallyl alcohol, polyvinyl alcohol, sorbitol, mannitol, inositol, trimethylolpropane, bis(4-hydroxycyclohexyl)dimethylmethane, 1,4 dimethylolbenzene, 4,4-dimethyloldiphenyl, dimethylol, toluenes, and the like.
  • the polyhydric ether alcohols include, among others, diglycerol, triglycerol, dipentaerythritol, tripentaerythritol, dimethylolanisoles, beta hydroxyethyl ethers of polyhydric alcohols, such as diethylene glycol, polyethylene glycols, bis(beta hydroxyethyl ether) of hydroquinone, bis(beta hydroxyethyl ether) of bisphenol, beta hydroxyethyl ethers of glycerol, pentaeryth'ritol, sorbitol, mannitol, etc., condensates of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, glycidyl, epichlorohydrin, glycidyl ethers, etc., with polyhydric alcohols, such as the foregoing and with polyhydric thioethers, such as 2,2'
  • the hydroxyaldehydes and ketones may be exemplified by dextrose, fructose, maltose, glyceraldehyde.
  • the mercapto (thiol) alcohols may be exemplified by alphamonothioglycerol, alpha,alpha'-dithioglycerol, etc.
  • the polyhydric alcohol esters may be exemplified by monoglycercides, such as monostearin, monoesters of pentaerythritol and acetic acid, butyric acid, pentanoic acid, and the like.
  • the halogenated polyhydric alcohols may be exemplified by the monochloride of pentaerythritol, monochloride of sorbitol, monochloride of mannitol, monochloride of glycerol, and the like.
  • a further group of the polyepoxides comprise the polyepoxy polyesters obtained by esterifying a polycarboxylic acid with an epoxy-containing alcohol, such as, for example the diglycidyl esters of polycarboxylic acids as diglycidyl phthalate, diglycidyl maleate, diglycidyl adipate and the like.
  • polyepoxides include the polyepoxypolyhydroxy polyethers obtained by reacting, preferably in an alkaline medium, a polyhydric alcohol or polyhydric phenol with a polyepoxide, such as the reaction product of a glycidyl ether of a polyhydric phenol with the same or different polyhydric phenol, the reaction product of glycerol and bis(2,3-epoxypropyl)ether, the reaction product of sorbitol and bis(2,3-epoxy-2-methylpropyl) ether, the reaction product of pentaerythritol and 1,2-epoxy-4,5-epoxypentane, and the reaction product of bis-phenol and bis(2,
  • a group of polymeric-type polyepoxides comprises the hydroxy-substituted polyepoxide polyethers obtained by reacting, preferably in an alkaline medium, a slight excess, e.g., 5 to 3 mole excess, of a halogen-containing epoxide, such as epichlorohydrin, with any of the aforedescribed polyhydric phenols, such as resorcinol, catechol, 2,2 bis(4' hydroxyphenyl)propane, bis [4-(2'-hydroxynaphth-1-yl)-2-2-hydroxynaphth-l-yl] methane, and the like.
  • a halogen-containing epoxide such as epichlorohydrin
  • polymeric polyepoxides include the polymers and copolymers of the allylic ether of epoxy-containing alcohols.
  • this type of monomer is polymerized in the substantial absence of alkaline or acidic catalysts, such as inthe presence of heat, oxygen, peroxy compounds, actinic light, and the like, they undergo additional polymerization at the multiple bond leaving the epoxy group unaffected.
  • allylic ethers may be polymerized with themselves or with other ethylenically unsaturated monomers, such as styrene, vinyl acetate, methacrylonitrile, acrylonitrile, vinyl chloride, vinylidene chloride, methyl acrylate, methyl methacrylate, diallyl phthalate, vinyl allyl phthalate, divinyl adipate, 2-chloroallyl acetate, and vinyl methllyl pimelate.
  • styrene vinyl acetate, methacrylonitrile, acrylonitrile, vinyl chloride, vinylidene chloride, methyl acrylate, methyl methacrylate, diallyl phthalate, vinyl allyl phthalate, divinyl adipate, 2-chloroallyl acetate, and vinyl methllyl pimelate.
  • polystyrene copolymer examples include poly(allyl 2,3-epoxypropyl ether), allyl 2,3-epoxypropyl ether-styrene copolymer, methyllyl 3,4- epoxybutyl ether-allyl benzoate copolymer, poly(vinyl 2,3- epoxypropyl) ether and an allyl glycidyl ether-vinyl acetate copolymer.
  • polyglycidyl polyethers of polyhydric alcohols obtained by reacting the polyhydric alcohol with epichlorohydrin, preferably in the presence of 0.1% to 5% by weight of an acid-acting compound, such as boron trifiuoride, hydrofluoric acid, stannic chloride or stannic acid.
  • an acid-acting compound such as boron trifiuoride, hydrofluoric acid, stannic chloride or stannic acid.
  • This reaction is effected at about 50 C. to .125 C. with the proportions of reactants being such that there is about one mole of epichlorohydrin for every equivalent of hydroxyl group in the polyhydric alcohol.
  • the resulting chlorohydrin ether is then. dehydrochlorinated by heating at about 50 C. to C. with a small, e.g., 10% stioichiometrical excess of a base, such as sodium aluminate.
  • polyether polyepoxide reaction products which in general contain at least three non-cyclic ether (O) linkages, terminal epoxidecontaining ether (OCHzC OHa) groups and halogen attached to a carbon of an intermediate (-OHz--(
  • halogen-containing polyether polyepoxide reaction products obtainable by partial dehydrohalogenation of polyhalohydrin alcohols may be considered to have the following general formula O [(OCH2CH),,OCH C CH2] OHz-Hal z in which R is the residue of the polyhydric alcohol which may contain unreacted hydroxyl groups, X indicates one or more of the epoxy ether groups attached to the alcohol residue, y may be one or may vary in different reaction products of the reaction mixture from zero to more than one, and Z is one or more, and X+Z, in the case of products derived from polyhydric alcohols containing three or more hydroxyl groups, averages around two or more so that the reaction product contains on the average two or more than two terminal epoxide groups per molecule.
  • the insoluble material was filtered from the reaction mixture and low boiling substances removed by distillation to a temperature of about 150 C. at 20 mm. pressure.
  • the polyglycidyl ether in amount of 261 parts, was a pale yellow viscous liquid. It had an epoxide value of 9.671 equivalent per 100 grams and the molecular weight was 324 as measured ebullioscopically in dioxane solution.
  • the epoxy equivalency of this product was 2.13. For convenience, this product will be referred to hereinafter as Polyether A.
  • Polyether B 10.5 moles of ethylene oxide was bubbled through 3.5 moles glycerine containing an acid catalyst at 4050 C.
  • the resulting product had a molecular weight of 224 and a hydroxyl value of 1.417 eq./ 100 g. 101 parts of this ethylene oxide glycerine condensate was placed in a reaction kettle and heated to 6570 C.
  • Sufiicient BF ethyl ether complex was added to bring the pH to about 1.0 and then 132 parts of epichlorohydrin added dropwise. After all the epi had been added, the reaction was continued for about 15 minutes to assure complete reaction.
  • This product was then dissolved in benzene and 57 parts of sodium hydroxide were added in 7 equal portions at about 8789 C. over a period of 4 hours and then filtered to remove the salt. The solvent and light ends were then removed by stripping at a low vacuum. The resulting product had a molecular weight of 455, and an epoxy value of .524 eq./ 100 g.
  • this polyether will be referred to herein as Polyether B.
  • Polyether C One equivalent of 1,2,6-hexanetriol was placed in a reaction kettle and heated to 65-70" C. Sufiicient BF ethyl ether complex was added to bring the pH to about 1.0 and then 1 equivalent of epichlorohydrin added dropwise. After all the epi had been added, the reaction was continued for about 15 minutes to assure complete reaction. This product was then dissolved in acetone and sodium orthosilicate was added at about 65 C. over a period of 0.5 hour and then filtered to remove the salt. The solvent and light ends were then removed by stripping at a low vacuum. The resulting product had a molecular weight of 325 and an epoxy value of .600 eq./ 100 g. For convenience, this polyether will be referred to herein as Polyether C.
  • Particularly preferred members of this group comprise the glycidyl polyethers of aliphatic polyhydric alcohols containing from 2 to carbon atoms and having from 2 to 6 hydroxyl groups and more preferably the alkane polyols containing from 2 to 8 carbon atoms and having from 2 to 6 hydroxyl groups.
  • Such products preferably have an epoxy equivalency greater than 1.0, and still more preferably between 1.1 and 4 and a molecular weight between 300 and 1000.
  • the monomeric and polymeric glycidyl polyethers of dihydric phenols obtained by reacting epichlorohydrin with a dihydric phenol in an alkaline medium.
  • the monomeric products of this type may be represented by the general formula wherein R represents a divalent hydrocarbon radical of the dihydric phenol.
  • the polymeric products will generally not be a single simple molecule but will be a complex mixture of glycidyl polyethers of the general formula C Hz- CHCHO-(R-O-CHz-CHOHCHrO),,-ROCH 6H CH wherein R is a divalent hydrocarbon radical of the dihydric phenol and n is an integer of the series 0, l, 2, 3,
  • n is an integer
  • the fact that the obtained polyether is a mixture of compounds causes the determined valueof n to be an average which is not necessarily zero or a whole number.
  • the polyethers may, in some cases, contain a very small amount of material with one or both of the terminal glycidyl radicals in hydrated form.
  • the aforedescribed preferred glycidyl polyethers of the dihydric phenols may be prepared by reacting the required proportions of the dihydric phenol and the epichlorohydrin in an alkaline medium.
  • the desired alkalinity is obtained by adding basic substances, such as sodium or potassium hydroxide, preferably in stoichiometric excess to the epichlorohydrin.
  • the reaction is preferably accomplished at temperatures within the range of from 50 C. to 150 C. The heating is continued for several hours to eifect the reaction and the product is then washed free of salt and base.
  • Polyether D About 2 moles of bis-phenol was dissolved in 10 moles of epichlorohydrin and 1% to 2% water added to the resulting mixture. The mixture was then brought to C. and 4 moles of solid sodium hydroxide added in small portions over a period of about 1 hour. During the addition, the temperature of the mixture was held at about C. to C. After the sodium hydroxide had been added, the water formed in the reaction and most of the epichlorohydrin was distilled off. The residue that remained was combined with an approximately equal amount of benzene and the mixture filtered to remove the salt. The benzene was then removed to yield a viscous liquid having a viscosity of about poises at 25 C.
  • Particularly preferred members of the above-described group are the glycidyl polyethers of the dihydric phenols, and especially 2,2-bis(4-hydroxyphenyl) propane, having an epoxy equivalency between 1.1 and 2.0 and a molecular Weight between 300 and 900. Particularly preferred are those having a Durrans mercury method softening point below about 60 C.
  • the glycidyl polyethers of polyhydric phenols obtained by condensing the polyhydric phenols with epichlorohydrin are also referred to as ethoxylene resins. See Chemical Week, vol. 69, page 27, for September 8, 1951.
  • the amine curing agent employed with the polyepoxide may be any monomeric or polymeric compound having at least one and preferably at least one '7 ylamine, diallylamine, dioleylamine, dicyclohexylamine, methylethylamine, ethylcyclohexylamine, o-tolylnaphthylamine, pyrrolidine, 2-methylpyrrolidine, tetrahydropyridine, Z-methylpiperidine, 2,6-dimethylpiperidine, diaminopyridine, tetraethylene pentamine, meta-phenylene diamine, and the like.
  • Particularly preferred amines are the primary amines, and particularly the aliphatic hydrocarbon primary amines, aromatic hydrocarbon primary amines, and the heterocyclic primary amines, and especially those containing no more than 12 carbon atoms.
  • the amount of the amine curing agent employed in the process will vary depending upon the nature of the curing agent and the desired degree of cure. In general, amounts of curing agent varying from 3% to 30% by weight of polyepoxide give satisfactory results. Particularly preferred amounts vary from 5% to by weight of polyepoxide.
  • the polyepoxide and amine curing agent are applied to the synthetic fibers or fabrics in an aqueous medium. If the polyepoxide is water-soluble it may be employed in a straight aqueous solution. Many of the polyepoxides, however, have limited solubility in water and it is usually preferred to employ aqueous mediums containing emulsifying agents and/or organic solvents.
  • Emulsifying agents employed may be anionic, cationic or nonionic, and may be exemplified by monooleate of sorbitan polyoxyethylene, the trioleate of sorbitan polyoxyethylene, sorbitan tristearate, sorbitan monolaurate, polyoxyethylene esters of 'alkylphenols, carboxymethylcellulose starch, gum arabic, polyvinyl alcohol, aryl and alkylated aryl sulfonates, such as cetyl sulfonate, oleylate sulfonate, sulfonated mineral oils, copolymers of vinyl methyl ether, maleic anhydride, and the like, and mixtures thereof.
  • the emulsifying agents are generally employed in amounts varying from 0.1% to 10% by weight and more preferably from .1% to 5% by weight.
  • the amount of the polyepoxide in the impregnating solution may vary over a considerable range depending chiefly on the amount of resin to be deposited on the fabric and this in turn, will depend on the number of applications and the pick-up allowed per application.
  • a concentration ranging from 3% to by Weight will ordinarily sufiice. If less than 65% pick-up is permitted, the concentration may in some cases go as high as to 50%.
  • the aqueous medium employed to treat the fibers or fabrics may also contain plasticizers to improve their flexibility, although these should not be present in such proportions as to render the finished materials soft or sticky at temperatures and hum-idities to which they would be so exposed. It is found, however, that the substances employed in the present invention yield products which are sufficiently flexible for most purposes without the use of plasticizers.
  • organic and inorganic derivatives of phenols for example, diphenylol propane and triphenyl and tricresyl phosphates, sulphonamides, sulphonarylides, alkyl phthalates, for example, diethyl phthalate and glycol phthalates, diethyl tartarate
  • derivatives of polyhydric alcohols for example, mono-, di
  • compositions may also contain natural resins, e.g., shellac, resin, and other natural resins and synthetic or semi-synthetic resins, e.g., ester gum, polyhydroxy-polybasic alkyd resins, phenol aldehyde and urea-aldehyde resins.
  • natural resins e.g., shellac, resin
  • synthetic or semi-synthetic resins e.g., ester gum, polyhydroxy-polybasic alkyd resins, phenol aldehyde and urea-aldehyde resins.
  • Textile softening agents may also be added in varying amounts to improve the feel of the treated fibers or fabrics.
  • these agents include, among others, epoxidized glycerides, such as epoxidized soybean oil, glycidyl delta-decyl ether, pentadecyl phenol, octodecyl succinic acid, octodecenyl succinic acid, sulfonated waxes and sulfonated alcohols, dimerized long-chain unsaturated acids, non-ionic fatty acid esters of higher polyglycols.
  • epoxidized glycerides such as epoxidized soybean oil, glycidyl delta-decyl ether, pentadecyl phenol, octodecyl succinic acid, octodecenyl succinic acid, sulfonated waxes and sulfonated alcohols, dimerized long-chain
  • Preferred softeners are the epoxidized triand diglycerides
  • the application of the solution containing the polyepoxide to the synthetic fibers or fabrics may be effected in any suitable manner as by spraying, dipping, or brushing. It is generally preferred, however, to impregnate the fibers or fabrics by simply dipping them in the solution and running them through conventional-type padding rollers.
  • the amount of the polyepoxides to be deposited on the fibers or fabric will vary over a wide range. If the fabric is to have a soft feel, such as that intended for use for dresses, shirts, etc., the amount of polyepoxide deposited will generally vary from 3% to 20% by weight of the fabric. If stiffer materials are required such as for shoe fabrics, draperies, etc., still higher amounts of resins, such as of the order of 25% to 50% by weight may be deposited.
  • the solution can be applied again or as many times as desired in order to bring the amount of the polyepoxide up to the desired level.
  • the treated material may be dried for a short period to remove some or all of the dispersing liquid, such as water, alcohol, and the like. Drying time will depend largely on the amount of pick-up permitted during the application of the solution and the concentration of the polyepoxide. In most instances, drying periods of from 1 to 30 minutes should be suflicient.
  • the dispersing liquid such as water, alcohol, and the like.
  • the drying may be omitted and the fibers or fabric exposed directly to relatively high temperatures to accelerate the cure of the polyepoxides.
  • Temperatures used for this cure generally range from C. to 200 C., and more preferably, from C. to C. At these preferred temperature ranges the cure can generally be accomplished in from 1 to 10 minutes. Exposures of less than 3 minutes, e.g., 1 minute, may probably be used in continuous, commercial processing.
  • the process of the invention may be applied to the treatment of any synthetic fiber or fabric.
  • synthetic refers to those materials that do not occur in nature and is meant to exclude materials, such as cotton, wool and the like.
  • Synthetic fibers and fabrics include, among others, those prepared from acrylonitrile polymers, vinyl chloride polymers, vinylidene chloride polymers, vinylidene cyanide polymers, polyesters, polyamides, polyester-polyamides, cellulose ethers and esters, and polymers prepared from corn protein and formaldehyde (Zein).
  • the polymers of acrylonitrile, vinyl chloride, vinylidene chloride and vinylidene cyanide referred to above includes the homopolymers of these monomers as Well as copolymers of the monomers with dissimilar monomers, particularly those containing at least one CH group, such as, for example, vinyl acetate, methacrylonitrile, allyl glycidyl ether, allyl alcohol, allyl mercaptan, methyl methacrylate, methyl acrylate, styrene, butadiene, methylpentadiene, methacrylamide, chlorostyrene, butyl chloroacrylate, diallyl phthalate, vinyl methyl ether, allyl butyl ketone, ethylene glycol dirnethacrylate, and the like, as Well as the above monomers themselves when dissimilar to the basic monomer, such as vinyl chloride, acrylonitrile and vinylidene chloride.
  • copolymers preferably contain at least 15%, and more preferably from 20% to 95% of at least one of the basic monomers vinyl chloride, acrylonitrile, vinylidene chloride and vinylidene cyanide.
  • examples of these copolymers include Acrylan (85% acrylonitrile and 15% vinyl acetate), Dynel (60% vinyl chloride and 40% acrylonitrile) and Saran (85% vinylidene chloride and 15% vinyl chloride).
  • polyesters used in preparation of the synthetic fibers are preferably those high molecular weight products obtained by reacting glycols, such as ethylene glycol, propylene glycol and the like, with polycarboxylic acids, such as, for example, terephthalic acid, isophthalic acid, adipic acid, succinic acid, stilbenedicarboxylic acids and the like.
  • glycols such as ethylene glycol, propylene glycol and the like
  • polycarboxylic acids such as, for example, terephthalic acid, isophthalic acid, adipic acid, succinic acid, stilbenedicarboxylic acids and the like.
  • the polyamides are preferably those high molecular weight products obtained by reacting polyamines, and particularly the alpha, omega-diamines as 1,6-hexamethylenediamine, 1,5-pentarnethylenediarnine and 1,8- octamethylenediamine, with polycarboxylic acids, such as adipic acid, succinic acid, phthalic acid, chlorophthalic acid and the like.
  • polycarboxylic acids such as adipic acid, succinic acid, phthalic acid, chlorophthalic acid and the like.
  • the polyamides may also be prepared by polymerization of aminocarboxylic acids, such as aminocaproic acid.
  • the polyesterpolyamides are preferably those high molecular weight products obtained by reacting polycarboxylic acids as described above with amino alcohols, such as 4-arninobutanol, S-aminohexanol, 6-aminooctanol and the like.
  • the cellulose derivatives are preferably the alkanoic acid esters of cellulose, such as cellulose acetate and cellulose butyrate.
  • Synthetic fibers that can be used include those prepared from polyethylenes, polyurethanes (Perluran), mineral fibers (Fiberglas) and alginic materials as A1- ginate rayon.
  • the synthetic fabrics or fibers treated with the polyepoxides and amine catalyst have excellent color-reception and can be easily colored by dipping or otherwise applying the desired coloring thereto
  • Printed material may also be obtained by first printing the polyepoxide on the material in the desired design and then applying the dyeing solution thereto.
  • coloring material such as Orlon and Dacron when printed with dyes such as acid and direct dyes
  • a color print on a white background can be obtained by this technique.
  • the above-described technique may be utilized to print with different shades.
  • any of the conventional organic and inorganic coloring materials may be used. This includes the known watersoluble or insoluble dyes and pigments. Particularly preferred material to be used are the direct, acid and acetate dyes for this purpose.
  • Examples of direct dyes include, among others, Calcodur Blue S1 Pr-7l, Calcodur Blue 4G1 533 (Col. Index), Calcodur Gray L-Pr. 24, Calcodur Orange G1 Conc. 653, Calcodur Violet 4 BL 325, Calcodur Yellow NN 814, Calcomine Black G 200% 581, Calcomirie Brilliant Green Y, Calcornine Fast Red 8 B-Pr. 246, Clorarnine Blue BX 472, Chloratine Fast Brown G1 Pr. 48, Chloratine Fast Orange 4G1-Pr 333, Congo Red 4BX conc. 370, Diamine Brown BGPA 596, Erie Scarlet 3B382, Interchem Direct Blue 2B-406 and Nyanza Fast Orange S41 9.
  • acid dyes include, among others, Ac'eko Brilliant Scarlet-1 85, Aceko Dark Brown RD-235, Acko Milling Blue B-Pr 136, Acid Black BX246, Acid Violet 4 BNS 698, Alizarine Blue SAE, 1053, Alizarine Cyanine Green CG 1078, Alizarine Violet R Pdr-1080, Amacid Red 2G-Pr. 194, Anthra Milling Red 313-487, Bixacid Fuschsine 6B-57, Brilliant Cyanine 6B-Pr. 222, Calcocid Orange AD-l51,- Chinoline Yellow.D conc.
  • acetate dyes include, among others, Acetamine Diazo Black 3B Pr. 58, Acetamine Yellow RR-Pr. 243, Acetate Yellow GC cone-Pr. 242, Amacel Brilliant Blue B Ex.- Pr. 228, Bixacyl Rubine 3B-Pr. 239, Celanthrene Pure Blue BRS 400%Pr. 62, Celliton Scarlet BA-Pr. 244, Nacelan Violet 4R-Pr. 237, Tetracele Black G and Tetracele Yellow R.
  • Other types of dyes such as vat, mordant acid, lakes, ink, pigments and the like as listed in the above-noted tech. manual are less preferred but may be utilized in the process.
  • the fibers or fabrics may then be dried by conventional techniques and utilized directly in commercial applications, such as in the preparation of dresses, blouses, suits, draperies, and the like.
  • EXAMPLE I Examples I to IV illustrate the superior properties imparted to Orlon acrolonitrile polymer) fabric by treatment with Polyether A and an amine curing agent.
  • 100 parts of Polyether A described above epoxy equivalency of 2.13 and molecular weight of about 324
  • 5 parts of a polyglycol fatty acid ester emulsifier 5 parts of a polyglycol fatty acid ester emulsifier and 100 pms of water.
  • the mixture was stirred and then 50 parts of a 5% solution of polyvinyl alcohol, 20 parts of diethylene triamine in 100 parts of water was then added and additional water added to bring the solution up to 666 parts (15% polyether A solution).
  • White Orlon fabric was then treated with the abovedescribed solution by means of a Butterworth 3-roll laboratory padder.
  • the cloth after padding showed a 100% wet pick-up.
  • the treated cloth was then cured at C., for 5.5 minutes.
  • the treated cloth had a soft feel, good hand and was free of pilling.
  • the treated cloth did not fray at the cut edges.
  • the treated cloth also had excellent dye-receptive properties as shown by the following.
  • a dye solution was prepared by adding .225 part of Calcodur Blue SLPr-7l (direct cotton dye-Pr71) and 1.22 parts of sodium chloride to 1000 parts of Water. This mixture was heated to boiling and the treated Orlon cloth was placed therein and the mixture boiled for 20 minutes. The cloth which was then dyed a good blue color was removed, rinsed, and dried. Repeated washings with soap and water failed to affect the color. The color also appeared to be resistant to solvents, such as acetone.
  • EXAMPLE II The white Orlon fabric treated with Polyether A, as shown in Example I, was also dyed with Kiton fast Red R. dye (acid dye). 5 parts of the dye was placed in 1000 parts of water and the mixture heated to boiling. The treated Orlon fabric was then placed in the dye and the mixture boiled for 20 minutes. The cloth was then removed, rinsed and dried. The dried cloth was dyed an even deep red color. The color underwent little change even after repeated washings with soap and water. The color was also resistant to solvents, such as acetone.
  • Kiton fast Red R. dye ascid dye
  • EXAMIPLE III The white Orlon fabric treated with Polyether A, as shown in Example I, was also dyed with Celanthrene Pure Blue BRS 400% (acetate dyePr62). parts of the dye was placed in 1000 parts of water and the mixture heated to boiling. The treated Orlon fabric was then placed in the dye and the mixture boiled for 20 minutes. The cloth was removed, rinsed and dried. The resulting fabric was dyed a deep blue color which underwent little change on repeated washing. The cloth after five washes had a much better color than a similar piece of Orlon fabric which had been treated with benzoic acid as a dye carrier before being dyed with the Celanthrene Pure Blue and washed five times.
  • Celanthrene Pure Blue BRS 400% acetate dyePr62
  • EXAMPLE IV The white Orlon fabric treated with Polyether A, as shown in Example I, was also dyed with Anthraquinone Blue SWF 150% (acid dyelrl2). 5 parts of the dye was placed in 1000 parts of water and the mixture heated to boiling. The treated Orlon fabric was then placed in the dye and boiled for 20 minutes. The cloth was then removed and dried. The fabric, after drying, had a good blue color which underwent little change on repeated washing. A similar untreated white Orlon fabric was still white after being placed in the dye solution and boiled for 20 minutes.
  • Anthraquinone Blue SWF 150% (acid dyelrl2). 5 parts of the dye was placed in 1000 parts of water and the mixture heated to boiling. The treated Orlon fabric was then placed in the dye and boiled for 20 minutes. The cloth was then removed and dried. The fabric, after drying, had a good blue color which underwent little change on repeated washing. A similar untreated white Orlon fabric was still white after being placed in the dye solution and boiled for 20
  • Examples V to VII illustrate the superior properties imparted to Dacron (a glycol-terephthalic acid polyester) fabric by treatment with Polyether A and an amine curing agent.
  • White Dacron fabric was then treated with the abovedescribed solution by means of a Butterworth 3-roll laboratory padder.
  • the cloth after padding showed a 100% wet pick-up.
  • the treated cloth was then cured at 160 C., for 5.5 minutes.
  • the treated cloth had a soft feel, good hand, and was free of pilling.
  • the treated cloth did not fray at the cut edges.
  • the treated cloth also had excellent dye-receptive properties.
  • a dye solution was prepared by adding .22 part of Calcodur Blue S1 and 1.22 parts of sodium chloride to 1000 parts of water. This mixture was heated to boiling and the treated Dacron fabric was placed therein and the mixture boiled for 20 minutes. The cloth was then rinsed and dried. The resulting cloth had a deep blue color which showed little change on repeated washing. The color also appeared to be resistant to solvents, such as acetone.
  • EXAMPLE VI The white Dacron fabric treated with Polyether A, as shown in Example V, was also dyed with Anthraquinone Blue SWF 150%. 5 parts of the dye was placed in 1000 parts of water and the mixture heated to boiling. The treated Dacron cloth was then placed in the dyeand the mixture boiled for 20 minutes. The cloth was removed, rinsed and dried. The resulting fabric was dyed a deep blue color which underwent little change'on repeated washing. The-dye was also resistant to solvents, such as acetone.
  • EXAMPLE VII The white Dacron fabric treated with Polyether A, as shown in Example V, was also dyed with Celanthrene Pure Blue BRS 400% by the method shown in Example III.
  • EXAMPLE VIII with 5 parts of a polyglycol fatty acid ester emulsifier and parts of water. The mixture was stirred and then 50 parts of a 5% solution of polyvinyl alcohol, 20 parts of diethylene triamine in 100 parts of water was then added and additional water added to bring the solution up to 666 parts.
  • White cellulose acetate fabric was then treated with the above described solution by means of a Butterworth 3-roll laboratory padder.
  • the cloth after padding showed a 100% wet pick-up.
  • the impregnated cloth was then cured at 160 C., for 5.5 minutes.
  • the treated cloth had a soft feel, good hand, and did not fray at the cut edges.
  • the treated cellulose acetate fabric also had excellent dye-receptive properties.
  • a solution of Calcodur Blue SL was prepared as shown in Example I and the treated cellulose acetate fabric placed therein. The mixture was boiled for 20 minutes and then the cloth was removed, rinsed, and dried. The resulting fabric was dyed an even deep blue color which was not affected by repeated washings with soap and water.
  • EXAMPLE IX The white cellulose acetate fabric treated with Polyether A as shown in Example VIII was also dyed with Kiton fast Red R dye.
  • the dye solution was prepared as shown in Example II and the treated cellulose acetate fabric placed therein. The mixture was boiled for 20 minutes. The cloth was removed, rinsed and dried. The dried cloth was dyed a deep red color which was not affected by repeated washings. A similar untreated cellu' lose acetate fabric was only a slight red color after being treated with the Kiton fast Red dye as described above.
  • EXAMPLE X The white cellulose acetate fabric treated with Polyether A as shown in Example VIII was also dyed with Anthraquinone Blue SWF dye by the method shown in Example IV. The fabric, after drying, had a deep blue color which underwent little change on repeated washing. A similar untreated cellulose acetate fabric had only a slight blue color after being treated with the Anthraquinone Blue dye.
  • EXAMPLE XI This example illustrates the superior properties imparted to nylon. fabric (super polyamide fiber) by treatment with Polyether A and amine curing agent.
  • White nylon fabric was then treated with the above. described solution by means of a Butterwo-rth 3-roll laboratory padder.
  • the cloth after padding showed a 100% wet pick-up.
  • the treated cloth was then cured at 160 C., for 5.5 minutes.
  • the treated cloth had a soft feel, good hand and did not fray at the cut e'dge's.
  • the treated nylon fabric also had excellent dye-receptive properties as shown by the following.
  • a dye solution was prepared by adding .22 part of Calcodur Blue 'SL and 1.22 parts of sodium chloride to 1000 parts of water. This mixture was heated to boiling and treated nylon fabric was placed therein and the mixture boiled for 20 minutes. The cloth which was then dyed an even deep blue color, was removed, rinsed, and dried.
  • Polyether B described above is combined with 5 parts of a polyglycol fatty acid ester and 100 parts of water. This mixture is stirred and then 50 parts of a 5% solution of polyvinyl alcohol, 15 parts of ethylene diamine in 100 parts of water is added and additional water added to bring the solution to 666 parts.
  • Orlon fabric is then padded with above'described solution.
  • the treated fabric is dried for 5 minutes at 160 C.
  • the resulting fabric had a soft feel, good hand, and is easily dyed with Calcodur blue SL and Kiton fast red R dye as shown in the preceding examples.
  • EXAIMPLE XIII This example illustrates the preparation of dye-receptive Vinyon fabric (prepared from vinyl chloride-vinyl acetate copolymer) using Polyether B and triaminotoluene as the curing agent.
  • Polyether B About 100 parts of Polyether B is combined with 5 parts of a polyglycol fatty acid ester and 100 parts of water. This mixture is stirred and then 5 parts of a solution of polyvinyl alcohol, 25 parts of triaminotoluene in 100 parts of water are added and additional water added to bring the solution to 666 parts.
  • the Vinyon fabric is then padded with the above-described solution.
  • the impregnated fabric is dried for 5 minutes at 160 C.
  • the resulting fabric has a soft feel, good hand, and is easily dyed with Calcodur Gray L and Kiton fast Red R dye.
  • EXAMPLE XIV The same procedure is used as in the preceding example with the exception that the amine curing agent employed is diamino pyridine. Nylon fabric treated in this manner is easily dyed with the Calcodur Brown 4 GL, Kiton fast-Violet 10B and Kiton Fast Yellow 36.
  • EXAMPLE XV This example illustrates the preparation of a dye-receptive Orlon fabric using Polyether C and phenylene diamine as the curing agent.
  • Orlon fabric is'then padded with the above-described solution.
  • the treated fabric is dfied for 5 minutes at C.
  • the resulting fabric has a soft feel, good hand, and is easily dyed with Calcodur blue S1 and Kiton Fast Orange GR.
  • Orlon fabric having related dyeing properties are obtained by replacing Poly-ether C in the above-described process with equivalent amounts of each of the following Polyether A, Polyether' B and the polyglycidyl ether of pentaerythritol.
  • a process for treating synthetic textile materials prepared from polymers selected from the group consisting of acrylonitrile polymers, vinyl chloride polymers, vinylidene chloride polymers, vinylidene cyanide polymers, polyester reaction products of glycols and polycarboxylic acids and polyamide reaction products of polycarboxylic acids and polyamines to impart resistance to fraying at edge Where cut and prevent pilling, which consists of dipping the said synthetictextile material into an aqueous medium containing a polyepoxide having a plurality of groups and containing elements selected from the group consisting of carbon, hydrogen, oxygen and halogen atoms and a minor amount of a curing agent of the group consisting of primary and secondary amines, removing any excess aqueous medium and then subjecting the treated material to a temperature above 100 C. to cure the polyepoxide.
  • polyepoxide is a glycidyl polyether of an aliphatic polyhydric alcohol wherein the polyepoxide had an epoxide equivalency between 1.1 and 3 and a molecular weight between and 800.
  • polyepoxide is a halogen-containing polyether polyepoxide composition which composition is a mixture of others of polyhydric alcohols, the polyhydric alcohols having from 2 to 5 hydroxyl groups with at least two of the hydroxyl groups replaced in part by the group -OCHz-C- CHz and in part by the group 4.
  • polyepoxide .15 is a glycidyl polyether of an alkanetriohethylene oxide condensate.
  • a process for treating synthetic textile materials prepared from polymers selected from the group consisting of acrylonitrile polymers, vinyl chloride polymers, vinylidene chloride polymers, vinylidene cyanide polymers, polyester reaction products of glycols and polycarboxylic acids and polyamide reaction products .of polycarboxylic acids and polyamines to impart resistance to fraying at the edge where cut and prevent pilling, which consists of padding the textile material with an aqueous emulsion containing a polyether polyepoxide having a plurality of groups and containing elements selected from the group consisting of carbon, hydrogen, oxygen and halogen atoms, a minor amount of an amine curing agent of the group consisting of primary and secondary amines, drying the treated material and subjecting the dried material to a temperature between 100 C. and 200 C. .to cure the polyether polyepoxide.
  • polyepoxide is a glycidyl polyether of glycerol.
  • polyepoxide is a polyglycidyl ether of a glycerol-ethylene oxide condensate.
  • amine is di ethylene triamine.
  • a process as in claim 6 wherein the amine curing agent is ethylene diarnine. .11. A process as in claim 6 wherein synthetic material is a fabric prepared from a polymer of acrylonitrile containing at least 20% acrylonitrile. I 12. A process as in claim 6 wherein the synthetic material is a fabric prepared from a glycol-terephthalic acid polyester.

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US454193A 1951-03-30 1954-09-03 Treatment of synthetic textiles with a polyepoxide having a plurality of 1,2 epoxy groups Expired - Lifetime US2903381A (en)

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DEJ3969A DE1006288B (de) 1951-03-30 1951-03-30 Lagerung fuer die Leit- und Spannrolle von Geschwindigkeitswechselgetrieben mit Kettenumschaltung
US454193A US2903381A (en) 1954-09-03 1954-09-03 Treatment of synthetic textiles with a polyepoxide having a plurality of 1,2 epoxy groups
FR1136341D FR1136341A (fr) 1954-09-03 1955-09-01 Procédé de traitement de fibres et tissus synthétiques
BE540980A BE540980A (nl) 1954-09-03 1955-09-01 Werkwijze voor de behandeling van synthetische vezels en weefsels.
GB25147/55A GB780288A (en) 1954-09-03 1955-09-01 Improvements in or relating to the treatment of synthetic fibres and fabrics

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US3998981A (en) * 1974-08-14 1976-12-21 Wolkro Aktiengesellschaft Method for producing a tire-mounted anti-skid device
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AU618849B2 (en) * 1988-10-14 1992-01-09 Dow Chemical Company, The Process for preparation of epoxy resin containing aliphatically-bound, non-hydrolyzable chloride
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US20100168279A1 (en) * 2006-03-30 2010-07-01 Shengqian Kong Thermally curable epoxy-amine barrier sealants
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US3154479A (en) * 1958-04-28 1964-10-27 Agency Ind Science Techn Process for improving the properties of synthetic fibres, fabrics, films and mouldedarticles by irradiation with radioactive rays
US3154429A (en) * 1958-07-29 1964-10-27 Ciba Ltd Process for producing an antistatic finish on synthetic fibers
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CN105636224A (zh) * 2015-05-28 2016-06-01 宇龙计算机通信科技(深圳)有限公司 网络资源优化方法及装置、无线接入点
CN105636224B (zh) * 2015-05-28 2019-06-11 宇龙计算机通信科技(深圳)有限公司 网络资源优化方法及装置、无线接入点
CN114574990A (zh) * 2022-03-16 2022-06-03 长乐恒申合纤科技有限公司 一种易染易定型氨纶纤维的制备方法
CN114574990B (zh) * 2022-03-16 2023-11-17 长乐恒申合纤科技有限公司 一种易染易定型氨纶纤维的制备方法

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Publication number Publication date
GB780288A (en) 1957-07-31
FR1136341A (fr) 1957-05-13
BE540980A (nl) 1959-08-14

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