US3666403A - Process for dyeing modified polyester fibers in the presence of quaternary ammonium salts - Google Patents

Process for dyeing modified polyester fibers in the presence of quaternary ammonium salts Download PDF

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US3666403A
US3666403A US804294A US3666403DA US3666403A US 3666403 A US3666403 A US 3666403A US 804294 A US804294 A US 804294A US 3666403D A US3666403D A US 3666403DA US 3666403 A US3666403 A US 3666403A
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dyed
fiber
dyeing
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dye
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Shiro Shimauchi
Norihiro Minemura
Kenji Ito
Takue Shima
Masataka Oshima
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Teijin Ltd
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Teijin Ltd
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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
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • D06P1/41—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 basic dyes
    • 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
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6426—Heterocyclic 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
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6429—Compounds containing nitrogen bound to a six-membered aromatic carbocyclic ring
    • 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
    • D06P1/642—Compounds containing nitrogen
    • D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
    • 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
    • D06P1/65112—Compounds containing aldehyde or ketone groups
    • 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
    • D06P1/653—Nitrogen-free carboxylic acids or their salts
    • D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
    • 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
    • D06P1/653—Nitrogen-free carboxylic acids or their salts
    • D06P1/6536—Aromatic
    • 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
    • D06P1/655—Compounds containing ammonium groups
    • 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
    • D06P1/655—Compounds containing ammonium groups
    • D06P1/6553—Compounds containing sulfonium groups
    • 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
    • D06P1/667—Organo-phosphorus 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
    • 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
    • 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
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/521—Polyesters using acid dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • This invention relates to a method of dyeing the modified polyester, poly vinyl chloride, acrylonitrile or cellulose acetate fiber with the anionic dyestuffs. More particularly, the invention relates to a method of dyeing a fiber selected from the group consisting of the modified polyester, polyvinyl chloride, acrylonitrile and cellulose acetate fibers with an anionic dyestuif in the presence of at least one compound selected from the group consisting of the tertiary amines of the formula wherein R, and R are each selected from the group consisting of alkyl and alkenyl groups of 3-5 carbon atoms, and R is selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl and aralkyl groups of l-l8 carbon atoms; the quaternary ammonium salts of the formula wherein R and R are each selected from the group consisting alkyl and alkenyl groups of 1-5 carbon atoms and their derivatives, R is
  • the fibers manufactured from such synthetic polyesters as polyethylene terephthalate did not have any afi'inity at all for the ionic dyestuffs and hence they were heretofore dyed principally by means of the disperse dyes.
  • the disperse dyes were costly and moreover the dyed products obtained by their use were not satisfactory with respect to brightness.
  • a second object of the invention is to provide a dyeing method by which the polyvinyl chloride fiber can be dyed to fully satisfactory deep shades.
  • the acrylonitrile fiber is usually dyes with the cationic dyestuffs.
  • a third object of the present invention is therefore to provide a dyeing method which expands the scope of color of the dyed products of acrylonitrile fiber as well as facilitates the dyeing of mixed spun products, especially the mixed spun products with wool.
  • a fourth object is therefore to provide a dyeing method which can impart excellent dye-ability to the cellulose acetate fiber and dye this fiber to bright shades.
  • tertiary amines to be used in the present invention are those having the hereinbefore indicated Formula I. Included as tertiary amines are such, for example, as tributylamine, monopropyl dibutylamine, monoethyl-dibutylamine, monoallyl-dibutylamine, monoamyl-dibutylamine, tripropylamine, triamylamine, N,N-dibutylaniline and dibutylbenzylamine.
  • the quaternary ammonium salts to be used in this invention are those having the hereinbefore indicated Formula H.
  • specific compounds of this formula mention can be made of such, for example, as tetrabutylammonium chloride, tributyllaurylammonium chloride, tetrabutylammoniurn bromide, tetrabutylammonium hydroxide, tributylallylammonium bromide, butyldirnethyllaurylammonium bromide, tributyloleilammonium bromide, butyldiethyllauryl bromide, tributylmethylammonium methosulfate, tributylamylammonium bromide, tributyl-stearylammonium bromide, butyldiethanollaurylammonium hydroxide.
  • the one other class of quaternary ammonium salts that are used in the present invention are those having the hereinbefore indicated Formula HI.
  • Specific compounds of this formula include such, for example, as dimethyllauryl-Z-chlorobenzylammonium chloride, diethylstearyl Z-chlorobenzylammonium bromide, dimethylstearyl 2- nitrobenzylammonium chloride, dimethyllauryl 3,4-dichlorobenzylammonium chloride, dipropyllauryl 4-ch1oronaphthylmethylammonium iodide, ethylmethyloleil 4- methoxybenzylammonium iodide, diethylpalrnityl 3,4-dichlorobenzylammonium chloride,
  • n-oleyldimethyl Z-nitrobenzylammonium chloride nstearyldimethyl 4-methylbenzylammonium chloride and nlauryldimethyl 4-methylphenylammonium chloride. These compounds can be used either alone or in combinations of two or more classes.
  • the sulfonium salts to be used in the present invention are compounds having the hereinbefore indicated Formula IV.
  • specific compounds in the case, for example,- where R R and R of the foregoing formula are saturated hydrocarbon residues, included are such as the dimethylstearylsulfonium salt, methylethyllaurylsulfonium salt, methylpropyllaurylsulfonium salt, methylbutyllaurylsulfonium salt, ethylpropylstearylsulfonium salt, tributylsulfonium salt, dibutylpropylsulfonium salt and diethylcyclohexylsulfonium salt.
  • alkenyl or the aryl or aralkyl groups such as phenyl, benzyl, naphthyl and naphthylmethyl.
  • alkenyl or the aryl or aralkyl groups such as phenyl, benzyl, naphthyl and naphthylmethyl.
  • hydrocarbon residues having substituents on their side or straight chain are those hydrocarbon residues having substituents on their side or straight chain.
  • the substituents include such as alkyl, aryl, alkenyl, nitro, alkoxy, halogens, cyancarboxy and sulfonic acid. Needless to say, the substituents are not restricted to those mentioned.
  • these derivatives included are such, for example, as dimethyl 4-chlorobenzylsulfonium salt, methylethyl 2-methoxybenzylsulfonium salt, diethyl 4 methylnaph-thylmethylsulfonium salt and dibutyl 4-carboxylbenzylsulfonium salt.
  • the one other class of sulfonium salts to be used in this invention is that having the hereinbefore indicated Formula V.
  • Polyester as used herein, is principally intended to be polyethylene terephthalate. However, it also refers to those polyesters which comprise at least 60 mol percent of ethylene terephthalate units and in which a part of the acid or dihydroxy component is substituted by one or more classes of either difunctional or hydroxy acids such as isophthalic acid, compounds having metal salts of sulfonic acid, beta-hydroxyethoxybenzoic, acid, p-hydroxybenzoic acid, diphenyldicarboxylic acid, naphthalenedicarboxylic acid, diphenylsulfonedicarboxylic acid, adipic acid and sebacic acid, or the aliphatic, alicyclic and aromatic dihydroxy compounds such as diethylene glycol, trimethylene glycol, hexamethylene glycol, neopentylene glycol, 1,4 cyclohexanedimethanol, 2,2,4,4- tetramethylcyclobutanediol (1,3), 1,4-bishydroxy
  • polyesters in which a minor proportion of a monofunctional compound such as benzoylbenzoic acid and/ or a polyfunctional compound of above trifunctional such as pentaerythitol and trimesic acid are copolymerized to a certain extent with substantial crosslinkings will also do.
  • a monofunctional compound such as benzoylbenzoic acid and/ or a polyfunctional compound of above trifunctional such as pentaerythitol and trimesic acid are copolymerized to a certain extent with substantial crosslinkings will also do.
  • the known catalysts and additives such as stabilizers, delustrants, etc., can be added with no trouble at all.
  • modified polyester compositions refer to the blended composition of a polyamide and a polyester obtained as hereinbefore described, the blended composition of a polyamide and a copolyester obtained by copolymerizing polyalkylene glycol with polyester, the blended composition of polyester and a polyamide blended containing a polyalkylene glycol, and the blended composition of polyester, polyamide and polyalkylene glycol.
  • Modified polyester fibers which are particularly desirable include: (a) that obtained by meltspinning a blended composition of 6099.5 wt. percent of polyester and 40-05 wt. percent of polyamide and drawing the resulting filaments; (b) that obtained by melt-spinning a blended composition of 400.5 wt.
  • ultraviolet absorbents can be used in the invention dyeing method for improving the light fastness of the dyed products.
  • the following compounds can be used as ultraviolet absorbents in the present invention.
  • R is H, -C,,H (wherein n is 1-18),
  • R is alkyl or aryl.
  • UV absorbents While the amount used of these ultraviolet absorbents will vary depending upon such as the class of the material to be dyed, the class of the dyestuff and the concentration and bath ratio, the use of about ll0% (O.-W.F.) of the material to be dyed will do. It is also possible to achieve the end desired by imparting the ultraviolet absorbent to the fiber using a separate bath.
  • the modified polyester composition of the present invention not only possesses excellent aflinity for anionic dyestuifs, as noted hereinbefore, but also demonstrates satisfactory afiinity for disperse dyes.
  • it can also be dyed satisfactorily by means of the basic dyes in the presence of anionic substances.
  • anionic substances included are such as the inorganic acids as sulfuric and acetic acids and the salts thereof; and benzenesulfonic acid, toluene-sulfonic acid, higher alkyl benzene sulfonic acid, and sulfuric esters of higher alcohols and the salts thereof; and phenols.
  • polyamides to be used in the present invention there are no particular restrictions as to the polyamides to be used in the present invention as long as they are serviceable with respect to such as their thermal resistance, etc. Mention can be made of such, for example, as polycaproamide, polyenanthamide, polynndecamide, polyhexamethylene adipamide and polymetaxylene adiparnide, or copolymers of these with other amideforming substances. These polyamides can be used either alone or in combinations of two or more thereof. Of these polyamides, the aromatic polyamides such, for example, as that which has copolymerized therewith the hexamethylene diammonium terephthalate component gives especailly desirable results with respect to such as compatibility.
  • polyamides are incorporated in the polyester in an amount of 05-40% by weight, and preferably 5 to 35% by weight. If the content of polyamide is less than 0.5% by weight, the atfinity of the resulting fiber for ionic dyestuffs is inadequate. On the other hand, if the content of polyamide exceeds 40% by weight, the properties as a polyester fiber are lost. Hence, it is undesirable for the content of the polyamide to be without the range indicated above.
  • the dyeability of the fiber can be further enhanced by the incorporation in the foregoing polyesters and/or polyamides in an amount not exceeding 30% by weight, based on the overall weight of the fiber, of a polyoxyalkylene glycol.
  • a polyoxyalkylene glycol mention can be made of such, for example, as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene-oxypropylene glycol block or random copolymer, methoxypolyoxyethylene glycol, phenoxypolyoxyethylene glycol and octylphenoxypolyoxyethlene glycol.
  • These poloxyalkylene glycols may be present in either the polyester or the polyamide, or in both components. It may be added either during the early stages of the manufacture of the polyester or during the blending of the components.
  • polyvinyl chloride fiber used in the present invention is a homopolymer, a copolymer or an after-chlorinated product.
  • the acrylic fibers to be used in the present invention useable are the acrylic fibers that do not possess dye receptive sites. That is to say, included are Orlon (trademark of Du Pont Company) type, Dynel (trademark of Union Carbide and Chemical Company) type, and the acrylic conjugated fiber. Again, it goes with out saying that the present invention has applicability to also the mixed textile products of the foregoing fibers with other classes of fibers.
  • the cellulose acetate fibers to be used in the present invention included are the usual diacetate to triacetate fibers.
  • the present invention can also be applied to the cellulose acetate fiber obtained by the after acetylation technique.
  • the invention can, of course, be applied to the mixed textile products of the foregoing fiber with the other classes of fibers.
  • the invention method is especially efilective in the case of mixed product of the acetate fiber with the polyamide fiber, since both fibers are dyeable with acid dyes.
  • the modified polyester fibers that can be dyed by means of the invention method are those so-called readily dyeable polyester fibers whose dyeability by means of disperse dyes has been improved, as hereinbefore described, by either an elevated temperature treatment or the introduction (blending or copolymerizing) of a third component.
  • readily dyeable polyester fibers denote those fibers having a dye adsorption of at least 60% as determined by the method of measurement of the rate of dye adsorption as defined below.
  • the rate of dye adsorption is determined in the following manner.
  • the specimen is washed in a 100-fold amount of distilled water (70 C.) for 30 minutes with stirring, followed by air drying and thorough opening of the fiber.
  • One gram of the so standardized specimen is Weighed and dyed under the following conditions:
  • d the optical density of the after-dyeing remaining liquor.
  • Polyester fibers having a dye adsorption of below 60% cannot provide satisfactory dyed products even though the invention method is used.
  • the results become negative. This is believed to be due to the fact that the dye is not dissociated as a result of the anionic dye forming a complex, with the consequence that in the case of the polyamide fibers having dye receptive sites the results become negative to result in the decline in the dye adsorption.
  • anionic dyestuffs denote all of the those dyes having an anionic group, i.e., the acid dyes, direct dyes, metal complex dyes, reactive dyes and acid mordant dyes.
  • the dyeing methods that can be used include the various methods such as the dip, padding and printing techniques.
  • the dyeing conditions will vary depending upon the class and form of the textile to be dyed and the class of dyeing method to be employed. For instance, in the case of the most widely practiced dip method, the dyeing conditions will be such as indicated below.
  • the aforementioned compounds are added to the dye bath in a concentration of 1100% O.W.F.
  • a dyeing temperature of below 100 C. does not result in a satisfactory dye adsorption, therefore a temperature exceeding 100 C. is required.
  • the dyeing is car- 10 ried out at a temperature of ll0l30 C. until the intended color deepness is obtained.
  • carrier dyeing can also be carried out effectively using conjointly the known carriers.
  • the dyeing may be carried out at 50-l00 C. using the aforesaid compounds in a concentration of about 1-50% O.W.F. (percentage based on the weight of the material to be dyed), though varying depending upon the dyestutf used.
  • carrier dyeing can also be carried out effectively using conjointly the known carriers.
  • the amount used of the aforesaid compounds will differ depending upon the concentration of the dyestuif used, but usually the amount ranges from 1% to 100%.
  • a dyeing temperature in the range of -120 C. is convenient and, if possible, the higher, the better.
  • carriers dyeing is also effectively carried out by conjointly using the known carriers.
  • phenolic compounds such as oand p-phenylphenol
  • chlorobenzene type compounds such as monochlorobenzene, o-dichlorobenzene and trichlorobenzene
  • benzoic acid and benzoic acid type compounds such as benzoic acid
  • naphthalenic compounds such as methyl naphthalene.
  • a suitable nonionic surfactant for carrying out the dyeing levelly by dispersing the dye-stuff thoroughly and for preventing the formation of tar, it is prefered to use a suitable nonionic surfactant in the invention method.
  • Surfactants such as indicated are those which are usually widely used as dispersants. Included are, for example, the polyethylene glycol type surfactants such as polyethylene glycol alkylamines, polyethylene glycol alkyl ethers and polyethyelne glycol aliphatic acid esters, and the ether or ester type surfactants which contain the poyhydric alcohols such sorbitan aliphatic acid esters and aliphatic acid monoglycerides as the hydrophilic group.
  • the textile which has been dyed in accordance with the invention method is thoroughly soaped after its dye ing and thereafter submitted to reduction clearing, if necessary.
  • the textile dyed by the invention method still retains adequate fastness even after it has undergone these after treatments.
  • the Water dissolved or dispersed dyestuff forms a complex with the aforesaid compounds of Formulas I-V II to become possessed with compatibility and atfinity with respect to the hydrophobic fibers and simultaneously to function at times as carrier at elevated temperature to become dilfused into the interior of the fiber and result in the adsorption of the dye.
  • the balance of the atfinity between the dyestuff and the aforesaid compounds of Formulas IVI'I become an important factor that determines the dye adsorption.
  • the compounds having the Formulas I, II, IV, V, VI and VII are suitable of the aforesaid compounds of Formulas I-VII.
  • An of these, as the compounds of Formula I, tributylamine, triamylamine and dibutylamine are especially desirable.
  • the compounds of 1 1 Formula VI the effects are great in the case of tributylphosphine and triphenylphosphine.
  • the pH of the dye bath is not greater than 5.
  • those having the tributyl group are especially desirable from the standpoint of dye adsorption.
  • tetrabutylammonium salts and tributyllaurylammonium salts.
  • sulfonium salts of Formulas IV and V the use of especially the tributylsulfonium salts and the OCHzCHr- S -CH2CH:0
  • the compounds of Formulas I, II, IV and VII of the compounds of Formulas I-VII are especially suitable.
  • compounds of Formula I tributylamine, triamylamine and N,N-dibutylaniline can be mentioned.
  • compounds of Formula II those having the tributyl group are satisfactory as regards dye adsorption. These are exemplified by such as tetrabutylammonium salts, tributyllaurylammonium salts, tributylstearylammonium salts and tributylallylammonium salts.
  • compounds of Formula IV mention can be made of the tributylsulfoniurn salts.
  • compounds of Formula VII included are those having the tributyl group such as tributylbenzylammoniurn salts and tributylallylphosphonium salts, or triphenylbutylphosphonium salts.
  • examples 1 la indicates the specific viscosity measured at 35 C. using orthochlorophenol as the solvent and intrinsic viscosity is defined as in which 0 is concentration in grams of polymer per 100 cc. of solution. Also all the parts are on a weight basis.
  • dyeability it was indicated by the rate of dye adsorption in the case disperse dyes, and in the case of ionic dyes it was indicated by a qualitative indication, rate of dye adsorption and classification into grades ranging from 1 to 10.
  • Grade 1 denotes that no dyeing at all took place, While Grades 2 and higher denote that as the grade becomes higher, the dyeing becomes better.
  • Dyeings which are of practical use are those having ratings of Grade 5 or higher.
  • TDI denotes the decomposition initiating temperature which has been measured in air at the rate of a temperature rise of 10 C. per minute using the differential heat analyzer.
  • EXAMPLE I An autoclave was charged with 291 parts of dimethyl terephthalate, 207 parts of ethylene glycol, 29.1 parts of polyoxyethylene glycol (molecular weight about 1500), 0.102 part of calcium acetate monohydrate and 0.75 part of antimony trioxide, after which the autoclave was gradually heated while slowly introducing nitrogen. The temperature was raised to 230 C. over a period of about 3 /3 hours while distilling off the methanol formed as a result of the ester-interchange reaction. After completion of the distillation off of the methanol, 0.051 part of phosphoric acid was added and the temperature was raised to 275 C. After stirring for 30 minutes at atmospheric pressure at this temperature, the pressure of the reaction system was gradually reduced to less than 0.4 mm. Hg over a period of about 1 hour and 10 minutes. The so obtained modified polyester had an intrinsic viscosity of 0.45 and a softening point of 252.3 C.
  • Acid dye (C.I. Acid Blue 129) percent '(O.W.F.) 4
  • EXAMPLE 2 An autoclave was charged with 291 parts of dimethyl terephthalate, 207 parts of ethylene glycol, 30 parts of methoxypolyoxyethylene glycol (molecular weight about 1000), 0.816 part of pentaerythritol, 0.102 part of calcium acetate monohydrate and 0.75 part of antimony trioxide, after which the autoclave was gradually heated While slowly introducing nitrogen thereinto. The temperature was raised to 225 C. over a period of about 3 hours while distilling off the methanol formed as a result of the ester-interchange reaction. After completion of the distillation off of the methanol, 0.051 part of phosphoric acid was added and the temperature was raised to 275 C.
  • the so obtained modified polyester had an intrinsic viscosity of 0.46 and a softening point of 254.4 C.
  • This fiber was dipped in a dye bath of the following composition.
  • EXAMPLE 3 An autoclave was charged with 194 parts of dimethyl terephthalate, 138 parts of ethylene glycol, 194 parts of dihydroxypolyethylene oxide-propylene oxide block copolymer (average molecular weight about 1700, polyethylene oxide portion about 40 mol percent), 0.068 part of calcium acetate monohydrate and 0.50 part of antimony trioxide. The autoclave was then gradually heated while slowly introducing nitrogen thereinto. The temperature was raised to about 230 C. over a period of about 3 hours while distilling off the methanol formed as a result of the ester-interchange reaction. After the distillation off of the methanol was completed, 0.034 part of phosphoric acid was added as a stabilizer and the temperature was raised to 235 C.
  • modified polyester had an intrinsic viscosity of 0.50 and a softening point of 258.1 C.
  • the modified polyester thus obtained and the copolyamide of the same sample as used in Example 2 were both rendered into granular form having maximum particle diameters from 3 mm. to 5 mm. or less. Fifty parts of this modified polyester and 5 parts of the copolyamide were thoroughly mixed and charged to an autoclave. After purging the autoclave with nitrogen, its pressure was reduced to less than 0.2 mm. Hg and the temperature was raised to 275 C. This temperature was held for 30 minutes to thoroughly melt the two polymers, followed by stirring for 30 minutes. The resulting blend had a softening point of 255.4 C.
  • This fiber was dipped in a dye bath of the following composition.
  • EXAMPLE 4 (a) Preparation of a polyamide-polyoxyalkylene glycol blend Seventy-nine parts of caprolactam, 85 parts of hexamethylenediammonium terephthalate and 37 parts of polyoxyethylene glycol (average molecular weight about 8000) were dissolved in 40 parts of water and then charged to a polymerization vessel. After purging the vessel with nitrogen, it was slowly heated, the water distilling off being removed. The temperature of the remaining por. tion was raised to 270 C. and was stirred at this tem- 15 perature for 60 minutes. This was followed by gradually reducing the pressure of the system to 0.77 mm. Hg at which pressure the polymerization reaction was carried out for 20 minutes. The 1 m of the resulting polyamidepolyoxyalkylene glycol blend was 1.02.
  • the temperature at the time of the completion of the distillation off of the methanol was 235 C.
  • 0.07 part of trimethyl phosphate was added.
  • the temperature of the system was raised to 280 C., stirring was carried out for 30 minutes and thereafter the pressure of the system was reduced to a high vacuum of below 0.2 mm. Hg over a period of 1 /2 hours.
  • the 1 of the resulting polyethylene terephthalate was 0.745.
  • Acid dye C.I. Acid Blue 1219 4 n-Tri'butyllaurylammonium bromide Actinol Rl00, 1 g./liter Bath ratio, 1:50
  • this fiber was dyed at 100 C. for 60 minutes in a dye bath of the following composition: disperse dye (C.I. Disperse Red 1, Cl. 11110) 4% (O.W.F.), Disper TL (Meisei Chemical Works Ltd.) 2 g./liter and acetic acid 4% (O.W.F.), and a bath ratio of 1:100, it was possible to dye the fiber to a deep shade of red.
  • the TDI of this drawn fiber was 205 C.
  • polyester fiber obtained by the method of Example 4-(a) (b)(c) was dipped in a dye bath of the following composition.
  • Acid dye C.I. Acid Blue 1219 4 Acetic acid 3 ActinolR100, 1 g./liter 16 When the dyeing was carriedout at 120 C. for 90 minutes, the fiber was dyed to only a medium shade.
  • the so obtained fiber was dyed using a dye bath composed of 4% (O.W.F.) of an acid dye Nylomin Blue GS (1. Cl.) (C.I. 62055), 5% (O.W.F.) of acetic acid, 4% (O.W.F.) of nonylphenoxypolyoxyethylene glycol and 4% (O.W.F.) of
  • EXAMPLE 6 S O Na 5% (O.W.F.) of acetic acid, 4% (O.W.F.) of nonylphenoxypolyethylene glycol and 4% (O.W.F.) of
  • EXAMPLE 7 Twenty parts of polymethoxylylene adipamide isp/0 was blended with 180 parts of 3 mol percent isophthalic component-copolymerized polyethylene terephthalate (a as in Example 5, after which the resulting blend was melt-spun at a spinning temperature of 280 C. in customary manner. The freshly spun filaments were then drawn 4.42x by means of an 85 C. pin, followed by being shrunk 22% at 205 C. and thereafter again being drawn 10% at 160 C.
  • the so obtained fiber was dyed using a dye bath composed of 4% (O.W.F.) of an acid dye Nylomin Blue 68-4, 5% (O.W.F.) of acetic acid, 4% (O.W.F) of nonylphenoxypolyoxyethylene glycol and 10% (O.W.F.) of tetrabutylphosphonium bromide, and under the condition of a bath ratio 1:100 and C. x 60 minutes. A dyed product of deep blue shade (Grades 8-9) was obtained.
  • a dye bath composed of 4% (O.W.F.) of Nylomin Blue GS, 5 (O.W.F.) of acetic acid, 4% (O.W.F.) of nonylphenoxypolyoxyethylene glycol and 4% (O.W. F.) of triphenylbutylphosphonium chloride was used and the foregoing fiber was dyed under the conditions of a bath ratio 1:100 and 120 C. x 60 minutes, with the consequence that the fiber was dyed to a deep blue shade (Grades 8-9)
  • the dyeing was carried out in a similar manner as described hereinabove but using instead of triphenylbutylphosphonium chloride the several compounds as indicated in the following table, the fiber was likewise dyed to deep shades of blue.
  • EXAMPLE 9 Thirteen parts of polyhexamethylene adipamide :063) and 87 parts of polyethylene terephthalate :105) were melt-blended as in Example 8, and the resulting blend was melt-spun at a spinning temperature of 285 C. in customary manner. The freshly spun filaments were drawn 4.25 by means of an 87 C. p n, then shrunk 30% at 215 C., and thereafter again drawn 15% at a temperature of 160 C.
  • this fiber was dyed as in Example 8, it was dyed to a deep blue shade (Grade 9) by means of the acid dye Nylomin Blue GS and was dyed to a deep green shade (Grade 9) by means of the basic dye Malachite Green.
  • EXAMPLE 13 Twenty parts of a copolyamide consisting of 70 mol percent of caprolactam and 30 mol percent of hexamethylenediammonium terephthalate was melt-blended with 80 parts of polyethylene terephthalate and then spun in customary manner at a spinning temperature of 285 C. The freshly spun filaments were drawn 4.3x by means of an 85 C. pin followed by again drawing with a pin heated at 80 C.
  • the so obtained fiber was dyed using a dye bath composed of 4% (O.W.F.) of the acid dye Nylomin Blue G5, 5% (O.W.F.) of acetic acid, 4% (O.W.F.) of nonylphenoxypolyoxyethylene glycol and 4% (O.W.F.) of butylstearylammonium chloride, and under the conditions of a bath ratio 1:100 and C. x 60 minutes.
  • a product dyed to a deep blue shade (Grades 5-6) was obtained.
  • EXAMPLE 14 EXAMPLE 15 An acetate cloth was dyed for 60 minutes at 80 C. in a dye bath of the following composition:
  • Valren (a polyvinyl chloride fiber) cloth was dyed at 80 C. for 60 minutes in a dye bath of the following composition:
  • Tetoron T-89 a (polyester fiber) was dyed at 130 C. for 90 minutes in a dye bath of the following composition:
  • the freshly spun filaments drawn 4.3x at 70 C. had a denier fineness of 3.2, a tensile strength of 4.2 g./den. and an elongation breakage of 38%.
  • This fiber was dipped in a dye bath of the following composition.
  • This dyed product was exposed for 80 hours in a Fade- O-meter, but no fading could be observed in the least.
  • the fiber was dyed in a bath of the above composition except that the Tinuvine P was eliminated. Although a product dyed to a blue shade was similarly obtained as in the case described previously, the fading in this case was marked when exposed for 80 hours in the Fade-O-meter.
  • EXAMPLE 19 (a) Preparation of a blend of a polyamide and a polyoxyalkylene glycol 250 parts of hexamethylenediammonium adipate and 56 parts of methoxypolyoxyethylene glycol were dissolved in 300 parts of water and charged to a polymerization vessel. After purging with nitrogen, the vessel was slowly heated and the water distilling off was eliminated. The
  • the so obtained fiber was dipped in a dye bath of the following composition:
  • the dyeing was carried out at 120 C. for 90 minutes. After completion of the dyeing operation, soaping of the dyed fiber was carried out as in Example 18. As a result, a product dyed to a bright shade of blue was obtained. Although this dyed product was exposed for 40 hours in a Fade-O-meter, there was observed no fading at all.
  • a specimen dyed in a dye bath of the above composition but from which 2,2'-dihydroxy-4,4'- diacetylbenzophenone was eliminated was similarly exposed for 40 hours in a Fade-O-meter, marked fading was noted.
  • EXAMPLE 22 A polyvinyl chloride fiber 'Ieviron" (trademark of Teijin Limited) was dipped in a dye bath of the following composition:
  • EXAMPLE 24 A polyacrylonitrile fiber was dipped in a dye bath of the same composition as that described in Example 21. After dyeing at 100 C. for 60 minutes, a product dyed to a deep shade of blue was obtained.
  • EXAMPLE 25 An acrylonitrile fiber Orlon" was dipped in a dye bath of identical composition as that of Example 23 and dyed at C. for 90 minutes, whereupon a product dyed to a deep shade of yellow was obtained.
  • EXAMPLE 26 As a cellulose acetate textile, a crepe de chine fabric of diacetate fiber was used. This was dipped in a dye bath of the following composition:
  • the temperature of the bath was then slowly raised and the dyeing was carried out at 100 C. for 60 minutes to yield a product dyed to a bright deep shade (Grade 8-9) of blue.
  • the colorfastness to light and washing of the so obtained product was very outstanding.
  • the dye adsorption was 80%.
  • the temperature of the bath was slowly raised and the dyeing was carried out at 90 C. for 60 minutes, whereupon was obtained a product dyed to a' bright shade (Grade 9-10) of red.
  • the dye adsorption was 95%.
  • EXAMPLE 33 The dyeing was carried out at C. for 60 minutes as in Example 29 except that a metal-containing dyestulf Kayakalan Red 2BL (C.-I. Acid Red 318) was used instead of the dyestuif used in Example 29, with the result that a product dyed to a deep shade of red was obtained.
  • a metal-containing dyestulf Kayakalan Red 2BL C.-I. Acid Red 3128 was used instead of the dyestuif used in Example 29, with the result that a product dyed to a deep shade of red was obtained.
  • EXAMPLE 34 The dyeing was carried out at 90 C. for 60 minutes as in Example 31, except that instead of the dyestuff used therein a reactive dye Remasole Red B (Cl. Reactive Red 22) was used, with the result that a product dyed to a deep shade of red was obtained.
  • a reactive dye Remasole Red B (Cl. Reactive Red 22) was used, with the result that a product dyed to a deep shade of red was obtained.
  • EXAMPLE 35 A crepe de chine fabric composed of diacetate fiber, a cellulose acetate textile, was dipped in a dye bath of the following composition:
  • the wet fastness of the resulting dyed product was of a degree excelling that obtainable by disperse dyes.
  • Example 35 was repeated except that instead of the cationic compound used therein was used. As a result, a product dyed to deep shade of blue was obtained.
  • EXAMPLE 37 A crepe de chine fabric composed of diacetate fiber was dipped in a dye bath of the following composition:
  • the dyeing was carried out at 80 C. for minutes. After completion of the dyeing of the fabric, it was washed in a bath containing an anionic surfactant, whereupon a product brightly dyed to a deep shade of yellow was obtained.
  • EXAMPLE 39 When the triacetate fiber was used instead of the diacetate fiber in Example 35 and the dyeing was carried out at 120 C. for 90 minutes, a product dyed to a deep shade of blue was obtained.
  • a crepe de chine fabric of diacetate fiber was printed using a paste of the foregoing composition. After drying the printed fabric, it was steamed at 100 C. for 40 minutes. The so-obtained dyed fabric was then waterwashed and laundered, whereupon was obtained a product which was dyed to a deep shade of blue.
  • EXAMPLE 42 Example 41 was repeated except that the dyeing was carried out at 110 C. for 90 minutes using Orlon instead of the Kanekalon used therein. A product dyed to a deep shade of red was obtained.
  • Example 43 was repeated except that Torevira WA (trademark of Hoechst Co.) was used as the modified polyester fiber instead of "Ietroron" T-89. A product dyed to a bright shade of purple was obtained.
  • Torevira WA trademark of Hoechst Co.
  • the modified polyester textile Tetroron T-89 was printed using a paste of the foregoing composition. After drying the textile, it was steamed at 120 C. for minutes. This was followed by waterwashing and laundering of the resulting dyed product to thus obtain a product dyed to a deep shade of red.
  • EXAMPLE 46 291 parts of dimethyl terephthalate, 207 parts of ethylene glycol, 29.1 parts of polyoxyethylene glycol (molecular weight about 1500), 0.102 part of calcium acetate monohydrate and 0.75 part of antimony trioxide were reacted in customary manner to obtain a copolymeric polyester having an intrinsic viscosity 0.45 and a softening point of 252.3 C. Fifty grams of this polyester and 10 grams of a polycaproamide of an intrinsic viscosity of 0.38 and a softening point of 213.7 C., both of which were rendered into particle size having maximum diameters 3-5 mm., were mixed together. The mixture was then charged to an autoclave which was reduced to a pressure below 2 mm.
  • the third component-containing modified polyester fiber obtained as hereinabove described was dipped in a dye bath of the following composition:
  • EXAMPLE 47 The modified polyester fiber obtained in Example 46 was dipped in a dye bath of the following composition:
  • Eriosin Red 2 BX (CI. Acid Red 116)
  • EXAMPLE 48 The polyvinyl chloride fiber Valren (trademark of Teijin Limited) was dipped in a dye bath of the following composition where it was dyed at 100 C. for 60 minutes to obtain a dyed product of a deep blue shade.
  • EXAMPLE 50 The polyvinyl chloride fiber Valren was dipped in a Bath ratio, 1:50
  • EXAMPLE l The polyacrylonitrile fiber Kanekalon was dipped in a dye bath of the same composition as that of Example 48. When the dyeing was carried out at 100 C. for 60 minutes, a product dyed to a deep shade of blue was obtained.
  • EXAMPLE 53 Using as a cellulose acetate textile a crepe de chine fabric composed of diacetate fiber, this fabric was dipped in a dye bath of the following composition:
  • the dyeing was carried out at 100 C. for 90 minutes and a product dyed to a deep shade of blue was obtained.
  • EXAMPLE 54 The polyester fiber Tetoron T-89 was dipped in a dye bath of identical composition as that of Example 53, wherein it was dyed at 120 C. for 90 minutes to yield a product dyed to a deep shade of blue.
  • EXAMPLE 55 As a modified polyester fiber, "Ietoron T-89 (dye adsorption of was used, and this fiber was dipped in a dye bath of the following composition:
  • EXAMPLE 56 An autoclave was charged with 291 parts of dimethyl terephthalate, 207 parts of ethylene glycol, 29.1 parts of polyoxyethylene glycol (molecular weight about 1500), 0.102 part of calcium acetate monohydrate and 0.75 part of antimony trioxide. The autoclave was then gradually heated while slowly introducing nitrogen thereto, and the temperature was raised to 230 C. over a period of about 3% hours while distilling off the methanol formed as a result of the ester-interchanging reaction.
  • the so obtained polyester had an intrinsic viscosity of 0.65 and a softening point of 252.4 C.
  • the so obtained fiber was dipped in a dye bath of the following composition:
  • the fiber was dyed at 120 C. for 9 minutes and thereafter soaped at 80 C. for 30 minutes in a 02% solution of Marseilles soap, with the result that a product dyed to a blue shade was obtained.
  • EXAMPLE 57 (a) Preparation of a blend of a polyamide and a polyoxyalkylene glycol 250 parts of hexamethylenediammonium adipate and 56 parts of methoxypolyoxyethylene glycol (average molecular weight about 4000) were dissolved in 300 parts of water and charged to a polymerization vessel. After purging the nitrogen, the vessel was slowly heated and the water distilling off was eliminated.
  • the temperature of the residuum was then raised to 280 C., at which temperature stirring was carried out for 60 minutes, after which the pressure of the system was gradually reduced to 0.7 mm. Hg, at which the polymerization reaction Was carried out for 20 minutes.
  • the so obtained polyamide-polyoxyalkylene glycol blend had an 1 of 1.13.
  • the freshly spun filaments were drawn 4.3x by means of an 85 C. pin, then shrunk 25% at a temperature of 230 C. and thereafter again drawn at a temperature of 150 C.
  • the so obtained fiber was dipped in a dye bath of the following composition:
  • Eriosin Red 2 BX C.I. Acid Red 116
  • Tributylphosphine 10 Bath adjusted to pH 2 with sulfuric acid Bath ratio, 1:50
  • a method of dyeing a modified polyester textile fiber which comprises dyeing said fiber with an anionic dyestuif in the presence of a quaternary ammonium salt of the wherein R and R are each selected from the group consisting of alkyl and alkenyl groups of 1-5 carbon atoms, R; is selected from the group consisting of alkyl and alkenyl groups of 5-18 carbon atoms, R; is selected from the group consisting of phenyl, benzyl, chlorobenzyl, naphthyl, alpha naphthylmethyl, diphenyl and cycloalkyl groups, and X is selected from the group consisting of halogens, alkoxy sulfate and OH group.
  • modified polyester fiber is one selected from the group consisting of:

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US804294A 1968-03-14 1969-03-04 Process for dyeing modified polyester fibers in the presence of quaternary ammonium salts Expired - Lifetime US3666403A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3753650A (en) * 1969-03-04 1973-08-21 Teijin Ltd Method of dyeing fibers
US4797131A (en) * 1984-10-05 1989-01-10 Sandoz Ltd. Use of certain quaternary ammonium compounds in dyeing leather with basic dyestuffs
US5741338A (en) * 1996-03-11 1998-04-21 High Point Chemical Corporation Biodegradable dye leveler compounds for acrylic fibers
US20140250611A1 (en) * 2013-03-05 2014-09-11 Nike, Inc. Acid dyeing of polyurethane materials
US11154479B1 (en) 2020-05-31 2021-10-26 L'oreal Methods of removing color from color-treated hair
US11160742B2 (en) 2018-12-21 2021-11-02 L'oreal Methods and compositions for improving hair color fastness and rejuvenating hair color
US11173102B1 (en) 2020-05-31 2021-11-16 L'oreal Methods and compositions for removing color from color-treated hair
WO2022069715A1 (en) 2020-10-02 2022-04-07 Helm Ag Trialkyl sulfonium chlorides as fungicides

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB438508A (en) * 1934-03-12 1935-11-12 Ig Farbenindustrie Ag Improvements in dyeing and printing vegetable or artificial textile materials
FR834420A (fr) * 1937-03-04 1938-11-21 Ig Farbenindustrie Ag Procédé pour teindre les esters et éthers cellulosiques
NL59058C (enrdf_load_stackoverflow) * 1941-08-06
US2746836A (en) * 1951-08-31 1956-05-22 Monsanto Chemicals Process of dyeing acrylonitrile fibers
DE1265700B (de) * 1961-11-11 1968-04-11 Hoechst Ag Stabile wasserhaltige Loesungen von Azopigmenten
BE634304A (enrdf_load_stackoverflow) * 1962-06-28 1963-12-30 Hoechst Ag
CH848066A4 (de) * 1965-07-09 1968-02-15 Bayer Ag Verfahren zum Bedrucken von Textilmaterial aus vollsynthetischen oder halbsynthetischen Fasern

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3753650A (en) * 1969-03-04 1973-08-21 Teijin Ltd Method of dyeing fibers
US4797131A (en) * 1984-10-05 1989-01-10 Sandoz Ltd. Use of certain quaternary ammonium compounds in dyeing leather with basic dyestuffs
US5741338A (en) * 1996-03-11 1998-04-21 High Point Chemical Corporation Biodegradable dye leveler compounds for acrylic fibers
US20140250611A1 (en) * 2013-03-05 2014-09-11 Nike, Inc. Acid dyeing of polyurethane materials
AU2014270035B2 (en) * 2013-03-05 2016-04-28 Nike Innovate C.V. Acid dyeing of polyurethane materials
US9970155B2 (en) * 2013-03-05 2018-05-15 Nike, Inc. Acid dyeing of polyurethane materials
US11160742B2 (en) 2018-12-21 2021-11-02 L'oreal Methods and compositions for improving hair color fastness and rejuvenating hair color
US11154479B1 (en) 2020-05-31 2021-10-26 L'oreal Methods of removing color from color-treated hair
US11173102B1 (en) 2020-05-31 2021-11-16 L'oreal Methods and compositions for removing color from color-treated hair
WO2022069715A1 (en) 2020-10-02 2022-04-07 Helm Ag Trialkyl sulfonium chlorides as fungicides
WO2022069714A1 (en) 2020-10-02 2022-04-07 Helm Ag Trialkyl sulfonium salts

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FR2007340B1 (enrdf_load_stackoverflow) 1974-02-01
DE1912874A1 (de) 1969-11-27

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