US3505220A - Textile-finishing composition and textile treated therewith - Google Patents

Textile-finishing composition and textile treated therewith Download PDF

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US3505220A
US3505220A US556918A US3505220DA US3505220A US 3505220 A US3505220 A US 3505220A US 556918 A US556918 A US 556918A US 3505220D A US3505220D A US 3505220DA US 3505220 A US3505220 A US 3505220A
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textile
fibers
yarn
oil
alkyl
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US556918A
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Lawrence R Blake
Joseph P Penick Jr
Harold W Connor
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Celanese Corp
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Celanese Corp
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40Reduced friction resistance, lubricant properties; Sizing compositions
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/2964Artificial fiber or filament
    • Y10T428/2965Cellulosic
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2311Coating or impregnation is a lubricant or a surface friction reducing agent other than specified as improving the "hand" of the fabric or increasing the softness thereof
    • Y10T442/2336Natural oil or wax containing
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861Coated or impregnated synthetic organic fiber fabric
    • Y10T442/2869Coated or impregnated regenerated cellulose fiber fabric

Definitions

  • the invention is concerned with a textile-finishing composition especially adapted for use as a conjoint lubricant and finish for acetate fibers having little, if any, twist; that is, either zero twist or a twist which by itself is insufiicient to cause the fibers to become sufficiently entangled for effective or satisfactory spinning of the fibers into a yarn, for example a low twist of the order of from 0 to 1 turn per inch, not exceeding about 2 turns per inch.
  • Such fibers properly may be described as having substantially zero twist, and for purpose of brevity the expression substantially zero is sometimes used herein to include both zero and the aforementioned low-twist fibers.
  • Another object of the invention is to provide articles comprised of textile fibers including fibers of a cellulose ester having on surfaces thereof a new textile-finishing composition of the invention.
  • the cellulose ester fibers may be comprised of organic esters of cellulose, but preferably are comprised or composed of lower alkanoic esters of cellulose, e.g., cellulose propionate, cellulose butyrate, cellulose acetatebutyrate, and especially cellulose acetate.
  • Still another object of the invention is to provide a method of cohesively bonding together textile fibers including fibers of a cellulose ester having little, if any (i.e., substantially zero) twist by applying to the said textile fibers a textile-finishing composition of the invention.
  • a further object of the invention is to provide means for producing high-quality, substantially zero twist cellulose acetate yarn from which can be knitted fabrics having excellent quality.
  • Another object of the invention is to provide means for the production of substantially zero twist cellulose acetate yarn that can be beamed and knitted with the performance characteristic heretofore expected only when twisted yarn was used.
  • Another object of the invention is to provide means for the production of cellulose acetate tricot yarn for the knitting trade.
  • Still another object of the invention is to provide means for the production of cellulose acetate yarn that is accept- -able to the weaving trade for use in making sleazy fabrics.
  • a further object of the invention is to provide a textilefinishing composition having an unobvious combination of physical, chemical and physiological properties that make the composition especially suitable for use in extruding, knitting and weaving secondary cellulose acetate (CA fibers, and particularly in the treatment of substantially zero twist CA fibers.
  • Secondary cellulose acetate fibers are generally considered to be those having an acetyl value of less than 59 weight percent, more particularly between about 50 and about 58 weight percent, calculated as acetic acid.
  • Another object of the invention is to provide means for imparting the necessary cohesiveness to substantially untwisted CA fibers so that loops, broken filaments and other defects frequently associated with substantially zero twist extruded yarn are completely (substantially completely) eliminated.
  • Still a further object of the invention is to provide a textile-finishing composition which, when applied to twisted cellulose acetate yarn, provides a treated yarn that eliminates shiers when said yarn is employed in the production of low sley, sleazy fabrics. Shiers is a defect that is frequently associated with sleazy fabrics.
  • the objects of the invention are attained by producing and using in textile-treating applications (especially in the treatment of textile fibers that include a cellulose ester) a textilefinishing composition
  • a textilefinishing composition comprising:
  • alkyl or alkenyl acid phosphate containing from about 13 to about 19 carbon atoms in the alkyl or alkenyl grouping thereof, e.g., oleyl acid phosphate, palmityl acid phosphate, etc.; and
  • An oxidized (autoxidized) vegetable oil e.g., oxidized soybean oil.
  • the above-described textile-finishing composition also contains a phenolic antioxidant, preferably a di-[tertiary-(lower-alkyl)]-p cresol, and more preferably di-(tertiarybutyl)-p-cresol; and, preferably in addition to the phenolic antioxidant, a di(loWer-alkyl)aminoalkanol containing from 2 through 5 carbon atoms in the alkanol grouping, e.g., di-n-butylaminoethanol,
  • the textile-finishing compositions of the invention are prepared by blending together the various components in any suitable manner.
  • One convenient way of combining the ingredients is as follows:
  • the mixing tank, pump and lines are suitably cleansed, e.g., by rinsing with a few gallons of white mineral oil.
  • the mineral oil, polybutene and oxidized vegetable oil are added to the mixing tank in that order. Stirring is begun after the addition of the mineral oil.
  • the alkyl 'or alkenyl acid phosphate is introduced next, preferably in the form of a previously prepared salt of (a) the said acid phosphate in mineral oil with (b) the di-(lower-alkyl) aminoalkanol.
  • the phenolic antioxidant e.g., di-(tertiary-butyl)-paracresol
  • a concentrated solution thereof e.g., a 20% by weight solution
  • Stirring is continued at ambient temperature for about to 20 minutes, e.g., about minutes, after the final addition has been completed.
  • a typical viscosity (SUV at 100 F.) of the textile-finishing composition (especially when the preferred in gredients are employed) is usually within the range of from about 195 to about 205 seconds.
  • a typical acidity value (calculated as oleic acid) is generally within the range of from about 12.2 to 13.2.
  • the preferred acid phosphate is oleyl acid phosphate; and, as has been indicated hereinbefore, it is advantageously introduced into the composition in the form of a previously prepared amine salt, preferably a di-n-butylaminoethanol salt, thereof.
  • the amine salt functions in the composition as an antistatic agent, and the oleyl phosphate (or other alkyl or alkenyl phosphate employed) is an antistatic component of the said agent.
  • the amine salt also promotes scouring of the textile material in fiber, fabric or other form.
  • oleyl acid phosphate or the previously mentioned palmityl acid phosphate
  • various other longchain alkyl and/or alkenyl acid phosphates especially those containing from about 13 through about 19 carbon atoms in the alkyl or alkenyl grouping thereof, e.g., stearyl acid phosphate, palmitoleyl acid phosphate, gadoleyl acid phosphate, myristyl acid phosphate and arachidyl acid phosphate.
  • the preferred oxidized vegetable oil is oxidized soybean oil.
  • the function of the oxidized vegetable oil is to provide for fiber-to-fiber lubrication, control fiber-to-fiber coefficient of friction, and to contribute beneficially to the hand of the fiber and/ or fabric.
  • oxidized vegetable oils that may be used (singly or a plurality of them) in lieu of or in addition to oxidized soybean oil are oxidized peanut, cottonseed, corn, rape, sesame, hempseed, saffiower, poppyseed and oiticica oils. Additional examples of oils, which in oxidized form may be employed as a component of the textile-finishing compositions of the invention, are given in Chemical Technology and Analysis of Oils, Fats and Waxes, by J. Lewkowitsch, Sixth Edition, vol. II, pp. 42-414, MacMillan and Co., Limited, London, England (1922).
  • oxidized oil(s) as used in this specification and in the appended claims are meant, as previously has been indicated, such oils that have been produced by autoxidation; or, as they are sometimes designated, autoxidized oils.
  • Autoxidation is oxygen by molecular oxidation of organic material in the liquid phase without an accompanying flame, and is now well known in the art.
  • Such oxidation is effected, for example, by contacting vegetable oil with air in a continuous, countercurrent recycle, single-column operation.
  • the oil is heated initially to a temperature within the range of, for instance, from about to about C.
  • Natural inhibitors in the oil usually cause an induction period of several hours during which there is no appreciable rise in temperature or viscosity. After the inhibitors have been destroyed, there is a rapid temperature rise as well as an accelerated rise in viscosity.
  • means for heating the oil e.g., steam
  • cooling means e.g., water.
  • the exothermic reaction is suitably controlled at the optimum temperature for the particular vegetable oil.
  • the desired degree of oxidation is obtained when-the viscosity of the oil output reaches a specified target value.
  • a specified target value This will vary with the different vegetable oils that have been autoxidized.
  • the viscosity target value may be a Saybolt Universal viscosity at 100 F. of 750 seconds (plus or minus 40 seconds); while for autoxidized peanut oil the viscosity target value, determined in the same manner, may be 825 seconds (plus or minus 50 seconds).
  • the preferred phenolic antioxidant is a tri-substituted, sterically hindered phenol, such as di(tertiary-butyl)-pcresol.
  • any other phenolic antioxidant especially those which are soluble in mineral oil, may be employed, e.g., the various alkylene bisphenols, and such phenols as octylphenol and p-phenylphenol.
  • the alkylene bisphenols that may be used are those compounds having from 1 through 4 carbon atoms in the alkylene group and having from zero to two alkyl substituents on each benzene ring, each alkyl substituent containing from 1 through 4 carbon atoms.
  • phenolic antioxidants of the alkylene bisphenoll type are 2,2'-rnethylene bis(4 methyl 6 tertiary butylphenol), 4,4- methylene bis(2,6 di tertiary butylphenol) and 4,4- butylidene bis(6 tertiary butyl 3 methylphenol).
  • Other examples of phenolic antioxidants that may be employed are 4 hydroxymethyl 2,6 di tertiary butylphenol and 1,3,4 trimethyl 2,4,6 tris(di tertiarybutyl-4-hydroxybenzyl benzene.
  • the preferred di (lower alkyl)aminoalkanol is di nbutylarninoethanol.
  • substituted-aminoalkanols that may be employed are the dimethy1amino-, diethylamino-, di n propylamino-, di isopro pylamino-, di isobutylamino-, di sec. butylaminoand di-tert.-butylaminoethanols and the corresponding substituted amino [as well as the di-(n-butyl)amino-substituted] propanols, butanols and pentanols in both normal and isomeric forms thereof.
  • the amine additive functions as a. corrosion inhibitor and to neutralize acidity. It is also an antistatic component as is also the alkyl or alkenyl acid phosphate.
  • the alkyl or alkenyl acid phosphate is preferably incorporated into the textile-finishing compositions of the invention in the form of a previously prepared salt of (a) the said acid phosphate in mineral oil with (b) a di-(lower-alkyl)aminoalkanol, and specifically di-n-butylarninoethanol (DBAE).
  • DBAE di-n-butylarninoethanol
  • the equipment includes a stainless steel reactor of adequate size, and which is provided with suitable agitating means, cooling or heating coils of stainless steel tubing, a temperature recorder-controller, an air vent with air ejector, and a circulation and discharge pump; also, an aluminum mixing tank provided with a stirrer that has a capacity about three times that of the mixing tank. Filtration means and meters for metering the components also are provided.
  • One hundred (100) gallons of the white mineral oil is measured into the reactor, slurried therein with 200 lbs. of P and after stirring for about minutes then onehalf of the oleyl alcohol is added. Care is taken (e.g., by controlling the rate of addition of the oleyl alcohol) that the temperature of the reaction mass does not exceed 80 C. Stirring is continued for about 2 hours while holding the reaction temperature at 80 C. The phosphonylated oleyl alcohol in mineral oil is then transferred hot to the aforementioned aluminum mixing tank. The line and mixing tank are purged with 20 gallons of the mineral oil.
  • a second batch is prepared from the remainder of the mineral oil, phosphoric anhydride and oleyl alcohol in the same manner described in the preceding paragraph.
  • the finish may be applied to freshly extruded filamentary yarn or during beaming, knitting, weaving or other operations.
  • the filamentary yarn may be continuous filament or staple yarn.
  • the finish viscosity can be adjusted to any desired value by controlling the temperature of the liquid finish in the trough at the metier. More particularly it was found that practical viscosity control can be attained at liquid finish temperatures ranging between about C. and about 90 C.
  • the use of temperature to control the viscosity of the finishing composition when it is applied to the yarn increases metier efiiciency, finish-application uniformity and the tensile properties of the yarn. It is believed that such viscosity control of the finish facilitates penetration of the finish into the filament bundle, thereby increasing the cohesiveness between individual filaments.
  • oxidized soybean oil instead of oxidized soybean oil one may use oxidized peanut oil or other oxidized vegetable oil of which numerous examples previously have been given.
  • Other alkyl or alkenyl acid phosphates may be employed in place of oleyl acid phosphate, e.g., palrnityl acid phosphate.
  • other di(lower-alkyl)aminoalkanols may be used instead of DBAE, e.g., di-n-pentylaminoethanol.
  • phenolic antioxidants may be employed in place of di- (tertiary-butyl)-p-cresol, e.g., 2,6-di-(tertiary-butyD-4- methylphenol.
  • the lubricant was applied at a 3.25% level to 55/0/ 15 secondary cellulose acetate yarn using a IO-end trough at a production metier.
  • the packages were evaluated on an experimental beamer together with an equal number of packages lubricated with a regular or standard lubricant (so-called H-oil") normally employed. All packages were removed and examined under magnification for broken fils and loops every 80,000 yards.
  • H-oil regular or standard lubricant
  • CA yarn A large-scale knitting and dyeing evaluation of secondary cellulose acetate (CA yarn was carried out. Twelve hundred (1200) packages of CA yarn (55/ 0/ 15) lubricated with the textile finish of this example and, likewise, 1200 packages of the same kind of CA, yarn lubricated with H-oil were beamed, knitted and dyed.
  • Static yarn-to-yarn friction data were obtained on the lubricating finish of this example and H-oil lubricated CA yarn using a modification of Guthrie and Olivers yarn friction apparatus (Journal of the Textile Institute, volume 43, December, 1952). Measurements were made over a period of one month on yarn from two packages that had been lubricated with the lubricating composition of this example and from two packages of I-i-lubricated yarn.
  • the technique used for friction measurements was a tentative procedure accepted for use with yarns of various deniers.
  • a 2 A-inch horizontal fiber is clamped in position under a tension of 2.6 grams.
  • a vertical fiber is allowed to hang free with a 2.6-gram weight attached.
  • the horizontal fiber is slowly brought into contact with the vertical fiber, and then is moved an additional distance x (11.2 mm.) carrying the vertical fiber with it.
  • the horizontal fiber mount is set in motion in a. direction perpendicular to the first movement. When the vertical fiber slips, the mount is stopped, and the distance required to cause slippage is recorded as y.
  • the coefiicient of static interfiber friction is then defined as the ratio y/x.
  • the average horizontal yarn mount Speed is 17 mm. per minute.
  • compositions may be applied as a finish to textile materials (e.g., fibers, yarns, fabrics, etc.) made from blends or mixtures of different cellulose esters, or of cellulose esters and fibers of any of the other known fiber-forming thermoplastic materials.
  • textile materials e.g., fibers, yarns, fabrics, etc.
  • the cellulose ester constitute a major proportion (more than 50%) by weight thereof.
  • the finishing compositions may be applied to the textile fibers described herein in varying amounts, e.g., in an amount corresponding to from about 2.5% to about 4.0% by weight of the said fibers.
  • a textile-finishing composition especially adapted for use as a finish for cellulose acetate fibers having a. twist not exceeding 2 turns per inch, said composition consisting essentially of (a) from 10 to 55 weight percent mineral oil having a Saybolt Universal viscosity at F. of less than about 100 seconds;
  • a textile-finishing composition additionally contains from 0.05 to a phenolic antioxidant.
  • a textile-finishing composition as in claim 2 which contains both a phenolic antioxidant and from 5 to 15 weight percent a di-(lower-alkyl)aminoalkanol containing from 2 through 5 carbon atoms in the alkanol grouping.
  • a textile-finishing composition as in claim 2 which contains a phenolic antioxidant, and the acid phosphate of (c) is incorporated in as in claim 1 which 1 weight percent of the said composition in the form of a previously prepared amine salt of the said phosphate with a di-(lower-alkyl)aminoalkanol containing from 2 to 5 carbon atoms in the alkanol grouping.
  • a textile-finishing composition as in claim 1 wherein the mineral oil of (a) has a Saybolt Universal viscosity at 100 F. of from about 35 to about 75 seconds; the polybutene of (b) has an average molecular weight of from about 200 to about 500; the acid phosphate of (c) is oleyl acid phosphate; the oxidized vegetable oil of (d) is oxidized soybean oil; and the composition additionally contains di-(tertiary-butyl)-p-creso1 and di-n-butylaminoethanol.
  • a textile-finishing composition adapted for use as a finish for cellulose acetate fibers having a twist not exceeding two turns per inch, said composition consisting essentially of: (a) about 22.8 weight percent of mineral oil having a Saybolt Universal viscosity at 100 degrees Fahrenheit of about 50 seconds, (b) about 22.8 weight percent of polybutene having a number average molecular weight (osmometer method) of about 320, (c) about 27.5 weight percent of an approximately 50 percent dispersion of oleyl acid phosphate in 50 SUV mineral oil, (d) about 19.9 weight percent of oxidized soybean oil, (e) about 0.5 percent of di-(tertiary-butyl)para-cresol (20% in 50 SUV mineral oil) and about 6.5 weight percent of di-n-butylaminoethanol.
  • An article consisting essentially of textile fibers including fibers of a cellulose ester having on surfaces thereof a textile-finishing composition consisting essentially of (a) from 10 to 55 weight percent mineral oil having a Saybolt Universal viscosity at 100 F. of less than about 100 seconds;
  • the textile fibers include cellulose acetate fibers having a twist not exceeding 2 turns per inch; the textile-finishing composition cohesively holds said fibers together; and the textilefinishing composition additionally contains from 0.05 to 1 weight percent of a phenolic antioxidant.
  • the textile fibers consist essentially of cellulose acetate fibers having a twist not exceeding 2 turns per inch and an acetyl value of less than 59 weight percent calculated as acetic acid; the textile-finishing composition cohesively holds said fibers together; and the textile-finishing composition contains both a phenolic antioxidant and from 5 to l5,weight percent a di-(lower'alkyl)aminoalkanol containing from 2 through 5 carbon atoms in the alkanol grouping.
  • the method of cohesively bonding together textile fibers including fibers of a cellulose ester having a twist not exceeding 2 turns per inch which comprises applying to the said fibers from about 2.5% to about 4.0% by weight of the said textile fibers a textile-finishing composition consisting essentially of (a) from 10 to weight percent mineral oil having a Saybolt Universal viscosity at F. of less than about 100 seconds;

Description

United States Patent 3,505,220 TEXTILE-FINISHING COMPOSITION AND TEXTILE TREATED THEREWITH Lawrence R. Blake, Cumberland, Joseph P. Penick, Jr.,
Bel Air, Cumberland, and Harold W. Connor, Frostburg, Md., assignors to Celanese Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed June 13, 1966, Ser. No. 556,918 Int. Cl. D06m N14 US. Cl. 2528.6 11 Claims ABSTRACT OF THE DISCLOSURE This invention relates broadly to a textile-finishing composition and to an article comprising textile fibers that have been treated with said composition.
More particularly the invention is concerned with a textile-finishing composition especially adapted for use as a conjoint lubricant and finish for acetate fibers having little, if any, twist; that is, either zero twist or a twist which by itself is insufiicient to cause the fibers to become sufficiently entangled for effective or satisfactory spinning of the fibers into a yarn, for example a low twist of the order of from 0 to 1 turn per inch, not exceeding about 2 turns per inch. Such fibers properly may be described as having substantially zero twist, and for purpose of brevity the expression substantially zero is sometimes used herein to include both zero and the aforementioned low-twist fibers.
It is a primary object of the present invention to provide a new textile-finishing composition.
Another object of the invention is to provide articles comprised of textile fibers including fibers of a cellulose ester having on surfaces thereof a new textile-finishing composition of the invention. The cellulose ester fibers may be comprised of organic esters of cellulose, but preferably are comprised or composed of lower alkanoic esters of cellulose, e.g., cellulose propionate, cellulose butyrate, cellulose acetatebutyrate, and especially cellulose acetate.
Still another object of the invention is to provide a method of cohesively bonding together textile fibers including fibers of a cellulose ester having little, if any (i.e., substantially zero) twist by applying to the said textile fibers a textile-finishing composition of the invention.
A further object of the invention is to provide means for producing high-quality, substantially zero twist cellulose acetate yarn from which can be knitted fabrics having excellent quality.
Another object of the invention is to provide means for the production of substantially zero twist cellulose acetate yarn that can be beamed and knitted with the performance characteristic heretofore expected only when twisted yarn was used.
Another object of the invention is to provide means for the production of cellulose acetate tricot yarn for the knitting trade.
3,505,220 Patented Apr. 7, 1970 Still another object of the invention is to provide means for the production of cellulose acetate yarn that is accept- -able to the weaving trade for use in making sleazy fabrics.
A further object of the invention is to provide a textilefinishing composition having an unobvious combination of physical, chemical and physiological properties that make the composition especially suitable for use in extruding, knitting and weaving secondary cellulose acetate (CA fibers, and particularly in the treatment of substantially zero twist CA fibers. Secondary cellulose acetate fibers are generally considered to be those having an acetyl value of less than 59 weight percent, more particularly between about 50 and about 58 weight percent, calculated as acetic acid.
Another object of the invention is to provide means for imparting the necessary cohesiveness to substantially untwisted CA fibers so that loops, broken filaments and other defects frequently associated with substantially zero twist extruded yarn are completely (substantially completely) eliminated.
Still a further object of the invention is to provide a textile-finishing composition which, when applied to twisted cellulose acetate yarn, provides a treated yarn that eliminates shiers when said yarn is employed in the production of low sley, sleazy fabrics. Shiers is a defect that is frequently associated with sleazy fabrics.
Other objects of the invention will be apparent to those skilled in the art from the following more detailed description and from the appended claims.
The objects of the invention are attained by producing and using in textile-treating applications (especially in the treatment of textile fibers that include a cellulose ester) a textilefinishing composition comprising:
(a) Mineral oil (more particularly white mineral oil) having a Saybolt Universal viscosity (SUV) at F. of less than about 100 seconds, more particularly from about 35 to about 75 seconds, and specifically about 50 seconds;
(b) Polybutene having a number average molecular weight (osmometer method) of from about to about 750, more particularly from about 200 to about 500, and specifically about 320;
(c) An alkyl or alkenyl acid phosphate containing from about 13 to about 19 carbon atoms in the alkyl or alkenyl grouping thereof, e.g., oleyl acid phosphate, palmityl acid phosphate, etc.; and
(d) An oxidized (autoxidized) vegetable oil, e.g., oxidized soybean oil.
Preferably, the above-described textile-finishing composition also contains a phenolic antioxidant, preferably a di-[tertiary-(lower-alkyl)]-p cresol, and more preferably di-(tertiarybutyl)-p-cresol; and, preferably in addition to the phenolic antioxidant, a di(loWer-alkyl)aminoalkanol containing from 2 through 5 carbon atoms in the alkanol grouping, e.g., di-n-butylaminoethanol,
slurry with the phosphate of (c) 10-55 Polybutene of (b) 10-45 Acid phosphate of (c), specifically oleyl acid phosphate 10-30 Oxidized vegetable oil of (d), specifically oxidized soybean oil 10-30 Optional, but preferably also one or both of the following:
The textile-finishing compositions of the invention are prepared by blending together the various components in any suitable manner. One convenient way of combining the ingredients is as follows:
Prior to compounding, the mixing tank, pump and lines are suitably cleansed, e.g., by rinsing with a few gallons of white mineral oil. Advantageously the mineral oil, polybutene and oxidized vegetable oil are added to the mixing tank in that order. Stirring is begun after the addition of the mineral oil. The alkyl 'or alkenyl acid phosphate is introduced next, preferably in the form of a previously prepared salt of (a) the said acid phosphate in mineral oil with (b) the di-(lower-alkyl) aminoalkanol. The phenolic antioxidant, e.g., di-(tertiary-butyl)-paracresol, is added last in the form of a concentrated solution thereof (e.g., a 20% by weight solution) in a portion of the total mineral oil component of the textile-finishing composition. Stirring is continued at ambient temperature for about to 20 minutes, e.g., about minutes, after the final addition has been completed.
A typical viscosity (SUV at 100 F.) of the textile-finishing composition (especially when the preferred in gredients are employed) is usually within the range of from about 195 to about 205 seconds. A typical acidity value (calculated as oleic acid) is generally within the range of from about 12.2 to 13.2.
The preferred acid phosphate is oleyl acid phosphate; and, as has been indicated hereinbefore, it is advantageously introduced into the composition in the form of a previously prepared amine salt, preferably a di-n-butylaminoethanol salt, thereof. The amine salt functions in the composition as an antistatic agent, and the oleyl phosphate (or other alkyl or alkenyl phosphate employed) is an antistatic component of the said agent. The amine salt also promotes scouring of the textile material in fiber, fabric or other form.
Instead of oleyl acid phosphate or the previously mentioned palmityl acid phosphate, one may use various other longchain alkyl and/or alkenyl acid phosphates, especially those containing from about 13 through about 19 carbon atoms in the alkyl or alkenyl grouping thereof, e.g., stearyl acid phosphate, palmitoleyl acid phosphate, gadoleyl acid phosphate, myristyl acid phosphate and arachidyl acid phosphate.
The preferred oxidized vegetable oil is oxidized soybean oil. The function of the oxidized vegetable oil is to provide for fiber-to-fiber lubrication, control fiber-to-fiber coefficient of friction, and to contribute beneficially to the hand of the fiber and/ or fabric.
Illustrative examples of other oxidized vegetable oils that may be used (singly or a plurality of them) in lieu of or in addition to oxidized soybean oil are oxidized peanut, cottonseed, corn, rape, sesame, hempseed, saffiower, poppyseed and oiticica oils. Additional examples of oils, which in oxidized form may be employed as a component of the textile-finishing compositions of the invention, are given in Chemical Technology and Analysis of Oils, Fats and Waxes, by J. Lewkowitsch, Sixth Edition, vol. II, pp. 42-414, MacMillan and Co., Limited, London, England (1922).
By oxidized oil(s) as used in this specification and in the appended claims are meant, as previously has been indicated, such oils that have been produced by autoxidation; or, as they are sometimes designated, autoxidized oils. Autoxidation is oxygen by molecular oxidation of organic material in the liquid phase without an accompanying flame, and is now well known in the art.
Such oxidation is effected, for example, by contacting vegetable oil with air in a continuous, countercurrent recycle, single-column operation. The oil is heated initially to a temperature within the range of, for instance, from about to about C. Natural inhibitors in the oil usually cause an induction period of several hours during which there is no appreciable rise in temperature or viscosity. After the inhibitors have been destroyed, there is a rapid temperature rise as well as an accelerated rise in viscosity. At this point means for heating the oil, e.g., steam, is replaced by cooling means, e.g., water. The exothermic reaction is suitably controlled at the optimum temperature for the particular vegetable oil. The desired degree of oxidation is obtained when-the viscosity of the oil output reaches a specified target value. This will vary with the different vegetable oils that have been autoxidized. For example, in the case of autoxidized soybean oil the viscosity target value may be a Saybolt Universal viscosity at 100 F. of 750 seconds (plus or minus 40 seconds); while for autoxidized peanut oil the viscosity target value, determined in the same manner, may be 825 seconds (plus or minus 50 seconds).
The preferred phenolic antioxidant. is a tri-substituted, sterically hindered phenol, such as di(tertiary-butyl)-pcresol. However, any other phenolic antioxidant, especially those which are soluble in mineral oil, may be employed, e.g., the various alkylene bisphenols, and such phenols as octylphenol and p-phenylphenol. Among the alkylene bisphenols that may be used are those compounds having from 1 through 4 carbon atoms in the alkylene group and having from zero to two alkyl substituents on each benzene ring, each alkyl substituent containing from 1 through 4 carbon atoms. Specific examples of phenolic antioxidants of the alkylene bisphenoll type are 2,2'-rnethylene bis(4 methyl 6 tertiary butylphenol), 4,4- methylene bis(2,6 di tertiary butylphenol) and 4,4- butylidene bis(6 tertiary butyl 3 methylphenol). Other examples of phenolic antioxidants that may be employed are 4 hydroxymethyl 2,6 di tertiary butylphenol and 1,3,4 trimethyl 2,4,6 tris(di tertiarybutyl-4-hydroxybenzyl benzene.
The preferred di (lower alkyl)aminoalkanol is di nbutylarninoethanol. Illustrative examples of other substituted-aminoalkanols that may be employed are the dimethy1amino-, diethylamino-, di n propylamino-, di isopro pylamino-, di isobutylamino-, di sec. butylaminoand di-tert.-butylaminoethanols and the corresponding substituted amino [as well as the di-(n-butyl)amino-substituted] propanols, butanols and pentanols in both normal and isomeric forms thereof.
The amine additive functions as a. corrosion inhibitor and to neutralize acidity. It is also an antistatic component as is also the alkyl or alkenyl acid phosphate.
It has been mentioned hereinbefore that the alkyl or alkenyl acid phosphate is preferably incorporated into the textile-finishing compositions of the invention in the form of a previously prepared salt of (a) the said acid phosphate in mineral oil with (b) a di-(lower-alkyl)aminoalkanol, and specifically di-n-butylarninoethanol (DBAE). One suitable means of preparing such a salt is described below, and for purpose of illustration the preparation of the di-nbutylaminoethanol salt of oleyl phosphate is given.
The equipment includes a stainless steel reactor of adequate size, and which is provided with suitable agitating means, cooling or heating coils of stainless steel tubing, a temperature recorder-controller, an air vent with air ejector, and a circulation and discharge pump; also, an aluminum mixing tank provided with a stirrer that has a capacity about three times that of the mixing tank. Filtration means and meters for metering the components also are provided.
5 Component:
White 50 SUV mineral oil240 gals. Phosphoric anhydride-400 lbs. Oleyl alcohol325 gals. DBAE-174.5 gals.
One hundred (100) gallons of the white mineral oil is measured into the reactor, slurried therein with 200 lbs. of P and after stirring for about minutes then onehalf of the oleyl alcohol is added. Care is taken (e.g., by controlling the rate of addition of the oleyl alcohol) that the temperature of the reaction mass does not exceed 80 C. Stirring is continued for about 2 hours while holding the reaction temperature at 80 C. The phosphonylated oleyl alcohol in mineral oil is then transferred hot to the aforementioned aluminum mixing tank. The line and mixing tank are purged with 20 gallons of the mineral oil.
A second batch is prepared from the remainder of the mineral oil, phosphoric anhydride and oleyl alcohol in the same manner described in the preceding paragraph.
When the phosphorylated oleyl alcohol in mineral oil contained in the aluminum mixing tank has cooled to 50 C., all of the DBAE (174.5 gals.) is added to the contents of the said tank while agitating the mixture. Stirring and circulation is continued for about minutes. The product is then filtered and transferred to storage.
The finish may be applied to freshly extruded filamentary yarn or during beaming, knitting, weaving or other operations. The filamentary yarn may be continuous filament or staple yarn.
In applying the finish to the freshly extruded, substantially zerotwist yarn, it has been found that the finish viscosity can be adjusted to any desired value by controlling the temperature of the liquid finish in the trough at the metier. More particularly it was found that practical viscosity control can be attained at liquid finish temperatures ranging between about C. and about 90 C. The use of temperature to control the viscosity of the finishing composition when it is applied to the yarn increases metier efiiciency, finish-application uniformity and the tensile properties of the yarn. It is believed that such viscosity control of the finish facilitates penetration of the finish into the filament bundle, thereby increasing the cohesiveness between individual filaments.
In order that those skilled in the art may better understand how the present invention can be carried into effect, the following example is given by way of illustration and not by way of limitation. All parts and percentages are by weight unless otherwise stated:
EXAMPLE Percent by weight White mineral oil (SUV=about 50 seconds at 100 F.) 22.8 Polybutene (M.V.=about 320) 22.8 Oxidized soybean oil 19.9
Approx. 50% dispersion of oleyl acid phosphate in 50 SUV white mineral oil 27.5 Di-n-butylaminoethanol (DBAE) 6.5 20% solution of di-tertiary-butyl)-p-cresol in 50 SUV white mineral oil The above textile-finishing composition of the invention is prepared by compounding the components in the manner described in the portion of the specification prior to this example; and, more particularly, in the preferred manner of incorporating the dispersion of oleyl acid phosphate in mineral oil into the textile-finish, namely, in the form of a salt thereof with the DBAE component.
Instead of oxidized soybean oil one may use oxidized peanut oil or other oxidized vegetable oil of which numerous examples previously have been given. Other alkyl or alkenyl acid phosphates may be employed in place of oleyl acid phosphate, e.g., palrnityl acid phosphate. Likewise, other di(lower-alkyl)aminoalkanols may be used instead of DBAE, e.g., di-n-pentylaminoethanol. Other phenolic antioxidants may be employed in place of di- (tertiary-butyl)-p-cresol, e.g., 2,6-di-(tertiary-butyD-4- methylphenol. Numerous examples of other contemplated alkyl and alkenyl acid phosphates, di(lower-alkyl)aminoalkanols and phenolic antioxidants for use in producing the textiledinishing compositions of the invention have been given in a portion of this specification prior to this exam- The textile lubricant or finish of this example was initially evaluated on four-pound packages of 55/ 15 zero twist dull secondary cellulose acetate yarn by quality control examinations on an experimental beamer. These evaluations were followed by a larger scale evaluation on a beaming, knitting and dyeing trial.
The lubricant was applied at a 3.25% level to 55/0/ 15 secondary cellulose acetate yarn using a IO-end trough at a production metier. The packages were evaluated on an experimental beamer together with an equal number of packages lubricated with a regular or standard lubricant (so-called H-oil") normally employed. All packages were removed and examined under magnification for broken fils and loops every 80,000 yards.
Table I, which follows, gives the results of the initial evaluation in comparison with H-oil.
TABLE I Lubricating Finish Used Lubricant of Example 1 H-Oil No. packages I No. package inspections No. packages detective Percent packages deiective Total defects Total defects/def. pkg Total yards removed MIY processed.
End breaks End breaks/M'IY Yards/minute=450. 1 Secondary cellulose acetate yarn, 55/0/15. 9 MTY=million thread yards.
e g a...
Non OOOOOOOOOO! och-cc Tension errangem ent=3 post.
In Table II, which follows, are given the results of a more complete evaluation of packages of other 55/0/ 15 yarn wherein the lubricant of this example had been applied at a 3.25% level using a 10-end trough on a production metier. H-oil was also evaluated at the same time both before and after guide alignment. All packages were examined under magnification for broken fils and loops every 80,000 yards.
TABLE II Lubricating Finish Used Lubricant H-Oilatter Guide Example 1 II-Oii Alignment No. packages 37 37 30 No. package inspections- 148 148 144 No. packages detective 1 37 26 Percent packages defective (avg 0 67 25.0 17. 4 Total percent defective 2. 7 64. 0 33. 3 No. loops 1 187 71 No. loops/detective pkg 1. 0 5. 0 2. 84 No. bro en fils 0 2 1 No. broken fils/def pk 0 0. 05 0. 007 Total defects 1 189 72 Total defects/def. pkg 1. 0 5. 11 2. 88 Yards removed 340, 220 310,220 340, 220 MT Y processed 12. 59 12. 69 12. 25 End breaks 4 3 3 End breaks/MTY 0. 318 0. 238 0. 245
A large-scale knitting and dyeing evaluation of secondary cellulose acetate (CA yarn was carried out. Twelve hundred (1200) packages of CA yarn (55/ 0/ 15) lubricated with the textile finish of this example and, likewise, 1200 packages of the same kind of CA, yarn lubricated with H-oil were beamed, knitted and dyed.
TABLE III Summary of Bobbin Inspection Data Summaryf Percent Total Defects] Textile Type of Lubricating Major Percent Defective Packing Finish Used Defects Defects Pkg. Data l Finish of invention 0. 7. 0 1.8 12. 2 H-oil finish 3. O 19. 0 3. 1 15. 0
1 Percent Total Rejccts-80% of all rejects were for mechanical reasons, bulged packages.
Static yarn-to-yarn friction data were obtained on the lubricating finish of this example and H-oil lubricated CA yarn using a modification of Guthrie and Olivers yarn friction apparatus (Journal of the Textile Institute, volume 43, December, 1952). Measurements were made over a period of one month on yarn from two packages that had been lubricated with the lubricating composition of this example and from two packages of I-i-lubricated yarn.
The technique used for friction measurements was a tentative procedure accepted for use with yarns of various deniers. In carrying out the procedure a 2 A-inch horizontal fiber is clamped in position under a tension of 2.6 grams. A vertical fiber is allowed to hang free with a 2.6-gram weight attached. The horizontal fiber is slowly brought into contact with the vertical fiber, and then is moved an additional distance x (11.2 mm.) carrying the vertical fiber with it. The horizontal fiber mount is set in motion in a. direction perpendicular to the first movement. When the vertical fiber slips, the mount is stopped, and the distance required to cause slippage is recorded as y. The coefiicient of static interfiber friction is then defined as the ratio y/x. The average horizontal yarn mount Speed is 17 mm. per minute.
For each measurement, a new vertical fiber is used. The horizontal fiber is replaced at the end of each group of measurements across a 25 mm. scale of a micrometer, so as to avoid contact with the same area twice. The estimated standard deviation of individual measurements varies with yarn items, age of yarn, lubricant type, etc. In this investigation, the standard deviations of individual coetiicients ranged from 0.0240 to 0.0748.
In Table IV, which follows, are given static friction data collected on CA 55/0/15 yarn lubricated with the finishing lubricant of this example andwith H-oil. The
data indicate a definite lowering of the coefficient of static interfiber friction by the use of the lubricating finish of the invention as compared with H-oil.
TABLE IV.-STATIC INTERFIBER FRICTION, 55/0/15 A Using II-Oil Package No 3 4 4 4 4 6/4 s/22 e/za e/24 7/2-7/8 3. 10 2.85 2. 58 0. 3790 0. 3820 0. 4170 0. 3640 0. 3484 0. 0748 0. 0247 0. 0303 0. 0500 0. 0410 11 5 4 9 13 2. 9S) 8. 26 3. 50 1. 70 4. 02 2. 07 2. 20 2. 36 2. 11 2. 06 Using Lubricating Finish of the Invention 60 Package N o 3 4 4 4 Date 6/4 6/22 fi/23 6/24 7/2-7/8 Percent application... 3. 61 3. 00 2. 09 2. 16 u l 0. 3074 0. 2071 0. 2952 0. 3164 0. 2056 0. 0441 0. 0242 0. 0634 0. 0502 0. 0262 It is to be understood that the foregoing detailed description is given merely by way of illustration and not by way of limitation and that many variations may be made therein without departing from the spirit of the invention. For example, the compositions may be applied as a finish to textile materials (e.g., fibers, yarns, fabrics, etc.) made from blends or mixtures of different cellulose esters, or of cellulose esters and fibers of any of the other known fiber-forming thermoplastic materials. In such blended textiles, it is preferred that. the cellulose ester constitute a major proportion (more than 50%) by weight thereof. Also, the finishing compositions may be applied to the textile fibers described herein in varying amounts, e.g., in an amount corresponding to from about 2.5% to about 4.0% by weight of the said fibers.
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A textile-finishing composition especially adapted for use as a finish for cellulose acetate fibers having a. twist not exceeding 2 turns per inch, said composition consisting essentially of (a) from 10 to 55 weight percent mineral oil having a Saybolt Universal viscosity at F. of less than about 100 seconds;
(b) from 10 to 45 weight. percentpolybutene having a number average molecular weight (osmometer method) of from about to about 750;
(c) from 10 to 30 weight percent an alkyl or alkenyl acid phosphate containing from about 13 through about 19 carbon atoms in the alkyl or alkenyl grouping thereof; and
(d) from 10 to 30 weight percent an oxidized vegetable oil.
2. A textile-finishing composition additionally contains from 0.05 to a phenolic antioxidant.
3. A textile-finishing composition as in claim 2 which contains both a phenolic antioxidant and from 5 to 15 weight percent a di-(lower-alkyl)aminoalkanol containing from 2 through 5 carbon atoms in the alkanol grouping.
4. A textile-finishing composition as in claim 2 which contains a phenolic antioxidant, and the acid phosphate of (c) is incorporated in as in claim 1 which 1 weight percent of the said composition in the form of a previously prepared amine salt of the said phosphate with a di-(lower-alkyl)aminoalkanol containing from 2 to 5 carbon atoms in the alkanol grouping.
5. A textile-finishing composition as in claim 1 wherein the mineral oil of (a) has a Saybolt Universal viscosity at 100 F. of from about 35 to about 75 seconds; the polybutene of (b) has an average molecular weight of from about 200 to about 500; the acid phosphate of (c) is oleyl acid phosphate; the oxidized vegetable oil of (d) is oxidized soybean oil; and the composition additionally contains di-(tertiary-butyl)-p-creso1 and di-n-butylaminoethanol.
6. A textile-finishing composition adapted for use as a finish for cellulose acetate fibers having a twist not exceeding two turns per inch, said composition consisting essentially of: (a) about 22.8 weight percent of mineral oil having a Saybolt Universal viscosity at 100 degrees Fahrenheit of about 50 seconds, (b) about 22.8 weight percent of polybutene having a number average molecular weight (osmometer method) of about 320, (c) about 27.5 weight percent of an approximately 50 percent dispersion of oleyl acid phosphate in 50 SUV mineral oil, (d) about 19.9 weight percent of oxidized soybean oil, (e) about 0.5 percent of di-(tertiary-butyl)para-cresol (20% in 50 SUV mineral oil) and about 6.5 weight percent of di-n-butylaminoethanol.
7. An article consisting essentially of textile fibers including fibers of a cellulose ester having on surfaces thereof a textile-finishing composition consisting essentially of (a) from 10 to 55 weight percent mineral oil having a Saybolt Universal viscosity at 100 F. of less than about 100 seconds;
(b) from 10 to 45 weight percent polybutene having a number average molecular weight (osmometer method) of from about 150 to about 750;
(c) from 10 to 30 weight percent an alkyl or alkenyl acid phosphate containing from about 13 through about 19 carbon atoms in the alkyl or alkenyl grouping thereof; and
(d) from 10 to 30 weight percent an oxidized vegetable oil.
8. An article as in claim 7 wherein the textile fibers include cellulose acetate fibers having a twist not exceeding 2 turns per inch; the textile-finishing composition cohesively holds said fibers together; and the textilefinishing composition additionally contains from 0.05 to 1 weight percent of a phenolic antioxidant.
9. An article as in claim 8 wherein the textile fibers consist essentially of cellulose acetate fibers having a twist not exceeding 2 turns per inch and an acetyl value of less than 59 weight percent calculated as acetic acid; the textile-finishing composition cohesively holds said fibers together; and the textile-finishing composition contains both a phenolic antioxidant and from 5 to l5,weight percent a di-(lower'alkyl)aminoalkanol containing from 2 through 5 carbon atoms in the alkanol grouping.
10. An article consisting essentially of textile fibers including fibres of a cellulose ester having on surfaces thereof a textile-finishing composition consisting essentially of (a) from to 55 weight percent mineral oil having a Saybolt Universal viscosity at 100 F. of less than about 100 seconds;
(b) from 10 to 45 weight percent polybutene having a number average molecular weight (osometer method) of from about 150 to about 750;
(c) from 10 to 30 weight percent an alkyl or alkenyl acid phosphate containing from about '13 through about 19 carbon atoms in the alkyl or alkenyl grouping thereof; and
(d) from 10 to 30 weight percent an oxidized vegetable wherein the textile fibers consist essentially of cellulose acetate fibers having a twist not exceeding 2 turns per inch and an acetyl value between about and about 58 weight percent calculated as acetic acid; the textile-finishing composition cohesively holds said fibers together.
11. The method of cohesively bonding together textile fibers including fibers of a cellulose ester having a twist not exceeding 2 turns per inch which comprises applying to the said fibers from about 2.5% to about 4.0% by weight of the said textile fibers a textile-finishing composition consisting essentially of (a) from 10 to weight percent mineral oil having a Saybolt Universal viscosity at F. of less than about 100 seconds;
(b) from 10 to 45 weight percent polybutene having a number average molecular weight (osometer method) of from about to about 750;
(c) from 10 to 30 weight percent an alkyl or alkenyl acid phosphate containing from about 13 through about 19 carbon atoms in the alkyl or alkenyl grouping thereof; and
(d) from 10 to 30 weight percent an oxidized vegetable oil.
References Cited UNITED STATES PATENTS 2,956,949 10/ 1960 White et. al. 252-8.6 X 3,317,344 5/1967 Mackey et al. 117-144 X 3,354,138 11/1967 Burr 252-8.6 X
LEON D. ROSDOV, Primary Examiner IRWIN GLUCK, Assistant Examiner
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977979A (en) * 1973-09-14 1976-08-31 George A. Goulston Company, Inc. Yarn finish formulations
US4105569A (en) * 1977-02-07 1978-08-08 George A. Goulston Co., Ltd. Yarn finish formulation
US4442249A (en) * 1982-10-07 1984-04-10 Fiber Industries, Inc. Partially oriented polyester yarn finish
US4469606A (en) * 1982-07-26 1984-09-04 Ciba-Geigy Corporation Stabilization systems for fiber finishes
US4816336A (en) * 1986-04-04 1989-03-28 Hoechst Celanese Corporation Synthetic fiber having high neutralized alkyl phosphate ester finish level
US5543065A (en) * 1995-06-07 1996-08-06 Henkel Corporation Smoke reduction of fiber lubricants

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US2956949A (en) * 1955-10-19 1960-10-18 Eastman Kodak Co Fiber treating compositions
US3317344A (en) * 1963-09-27 1967-05-02 Gen Aniline & Film Corp Antistatic photographic film
US3354138A (en) * 1963-11-22 1967-11-21 Phillips Petroleum Co Production of antistatic polymers

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Publication number Priority date Publication date Assignee Title
US2956949A (en) * 1955-10-19 1960-10-18 Eastman Kodak Co Fiber treating compositions
US3317344A (en) * 1963-09-27 1967-05-02 Gen Aniline & Film Corp Antistatic photographic film
US3354138A (en) * 1963-11-22 1967-11-21 Phillips Petroleum Co Production of antistatic polymers

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977979A (en) * 1973-09-14 1976-08-31 George A. Goulston Company, Inc. Yarn finish formulations
US4098703A (en) * 1973-09-14 1978-07-04 George A. Goulston Company, Inc. Yarn finish formulations
US4105569A (en) * 1977-02-07 1978-08-08 George A. Goulston Co., Ltd. Yarn finish formulation
US4469606A (en) * 1982-07-26 1984-09-04 Ciba-Geigy Corporation Stabilization systems for fiber finishes
US4442249A (en) * 1982-10-07 1984-04-10 Fiber Industries, Inc. Partially oriented polyester yarn finish
US4816336A (en) * 1986-04-04 1989-03-28 Hoechst Celanese Corporation Synthetic fiber having high neutralized alkyl phosphate ester finish level
US5543065A (en) * 1995-06-07 1996-08-06 Henkel Corporation Smoke reduction of fiber lubricants

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