US2807865A - Sized textile and method of fabricating yarn into fabric - Google Patents

Sized textile and method of fabricating yarn into fabric Download PDF

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US2807865A
US2807865A US436687A US43668754A US2807865A US 2807865 A US2807865 A US 2807865A US 436687 A US436687 A US 436687A US 43668754 A US43668754 A US 43668754A US 2807865 A US2807865 A US 2807865A
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yarn
mole percent
copolymer
sizing
salt
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US436687A
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Fred B Shippee
Melvin D Hurwitz
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Rohm and Haas Co
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Rohm and Haas Co
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Priority to NL197897D priority Critical patent/NL197897A/xx
Priority to NL197987D priority patent/NL197987A/xx
Priority to NL90438D priority patent/NL90438C/xx
Priority to US436687A priority patent/US2807865A/en
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Priority to GB16147/55A priority patent/GB804952A/en
Priority to FR1132921D priority patent/FR1132921A/en
Priority to CH338425D priority patent/CH338425A/en
Priority to DER16841A priority patent/DE1042516B/en
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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
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • 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
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03Polysaccharides or derivatives thereof
    • D06M15/11Starch or derivatives thereof
    • 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
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof

Definitions

  • This invention relates to the sizing or dressing of fibers, filaments, and yarns whether of spun or continuous filament type, to render such textile materials amenable to textile operations, for example, twisting, doubling, weaving, knitting, braiding, and so forth. It is particularly concerned with sizes of removable type which are adapted to be applied to hydrophobic artificial filaments an fibers, such as nylon.
  • a more particular object of the invention is to provide a readily removable size for rendering spun yarns of hydrophobic artificial fibers more amenable to textile processing.
  • Other objects and advantages of the invention will be apparent from the description thereof beneficial as sizes for textile materials and especially for .spunyarns of hydrophobic artificial filamentary materials, such as nylon.
  • the particular copolymer salts are the ammonium or alkali metal salts of copolymers of 5 2 T to 20 mole percent of acrylic acid or methacrylic acid with to of at least one ester selected from the group consisting of the acrylates and methacrylates of aliphatic alcohols having from 1 to 18 carbon atoms, a sufficient proportion amounting to at least 50 mole percent of the total ester component of the copolymer being selected from acrylates of primary and secondary acyclic alcohols having from 1 to 18 carbon atoms, methacrylates of primany and secondary acyclic alcohols having from 6 to 18 carbon atoms, and mixtures thereof to impart to the salt of the copolymer a Knoop hardness of not over 7 and preferably about 1 or less.
  • the molecular weight of the copolymer salts may be from about 3,000 to 1,000,000.
  • the Knoop hardness number is determined in accordance with the procedure described in Indentation Hard ness Testing, by V. E. Lysaght, 1949, Reinhold Publishing Company, p. 189.
  • a Tukon Hardness Tester of the Wilson Mechanical Instrument Company was used. Its pressure element was applied without impact under a 25-gram load to a film of the copolymer to be tested cast on glass, which had been dried at C. and conditioned at 55% relative humidity and 77 F., and held in contact for a period of ten seconds. The indentation resulting was measured with the aid of a microscope.
  • salts of copolymers are either water-soluble when the proportion of the acid component is between 10 a and 20 mole percent or readily dispersible in water when the proportion of the acid component is between 5 and 10 mole percent.
  • the ammonium salt is preferred as it seems to have appreciably greater adhesion to the hydrophobic filamentary materials than the salts of the alkali metals, possibly because of partial hydrolysis to provide free carboxyl groups in the copolymer. It is essential that the salts of the copolymers be soft and have an upper limit of Knoop hardness of seven, and preferred copolymers have a Knoop hardness number of not over one.
  • the acrylic acid or methacrylic acid may be copolymerized with an ester of acrylic acid with an alcohol from methyl to octadecyl to yield copolymers having the necessary softness, the acid cannot be :copolymerized with an ester consisting entirely of a lower methacrylate, that is one obtained from an alcohol having less than six carbon atoms without producing a copolymer having a hardness far in excess of the limit required for the present invention.
  • the acrylic acid or methacrylic acid may be combined with a lower methacrylate in ternary copolymers provided the lower methacrylate having less than six carbon atoms does not amount to more than 50 mole percent of the total ester component.
  • a ternary copolymer of 20 mole percent methacrylic acid, 27 mole percent of methyl methacrylate and 54 mole percent of octyl methacrylate is of sufficient softness for the purpose of the present invention.
  • an adequately soft copolymer may be obtained by the copolymerization of 20 mole percent methacrylic acid, 14 mole percent methyl methacrylate and 66 mole percent of n-lauryl methacrylate.
  • the corresponding ternary copolymers in which the methacrylic acid is replaced entirely with a corresponding proportion of acrylic acid are also adequately soft for the purposes of the invention.
  • copolymer salts when applied to yarns, especially of spun nylon or the like, are substantially free from corrosion difiiculties. They do not stick to metal, such as that of guides, or that on the dryer drums of a slasher.
  • these copolymers are compatible with many materials which may be introduced into the sizing composition for various purposes. They do not degrade starch or other carbohydrate materials and they are quite compatible with a wide variety of hydrophilic 3 polymeric colloids with which it may be advantageous to mix the copolymers before application to the yarns.
  • the amount of copolymer salt applied to the textile material may vary from 1 to by weight depending upon the purposefor which application is intended and upon whether or not auxiliary conditioning or sizing agents are included in the composition by which it is applied to the textile.
  • the method or means taken to apply the sizing composition whether it consists of an aqueous solution of the copolymer alone or of a mixture of the copolymer with other ingredients, may be selected according to the ultimate purpose.
  • the composition may be applied by spraying, dipping, padding, by sizing rolls, transfer rolls, or the like.
  • an entire Warp thereof may be passed through a conventional slasher or a yarn may be individually treated in a single end sizer.
  • the excess solution may be removed such as by squeeze rolls or wipers and the treated yarn may then be dried. Drying may be effected by any suitable means such'as by heated air or drying cans. Since the compositions do not transfer from the yarns to the cans and do not stick to the metal of such cans, metal drying cans can be effectively used without difficulty.
  • the drying may be effected at temperatures of 160-250 F., a temperature in this range being selected in accordance with the particular type of yarn to prevent any damage as a result or excessive heating.
  • the aqueous solution containing the copolymer may be at room temperature up to about 190 F., or more during application, the higher temperatures favoring penetration.
  • the preferred proportion applied to the yarn is from 5 to 15% by weight on the initial weight of the yarn.
  • the preferred proportion is from 0.5 to 2.5% of the copolymer on the weight of the yarn.
  • copolymers of the present invention may be used on yarns of fibers and filaments of a wide variety of hydro phobic synthetic materials such as nylon, polyethylene terephthalate, copolymers containing .a predominant proportion of vinyl chloride or vinylidene chloride such as Vinyon (a copolymer of about 75 to 95% vinyl chloride with the balance of vinyl acetate), Dynel (copolymers of 60 to 85% vinyl chloride with the balance of acrylonitrile), Saran (copolymers of about 70 to 90% vinylidene chloride with a balance either of vinyl chloride or acrylonitrile), and acrylonitrile ploymers such as polyacrylonitrile itself or copolymers containing at least 75% by weight of acrylonitrile with vinyl acetate, vinyl pyridines, vinyl chloride, mixtures thereof, or the like.
  • vinyl chloride or vinylidene chloride such as Vinyon (a copolymer of about 75 to 95% vinyl chloride with the balance of vinyl
  • compositions are particularly valuable with yarns comprising such fibers or filaments because of their ability to adhere to the hydrophobic materials of which such yarns are composed.
  • the compositions of the present invention may also be applied to yarns formed of blends of fibers or filaments comprising one or more of the above hydrophobic filamentary materials with themselves or natural or artificial fibers or filaments such as cotton, wool, silk, viscose rayon, cuprammonium rayon, cellulose acetate, and the like.
  • copolymer salts of this invention may be applied to textiles, such as yarns, fibers, or filaments, threads or cords, felts, fabrics, or the like, to modify their properties and especially to render them more amenable to textile processing operations.
  • the copolymers may be applied to threads or cords to protect them during sewing operations.
  • Copolymers of the present invention maybe mixed with hydrophilic polymeric colloids, Water-soluble or selfdispersible in water, such as starch, starch derivatives including chlorinated starch, starch esters including starch 4 acetate, starch ethers including particularly ethylene oxidemodified starches in which the starch is combined with l to 5% or more of its weight of ethylene oxide, dextrins, water-soluble cellulose others including sodium carboxymethyl cellulose, sodium carboxyethyl cellulose, methyl cellulose and hydroxyethyl cellulose; polyvinyl alcohols, gelatins, partially hydrolyzed polyvinyl acetates which are water-dispersible or Water-soluble, casein, natural gums such as gum arabic and tragacanth.
  • hydrophilic polymeric colloids such as starch, starch derivatives including chlorinated starch, starch esters including starch 4 acetate, starch ethers including particularly ethylene oxidemodified starches in which the starch is combined with l
  • water-dis persible colloids may be combined with the acrylic copoly mer in the proportions of 25 to by weight of the colloid to 75 to 5% respectively of the copolymer. They form compatible sizing coatings on yarns and are not degraded by the copolymer. There is no need for auxiliary dispersing agents in order to disperse both the copolymer and the colloid in water.
  • Coloring agents such as dyes, anti-static agents, and auxiliary lubricating, softening, or conditioning agents may be incorporated but are not essential.
  • higher hydrocarbons such as mineral'oil and paraffin wax and other lubricants, such as vegetable orv animal fats and oils, such as talloW, have been found advantageous when incorporated in an amount of l to 5% on the weight of the copolymer salt dispersion.
  • Examples of preferred lubricants that may be used, without requiring an additional dispersing agent, and are compatible in the final sizing coating are ethylene oxide-modified long chain fatty acids, alcohols or amines such as those of 8 to 20 carbon atoms containing from 1 to 50 or more ethylene oxide units per mole of acid, alcohol or amine.
  • ethylene oxide-modified long chain fatty acids, alcohols or amines such as those of 8 to 20 carbon atoms containing from 1 to 50 or more ethylene oxide units per mole of acid, alcohol or amine.
  • the condensation product of stearic acid with 2 to 4 moles of ethylene oxide may be used quite effectively.
  • Other water-dispersible lubricants include sulfo nated oils, such as Turkey'Red Oil; and self-dispersible waxes, such as monostearin, and sorbitan mono-oleate modified with ethylene oxide.
  • Dispersing agents may be included to assist the dispersion of certain lubricants, such as
  • the sizing composition may contain swelling or plasticizing agents for the material of which the fibers or filaments of the yarn is composed.
  • swelling or plasticizing agents for the material of which the fibers or filaments of the yarn is composed.
  • the use of such an agent markedly improves the adhesion of the sizing composition to the yarn and increases the weaving efliciency without decreasing the strength of the yarn and without interfering with subsequent removal of the size by scouring or, when a starch or starch derivative adjunct is present, by degrading with an enzyme and subsequent scouring.
  • a swelling agent may be used in the sizing composition.
  • Preferably 10 to 15% by weightof the swelling agent is employed, based on the weight of copolymer salt.
  • the improved adhesion obtained when the swelling agent is added to the sizing compositions of the present invention is surprising since compositions obtained by the addition of a swelling agent to sizes containing starch or starch derivatives but no copolymer salt of the present invention have not been found to benefit in weaving efiiciency from such addition.
  • the use of a swelling agent has been especially beneficial when sizing compositions are applied to polyester yarns of the polyethylene terephthalate type known as Dacron.
  • the swelling agent used is selectedaocording to the particular material of which the yarn is composed.
  • polyalkylene polyarnines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are generally useful and especially effective with polyethylene terephthalate yarns.
  • the article obtained after application of the sizing composition of the present invention to the textile material and drying is essentially free from the disadvantage of developing static charges, loss of sizing material by transfer to guides or shedding, and it is free of deleterious corrosive effects on the metals of textile machinery.
  • sizing material is readily removed by common scouring operations because of the ready dis- Example 1
  • a warp of -75 denier, 34 filament poly- -"ethylene' terephthalate yarns each containing 17 turns of twist per inch was passed through the slasher at 50 yards "per minute and dried on the 7 drier cans thereof at 160 to 170 F. No sizing material stuck to the drier cans.
  • the resulting yarn was woven into a marquisette fabric (56 x 40) without appreciable breakage of yarn or filaments or transfer of sizing to the shuttle.
  • the size was readily removed from the fabric by scouring.
  • Example 2 An aqueous solution containing 17.5% of a waterdispersible ethylene oxide-modified starch (containing about 3% oxyethylene units based on the weight of starch and available under the tradename Penford Gum 260), 0.9% of a lubricant in the form of a solubilized tallow (sulfonated), and 4% of the copolymer of Example 1 was placed in the size box of a slasher. A warp of 100% spun nylon yarns, 16.5 cotton count, single ply, 18.2 turns of Z twist per inch was passed through the slasher and dried on the drying cans thereof at 190 to 210 F. No sizing material stuck to the dam. The size exhibited excellent adhesion to the yarns and very good fiber lay. The warp (containing 17% size on the initial weight of fabric) was then woven into a plain weave industrial fabric (44 x 44) without appreciable breakage of yarns or transfer of size to the shuttles. The size was readily removed on scouring.
  • Example 3 An aqueous solution containing 18% of the modified starch of Example 2 and 4.6% of the copolymer of Example 1 was introduced into the size box of a slasher.
  • a Warp of a spun yarn of a copolymer of about 90% acrylonitrile available under the tradename Acrilan, 30 cotton count, single ply was passed through the slasher and dried on the cans thereof at 180 F. No sizing was retained on the cans. The size exhibited excellent adhesion to the yarns and very good fiber lay. The warp was then woven into a plain weave fabric without appreciable breakage of yarn or transfer of size to the shuttles. The size was readily removed on scouring.
  • Example 4 An aqueous solution of 12.5% of an ammonium salt of a copolymer of 80 mole percent ethyl acrylate and 20 mole percent methacrylic acid, having a Knoop hardness of about 4, was introduced into the size box of a two-roll slasher.
  • a Warp hereinbelow referred to as warp A
  • warp A of single yarns (30 cotton count) of spun nylon was passed through the slasher and was dried by passage through a hot-air chamber.
  • Warp Cycles A 2,000 (average of 12 tests). B 88 to 170 (average of 12 tests). 0 140 to 170 (average of 12 tests).
  • Example 5 An aqueous solution of 2.5% of an ammonium salt of a copolymer of mole percent ethyl acrylate and 15 mole percent methacrylic acid (having a molecular weight of about 5200 and a Knoop hardness of 1.0) and 10% of the modified starch of Example 1 was put in a size box of a slasher. A warp of the same nylon yarn as in Example 4 was passed through the slasher and tested with the abrader referred to in Example 4. It withstood 1250 cycles.
  • Example 6 The same nylon yarn as in Example 4 was sized by passing through a 12.5% aqueous solution of the sodium salt of the copolymer of Example 1. It withstood 700 to 900 cycles of abrasion.
  • Example 7 The same nylon yarn as in Example 4 was sized by passing through a 12.5% aqueous solution of the ammonium salt of a copolymer of 80 mole percent butyl acrylate and 20 mole percent acrylic acid having a Knoop hardness of about 5. It withstood 400 cycles of abrasion.
  • Example 8 The same nylon yarn as in Example 4 was sized by passing through an aqueous solution of 2.5% of the ammonium salt of a copolymer of 75 mole percent ethyl acrylate, 5 mole percent butyl acrylate, and 20 mole percent methacrylic acid having a Knoop hardness of about 5 and 10% of the modified starch of Example 1. It withstood 430 cycles of abrasion.
  • Example 9 A continuous filament yarn of cellulose acetate was sized by passing through an aqueous solution of 5% of the ammonium salt of a copolymer of 75 mole percent ethyl acrylate, 20 mole percent butyl methacrylate and 5 mole percent acrylic acid having a Knoop hardness of about 7. The size adhered well to the yarn, and caused the filaments to adhere together firmly, producing a wellsized yarn adapted to be woven with facility.
  • Example 10 A spun yarn of Acrilan (a copolymer containing about acrylonitn'le) was sized by passing through an aqueous solution containing 20% of chlorinated starch and 5% of the ammonium salt of a copolymer of 80 mole percent propyl acrylate and 20 mole percent methacrylic acid having a Knoop hardness of about 6. The sized yarn did not stick to the drier cans, gave good fiber lay and coherence, and had excellent adhesion to the yarn.
  • Acrilan a copolymer containing about acrylonitn'le
  • Example 11 A spun polyethylene terephthalate yarn was sized by passingthrough an aqueous solution of 10% of polyvinyl alcohol and 5% of the ammonium salt of a copolymer of 70 mole percent ethyl acrylate, 10 mole percent lauryl acrylate and 20 mole percent methacrylic acid having a Knoop hardness of about 3. The sizing did not stick to the drying cans and produced a yarn which could be easily woven without appreciable yarn breakage or transfer of sizing to the shuttle.
  • Example 12 An aqueous solution containing 12.5% of a waterdispersible ethylene oxide-modified starch (containing about 3% oxyethylene units based on the weight of 3.1% ofthe copolymer of Example .1 ,wasplaced in the size box of a slasher.
  • An endand end warp of spun Dacron yarns, 27 cottoncounntwoeply, having 19 turns of S twist per, inch in one set of the plied yarnsand 17 turns of Z twist in the alternate yarns was passed through the slasher and dried with heated air at 180 to 200 F.
  • the size exhibited excellent adhesion to the yarns and weave 9.2 oz./yd. suiting fabric (50 x 44) without appreciable breakage of yarns or transfer of size to the shutties. The size was readily removed on scouring.
  • a dry, sized textile comprising hydrophobic filamentary material carrying thereon l to 20% by weight of a sizing composition comprising a water-dispcrsible saltof a cation of the class consisting of ammonium and alkali metals and of an anion of the class consisting of copolymers consisting exclusively of to 20 mole percent of at least one acid selected from acrylic and methacrylic acids with 80 to 95 1 carbon atoms, and mixtures thereof to impart.
  • a Knoop hardness of not over 7, said sizing being readily removable by common scouring operations.
  • a dry, sized textile yarn comprising hydrophobic filamentary material sized with 1 to by weight of a sizing composition
  • a sizing composition comprising (1) a water-dispersible salt of a cation of the class consisting of ammonium and alkali metals and of an anion of the class consisting of copolymers consisting exclusively of 5 to 20 mole percent of at least one acid selected from acrylic and methacrylic acids with'80 to 95 mole percent of at least one ester selected from the group consisting of the acrylates and methacrylates of aliphatic alcohols having from 1 to 18 carbon atoms, a sufiicient proportion amounting to at least 50 mole percent of the total ester component of the copolymer salt being selected from acrylates of primary and secondary acyclic alcohols having from 1 to 18 carbon atoms, methacrylates of primary and secondary acyclic alcohols having 6 to 18 carbon atoms, and mixtures thereof to impart to the copolymer a Knoop hardness
  • a method ofhandling a textile yarn comprising hydrophobic filamentary material comprising applying thereto a readily removable sizing comprising a waterdispersiblesalt of a cation of the class consisting of am- .monium and alkali metals and of an anion of the class consisting of copolymers consisting exclusively of 5 to 20 mole percent of at least one acid selected from acrylic and methacrylic acids with 80 to mole percent of at least one ester selected from the group consisting of the acrylates and methacrylates of aliphatic alcohols having from 1 to 18 carbon atoms, a sufficient proportion amounting to at least 50 mole percent of the total cster component of the copolymer salt being selected from acrylates of primary and secondary acyclic alcohols having from 1 to 18 carbon atoms, methacrylates of primary and secondary acyclic alcohols having 6 to 18 carbon atoms, and mixtures thereof to impart to the copolymer a Knoop hardness of not over 7, said sizing being applied by imp

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  • Chemical & Material Sciences (AREA)
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Description

United States Patent SIZED TEXTILE AND METHOD OF FABRICATING YARN INTO FABRIC Fred B. Shippee, Churchville, and Melvin D. Hurwitz, Huntingdon Valley, Pa., assignors to Rohm 85 Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application June 14, 1954, Serial No. 436,637
16 Claims. (Cl. 28-76) This invention relates to the sizing or dressing of fibers, filaments, and yarns whether of spun or continuous filament type, to render such textile materials amenable to textile operations, for example, twisting, doubling, weaving, knitting, braiding, and so forth. It is particularly concerned with sizes of removable type which are adapted to be applied to hydrophobic artificial filaments an fibers, such as nylon.
Heretofore, attempts have been made to use watersoluble or water-dispersible polymeric colloidal substances, such as starch or polyvinyl alcohol for the sizing of nylon yarns, but such materials generally show little adhesion to hydrophobic materials, such as nylon. The lack of adhesion requires the application of excessive amounts of the sizing material to protect the filaments or fibers and to reduce the tendency for the size to rub off on guides or other surfaces of the textile fabricating machinery. Various polymers and copolymers of acrylic acid and of methacrylic acid and also styrenemaleic acid copolymers as well as their salts have been suggested but the general experience with such materials has been that they are hard and brittle and tend to shed particles thereof during their passage through the textile fabricating machinery, or they are corrosive to metals and damage the equipment, or they have disadvantages of adhering more readily to metal than to the materials of which the fibers and filaments are composed. Because of this latter characteristic, the sized yarns tend to leave deposits of the sized material on metal guides and on metal drying drums. Because of their hardness, it is necessary in many uses to combine these polymeric materials with other substances, especially plasticizers, but in general, because of their high acidity, the particular materials which can be effectively combined or mixed with the polymeric acids or their salts is somewhat limited. For example, starch and cellulosic derivatives are unsuitable because they are degraded by the acidity of the polymers or copolymers.
It is an object of the present invention to provide as textile sizing materials certain acrylic copolymers which have been found to have outstanding qualities adapting them to provide improved properties in textile articles sized therewith without the disadvantages heretofore encountered. A more particular object of the invention is to provide a readily removable size for rendering spun yarns of hydrophobic artificial fibers more amenable to textile processing. Other objects and advantages of the invention will be apparent from the description thereof beneficial as sizes for textile materials and especially for .spunyarns of hydrophobic artificial filamentary materials, such as nylon. The particular copolymer salts are the ammonium or alkali metal salts of copolymers of 5 2 T to 20 mole percent of acrylic acid or methacrylic acid with to of at least one ester selected from the group consisting of the acrylates and methacrylates of aliphatic alcohols having from 1 to 18 carbon atoms, a sufficient proportion amounting to at least 50 mole percent of the total ester component of the copolymer being selected from acrylates of primary and secondary acyclic alcohols having from 1 to 18 carbon atoms, methacrylates of primany and secondary acyclic alcohols having from 6 to 18 carbon atoms, and mixtures thereof to impart to the salt of the copolymer a Knoop hardness of not over 7 and preferably about 1 or less. The molecular weight of the copolymer salts may be from about 3,000 to 1,000,000.
The Knoop hardness number is determined in accordance with the procedure described in Indentation Hard ness Testing, by V. E. Lysaght, 1949, Reinhold Publishing Company, p. 189. In the examples herein, a Tukon Hardness Tester of the Wilson Mechanical Instrument Company was used. Its pressure element was applied without impact under a 25-gram load to a film of the copolymer to be tested cast on glass, which had been dried at C. and conditioned at 55% relative humidity and 77 F., and held in contact for a period of ten seconds. The indentation resulting was measured with the aid of a microscope.
These salts of copolymers are either water-soluble when the proportion of the acid component is between 10 a and 20 mole percent or readily dispersible in water when the proportion of the acid component is between 5 and 10 mole percent. The ammonium salt is preferred as it seems to have appreciably greater adhesion to the hydrophobic filamentary materials than the salts of the alkali metals, possibly because of partial hydrolysis to provide free carboxyl groups in the copolymer. It is essential that the salts of the copolymers be soft and have an upper limit of Knoop hardness of seven, and preferred copolymers have a Knoop hardness number of not over one. While the acrylic acid or methacrylic acid may be copolymerized with an ester of acrylic acid with an alcohol from methyl to octadecyl to yield copolymers having the necessary softness, the acid cannot be :copolymerized with an ester consisting entirely of a lower methacrylate, that is one obtained from an alcohol having less than six carbon atoms without producing a copolymer having a hardness far in excess of the limit required for the present invention. However, the acrylic acid or methacrylic acid may be combined with a lower methacrylate in ternary copolymers provided the lower methacrylate having less than six carbon atoms does not amount to more than 50 mole percent of the total ester component. For example, a ternary copolymer of 20 mole percent methacrylic acid, 27 mole percent of methyl methacrylate and 54 mole percent of octyl methacrylate is of sufficient softness for the purpose of the present invention. Similarly, an adequately soft copolymer may be obtained by the copolymerization of 20 mole percent methacrylic acid, 14 mole percent methyl methacrylate and 66 mole percent of n-lauryl methacrylate. The corresponding ternary copolymers in which the methacrylic acid is replaced entirely with a corresponding proportion of acrylic acid are also adequately soft for the purposes of the invention.
These copolymer salts when applied to yarns, especially of spun nylon or the like, are substantially free from corrosion difiiculties. They do not stick to metal, such as that of guides, or that on the dryer drums of a slasher.
Because of their softness they provide a sized yarn which is extremely flexible and substantially free of shedding difficulties. In addition, these copolymers are compatible with many materials which may be introduced into the sizing composition for various purposes. They do not degrade starch or other carbohydrate materials and they are quite compatible with a wide variety of hydrophilic 3 polymeric colloids with which it may be advantageous to mix the copolymers before application to the yarns.
The amount of copolymer salt applied to the textile material may vary from 1 to by weight depending upon the purposefor which application is intended and upon whether or not auxiliary conditioning or sizing agents are included in the composition by which it is applied to the textile. The method or means taken to apply the sizing composition, whether it consists of an aqueous solution of the copolymer alone or of a mixture of the copolymer with other ingredients, may be selected according to the ultimate purpose. Thus, the composition may be applied by spraying, dipping, padding, by sizing rolls, transfer rolls, or the like. For sizing of spun or continuous filament yarns, an entire Warp thereof may be passed through a conventional slasher or a yarn may be individually treated in a single end sizer. After application of the aqueous solution which may have a concentration of l to by weight of solids (that is either the copolymer alone or in conjunction With other yarn-treating agents) the excess solution may be removed such as by squeeze rolls or wipers and the treated yarn may then be dried. Drying may be effected by any suitable means such'as by heated air or drying cans. Since the compositions do not transfer from the yarns to the cans and do not stick to the metal of such cans, metal drying cans can be effectively used without difficulty. The drying may be effected at temperatures of 160-250 F., a temperature in this range being selected in accordance with the particular type of yarn to prevent any damage as a result or excessive heating. The aqueous solution containing the copolymer may be at room temperature up to about 190 F., or more during application, the higher temperatures favoring penetration.
For warp sizing spun yarns, the preferred proportion applied to the yarn is from 5 to 15% by weight on the initial weight of the yarn. However, for the sizing of continuous filament yarns the preferred proportion is from 0.5 to 2.5% of the copolymer on the weight of the yarn.
The copolymers of the present invention may be used on yarns of fibers and filaments of a wide variety of hydro phobic synthetic materials such as nylon, polyethylene terephthalate, copolymers containing .a predominant proportion of vinyl chloride or vinylidene chloride such as Vinyon (a copolymer of about 75 to 95% vinyl chloride with the balance of vinyl acetate), Dynel (copolymers of 60 to 85% vinyl chloride with the balance of acrylonitrile), Saran (copolymers of about 70 to 90% vinylidene chloride with a balance either of vinyl chloride or acrylonitrile), and acrylonitrile ploymers such as polyacrylonitrile itself or copolymers containing at least 75% by weight of acrylonitrile with vinyl acetate, vinyl pyridines, vinyl chloride, mixtures thereof, or the like. The sizing compositions are particularly valuable with yarns comprising such fibers or filaments because of their ability to adhere to the hydrophobic materials of which such yarns are composed. The compositions of the present invention may also be applied to yarns formed of blends of fibers or filaments comprising one or more of the above hydrophobic filamentary materials with themselves or natural or artificial fibers or filaments such as cotton, wool, silk, viscose rayon, cuprammonium rayon, cellulose acetate, and the like.
The copolymer salts of this invention may be applied to textiles, such as yarns, fibers, or filaments, threads or cords, felts, fabrics, or the like, to modify their properties and especially to render them more amenable to textile processing operations. The copolymers may be applied to threads or cords to protect them during sewing operations.
Copolymers of the present invention maybe mixed with hydrophilic polymeric colloids, Water-soluble or selfdispersible in water, such as starch, starch derivatives including chlorinated starch, starch esters including starch 4 acetate, starch ethers including particularly ethylene oxidemodified starches in which the starch is combined with l to 5% or more of its weight of ethylene oxide, dextrins, water-soluble cellulose others including sodium carboxymethyl cellulose, sodium carboxyethyl cellulose, methyl cellulose and hydroxyethyl cellulose; polyvinyl alcohols, gelatins, partially hydrolyzed polyvinyl acetates which are water-dispersible or Water-soluble, casein, natural gums such as gum arabic and tragacanth. These water-dis persible colloids may be combined with the acrylic copoly mer in the proportions of 25 to by weight of the colloid to 75 to 5% respectively of the copolymer. They form compatible sizing coatings on yarns and are not degraded by the copolymer. There is no need for auxiliary dispersing agents in order to disperse both the copolymer and the colloid in water.
Coloring agents, such as dyes, anti-static agents, and auxiliary lubricating, softening, or conditioning agents may be incorporated but are not essential. For' cer,tain purposes, higher hydrocarbons, such as mineral'oil and paraffin wax and other lubricants, such as vegetable orv animal fats and oils, such as talloW, have been found advantageous when incorporated in an amount of l to 5% on the weight of the copolymer salt dispersion. Examples of preferred lubricants that may be used, without requiring an additional dispersing agent, and are compatible in the final sizing coating are ethylene oxide-modified long chain fatty acids, alcohols or amines such as those of 8 to 20 carbon atoms containing from 1 to 50 or more ethylene oxide units per mole of acid, alcohol or amine. For example, the condensation product of stearic acid with 2 to 4 moles of ethylene oxide may be used quite effectively. Other water-dispersible lubricants include sulfo nated oils, such as Turkey'Red Oil; and self-dispersible waxes, such as monostearin, and sorbitan mono-oleate modified with ethylene oxide. Dispersing agents may be included to assist the dispersion of certain lubricants, such as hydrocarbons and tallow.
The sizing composition may contain swelling or plasticizing agents for the material of which the fibers or filaments of the yarn is composed. In some cases, the use of such an agent markedly improves the adhesion of the sizing composition to the yarn and increases the weaving efliciency without decreasing the strength of the yarn and without interfering with subsequent removal of the size by scouring or, when a starch or starch derivative adjunct is present, by degrading with an enzyme and subsequent scouring. From 1 to 50% by weight, based on the weight of copolymer salt, of a swelling agent may be used in the sizing composition. Preferably 10 to 15% by weightof the swelling agent is employed, based on the weight of copolymer salt. The improved adhesion obtained when the swelling agent is added to the sizing compositions of the present invention is surprising since compositions obtained by the addition of a swelling agent to sizes containing starch or starch derivatives but no copolymer salt of the present invention have not been found to benefit in weaving efiiciency from such addition. The use of a swelling agent has been especially beneficial when sizing compositions are applied to polyester yarns of the polyethylene terephthalate type known as Dacron. The swelling agent used is selectedaocording to the particular material of which the yarn is composed. However, polyalkylene polyarnines, such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are generally useful and especially effective with polyethylene terephthalate yarns.
'The article obtained after application of the sizing composition of the present invention to the textile material and drying is essentially free from the disadvantage of developing static charges, loss of sizing material by transfer to guides or shedding, and it is free of deleterious corrosive effects on the metals of textile machinery.
Furthermore, the sizing material is readily removed by common scouring operations because of the ready dis- Example 1 An aqueous solution of 7.2% concentration of the ammonium salt of a copolymer of 20 mole percent acrylic acid and 80 mole percent ethyl acrylate, having a Knoop hardness of l, was introduced into the size box of a tworoll slasher. A warp of -75 denier, 34 filament poly- -"ethylene' terephthalate yarns each containing 17 turns of twist per inch was passed through the slasher at 50 yards "per minute and dried on the 7 drier cans thereof at 160 to 170 F. No sizing material stuck to the drier cans.
' The resulting yarn was woven into a marquisette fabric (56 x 40) without appreciable breakage of yarn or filaments or transfer of sizing to the shuttle. The size was readily removed from the fabric by scouring.
Example 2 An aqueous solution containing 17.5% of a waterdispersible ethylene oxide-modified starch (containing about 3% oxyethylene units based on the weight of starch and available under the tradename Penford Gum 260), 0.9% of a lubricant in the form of a solubilized tallow (sulfonated), and 4% of the copolymer of Example 1 was placed in the size box of a slasher. A warp of 100% spun nylon yarns, 16.5 cotton count, single ply, 18.2 turns of Z twist per inch was passed through the slasher and dried on the drying cans thereof at 190 to 210 F. No sizing material stuck to the dam. The size exhibited excellent adhesion to the yarns and very good fiber lay. The warp (containing 17% size on the initial weight of fabric) was then woven into a plain weave industrial fabric (44 x 44) without appreciable breakage of yarns or transfer of size to the shuttles. The size was readily removed on scouring.
Example 3 An aqueous solution containing 18% of the modified starch of Example 2 and 4.6% of the copolymer of Example 1 was introduced into the size box of a slasher. A Warp of a spun yarn of a copolymer of about 90% acrylonitrile available under the tradename Acrilan, 30 cotton count, single ply was passed through the slasher and dried on the cans thereof at 180 F. No sizing was retained on the cans. The size exhibited excellent adhesion to the yarns and very good fiber lay. The warp was then woven into a plain weave fabric without appreciable breakage of yarn or transfer of size to the shuttles. The size was readily removed on scouring.
Example 4 An aqueous solution of 12.5% of an ammonium salt of a copolymer of 80 mole percent ethyl acrylate and 20 mole percent methacrylic acid, having a Knoop hardness of about 4, was introduced into the size box of a two-roll slasher. A Warp (hereinbelow referred to as warp A) of single yarns (30 cotton count) of spun nylon was passed through the slasher and was dried by passage through a hot-air chamber.
cause yarn rupture is measured. The several sized yarns showed the following results:
Warp Cycles A 2,000 (average of 12 tests). B 88 to 170 (average of 12 tests). 0 140 to 170 (average of 12 tests).
Example 5 An aqueous solution of 2.5% of an ammonium salt of a copolymer of mole percent ethyl acrylate and 15 mole percent methacrylic acid (having a molecular weight of about 5200 and a Knoop hardness of 1.0) and 10% of the modified starch of Example 1 was put in a size box of a slasher. A warp of the same nylon yarn as in Example 4 was passed through the slasher and tested with the abrader referred to in Example 4. It withstood 1250 cycles.
Example 6 The same nylon yarn as in Example 4 was sized by passing through a 12.5% aqueous solution of the sodium salt of the copolymer of Example 1. It withstood 700 to 900 cycles of abrasion.
Example 7 The same nylon yarn as in Example 4 was sized by passing through a 12.5% aqueous solution of the ammonium salt of a copolymer of 80 mole percent butyl acrylate and 20 mole percent acrylic acid having a Knoop hardness of about 5. It withstood 400 cycles of abrasion.
Example 8 The same nylon yarn as in Example 4 was sized by passing through an aqueous solution of 2.5% of the ammonium salt of a copolymer of 75 mole percent ethyl acrylate, 5 mole percent butyl acrylate, and 20 mole percent methacrylic acid having a Knoop hardness of about 5 and 10% of the modified starch of Example 1. It withstood 430 cycles of abrasion.
Example 9 A continuous filament yarn of cellulose acetate was sized by passing through an aqueous solution of 5% of the ammonium salt of a copolymer of 75 mole percent ethyl acrylate, 20 mole percent butyl methacrylate and 5 mole percent acrylic acid having a Knoop hardness of about 7. The size adhered well to the yarn, and caused the filaments to adhere together firmly, producing a wellsized yarn adapted to be woven with facility.
Example 10 A spun yarn of Acrilan (a copolymer containing about acrylonitn'le) was sized by passing through an aqueous solution containing 20% of chlorinated starch and 5% of the ammonium salt of a copolymer of 80 mole percent propyl acrylate and 20 mole percent methacrylic acid having a Knoop hardness of about 6. The sized yarn did not stick to the drier cans, gave good fiber lay and coherence, and had excellent adhesion to the yarn.
Example 11 A spun polyethylene terephthalate yarn was sized by passingthrough an aqueous solution of 10% of polyvinyl alcohol and 5% of the ammonium salt of a copolymer of 70 mole percent ethyl acrylate, 10 mole percent lauryl acrylate and 20 mole percent methacrylic acid having a Knoop hardness of about 3. The sizing did not stick to the drying cans and produced a yarn which could be easily woven without appreciable yarn breakage or transfer of sizing to the shuttle.
Example 12 An aqueous solution containing 12.5% of a waterdispersible ethylene oxide-modified starch (containing about 3% oxyethylene units based on the weight of 3.1% ofthe copolymer of Example .1 ,wasplaced in the size box of a slasher. An endand end warp of spun Dacron yarns, 27 cottoncounntwoeply, having 19 turns of S twist per, inch in one set of the plied yarnsand 17 turns of Z twist in the alternate yarns was passed through the slasher and dried with heated air at 180 to 200 F. The size exhibited excellent adhesion to the yarns and weave 9.2 oz./yd. suiting fabric (50 x 44) without appreciable breakage of yarns or transfer of size to the shutties. The size was readily removed on scouring.
It is to be understood that variations and changes may be made without departing from the spirit and scope of the invention as defined in the appended claims.
We claim:
1. As an article of manufacture, a dry, sized textile comprising hydrophobic filamentary material carrying thereon l to 20% by weight of a sizing composition comprising a water-dispcrsible saltof a cation of the class consisting of ammonium and alkali metals and of an anion of the class consisting of copolymers consisting exclusively of to 20 mole percent of at least one acid selected from acrylic and methacrylic acids with 80 to 95 1 carbon atoms, and mixtures thereof to impart. to the copolymer a Knoop hardness of not over 7, said sizing being readily removable by common scouring operations.
2. An article as defined in claim .1 in which the textile material carries from 5 to byweight of said waterdispersible salt.
3. As an article of manufacture, a dry, sized textile yarn comprising hydrophobic filamentary material sized with 1 to by weight of a sizing composition comprising (1) a water-dispersible salt of a cation of the class consisting of ammonium and alkali metals and of an anion of the class consisting of copolymers consisting exclusively of 5 to 20 mole percent of at least one acid selected from acrylic and methacrylic acids with'80 to 95 mole percent of at least one ester selected from the group consisting of the acrylates and methacrylates of aliphatic alcohols having from 1 to 18 carbon atoms, a sufiicient proportion amounting to at least 50 mole percent of the total ester component of the copolymer salt being selected from acrylates of primary and secondary acyclic alcohols having from 1 to 18 carbon atoms, methacrylates of primary and secondary acyclic alcohols having 6 to 18 carbon atoms, and mixtures thereof to impart to the copolymer a Knoop hardness of not over 7, and (2) a water-dispersible hydrophilic polymeric colloid, said sizing being readily removable by common scouring operations.
4. An article as defined in claim 3 in which the sizing comprises 5 to 75% of the water-dispersible salt and 95 to respectively of the colloid.
.8 5. .An article as defined in claim 4 in which the textile yarn carries from 5 to 10% by weight of said sizing.
6. An article as defined in claim 3 in which the salt .is an ammonium salt of a copolymer of 20 mole percent acrylic acid and mole percent ethyl acrylate.
7. An article as defined in claim 3 in which the salt is an ammonium salt of a copolymer of 20 mole percent :acrylic .acid and 80.:mole percent ethyl acrylate and the colloid is an :ethylene oxide-modified starch.
8." An article as defined in claim 3 in which the salt is an ammonium salt of a copolymer of 20 mole percent methacrylic acid and 80 mole percent ethyl acrylate.
9. .An article as defined in claim 3 in which the salt is'an ammonium salt of a copolymer of 15 mole percent methacrylic acid and mole percent ethyl acrylate.
10. An article as defined in claim 3 in which the salt is a sodium salt of a copolymer of 20 mole percent acrylic acid and 80 mole percent ethyl acrylate.
11. An article as defined in claim 3 in which the salt is an ammonium salt of a copolymer of 20 mole percent methacrylic acid, 75 mole percent ethyl acrylate, and 5 mole percent butyl acrylate.
12. An article as defined in claim 3 in which the textile is a nylon yarn.
13. An article as defined in claim 3 in which the textile is a spunnylon yarn.
14. An article as defined in claim 3 in which the textile is yarn spun of polyethylene terephthalate staple fibers.
15. An article asdefined in claim 3 in which the textile is yarn spun of copolymers of at least 75% by weight of acrylonitrile.
16. A method ofhandling a textile yarn comprising hydrophobic filamentary material comprising applying thereto a readily removable sizing comprising a waterdispersiblesalt of a cation of the class consisting of am- .monium and alkali metals and of an anion of the class consisting of copolymers consisting exclusively of 5 to 20 mole percent of at least one acid selected from acrylic and methacrylic acids with 80 to mole percent of at least one ester selected from the group consisting of the acrylates and methacrylates of aliphatic alcohols having from 1 to 18 carbon atoms, a sufficient proportion amounting to at least 50 mole percent of the total cster component of the copolymer salt being selected from acrylates of primary and secondary acyclic alcohols having from 1 to 18 carbon atoms, methacrylates of primary and secondary acyclic alcohols having 6 to 18 carbon atoms, and mixtures thereof to impart to the copolymer a Knoop hardness of not over 7, said sizing being applied by impregnating the yarn with an aqueous dispersion containing about 1 to 25% by weight of said water-dispersible salt, drying the treated yarn, then fabricating the yarn into a textile material comprising interlocked yarns, and then scouring the textile material to remove the sizing therefrom.
References Cited in the file of this patent UNITED STATES PATENTS 2,046,885 Strain July 7, 1936 2,183,226 Rein Dec. 12, 1939 2,244,702 Hubbuch June 10, 1941 2,244,703 Hubbuch June 10, 1941 2,244,704 Brubaker June 10, 1941 2,651,587 Rossin Sept. 8, 1953 2,653,140 Allenby et al Sept. 22, 1953

Claims (1)

16. A METHOD OF HANDLING A TEXTILE YARN COMPRISING HYDROPHOBIC FILAMENTARY MATERIAL COMPRISING APPLYING THERETO A READILY REMOVABLE SIZING COMPRISING A WATERDISPERSIBLE SALT OF A CATION OF THE CLASS CONSISTING OF AMMONIUM AND ALKALI METALS AND OF AN ANION OF THE CLASS CONSISTING OF COPOLYMERS CONSISTING EXCLUSIVELY OF 5 TO 20 MOLE PERCENT OF AT LEAST ONE ACID SELECTED FROM ACRYLIC AND METHACRYLIC ACIDS WITH 80 TO 95 MOLE PERCENT OF AT LEAST ONE ESTER SELECTED FROM THE GROUP CONSISTING OF THE ACRYLATES AND METHACRYLATES OF ALIPHATIC ALCOHOLS HAVING FROM 1 TO 18 CARBON ATOMS, A SUFFICIENT PROPORTION AMOUNTING TO AT LEAST 50 MOLE PERCENT OF THE TOTAL ESTER COMPONENT OF THE COPOLYMER SALT BEING SELECTED FROM ACRYLATES OF PRIMARY AND SECONDARY ACYCLIC ALCOHOLS HAVING FROM 1 TO 18 CARBON ATOMS, METHACRYLATES OF PRIMARY AND SECONDARY ACYCLIC ALCOHOLS HAVING 6 TO 8 CARBON ATOMS, AND MIXTURES THEREOF TO IMPART TO THE COPOLYMER A KNOOP HARDNESS OF NOT OVER 7, SAID SIZING BEING APPLIED BY IMPREGNATING THE YARN WITH AN AQUEOUS DISPERSION CONTAINING ABOUT 1 TO 25% BY WEIGHT OF SAID WATER-DISPERSIBLE SALT, DRYING THE TREATED YARN THEN FABRICATING THE YARN INTO A TEXTILE MATERIAL COMPRISING INTERLOCKED YARNS, AND THEN SCOURING THE TEXTILE MATERIAL TO REMOVE THE SIZING THEREFROM.
US436687A 1954-06-14 1954-06-14 Sized textile and method of fabricating yarn into fabric Expired - Lifetime US2807865A (en)

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US436687A US2807865A (en) 1954-06-14 1954-06-14 Sized textile and method of fabricating yarn into fabric
GB16147/55A GB804952A (en) 1954-06-14 1955-06-06 Improvements in textiles and sizing compositions
FR1132921D FR1132921A (en) 1954-06-14 1955-06-09 Finishing compositions for textiles
CH338425D CH338425A (en) 1954-06-14 1955-06-13 Stable composition for finishing textiles
DER16841A DE1042516B (en) 1954-06-14 1955-06-14 Resistant sizing or finishing agents

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US2899341A (en) * 1959-08-11 Textile finishing process
US2969791A (en) * 1956-04-30 1961-01-31 Bofors Ab Rigid supporting dressing
US2992943A (en) * 1959-06-19 1961-07-18 Eastman Kodak Co Sizing compositions for textile yarns
US3008215A (en) * 1958-01-31 1961-11-14 Du Pont Antistatic textile material
US3036537A (en) * 1957-04-09 1962-05-29 Marcus I Breier Materials handling method
US3236685A (en) * 1962-06-20 1966-02-22 Eastman Kodak Co Process for treating textile fibers and other shaped products with coatings
US3296023A (en) * 1964-03-11 1967-01-03 Rockland Bleach And Dye Works Fabric coated with light reflecting filler and acrylic polymer
US3364164A (en) * 1964-10-06 1968-01-16 Gulf Oil Corp Aqueous dispersion of hydrocarbonalkyl acrylate copolymer containing hydrophilic substituents, and a dispersing agent
US3386938A (en) * 1966-02-16 1968-06-04 Du Pont Acrylic wax abrasion resistant fiber finish composition
US3503916A (en) * 1965-08-13 1970-03-31 Dunlop Rubber Co Solutions of alkali-soluble copolymers
US3607374A (en) * 1967-09-25 1971-09-21 Keuffel & Esser Co Drafting film materials
US3632422A (en) * 1969-12-04 1972-01-04 Burlington Industries Inc Textile fabric having soil release finish and method of making same
US3900606A (en) * 1971-08-12 1975-08-19 Pennwalt Corp Temporary soil release resins applied to fabrics by spraying
US4394128A (en) * 1980-10-31 1983-07-19 Rohm And Haas Company Method of sizing polyester yarn
US4448839A (en) * 1981-10-16 1984-05-15 Rohm And Haas Company Method of sizing hydrophobic yarn
US5082896A (en) * 1989-01-17 1992-01-21 Milliken Research Corporation Polymeric materials useful for sizing synthetic yarns to be used in water jet weaving
US5354815A (en) * 1992-06-05 1994-10-11 Comfort Technologies Polymers having enhanced hydrophilicity and thermal regulated properties and process of producing the same
US5408012A (en) * 1993-05-27 1995-04-18 Comfort Technologies, Inc. Polymers having enhanced durable hydrophilicity and durable rewetting properties and process of producing the same
US5614598A (en) * 1992-06-05 1997-03-25 Comfort Technologies, Inc. Polymers having enhanced hydrophilicity and thermal regulated properties and process of producing the same

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US3634295A (en) * 1968-07-24 1972-01-11 Donald Thomas Dunlap Textile sizing composition
US4595394A (en) * 1983-04-08 1986-06-17 Kao Corporation Agent for improving processability of cellulose fibers: acid polymer salts for improved scouring

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US2183226A (en) * 1936-01-17 1939-12-12 Ig Farbenindustrie Ag Sizing of textile materials
US2244704A (en) * 1937-08-30 1941-06-10 Du Pont Sizing of textile materials
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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2899341A (en) * 1959-08-11 Textile finishing process
US2969791A (en) * 1956-04-30 1961-01-31 Bofors Ab Rigid supporting dressing
US3036537A (en) * 1957-04-09 1962-05-29 Marcus I Breier Materials handling method
US3008215A (en) * 1958-01-31 1961-11-14 Du Pont Antistatic textile material
US2992943A (en) * 1959-06-19 1961-07-18 Eastman Kodak Co Sizing compositions for textile yarns
US3236685A (en) * 1962-06-20 1966-02-22 Eastman Kodak Co Process for treating textile fibers and other shaped products with coatings
US3296023A (en) * 1964-03-11 1967-01-03 Rockland Bleach And Dye Works Fabric coated with light reflecting filler and acrylic polymer
US3364164A (en) * 1964-10-06 1968-01-16 Gulf Oil Corp Aqueous dispersion of hydrocarbonalkyl acrylate copolymer containing hydrophilic substituents, and a dispersing agent
US3503916A (en) * 1965-08-13 1970-03-31 Dunlop Rubber Co Solutions of alkali-soluble copolymers
US3386938A (en) * 1966-02-16 1968-06-04 Du Pont Acrylic wax abrasion resistant fiber finish composition
US3607374A (en) * 1967-09-25 1971-09-21 Keuffel & Esser Co Drafting film materials
US3632422A (en) * 1969-12-04 1972-01-04 Burlington Industries Inc Textile fabric having soil release finish and method of making same
US3900606A (en) * 1971-08-12 1975-08-19 Pennwalt Corp Temporary soil release resins applied to fabrics by spraying
US3909476A (en) * 1971-08-12 1975-09-30 Pennwalt Corp Temporary soil release resins applied to fabrics in laundering
US4394128A (en) * 1980-10-31 1983-07-19 Rohm And Haas Company Method of sizing polyester yarn
US4448839A (en) * 1981-10-16 1984-05-15 Rohm And Haas Company Method of sizing hydrophobic yarn
US5082896A (en) * 1989-01-17 1992-01-21 Milliken Research Corporation Polymeric materials useful for sizing synthetic yarns to be used in water jet weaving
US5354815A (en) * 1992-06-05 1994-10-11 Comfort Technologies Polymers having enhanced hydrophilicity and thermal regulated properties and process of producing the same
US5614598A (en) * 1992-06-05 1997-03-25 Comfort Technologies, Inc. Polymers having enhanced hydrophilicity and thermal regulated properties and process of producing the same
US5408012A (en) * 1993-05-27 1995-04-18 Comfort Technologies, Inc. Polymers having enhanced durable hydrophilicity and durable rewetting properties and process of producing the same

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GB804952A (en) 1958-11-26
DE1042516B (en) 1958-11-06
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NL90438C (en)
CH338425A (en) 1959-05-31
FR1132921A (en) 1957-03-19

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