US3519477A - Sizing cellulosic and acrylic staple fiber yarns with acrylonitrile/acrylic acid copolymer - Google Patents

Sizing cellulosic and acrylic staple fiber yarns with acrylonitrile/acrylic acid copolymer Download PDF

Info

Publication number
US3519477A
US3519477A US612811A US3519477DA US3519477A US 3519477 A US3519477 A US 3519477A US 612811 A US612811 A US 612811A US 3519477D A US3519477D A US 3519477DA US 3519477 A US3519477 A US 3519477A
Authority
US
United States
Prior art keywords
sizing
liquor
percent
yarns
acrylonitrile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US612811A
Other languages
English (en)
Inventor
Hans Wolf
Herbert Spoor
Wilhelm Ruemens
Heinz Pohlemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Application granted granted Critical
Publication of US3519477A publication Critical patent/US3519477A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles

Definitions

  • Lubricants such as tallow
  • sizing liquors containing mainly starches The fatty substance is added to improve the slip of the threads and to prevent them becoming too brittle.
  • the sizing agent has to be removed from the woven material prior to further treatment, and this is achieved to a more or less satisfactory extent only by subjecting it to the action of enzymes for several hours.
  • cotton or other cellusoic yarns are sized with substances that have been produced by the chemical modification of cellulose.
  • substances include cellulose ethers, for example carboxymethylcellulose or methylcellulose.
  • cellulose ethers for example carboxymethylcellulose or methylcellulose.
  • These are commonly marketed in the form of powders which can be made up as collodial aqueous solutions only by prolonged standing in water, by vigorous stirring or kneading, or by heating. In general, their solutions are not homogeneous, but turbid and comparatively highly viscous. Frequently, the powders, owing on the chemical modification of the cellulose, contain large quantites of common salt.
  • Another object of the invention is to provide sizing agents for the type of yarns mentioned which are particularly readily soluble in Water.
  • Still another object of the invention is to provide sizing agents for the type of fibers mentioned which are chemically and mechanically very stable in the treatment liquors.
  • a further object of this invention is to provide sizing agents for the type of yarns mentioned which can be removed from the yarns particularly easily.
  • a still further object of the invention is to provide an improved process for sizing the type of yarns mentioned which, compared with processes employed hitherto, effects savings in energy and personnel costs and an increase in productivity when processing the sized yarns, and which also ensures more satisfactory and easier desizing.
  • staple yarns consisting of or containing cellulosic fibers and/or acrylic fibers in an amount of at least 30' percent by weight can be sized better than hitherto by applying to the yarn an aqueous solution of a polymer containing copolymerized units of (a) acrylonitrile and (b) acrylic acid and its sodium or ammonium salt in the molar ratio of (a) (b) of 1:15 to 1:7, preferably from 1:2 to 1:6, its 10 percent by Weight aqueous solution at 20 C. having a viscosity of 20 to 2000 cp. and a pH value of 2.5 to 6.5, preferably 3 to 5.5, and drying the yarn thus treated.
  • Staple yarns that can be sized according to the invention include, for example, those of natural and/or regenerated cellulose such as cotton, rayon staple, linen and their blends with one another and with other staple fibers such as polyester and acrylic fibers and their blends with other staple fibers.
  • Our acrylic fibers are understood both fibers prepared from acrylonitrile homopolymers and those of copolymers of acrylonitrile with up to approximately 20 percent by weight of other monomers, e.g., methyl acrylate, vinyl acetate and vinyl pyridine.
  • polymers used in the form of their solutions in accordance with the invention can, in addition to the monomers described under (a) and -(b) above, incorporate up to 20 percent by weight of coplymerized units of other, at least partially water-soluble, monomers, such as acrylamide, methacrylamide, methyl acrylate, methacrylic acid or its alkali or ammonium salts, maleic acid or its salts or semiesters, methacrylonitrile and vinyl pyrrolidone.
  • monomers such as acrylamide, methacrylamide, methyl acrylate, methacrylic acid or its alkali or ammonium salts, maleic acid or its salts or semiesters, methacrylonitrile and vinyl pyrrolidone.
  • They can be prepared by conventional processes, preferably by the copolymerization of acrylic acid with acrylonitrile and, if desired, other monomers in aqueous solution, and by subsequent partial neutralization of the carboxyl groups contained in the polymers by means of an alkali or ammonium hydroxide to set up the molar ratio between the free acrylic acid groups and the sodium or ammonium carboxylate groups which produces the required pH value of the polymer solution.
  • a further method of preparation consists in copolymerizing mixtures which already contain acrylic acid, sodium or ammonium acrylate and acrylonitrile in the desired molar proportions.
  • the polymers to be used in accordance with the invention contain carboxylic acid groups and sodium or ammonium carboxylate groups in the molar ratio of approximately 1:03 to 1:3, preferably from 1:0.8 to 1:2.
  • the polymers can be applied as sizing agents either in the form obtained in manufacture or after dilution. However, they can also be dried to a powder and dissolved in water before use.
  • the polymers should have a viscosity of from 20 to 2000 cp., polymers having a viscosity of from 250 to 2000 cp. under the said conditions being preferred.
  • the viscosity is expediently determined with a Hoppler falling sphere viscometer according to German standard specification DIN 53,015.
  • the solutions employed in accordance with the invention preferably contain 0.5 to 20 percent by weight of polymer.
  • concentrations have proved particularly satisfactory: 0.5 to for rayon staple and linen, 3 to for cotton, and 5 to percent by weight for acrylic staple fiber.
  • the size solutions have pH values ranging from approximately 2.5 to 6.5, preferably from approximately 3 to 5.5, depending on the molar ratio of free carboxylic acid groups to sodium or ammonium carboxylate groups present in the polymer.
  • the solutions according to the invention can contain conventional sizing agents and/or sizing auxiliaries, e.g., chemically moditied starches, carboxymethylcellulose, methylcellulose, polyvinyl alcohol and emulsified fats; such additives, however, should not constitute more than 50 percent by weight of the solids content of the sizing liquors, and preferably not more than percent by weight.
  • conventional sizing agents and/or sizing auxiliaries e.g., chemically moditied starches, carboxymethylcellulose, methylcellulose, polyvinyl alcohol and emulsified fats
  • the polymer solution employed for sizing in accordance with the invention can be brought on to the yarn at temperatures of between 0 and 100 C. In many cases, however, it is particularly advantageous to employ the liquor at a temperature of between 10 and C., that is, at approximately room temperature. Nevertheless, the polymer solution can also be used at higher temperatures, in which case the associated fall in viscosity permits working at a higher concentration resulting in a considerable increase in the output of the sizing machine since less water has to be evaporated from more concentrated solutions on drying.
  • the application of the size to the yarn is carried out in the usual manner, that is, mainly on machines well known in the open width sizing of warps. However, it may also be applied to the individual yarn, for instance, on a cross-Wound package. It is also possible to apply the size to bobbins or warp beams by means of appropriate dyeing machinery. It is preferable to apply the sizing agent in such an amount that the treated yarn carries 0.5 to 10 percent of polymer, referred to the weight of the untreated, dry yarn.
  • the polymers of the invention are particularly readily soluble in water. A consequence of this is that the sizing liquors can be prepared with cold water and require only moderate stirring, particularly when the polymer is in the form of an aqueous solution.
  • the use of pressure boilers and steam or other thermal energy for preparing the sizing liquors such as is necessary with most of the existing sizing agents and especially with starch products, can be dispensed with. Labor costs can be saved as a result of the considerably simpler and more rapid preparation of the liquor, and the danger of personnel being scalded is reduced.
  • Another important advantage is the stability of the sizing liquors which can, if necessary, be stored for weeks without undergoing change. Sizing liquors based on starch, on the other hand, lose considerably in efficiency even on storing for only a few hours, so that they have to be discarded in the evening or at the end of the week. Thus, compared with prior processes, the new process offers the possibility of savings in the cost of materials. A considerable reduction in the number of broken ends on the loom can be achieved as a result of the invention. This also means that the productivity of the loom is increased. Warps sized in accordance with the invention does considerably less than warps sized by conventional processes.
  • Yarns sized in accordance with the invention are more resistant to abrasion than yarns treated with starch products, cellulose ethers, or in accordance with the invention described in U.S. Pat. 2,819,189. Furthermore, the yarns can be desized more easily, since simple scouring or rinsing is all that is required. Faulty dyeings and difiiculties in finishing, so very often attributable to inadequate desizing, are largely elminated by the process of the invention.
  • the mechanical values given in the stables constitute the mean values of or individual determinations, as the case may be.
  • the abrasion number is the average number of abrasions up to breakage of the yarn, and has been measured on the apparatus described by E. Kenk in Textil-Praxis, 7, 9, 6 98 (1952).
  • EXAMPLE 1 A cotton yarn, of Nm. 34/ 1 count, was treated with two different sizing liquors on a laboratory sizing machine consisting of one pair of squeeze rollers with a sizing trough capable of being heated, a drying tube heated with hot air, and a wind-on device operating at constant tension; the conditions were otherwise identical in both cases.
  • This mixture which has a formulation well tried in practice, was boiled up for minutes and then applied at 85-90 C.
  • Liquor 1(b) This comprised a 15 percent aqueous solution of a polymer which was made up, on the one hand, with acrylic acid and sodium acrylate and, on the other, acrylonitrile, the two groups of components being in the molar ratio of 2:1. When diluted to 10 percent, the solution had a viscosity of 315 cp. at 20 C. and a pH value of 4.5. The liquor contained no other additives and was applied at 20 C.
  • Liquor 2(a) 120 parts of a commercial carboxymethylcellulose powder recommended for sizing cotton, and 880 parts water.
  • the liquor 2(b) obtained in this manner is color less, clear, and homogeneous.
  • 0 Treated with liquor In spite of the low liquor concentration and in spite of the small amount applied, the superiority of the size applied in accordance with formulation 2(b) of the invention is made evident by the resultant higher breaking load and considerably higher number of abrasion cycles required to effect rupture of the fiber.
  • EXAMPLE 3 Two 10,000 m. long warps containing 4,600 cotton threads (Nm. 68/ 1) were sized for comparison purposes in different liquors on an open-width sizing machine equipped with a cylinder dryer. Liquor 3(a) was prepared by submitting a suspension of 35 parts of potato starch and 35 parts of a commercial esterified starch ether sizing agent in 430 parts of water to boiling for about 40 minutes while stirring.
  • liquor 3(a) had to be applied to the warp at 85 to 90 C. inorder to prevent gelling of the starch paste
  • liquor 3(b) could be applied at room temperature. Both warps were subsequently lubricated on the sizing machine with a molten commercial grease.
  • the above two warps were then woven on similar looms and under the same conditions.
  • the warp sized with liquor 3(a) had an average of 47 broken ends per 100,000 picks, while the warp sized according to the invention with liquor 3(b) had an average of only 1.6 broken ends per 100,000 picks.
  • Each of these constitutes the mean values of observations made over approximately 500,000 picks.
  • the goods 5 f r wels was sized in one of two difl'erent sized with liquor 3(a) had to be subjected to a desizing l q n an pp machlue q pp W 1th a Y process lasting several hours in the presence of enzymatic l der dryer.
  • L1quor 6(a) compnsed a suspension of desizing agents, this being followed by open-width scour- Parts Of a com crclal starch der1vat1ve and 1.5 parts of ing, whereas the goods sized with liquor 3(b) simply r 10 an emuls1fiable fat 1n 490 parts of water, whlch had been quired a cold cour to remove the size boiled up for 10 minutes WhllC being Slill'ffid and then applied at 60 C.
  • Liquor 4(a) 1e r0021 e e 10 percent was prepared by boiling and stirring a suspension of 40 t g a vlseoslty of 1130 and a parts of potato starch and 25 parts of a chemically modi- P Va ue 0 fied starch with 335 parts of water for 1 hour.
  • Liquor ,T warps Slzed Wlth the orespeetlve hquors were 9 4(b) consisted of an 8 percent aqueous solution of the P F for 24 hours at 20 65 percent relatlve polymer described in Example 3.
  • Liquor 4( a) was applied hemldlty whereupon they were mvestlgated and eompared to the yam at c and liquor 4(b) at C an other with untreated yarn. The values 1n the followlng table conditions being identical. Investigation of the yarns in were obtamed: comparison with untreated yarn gave the values presented 25 in the fOllOWiHg table: Coating Elongaweight Breaking tion at (weight; Abrasion load break Coating Elon percent) number (g.) (percent) h B k t" t $3511?
  • Abrasion 132 b'ie k gfiggg g m g 662 11732 percent) number (g.) cent) T g H t ⁇ ; 1 0 1' 144 1 595 2 o a 1 I101 gg g 116 489 2 eliv 0. e 1, 554 1, 689 2. e
  • warp 6(b) which had been sized in accordance In assessing the weaving behavior of the two warps with the invention with a cold liquor, behaved better on practically no difference can be established without the WeaYmg than warp as shown by betterfiheddmg, less statistical determination of the number of broken ends, dustlng, and fewer k n ends.
  • Liquor 7(a) loom-state cloth sized with formulation 4(a) has to be This consi o sted of a hot (85 C.) aqueous preparation of i ig g fg i g gg gi gg 55 52 g i g g ggi g 30 parts of carboxymethylcellulose, 30 parts sodium polyf0 methacrylate solut1on (30 percent in water), 2 parts of open'wl or m rope mineral oil emulsion and 938 parts of water.
  • EXAMPLE 8 A polyester fiber/cotton blend (67/33) yarn (Nm. 69/1) was sized with two different liquors on the lab oratory sizing machine described in Example 1. Liquor 8(a) was obtained by boiling up a suspension of 230 parts of a commercial starch derivative and 16 parts of a commercial emulsified fat in 850 parts of water until the viscosity became approximately constant, this taking about 45 minutes. This liquor, which is representative of a commercially employed formulation, was applied at 90 C.
  • Liquor 8(b) was obtained by stirring 300 parts of an aqueous 30 percent solution of a copolymer of acrylic acid, sodium acrylate and acrylonitrile in the molar ratio of 1:2:1 (corresponding to the molar ratio of (a) :(b): 1:3) into 700 parts of water at room temperature; a percent solution of the polymer had a viscosity of 420 cp. and a pH value of 5.2. The liquor was applied to the yarn at room temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Woven Fabrics (AREA)
US612811A 1966-02-01 1967-01-31 Sizing cellulosic and acrylic staple fiber yarns with acrylonitrile/acrylic acid copolymer Expired - Lifetime US3519477A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1594905A DE1594905C3 (de) 1966-02-01 1966-02-01 Verwendung von wasserlöslichen Polymerisaten als Schlichtemittel

Publications (1)

Publication Number Publication Date
US3519477A true US3519477A (en) 1970-07-07

Family

ID=6983000

Family Applications (1)

Application Number Title Priority Date Filing Date
US612811A Expired - Lifetime US3519477A (en) 1966-02-01 1967-01-31 Sizing cellulosic and acrylic staple fiber yarns with acrylonitrile/acrylic acid copolymer

Country Status (9)

Country Link
US (1) US3519477A (en, 2012)
AT (1) AT269797B (en, 2012)
BE (1) BE693351A (en, 2012)
CH (1) CH467376A (en, 2012)
DE (1) DE1594905C3 (en, 2012)
FR (1) FR1603324A (en, 2012)
GB (1) GB1119133A (en, 2012)
NL (1) NL142211B (en, 2012)
SE (1) SE330679B (en, 2012)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770494A (en) * 1969-12-18 1973-11-06 Asahi Chemical Ind Modified acrylonitrile polymer fibers
US3844825A (en) * 1972-11-30 1974-10-29 American Cyanamid Co Method of producing an acrylic fiber having an improved touch like animal hair
US4167485A (en) * 1977-04-02 1979-09-11 Basf Aktiengesellschaft Water-soluble alkaline earth metal salts of polymers of acrylic acid, and their use as sizes
JPS60120773A (ja) * 1983-12-01 1985-06-28 Matsumoto Yushi Seiyaku Kk 経糸糊付用アルカリ糊化澱粉糊の中和剤
US20080020205A1 (en) * 2004-09-21 2008-01-24 Cordenka Gmbh Industrie Center Obernburg Free-Flowing Pellets Based on Cellulose Textile Fibers and a Method for the Production Thereof
CN102839476A (zh) * 2012-09-25 2012-12-26 江苏恒州特种玻璃纤维材料有限公司 一种高强高硅氧玻璃纤维纱的生产工艺

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2926230C2 (de) * 1979-06-29 1986-07-03 Basf Ag, 6700 Ludwigshafen Verfahren zum Schlichten von Stapelfasergarnen
US5208075A (en) * 1990-09-15 1993-05-04 Basf Aktiengesellschaft Sizing agent for staple fiber and filament yarns
DE4029348A1 (de) * 1990-09-15 1992-03-19 Basf Ag Verwendung von wasserloeslichen oder in wasser dispergierbaren gepfropften proteinen als schlichtemittel
CN108330687B (zh) * 2018-01-29 2020-09-18 西安工程大学 基于本体聚合法的热熔性纺织浆料制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2819189A (en) * 1954-11-15 1958-01-07 American Cyanamid Co Process of sizing textile yarn and product thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2819189A (en) * 1954-11-15 1958-01-07 American Cyanamid Co Process of sizing textile yarn and product thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770494A (en) * 1969-12-18 1973-11-06 Asahi Chemical Ind Modified acrylonitrile polymer fibers
US3844825A (en) * 1972-11-30 1974-10-29 American Cyanamid Co Method of producing an acrylic fiber having an improved touch like animal hair
US4167485A (en) * 1977-04-02 1979-09-11 Basf Aktiengesellschaft Water-soluble alkaline earth metal salts of polymers of acrylic acid, and their use as sizes
JPS60120773A (ja) * 1983-12-01 1985-06-28 Matsumoto Yushi Seiyaku Kk 経糸糊付用アルカリ糊化澱粉糊の中和剤
US20080020205A1 (en) * 2004-09-21 2008-01-24 Cordenka Gmbh Industrie Center Obernburg Free-Flowing Pellets Based on Cellulose Textile Fibers and a Method for the Production Thereof
US8419991B2 (en) * 2004-09-21 2013-04-16 Cordenka Gmbh & Co. Kg Free-flowing pellets based on cellulose textile fibers and a method for the production thereof
CN102839476A (zh) * 2012-09-25 2012-12-26 江苏恒州特种玻璃纤维材料有限公司 一种高强高硅氧玻璃纤维纱的生产工艺
CN102839476B (zh) * 2012-09-25 2014-12-03 江苏恒州特种玻璃纤维材料有限公司 一种高强高硅氧玻璃纤维纱的生产工艺

Also Published As

Publication number Publication date
FR1603324A (en) 1971-04-05
DE1594905C3 (de) 1979-07-05
NL142211B (nl) 1974-05-15
NL6701186A (en, 2012) 1967-08-02
CH467376A (de) 1969-02-28
BE693351A (en, 2012) 1967-07-31
AT269797B (de) 1969-04-10
DE1594905A1 (de) 1969-08-28
SE330679B (en, 2012) 1970-11-30
GB1119133A (en) 1968-07-10
DE1594905B2 (de) 1973-11-08
CH30667A4 (en, 2012) 1968-08-30

Similar Documents

Publication Publication Date Title
US3519477A (en) Sizing cellulosic and acrylic staple fiber yarns with acrylonitrile/acrylic acid copolymer
US3717689A (en) Process for improving the antistatic properties of hydrophobic synthetic fibers
US2807865A (en) Sized textile and method of fabricating yarn into fabric
US3981836A (en) Yarn sizes, sizing treatments and resulting sized yarns
US2717842A (en) Antistatic treatment and treated products
US3050419A (en) Process for fixing aminoplasts in the wet state on cellulosic fibrous materials
EP0063329A1 (en) Polyvinyl alcohol based size composition
US2566149A (en) Textile size containing polymethacrylic acid, a polymethacrylic acid salt, and a wetting agent
US4640946A (en) Polyvinyl alcohol based wax-free size composition
US2819189A (en) Process of sizing textile yarn and product thereof
US5626952A (en) Process for sizing spun yarns
US2845689A (en) Warp size containing dicyandiamide and a polyacrylate salt
US2802713A (en) Fugitive tinting of textile materials
US3983271A (en) Yarn sizes, sizing treatments and resulting sized yarns
US2909447A (en) Process of treating textile yarns
US3280039A (en) Aqueous bleaching solution
US2046885A (en) Textile material
US2694021A (en) Textile bearing a starch size
US3366509A (en) Textile process and composition
US3711323A (en) Textile size
US2697672A (en) Casein-copolymeric styrene-maleic anhydride type compositions for and method of sizing textile warp yarns
EP0173528B1 (en) Polyvinyl alcohol based wax-free size composition
US4167485A (en) Water-soluble alkaline earth metal salts of polymers of acrylic acid, and their use as sizes
US3984594A (en) Method for producing cellulosic fiber-containing yarns with a non-aqueous sizing solution
US5397633A (en) Process for sizing spun cotton yarns