US3928528A - Process for producing acrylic fibers having excellent pilling resistance - Google Patents

Process for producing acrylic fibers having excellent pilling resistance Download PDF

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US3928528A
US3928528A US385290A US38529073A US3928528A US 3928528 A US3928528 A US 3928528A US 385290 A US385290 A US 385290A US 38529073 A US38529073 A US 38529073A US 3928528 A US3928528 A US 3928528A
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fibers
acrylic fibers
treating agent
fiber
treated
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Zen-Ichi Orito
Minoru Uchida
Masatoshi Takesue
Hajime Sahara
Kihiro Fujii
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Mitsubishi Rayon Co Ltd
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    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/63—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with hydroxylamine or hydrazine
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/232—Organic carbonates
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/268—Sulfones
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/345—Nitriles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06Q—DECORATING TEXTILES
    • D06Q1/00—Decorating textiles
    • D06Q1/02—Producing patterns by locally destroying or modifying the fibres of a web by chemical actions, e.g. making translucent

Definitions

  • PROCESS FOR PRODUCING ACRYLIC FIBERS HAVING EXCELLENT PILLING RESISTANCE Inventors: Zen-ichi Orito; Minoru Uchida;
  • Acrylic fibers having excellent pilling resistance are disclosed.
  • the acrylic fibers have a plurality of elongated wedge shaped concave depressions extending into the fiber surface.
  • the acrylic fibers are produced by pre-treating acrylic fibers with a modifier to modify the outer layer of individual fiber and then aftertreating the fibers with an organic solvent for acrylic fiber.
  • the present invention relates to acrylic fibers having a plurality of elongated wedge shaped concave depressions extending into the fiber surface and process for producing the same.
  • fibers herein used includes the staple fibers, spun yarns, tow, knitted fabrics and woven fabrics.
  • Acrylic fibers have various excellent physical and chemical properties so that the fibers have been used in many fields including clothes.
  • acrylic fibers have a defect that when the knitted or woven fabrics made of acrylic fibers are worn for long time or just under an action of rubbing such as washing, pills are formed on the surface of the fabrics. This phenomenon is well known as pilling and the pills spoil the beautiful appearance of the fabrics. Therefore, prevention of pilling has been earnestly desired.
  • the method has been used of making the fiber surface rough by embossing the fibers.
  • the acrylic fibers obtained by this method have not been satisfactory from the point'of pilling resistance.
  • an object of the present invention is to provide acrylic fibers having excellent pilling resistance.
  • Another object of the present invention is to provide a process for'producing acrylic fibers having excellent pilling resistance.
  • acrylic fibers having excellent pilling resistance as well as other excellent fiber properties can be produced without losing the preferably fiber properties of acrylic fiber.
  • FIGS. 1, 2 and 3 are scanning electron microscopic photographs showing the concave depressions formed into the surface of fibers.
  • FIG. 4 illustrates the method of measuring depth of the depression.
  • the important characteristic of the fibers of the present invention is that the fibers have a plurality of elongated wedge shaped concave depressions extending into the surface thereof, the number of said depressions is more than 3 per inch along the length of an individual fiber and the elongated axis of said depressions is axially aligned in the lengthwise direction of the fiber by which pilling resistance of the fiber is extremely improved.
  • the concave depressions shown in scanning electron microphotographs of FIGS. 1 and 2 are somewhat different from the definite rhombic concaves shown in the photograph of FIG. 3 and this is due to the difference in spinning conditions. Therefore, the elongated wedge shaped concaves into the surface of the fibers of the present invention include those having the shapes as shown in FIGS. 1 and 2 and those having the shape as shown in FIG. 3,
  • Acrylic fibers of the present invention have a plurality of elongated wedge shaped concave depressions described hereinbefore.
  • the number of the concave depressions is preferably from 5 to 50 per inch along the length of an individual fiber.
  • the concave depressions are preferably in rhombic shape.
  • Length (a) of the major axis (elongated axis) of the individual depression is in the range of 0.5 2 to 20p. and the maximum depth (b) of the concave depressions is in the range of 0.2g. to 1011..
  • the major axis of the rhombic depressions is aligned in the direction offthe fiber axis and the minor axis of the rhombic depressions is aligned in the direction perpendicular to the fiber axis. 1
  • FIG. 4(A) is a schematic view of the concave depression and FIG. 4(13) is an inclined schematic view of FIG. 4(A) at an angle of 0.
  • p Distance from the point 0 to the end point x of major axis.
  • pf Distance from the point 0 to the end point x of major axis after inclination by 0.
  • a sample inclining apparatus (Goniometer specimen stage Type JSM-GS manufactured by Japan Electron Optics Laboratory Co., Ltd.) is used with an angle of inclination of 20.
  • the fibers of the present invention are produced, for example, by the following method.
  • acrylic fibers are produced from acrylonitrile homopolymer, copolymer of acrylonitrile with at least one other monomer copolymerizable with acrylonitrile or their blend by the conventional spinning methods.
  • the acrylonitrile copolymer preferably contains more than by weight of acrylonitrile and up to 20% by weight of at least one other monomer copolymerizable with acrylonitrile.
  • the other monomer includes vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene, vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, acrylamide,
  • methacrylamide methacrylonitrile, and monomers containing sulfoxyl group or their salts.
  • Acrylic fibers thus obtained are pre-treated with a modifier to modify the outer layer of individual fiber.
  • the outer layer of individual fiber is made insoluble in dimethyl formamide at 100C, and the pre-treatment is preferably carried out under such a condition that modified outer layer is 0.5 to 40% of the total cross sectional area of an individual fiber.
  • pre-treated acrylic fibers are after-treated with at least one organic treating agent which is nonsolvent for the modified outer layer, but is solvent for the un-modified inner layer of the acrylic fibers.
  • Method of said after-treatment with the organic treating agent is as follows: (A) The pre-treated acrylic fibers are immersed in the organic treating liquid and then washed with water and dried. (B) the pre-treated acrylic fibers are immersed in an aqueous organic treating liquid, then squeezed and heat treated, or (C) the pre-treated acrylic fibers are treated with a vapor of the organic treating agent.
  • the pre-treatment may be carried out on the acrylic fibers in a form of staple, tow, spun yarn, knitted or woven fabric.
  • Acrylic fibers of the present invention may be mix spun with other kind of fibers.
  • the present acrylic fibers are mix spun with fibers which are degraded with the modifier to be used, it is preferable that the present acrylic fibers are pre-treated with the modifier, mix spun with other kind of fibers and then after treated with the organic treating agent.
  • the cross sectional area of the modified outer layer is measured as follows: the sample of the pre-treated fibers is embedded in monomeric n-butyl methacrylate and heated to cause polymerization. A specimen of the cross section of the fibers is prepared by the same means as in the preparation by optical microscope. Thereafter, the specimen is immersed in dimethyl formamide at 100C. to dissolve unmodified inner layer of the fiber and the modified outer layer which remained insoluble is photographed with a scanning electron microscope. The sectional area is calculated from the photograph.
  • the modifiers to be used for the pre-treatment include, for example, saponifying agents such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sulfuric acid and chemical reacting agents such as hydroxylamine sulfate, and hydroxylamine phosphate.
  • saponifying agents such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sulfuric acid
  • chemical reacting agents such as hydroxylamine sulfate, and hydroxylamine phosphate.
  • the modification treatment is carried out so that area of the modified outer layer is 0.5 to 40% of cross sectional area of an individual acrylic fibers.
  • area of the modified outer layer is 0.5 to 40% of cross sectional area of an individual acrylic fibers.
  • suitable modification treatment may be carried out within the scope of the present invention.
  • Preferable organic treating agents for producing acrylic fibers of the present invention are as follows:
  • organic treating agents may be used singly or jointly in the form of 100% solution or dilute solution.
  • an inert viscosity increasing agent such as ethylene glycol or glycerine may be added thereto.
  • the pre-treated acrylic fibers are immersed in a solution of the organic treating agent.
  • the concentration of the solution is higher than treating temperature is 10 to C. and treating time is 2 minutes to 1 hour.
  • a mixture such as dimethyl formamide-ethylene carbonate, dimethyl acetamide-ethylene carbonate may be used.
  • the pretreated fibers are immersed in an aqueous solution of the organic treating agent.
  • the agents include dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide and ethylene carbonate. These organic treating agents may be preferably used in such a manner that amount of the agent adhered to the fibers immediately after squeezing is more than 15%, more preferably 15 to 100% of the weight of the dried fiber.
  • the heat treating temperature is preferably 50 to C.
  • concentration of the aqueous solution heating temperature and heating time, there is no special limitation.
  • the pre-treated fibers are exposed in a vapour of organic solvents for acrylic fibers having a boiling point of lower than 250C.
  • inorganic solvents may be used beside the organic solvents.
  • the organic solvents such as dimethyl formamide, dimethyl acetamide and dimethyl sulfoxide are the most preferably used.
  • the concave depressions are formed due to extraction of the unmodified inner layer (soluble in dimethyl formamide) through the modified outer layer (insoluble in dimethyl formamide) by the treatment with the organic treating agent.
  • the fibers In the knitted or woven fabrics of the acrylic fibers of the present invention, the fibers have particular concave depressions, which provide weak points in strength of the fibers to cause easy falling off of pills. As a result, prevention of pilling can be accomplished.
  • the concave depressions of the fibers of the present invention have an elongated wedge shape and the major axis of the depressions is aligned in the lengthwise direction of the fiber axis and the minor axis of the depression is aligned in the direction perpendicular to the fiber axis.
  • Said concave depressions extend into the surface of the fibers and are dispersed in the whole surface of the fibers. Therefore, contact area between single fibers is decreased and thus the knitted or woven fabrics have soft hand and excellent shape stability.
  • EXAMPLE I A polymer comprising 93% by weight of acrylonitrile and 7% by weight of vinyl acetate was spun by the conventional wet spinning method to obtain a tow having monofilamentary denier of 3 andtotal denier of 480,000. The tow was cut by the turbo stapler to obtain slivers (high bulk fibers). A part of said slivers were shrunk by a fiber setter to obtain regular fibers. Forty parts of the high bulk fibers and 60 parts of the regular fibers were worsted-spun to obtain high bulk two folded yarns (250/360 T/M) of 36 metric counts. Said high bulk yarns were pre-treated with 0.5% aqueous solution of sodium hydroxide at 90C.
  • microphotograph of the fibers treated with treating agent l in Table A by a scanning electron microscope is shown in FIG. 1.
  • a part of the pre-treated fibers were embedded in monomeric n-butyl methacrylate and heated to effect polymerization. Thereafter, a specimen of cross section of the fibers having a thickness of about 5 p was prepared. This specimen was immersed in dimethylformamide kept at 100C. to cause partial dissolution thereof. By this procedure, it was acknowledged that undissolved part was the outer layer of the fibers and the area of this outer layer was 21% of total cross sectional area.
  • the pre-treated fibers were immersed in dimethylformamide at 25C. for 5 minutes. Then, solvent was removed by washing with water and dried. Elongated wedge-shaped concave depressions, most of which were rhombic in shape, were intermittently formed extending into the surface of the fibers. The shapes of the concaves are shown in Table C. As referential Example, non-pretreated fibers were immersed in dimethylformamide at 25C. to cause dissolution of the fibers.
  • Table A I Concen- Tempera- Immersion Major axis Maximum depth Number of Treating agent tration ture time (a) o (b) of depression (70) ("C) (min.) depression 1.) depression 1) inch Dimethylformamide 98 25 5 12 0.5 2 40 Dimethylformamide 50/50 20 4 10 0.5 2 25 Ethylene carbonate Ethylene carbonate 90/i0 28 20 3 8 0.4 2 20 Water Dimethylacetamide 98 25 20 S l2 0 5 2 Acetonitrile 98 20 2 8 0.5 2 l8 EXAMPLE 2 Table C I Major axis (a) of Depth (b) of Number of The high bulk yarns produced by the same method as Fi rs depressi n (a) depression depression in Example 1 were pre-treated with aqueous solution of the modifiers shown in Table B to make the outer layer This Example 3 10 0.3 l 12 of the fibers insoluble in'dimethylformamide at 100C. ggzg' o o 0 Rat
  • a copolymer of 93% by weight of aerylonitrile and 7% by weight of vinyl acetate was spun by the conventional dryspinning methodto obtain staple fibers (3 deniers per filament'serni dull).
  • the staple fibers were EXAMPLE 4 30 minutes, and then bleached with 1% aqueous solution of acetic acid at 98C. for minutes, washed with water and dried.
  • the outer layer of the fibers was insoluble in dimethylformamide at 100C. and this insolubilized part was 21% of total cross sectional area of the fibers.
  • pre-treated high bulk yarns were immersed in 30% aqueous solution of dimethyiformamide kept at C. and then squeezed in such a manner that the amount of dimethyiformamide solution adhered tothe yarns was 70% of weight of dried fibers. Then, the yarns were heat treated for one hour in a drier kept at 90C. Said yarns were dyed and subjected to softening treatment and then were made into a sweater by 140 Full Fashion knitting machine. M
  • the concave depressions have a length of major axis of 1.2 to 7 p. and a depth of 0.4 to l p. and number depressions per 1 inch was 15.
  • Table D comparatively shows the test results on a knitted fabric obtained from conventional acrylic fibers.
  • EXAMPLE 5 36 counts (metric count) two folded yarns.
  • the yarns were immersed in aqueous solutions of the'treating agents in Table E and were squeezed in such a manner that the'amount of the solution adhered to the fibers was of weight of the dried fibers. Thereafter, the yarns were heat treated for l hour in a drier kept at C.
  • Acrylic fibers (3 dealers per filament) were pretreated with 2% aqueous soiution'of sodium hydroxide at 90C. for 30 minutes and then bleached with 2% aqueous solution of oxalic acid at 98C. for 15 minutes.
  • the outer layer of the fibers thus pro-treated was insoluble in dimethylformamide at 100C. and this outer layer was-21% of total cross sectional area of the fibers.
  • Said fibers were spun into two folded yarns (185/320 T/M) of 36 metric counts, which were exposed to saturated vapor of dimethylformamide at 100C. for 5 minutes, washed with water and dried.
  • treated yarns were dyed and subjected tosoftening-treatment and then made into knitted fabric.
  • elongated wedge-shaped concave depressions having a major axis of L341. to 5p. and a depth of 0.4 a to 0.8 a were formed. Numberof the depressions was 20/inch.
  • Said knitted fabric had an excellent pilling resistance as shown in Table F.
  • the outer layer of the fibers was Table G Vapor Length (a) of After treating temperature major axis of Maximum depth (b) Number of depression/inch agent ("C) depression (,u.) of depression (a) Dimethylformamide I 1.2 6 0.5 L 19 Dimethylsulfoxide 120 L0 8 0.5 1.5 20 Acetonitrile 8O [.4 10 0.4 L0 19 What is claimed is: r
  • a process for producing acrylic fibers having a plurality of elongated wedge shaped concave depressions extending into the surface thereof, the number of said depressions being more than 3 per inch along the length of an individual fiber and the elongated axis of said depressions being axially aligned in the lengthwise direction of the fiber which comprises 'pre-treating acrylic fibers with a modifier selected from the group consisting of alkali metal hydroxides, sulfuric acid and hydroxylamine salts to modify the outer portion of individual fiber to make the outer portion of individual fiber insoluble in dimethyl formamide at 100C.
  • an organic treating agent which is non-solvent for the modified outerportion, but is solvent for the unmodified inner portion of the acrylic fibers and which is selected from the group consisting of dimethyl formamide, dimethyl acetamide, dimethyl su1fon,-dimethyl sulfoxide, ethylene carbonate, acetonitrile, malonitrile and adiponitrile.
  • said organic treating agent is selected from the group consisting of a mixture of dimethyl formamide and ethylene carbonate and a mixture of dimethyl acetamide and ethylene carbonate.

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Abstract

Acrylic fibers having excellent pilling resistance are disclosed. The acrylic fibers have a plurality of elongated wedge shaped concave depressions extending into the fiber surface. The acrylic fibers are produced by pre-treating acrylic fibers with a modifier to modify the outer layer of individual fiber and then after-treating the fibers with an organic solvent for acrylic fiber.

Description

United States Patent Orito et a1.
PROCESS FOR PRODUCING ACRYLIC FIBERS HAVING EXCELLENT PILLING RESISTANCE Inventors: Zen-ichi Orito; Minoru Uchida;
Masatoshi Takesue; Hajime Sahara; Kihiro Flljii, all of Nagoya, Japan Mitsubishi Rayon Co., Ltd., Tokyo, Japan Filed: Aug. 3, 1973 Appl. No.: 385,290
Related US. Application Data Division of Ser. No. 146,148, May 24, 1971, Pat. No. 3,802,954.
Assignee:
Foreign Application Priority Data May 27, 1970 Japan 45-45502 June 5, 1970 Japan..... 45-48614 June 8, 1970 Japan..... 45-49308 June 12, 1970 Japan 45-50834 US. Cl. 264/344; 8/1 15.5; 8/130.1; 264/ 167; 264/ 182; 264/343 Int. Cl. B29C 25/00; DO6M 3/26 Field of Search 264/210 F, 182, 344, 343,
[ Dec. 23, 1975 [56] References Cited UNITED STATES PATENTS 2,590,402 3/1952 Hall et a1. 8/115.5 2,889,611 6/1959 Bedell 8/115.5 3,124,413 3/1964 Lowes...... 8/115.5 3,620,666 11/1971 Lenz et a1. 8/115.5 3,679,355 7/1972 Yamaguchi et a1 161/172 3,728,072 4/1973 Orito et a1. 8/115.5 3,752,648 8/1973 Shichijo et al. 8/1 15.5
Primary Examiner-Jay H. Woo Attorney, Agent, or Firm-Armstrong, Nikaido & Wegner [5 7] ABSTRACT Acrylic fibers having excellent pilling resistance are disclosed. The acrylic fibers have a plurality of elongated wedge shaped concave depressions extending into the fiber surface. The acrylic fibers are produced by pre-treating acrylic fibers with a modifier to modify the outer layer of individual fiber and then aftertreating the fibers with an organic solvent for acrylic fiber.
9 Claims, 5 Drawing Figures US. Patent Dec. 23, 1975 Sheet1of2 3,928,528
FIG
US Patent Dec. 23, 1975 She et20f2 3,928,528
PROCESS FOR PRODUCING ACRYLIC FIBERS HAVING EXCELLENT PILLING RESISTANCE This is a division of application Ser. No. 146,148, filed May 24, 1971 and now US. Pat. No. 3,802,954.
The present invention relates to acrylic fibers having a plurality of elongated wedge shaped concave depressions extending into the fiber surface and process for producing the same.
The term fibers herein used includes the staple fibers, spun yarns, tow, knitted fabrics and woven fabrics.
Acrylic fibers have various excellent physical and chemical properties so that the fibers have been used in many fields including clothes. However, acrylic fibers have a defect that when the knitted or woven fabrics made of acrylic fibers are worn for long time or just under an action of rubbing such as washing, pills are formed on the surface of the fabrics. This phenomenon is well known as pilling and the pills spoil the beautiful appearance of the fabrics. Therefore, prevention of pilling has been earnestly desired.
Many attempts have been made to prevent or eliminate the formation of pills on the surface of the fabrics.
For instance, such methods that particular conditions in fiber denier, fiber length and fiber cross section are used, or fibers are subjected to a finishing treatment with a resin have been used. However, satisfactory results have never been attained by such methods.
Further, in order to produce acrylic fibers having particular hand, the method has been used of making the fiber surface rough by embossing the fibers. However, the acrylic fibers obtained by this method have not been satisfactory from the point'of pilling resistance.
Accordingly, an object of the present invention is to provide acrylic fibers having excellent pilling resistance. 1
Another object of the present invention is to provide a process for'producing acrylic fibers having excellent pilling resistance. a i I Further objects of the present invention will be clear from the description that follows:
These objects of the present invention are achieved by pre-treating acrylic fibers with a modifier to make the outer layer of individual fiber insoluble in dimethyl formamide at 100C. and then after-treating the acrylic fibers with an organic treating agent whereby a plurality of elongated wedge shaped concave depressions extending into the fiber surface is formed.
According to the present invention, acrylic fibers having excellent pilling resistance as well as other excellent fiber properties can be produced without losing the preferably fiber properties of acrylic fiber.
FIGS. 1, 2 and 3 are scanning electron microscopic photographs showing the concave depressions formed into the surface of fibers. FIG. 4 illustrates the method of measuring depth of the depression.
As is shown in the scanning electron microphotographs of FIGS. 1, 2 and 3, the important characteristic of the fibers of the present invention is that the fibers have a plurality of elongated wedge shaped concave depressions extending into the surface thereof, the number of said depressions is more than 3 per inch along the length of an individual fiber and the elongated axis of said depressions is axially aligned in the lengthwise direction of the fiber by which pilling resistance of the fiber is extremely improved.
The concave depressions shown in scanning electron microphotographs of FIGS. 1 and 2 are somewhat different from the definite rhombic concaves shown in the photograph of FIG. 3 and this is due to the difference in spinning conditions. Therefore, the elongated wedge shaped concaves into the surface of the fibers of the present invention include those having the shapes as shown in FIGS. 1 and 2 and those having the shape as shown in FIG. 3,
Acrylic fibers of the present invention have a plurality of elongated wedge shaped concave depressions described hereinbefore.
The number of the concave depressions is preferably from 5 to 50 per inch along the length of an individual fiber. And the concave depressions are preferably in rhombic shape. Length (a) of the major axis (elongated axis) of the individual depression is in the range of 0.5 2 to 20p. and the maximum depth (b) of the concave depressions is in the range of 0.2g. to 1011.. The major axis of the rhombic depressions is aligned in the direction offthe fiber axis and the minor axis of the rhombic depressions is aligned in the direction perpendicular to the fiber axis. 1
The major axis and depth of the elongated Wedge shaped concave depressions in the fibers of the present invention are measured with a scanning electron microscope (.ISM Type II manufactured by Japan Electron Optics Laboratory Co., Ltd.). Depth of the concave depressions is measured by taking photographs of the depression at two different angles in the same field of vision and calculating the depth in accordance with the following equation in reference to FIG. 4. FIG; 4(A) is a schematic view of the concave depression and FIG. 4(13) is an inclined schematic view of FIG. 4(A) at an angle of 0.
wherein b; Maximum depth of the elongated wedge shaped concave depression. 1
p: Distance from the point 0 to the end point x of major axis. pf: Distance from the point 0 to the end point x of major axis after inclination by 0.
6: Angle of inclination of sample fiber.
For taking said two photographs, a sample inclining apparatus (Goniometer specimen stage Type JSM-GS manufactured by Japan Electron Optics Laboratory Co., Ltd.) is used with an angle of inclination of 20.
The fibers of the present invention are produced, for example, by the following method.
In the present invention, acrylic fibers are produced from acrylonitrile homopolymer, copolymer of acrylonitrile with at least one other monomer copolymerizable with acrylonitrile or their blend by the conventional spinning methods. The acrylonitrile copolymer preferably contains more than by weight of acrylonitrile and up to 20% by weight of at least one other monomer copolymerizable with acrylonitrile.
The other monomer includes vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene, vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, acrylamide,
methacrylamide, methacrylonitrile, and monomers containing sulfoxyl group or their salts.
Acrylic fibers thus obtained are pre-treated with a modifier to modify the outer layer of individual fiber. By this treatment, the outer layer of individual fiber is made insoluble in dimethyl formamide at 100C, and the pre-treatment is preferably carried out under such a condition that modified outer layer is 0.5 to 40% of the total cross sectional area of an individual fiber.
Then, thus pre-treated acrylic fibers are after-treated with at least one organic treating agent which is nonsolvent for the modified outer layer, but is solvent for the un-modified inner layer of the acrylic fibers. Method of said after-treatment with the organic treating agent is as follows: (A) The pre-treated acrylic fibers are immersed in the organic treating liquid and then washed with water and dried. (B) the pre-treated acrylic fibers are immersed in an aqueous organic treating liquid, then squeezed and heat treated, or (C) the pre-treated acrylic fibers are treated with a vapor of the organic treating agent.
The pre-treatment may be carried out on the acrylic fibers in a form of staple, tow, spun yarn, knitted or woven fabric.
Acrylic fibers of the present invention may be mix spun with other kind of fibers. When the present acrylic fibers are mix spun with fibers which are degraded with the modifier to be used, it is preferable that the present acrylic fibers are pre-treated with the modifier, mix spun with other kind of fibers and then after treated with the organic treating agent.
The cross sectional area of the modified outer layer is measured as follows: the sample of the pre-treated fibers is embedded in monomeric n-butyl methacrylate and heated to cause polymerization. A specimen of the cross section of the fibers is prepared by the same means as in the preparation by optical microscope. Thereafter, the specimen is immersed in dimethyl formamide at 100C. to dissolve unmodified inner layer of the fiber and the modified outer layer which remained insoluble is photographed with a scanning electron microscope. The sectional area is calculated from the photograph.
The modifiers to be used for the pre-treatment include, for example, saponifying agents such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sulfuric acid and chemical reacting agents such as hydroxylamine sulfate, and hydroxylamine phosphate.
The modification treatment is carried out so that area of the modified outer layer is 0.5 to 40% of cross sectional area of an individual acrylic fibers. However, actual conditions vary depending upon the kind of the modifiers, size of fibers, etc. Therefore, suitable modification treatment may be carried out within the scope of the present invention.
Preferable organic treating agents for producing acrylic fibers of the present invention are as follows:
i. Amide compounds dimethyl formamide, di-
methyl acetamide ii. Sulfon and sulfoxide compounds dimethyl sulfoxide, dimethyl sulfon iii. Carbonate compounds ethylene carbonate iv. Nitrile compounds malononitrile, adiponitrile,
acetonitrile These organic treating agents may be used singly or jointly in the form of 100% solution or dilute solution. Furthermore, an inert viscosity increasing agent such as ethylene glycol or glycerine may be added thereto.
Embodiments of the after-treating methods with these organic treating agents are as follows:
A. In the method where fibers are immersed in the treating agent, the pre-treated acrylic fibers are immersed in a solution of the organic treating agent. The concentration of the solution is higher than treating temperature is 10 to C. and treating time is 2 minutes to 1 hour. In this embodiment, a mixture such as dimethyl formamide-ethylene carbonate, dimethyl acetamide-ethylene carbonate may be used.
B. In the method where fibers are immersed in the organic agent, squeezed and then heat treated, the pretreated fibers are immersed in an aqueous solution of the organic treating agent. Representative examples of the agents include dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide and ethylene carbonate. These organic treating agents may be preferably used in such a manner that amount of the agent adhered to the fibers immediately after squeezing is more than 15%, more preferably 15 to 100% of the weight of the dried fiber. The heat treating temperature is preferably 50 to C. As to the concentration of the aqueous solution, heating temperature and heating time, there is no special limitation.
C. In the method where fibers are treated with a vapour of the organic agent, the pre-treated fibers are exposed in a vapour of organic solvents for acrylic fibers having a boiling point of lower than 250C.
As the solvents for acrylic fibers, inorganic solvents may be used beside the organic solvents. However, the organic solvents such as dimethyl formamide, dimethyl acetamide and dimethyl sulfoxide are the most preferably used. When the pre-treated fibers are after-treated with inorganic solvents, the fibers themselves are swollen or dissolved to cause adhesion between the fibers. Furthermore, inorganic solvents are vapourized with difficulty.
It is difficult to give a clear explanation of the mechanism of formation of the concave depressions extending into the fiber surface by treating the pre-treated acrylic fibers with the organic treating agent. However,
it is considered that the concave depressions are formed due to extraction of the unmodified inner layer (soluble in dimethyl formamide) through the modified outer layer (insoluble in dimethyl formamide) by the treatment with the organic treating agent.
In the knitted or woven fabrics of the acrylic fibers of the present invention, the fibers have particular concave depressions, which provide weak points in strength of the fibers to cause easy falling off of pills. As a result, prevention of pilling can be accomplished.
Furthermore, the concave depressions of the fibers of the present invention have an elongated wedge shape and the major axis of the depressions is aligned in the lengthwise direction of the fiber axis and the minor axis of the depression is aligned in the direction perpendicular to the fiber axis. Said concave depressions extend into the surface of the fibers and are dispersed in the whole surface of the fibers. Therefore, contact area between single fibers is decreased and thus the knitted or woven fabrics have soft hand and excellent shape stability.
The present invention will be illustrated by the Examples.
EXAMPLE I A polymer comprising 93% by weight of acrylonitrile and 7% by weight of vinyl acetate was spun by the conventional wet spinning method to obtain a tow having monofilamentary denier of 3 andtotal denier of 480,000. The tow was cut by the turbo stapler to obtain slivers (high bulk fibers). A part of said slivers were shrunk by a fiber setter to obtain regular fibers. Forty parts of the high bulk fibers and 60 parts of the regular fibers were worsted-spun to obtain high bulk two folded yarns (250/360 T/M) of 36 metric counts. Said high bulk yarns were pre-treated with 0.5% aqueous solution of sodium hydroxide at 90C. for 30 minutes, then bleached with 1% aqueous solution of acetic acid at 98C. for 15 minutes, washed with water and dried. The fibers were insoluble in dimethyl formamide at iO0C. Said insolubilized portion was 7% of total cross sectional area of the fiber.
Thus treated yarns were immersed at a liquid ratio of l 50 in the treating agents as shown in Table A to form concave depression having characteristics shown in Table A.
As one example, microphotograph of the fibers treated with treating agent l in Table A by a scanning electron microscope is shown in FIG. 1.
pre-treated with 2% aqueous solution of sodium hydroxide at 90C for 30 minutes, washed with water and dried.
A part of the pre-treated fibers were embedded in monomeric n-butyl methacrylate and heated to effect polymerization. Thereafter, a specimen of cross section of the fibers having a thickness of about 5 p was prepared. This specimen was immersed in dimethylformamide kept at 100C. to cause partial dissolution thereof. By this procedure, it was acknowledged that undissolved part was the outer layer of the fibers and the area of this outer layer was 21% of total cross sectional area.
The pre-treated fibers were immersed in dimethylformamide at 25C. for 5 minutes. Then, solvent was removed by washing with water and dried. Elongated wedge-shaped concave depressions, most of which were rhombic in shape, were intermittently formed extending into the surface of the fibers. The shapes of the concaves are shown in Table C. As referential Example, non-pretreated fibers were immersed in dimethylformamide at 25C. to cause dissolution of the fibers.
Table A I Concen- Tempera- Immersion Major axis Maximum depth Number of Treating agent tration ture time (a) o (b) of depression (70) ("C) (min.) depression 1.) depression 1) inch Dimethylformamide 98 25 5 12 0.5 2 40 Dimethylformamide 50/50 20 4 10 0.5 2 25 Ethylene carbonate Ethylene carbonate 90/i0 28 20 3 8 0.4 2 20 Water Dimethylacetamide 98 25 20 S l2 0 5 2 Acetonitrile 98 20 2 8 0.5 2 l8 EXAMPLE 2 Table C I Major axis (a) of Depth (b) of Number of The high bulk yarns produced by the same method as Fi rs depressi n (a) depression depression in Example 1 were pre-treated with aqueous solution of the modifiers shown in Table B to make the outer layer This Example 3 10 0.3 l 12 of the fibers insoluble in'dimethylformamide at 100C. ggzg' o o 0 Ratio of area of the outer layer to that oftotal sectional area of the fibers is also shown in Table B.
. Then, thus treated yams were immersed in 100% dimethylformamide at 25C for 20 minutes to obtain the fibers having concave depressions shown in Table B.
Table B Concen- Treating Area of Meier axis Maximum depth Number of Treating tration Temperature time outer layer (a) of (b) of depression agent (10 (C) (min) depression (a) deprelslon (u) inch Sodium 1.5 30 i5 3 8 0.5 L5 19 hydroxide 0.5 90 30 7 5 12 0.5 2.0 40 Potassium 3.0 95 30 i3 3 9 0.5 1.5 20 hydroxide I Sodium 1.5 95 30 i4 3 10 0.5 L5 20 hydroxide I Sulfuric 60.0 25 i5 18 1.0 5 0.3 0.8 l7
acid
EXAMPLE 3 obtained in this Example is shown in FIG. 3.
A copolymer of 93% by weight of aerylonitrile and 7% by weight of vinyl acetate was spun by the conventional dryspinning methodto obtain staple fibers (3 deniers per filament'serni dull). The staple fibers were EXAMPLE 4 30 minutes, and then bleached with 1% aqueous solution of acetic acid at 98C. for minutes, washed with water and dried. The outer layer of the fibers was insoluble in dimethylformamide at 100C. and this insolubilized part was 21% of total cross sectional area of the fibers.
Thus pre-treated high bulk yarns were immersed in 30% aqueous solution of dimethyiformamide kept at C. and then squeezed in such a manner that the amount of dimethyiformamide solution adhered tothe yarns was 70% of weight of dried fibers. Then, the yarns were heat treated for one hour in a drier kept at 90C. Said yarns were dyed and subjected to softening treatment and then were made into a sweater by 140 Full Fashion knitting machine. M
In the surface of the fibers, elongated wedge-shaped concave depressions were formed. The concave depressions have a length of major axis of 1.2 to 7 p. and a depth of 0.4 to l p. and number depressions per 1 inch was 15.
Said knitted fabric was tested by Random tumble type pilling tester and the results thereof are shown in Table D. It is clear from the Table D that the knitted fabric obtained in this Example had conspicuously excellent pilling resistance.
Table D comparatively shows the test results on a knitted fabric obtained from conventional acrylic fibers. i
Table D Fabric Piiiing resistance (grade) Fabric of this Example 5 Fabric of conventional acrylic fibers 2 3 Grade of pilling resistance was decided by surface changes resulted after operation of random su'mpic type tester for minutes in accordance with JiS'. L-ltilii- 5th grade No formation of pills and no change of surface A few pills and changes Medium number of pills and changes Many pills and changes Extremely many pills and changes 4th grade 3rd grade 2nd grade lst grade Furthermore, the knittedfabric obtained in this Example had soft hand and completely maintained excellent properties of acrylic fibers.
EXAMPLE 5 36 counts (metric count) two folded yarns. The yarns were immersed in aqueous solutions of the'treating agents in Table E and were squeezed in such a manner that the'amount of the solution adhered to the fibers was of weight of the dried fibers. Thereafter, the yarns were heat treated for l hour in a drier kept at C.
The states of the acrylic fibers in the yarns obtained are shown in Table E.
Acrylic fibers (3 dealers per filament) were pretreated with 2% aqueous soiution'of sodium hydroxide at 90C. for 30 minutes and then bleached with 2% aqueous solution of oxalic acid at 98C. for 15 minutes. The outer layer of the fibers thus pro-treated was insoluble in dimethylformamide at 100C. and this outer layer was-21% of total cross sectional area of the fibers.
Said fibers were spun into two folded yarns (185/320 T/M) of 36 metric counts, which were exposed to saturated vapor of dimethylformamide at 100C. for 5 minutes, washed with water and dried. Thus treated yarns were dyed and subjected tosoftening-treatment and then made into knitted fabric. in the fiber surface of this knitted fabric, elongated wedge-shaped concave depressions having a major axis of L341. to 5p. and a depth of 0.4 a to 0.8 a were formed. Numberof the depressions was 20/inch.
Said knitted fabric had an excellent pilling resistance as shown in Table F.
. Table F Filling resistance Knitted fabric of this Example ,5th grade EXAMPLE 7 Acrylic fiber two folded spun yarns (250/360 TIM) of 32 metric counts were immersed in a mixed aqueous solution of 10% of glycerine and 10% sulfuric acid, and then squeezed. Thereafter, the yarns were heated at C. for 10 minutes to pre=treat the yearns, washed with water and dried. The outer layer of the fibers was Table G Vapor Length (a) of After treating temperature major axis of Maximum depth (b) Number of depression/inch agent ("C) depression (,u.) of depression (a) Dimethylformamide I 1.2 6 0.5 L 19 Dimethylsulfoxide 120 L0 8 0.5 1.5 20 Acetonitrile 8O [.4 10 0.4 L0 19 What is claimed is: r
l. A process for producing acrylic fibers having a plurality of elongated wedge shaped concave depressions extending into the surface thereof, the number of said depressions being more than 3 per inch along the length of an individual fiber and the elongated axis of said depressions being axially aligned in the lengthwise direction of the fiber, which comprises 'pre-treating acrylic fibers with a modifier selected from the group consisting of alkali metal hydroxides, sulfuric acid and hydroxylamine salts to modify the outer portion of individual fiber to make the outer portion of individual fiber insoluble in dimethyl formamide at 100C. and then after-treating the fibers with an organic treating agent which is non-solvent for the modified outerportion, but is solvent for the unmodified inner portion of the acrylic fibers and which is selected from the group consisting of dimethyl formamide, dimethyl acetamide, dimethyl su1fon,-dimethyl sulfoxide, ethylene carbonate, acetonitrile, malonitrile and adiponitrile.
2. A process according to claim 1, wherein said acrylic fibers are pre-treatedwith said modifier, and then immersed in an 85100% solution of said organic treating agent at a temperature of lO100C.
3. A process according to claim 1, wherein said acrylic fibers are pretreated with said modifier, and
then immersed in a 30-IOO% solution of said organic treating agent, squeezed and then heat treated at a temperature of from l20C.
4. .A process according t0 claim 1, wherein said acrylic fibers are pre-treated with said modifier and then treated withv a vapour of said organic treating agent. r
5. A process according to claim 1, wherein said organic treating agent is selected from the group consisting of a mixture of dimethyl formamide and ethylene carbonate and a mixture of dimethyl acetamide and ethylene carbonate.
6. A process according to claim 3, wherein the amount of said organic treating agent adhered to the fibers immediately after said squeezing is more than 15% of the weight of dried fiber.
7. A process according to claim 6, wherein the amount of said organic treating agent adhered to the fibers immediately after said squeezing is 15-100% of the weight of dried fiber.
8. The process of claim 2 wherein said solution of organic treating agent is an aqueous solution.
9. The. process of claim 3 wherein said solution of organic treating agent is an aqueous solution.

Claims (9)

1. A PROCESS FOR PRODUCING ACRYLIC FIBERS HAVING A PLURALITY OF ELONGATED WEDGE SHAPED ONCAVE DEPRESSIONS EXTENDING INTO THE SURFACE THEREOF, THE NUMBER OF SAID DEPRESSIONS BEING MORE THAN 3 PER INCH ALONG THE LENGTH OF AN INDIVIDUAL FIBER AND THE ELONGATED AXIS OF SAID DEPRESSIONS BEING AXIALLY ALIGNED IN THE LENGTHWISE DIRECTION OF THE FIBER, WHICH COMPRISES PRETREATING ACRYLIC FIBERS WITH A MODIFIER SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL HYDROXIDES, SULFURIC ACID AND HYDROXYLAMINE SALTS TO MODIFY THE OUTER PORTION OF INDIVIDUAL FIBER TO MAKE THE OUTER PORTION OF INDIVIDUAL FIBER INSOLUBLE IN DIMETHYL FORMAMIDE AT 100*C. AND THEN AFTER-TREATING THE FIBER TO WITH AN ORGANIC TREATING AGENT WHICH IS NON-SOLVENT FOR THE MODIFIED OUTER PORTION, BUT IS SOLVENT FOR THE UNMODIFIED INNER PORTION OF THE ACRYLIC FIBERS AND WHICH IS SELECTED FROM THE GROUP CONSISTING OF DIMETHYL FORMAMIDE, DIMETHYL ACETAMIDE, DIMETHYL SULFON, DIMETHYL SULFOXIDE, ETHYLENE CARBONATE, ACETONITRILE, MALONITRILE AND ADIPONITRILE.
2. A process according to claim 1, wherein said acrylic fibers are pre-treated with said modifier, and then immersed in aN 85-100% solution of said organic treating agent at a temperature of 10*-100*C.
3. A process according to claim 1, wherein said acrylic fibers are pre-treated with said modifier, and then immersed in a 30-100% solution of said organic treating agent, squeezed and then heat treated at a temperature of from 50*-120*C.
4. A process according to claim 1, wherein said acrylic fibers are pre-treated with said modifier and then treated with a vapour of said organic treating agent.
5. A process according to claim 1, wherein said organic treating agent is selected from the group consisting of a mixture of dimethyl formamide and ethylene carbonate and a mixture of dimethyl acetamide and ethylene carbonate.
6. A process according to claim 3, wherein the amount of said organic treating agent adhered to the fibers immediately after said squeezing is more than 15% of the weight of dried fiber.
7. A process according to claim 6, wherein the amount of said organic treating agent adhered to the fibers immediately after said squeezing is 15-100% of the weight of dried fiber.
8. The process of claim 2 wherein said solution of organic treating agent is an aqueous solution.
9. The process of claim 3 wherein said solution of organic treating agent is an aqueous solution.
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US5418284A (en) * 1989-05-08 1995-05-23 Cytec Technology Corp. Surface-modified polyacrylonitrile beads
US6051034A (en) * 1998-09-30 2000-04-18 Springs Industries, Inc. Methods for reducing pilling of towels

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* Cited by examiner, † Cited by third party
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US4061834A (en) * 1976-06-03 1977-12-06 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Durable antistatic coating for polymethylmethacrylate
US5418284A (en) * 1989-05-08 1995-05-23 Cytec Technology Corp. Surface-modified polyacrylonitrile beads
US6051034A (en) * 1998-09-30 2000-04-18 Springs Industries, Inc. Methods for reducing pilling of towels

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