WO2016031820A1 - Glossy pilling-resistant acrylic fiber, method for producing same, and spun yarn and knitted fabric including said acrylic fiber - Google Patents

Glossy pilling-resistant acrylic fiber, method for producing same, and spun yarn and knitted fabric including said acrylic fiber Download PDF

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Publication number
WO2016031820A1
WO2016031820A1 PCT/JP2015/073883 JP2015073883W WO2016031820A1 WO 2016031820 A1 WO2016031820 A1 WO 2016031820A1 JP 2015073883 W JP2015073883 W JP 2015073883W WO 2016031820 A1 WO2016031820 A1 WO 2016031820A1
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Prior art keywords
fiber
mass
less
acrylic fiber
dtex
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PCT/JP2015/073883
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French (fr)
Japanese (ja)
Inventor
志茉 中西
秀人 団
慎吾 中橋
透雄 小野原
達彦 稲垣
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三菱レイヨン株式会社
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Application filed by 三菱レイヨン株式会社 filed Critical 三菱レイヨン株式会社
Priority to EP15837071.8A priority Critical patent/EP3187629A4/en
Priority to US15/502,654 priority patent/US20170233897A1/en
Priority to JP2015543180A priority patent/JP6145723B2/en
Priority to KR1020177000002A priority patent/KR101913970B1/en
Priority to CN201580035557.1A priority patent/CN106661771B/en
Publication of WO2016031820A1 publication Critical patent/WO2016031820A1/en

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/20—Physical properties optical

Definitions

  • the present invention relates to an acrylic fiber having excellent gloss, soft texture and anti-pilling property, a method for producing the same, and a spun yarn and a knitted fabric containing the acrylic fiber.
  • Acrylic fibers have excellent characteristics such as soft texture, heat retention, form stability, weather resistance, and dyeability. Like synthetic fibers such as nylon fibers and polyester fibers, acrylic fibers are used in clothing and interior fields. It is used a lot. However, the fiber product made of this acrylic fiber has a problem that pilling is likely to occur during wearing, and the appearance and texture of the knitted fabric are remarkably impaired and the commercial value is lowered. For some time, acrylic fibers have been required to improve so-called anti-pilling property, in which pilling hardly occurs.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 11-222716 discloses that a thick fiber acrylic fiber having a single fiber fineness of 6 to 34 dtex has a flat fiber cross section and a smooth surface of a certain area or more on the fiber surface.
  • Patent Document 2 Japanese Patent Laid-Open No. 2012-36512
  • the cross section of the fiber has a circular or oval outer edge that is nearly circular, and a curved portion that is recessed inward.
  • Some forms of glossy fibers have been proposed.
  • Each of these fibers was a thick fiber having a single fiber fineness of 6 dtex or more, or a flat or broad bean-shaped cross section.
  • Patent Document 3 Japanese Patent Laid-Open No. 2006-176937
  • Patent Document 4 Japanese Patent Laid-Open No. 2008-38309 propose a spun yarn containing an anti-pill fine acrylic fiber and a method for producing the same. ing. However, it was not a fine-fine acrylic fiber having both anti-pilling properties and glossiness.
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2011-12363 proposes an acrylic fiber having a carbon fiber precursor acrylic fiber with less irregularities on the fiber surface and a single fiber fineness of 1.1 dtex. However, since the strength of the carbon fiber precursor acrylic fiber is increased, the knot strength and the knot elongation are small. For this reason, the carbon fiber precursor acrylic fiber was not able to be formed into a spun yarn because of many fiber breakage in the spinning process.
  • the present invention provides an acrylic fiber of 0.5 dtex or more and 3.5 dtex or less excellent in gloss, anti-pill property and soft texture, a method for producing the same, and a spun yarn and a knitted fabric containing the acrylic fiber.
  • the acrylic fiber of the present invention has a single fiber surface centerline average roughness (Ra) of 3 nm to 12 nm and a single fiber fineness of 0.5 dtex to 3.5 dtex.
  • the product K of the value of knot strength (cN / dtex) and the value of knot elongation (%) is preferably 10 or more and 30 or less.
  • the acrylic fiber of the present invention has a single fiber surface centerline average roughness (Ra) of 3 nm to 12 nm, and the product K of the value of knot strength (cN / dtex) and the value of knot elongation (%). Is 10 or more and 30 or less.
  • the acrylic fiber of the present invention preferably has a single fiber fineness of 0.5 dtex or more and 3.5 dtex or less.
  • the maximum height difference (Ry) of the surface of the single fiber is 40 nm or more and 150 nm or less
  • the 30-point average roughness (Rz) is 20 nm or more and 80 nm or less
  • the distance between the vertices of the convex portion on the surface of the single fiber ( S) is preferably 800 nm or more and 1100 nm or less.
  • the acrylic fiber of the present invention preferably has 10 or less recesses having a depth of 0.1 ⁇ m or more on the surface of the single fiber in a cross section perpendicular to the fiber axis.
  • the acrylic fiber of the present invention has an acrylonitrile unit of 92% by mass to 96.8% by mass, a vinyl monomer unit of 2% by mass to 6% by mass, and a sulfonic acid group-containing vinyl monomer unit of 0.2% by mass to 2.0%.
  • the elongation is preferably 8% or more and 20% or less.
  • the method for producing an acrylic fiber of the present invention comprises an acrylonitrile copolymer containing 92% by mass or more and 96.8% by mass or less of an acrylonitrile unit and 0.2% by mass or more and 2.0% by mass or less of a sulfonic acid group-containing vinyl monomer unit.
  • the combined solution is dissolved in an organic solvent to form a spinning dope, and the spinning dope is discharged into a coagulation bath having a temperature of 35 ° C. or more and 50 ° C. or less at a jet stretch of 0.4 or more and 2.2 or less from a plurality of discharge holes of a spinning nozzle.
  • the coagulated fiber bundle is stretched at a draw ratio of 2 to 3.8 times in hot water at 80 ° C.
  • the temperature is set to 150 ° C. or more and 170 ° C. or less and stretched by dry heat at a draw ratio of 1.2 to 3 times, and the product S of the hot water draw ratio and the dry heat draw ratio is set to 4 to 6 times.
  • the acrylonitrile-based copolymer further includes 2% by mass to 6% by mass of a vinyl monomer unit, and the solvent concentration of the coagulation bath is 40% by mass to 60% by mass.
  • the annealing temperature of the thermal relaxation treatment is 120 ° C. or higher and 135 ° C. or lower, and the fiber relaxation rate is 5% or higher and 20% or lower.
  • the spun yarn of the present invention contains 40% by mass or more of the acrylic fiber, and the yarn count is 40 to 70.
  • the spun yarn of the present invention preferably contains 10 to 40% by mass of cellulosic fibers.
  • the knitted fabric of the present invention contains 40% by mass or more of the spun yarn, has a basis weight of 150 g / m 2 or more and 230 g / m 2 or less, and has an anti-pill performance of 4 or more.
  • the knitted fabric of the present invention preferably has a heat retention rate of 15% or more and 50% or less.
  • an acrylic fiber capable of obtaining a textile product having a soft texture, a high-grade glossiness, and a good anti-pilling property, particularly in apparel for innerwear such as underwear.
  • the copolymer constituting the acrylic fiber of the present invention preferably has 92% by mass or more and 96.8% by mass or less of acrylonitrile units copolymerized. If the copolymerization rate of the acrylonitrile unit is 92% by mass or more, the fiber strength required as a fiber for clothing is easily obtained. From this viewpoint, the copolymerization rate of acrylonitrile units is more preferably 95% by mass or more. Further, when the copolymerization ratio of the acrylonitrile unit is 96.8% by mass or less, dyeability, fiber strength, and elongation are easily obtained.
  • the copolymerization rate of the vinyl-type monomer unit copolymerizable with acrylonitrile is 3.0 mass% or more and 6.0 mass% or less. If the copolymerization rate of vinyl monomer units is within this range, sufficient physical properties and dyeability can be obtained as a knitted fabric product. Further, the copolymer preferably has a copolymerization rate of the sulfonic acid group-containing vinyl monomer of 0.2% by mass or more and 2.0% by mass or less. If the copolymerization rate of the sulfonic acid group-containing vinyl monomer is 0.2% by mass or more, the dyeability is easily improved, and if it is 2.0% by mass or less, the increase in cost can be reduced.
  • Examples of vinyl monomers copolymerizable with acrylonitrile include methyl acrylate, methyl methacrylate, or their (meth) acrylic acid esters, vinyl acetate, styrene, acrylic acid amide, 2-hydroxyethyl methacrylate, glycidyl methacrylate, etc. Is mentioned.
  • Examples of the sulfonic acid group-containing vinyl monomer include allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, or metal salts and amine salts thereof. Etc. are preferably used, but the present invention is not limited to the monomers listed here.
  • the polymerization method for obtaining such an acrylonitrile copolymer is preferably a suspension polymerization method carried out in an aqueous medium.
  • the single fiber fineness of the acrylic fiber of the present invention is preferably 0.5 dtex or more and 3.5 dtex or less. Generally, when the fiber is thin, the dyeing sharpness tends to be lowered. However, the acrylic fiber of the present invention has dyeing sharpness even if it is 1.2 dtex or less. If the single fiber fineness is 0.5 dtex or more, the effect of dyeing clarity is likely to appear, and if it is 3.5 dtex or less, a soft texture is easily obtained when knitted. From these viewpoints, the single fiber fineness is more preferably 0.7 dtex or more and 2.0 dtex or less, and further preferably 0.8 dtex or more and 1.2 dtex or less.
  • the acrylic fiber of the present invention preferably has a product K of 10 to 30 in terms of the value of knot strength (cN / dtex) and the value of knot elongation (%).
  • the value of the product K is a value used by those skilled in the art as an index of anti-pill property.
  • the product K is 10 or more, the occurrence of fly that finely cuts the single fiber in the spinning process is reduced, and if it is 30 or less, the anti-pill property is good. From this viewpoint, the product K is more preferably 12 or more and 25 or less, and further preferably 14 or more and 20 or less.
  • the acrylic fiber of the present invention has excellent gloss because there are few grooves on the fiber surface.
  • the center line average roughness (Ra) of the surface of the single fiber is 3 nm or more and 12 nm or less. If the Ra is 3 nm or more, friction between the roll and the fiber is generated during spinning, and slippage in the roll is less likely to occur, and if it is 12 nm or less, gloss is easily developed, which is preferable. From this viewpoint, the Ra is more preferably 4 nm or more and 10 nm or less, and further preferably 5 nm or more and 9 nm or less.
  • the maximum height difference (Ry) of the surface of the single fiber is 40 nm or more and 150 nm or less
  • the 30-point average roughness (Rz) is 20 nm or more and 80 nm or less
  • the distance between the vertices of the convex portion on the surface of the single fiber ( S) is preferably 800 nm or more and 1100 nm or less.
  • the Ry is 40 nm or more, friction occurs between the fibers and the processability in the spinning process is good, and when the Ry is 150 nm or less, specular reflection is likely to occur. From this viewpoint, the Ry is more preferably 50 nm to 100 nm, and further preferably 55 nm to 90 nm.
  • the Rz is 20 nm or more, it is preferable in terms of good passability during spinning, and if it is 80 nm or less, it is preferable in terms of improving glossiness. From this viewpoint, the Rz is more preferably 30 nm to 65 nm, and more preferably 35 nm to 50 nm.
  • S is 800 nm or more, it is preferable from the viewpoint of spinnability, and if it is 1100 nm or less, it is preferable from the viewpoint that the number of irregularities on the fiber surface is small and irregular reflection hardly occurs. From the viewpoint, the S is more preferably 900 nm or more and 1000 nm or less.
  • the acrylic fiber of the present invention preferably has 10 or less recesses having a depth of 0.1 ⁇ m or more on the surface of the single fiber in a cross section perpendicular to the fiber axis.
  • the depth of the recesses is good when the number of recesses having a depth of 0.1 ⁇ m or more on the fiber surface is 10 or less when the cross section perpendicular to the fiber axis direction is observed by a method described later. It is preferable. If there is a recess having a depth of 0.1 ⁇ m or more on the fiber surface, diffuse reflection of light occurs.
  • the number of recesses of 0.1 ⁇ m or more is 10 or less in the fiber cross section, the irregular reflection of light can be reduced and the gloss is hardly lowered, so that the gloss is easily obtained.
  • the number of recesses of 0.1 ⁇ m or more is more preferably 5 or less. In order to reduce the unevenness of the fiber surface, it is effective to lower the draw ratio when the coagulated fiber is drawn by wet heat.
  • the single fiber tensile strength of the acrylic fiber of the present invention is preferably 1.8 cN / dtex or more, more preferably 2.0 cN / dtex or more, from the viewpoint of passing through a processing step such as a spinning step.
  • the upper limit of the tensile strength is not particularly limited, but 3.0 cN / dtex is sufficient.
  • the single fiber knot strength of the acrylic fiber of the present invention is preferably 1.0 cN / dtex or more and 1.8 cN / dtex or less. If the knot strength is 1.0 cN / dtex or more, the occurrence of fly in the spinning process is reduced and the processing process is good, and if the knot strength is 1.8 cN / dtex or less, the anti-pill performance. Tends to be good. From this viewpoint, the knot strength is more preferably 1.2 cN / dtex or more and 1.6 cN / dtex or less, and further preferably 1.4 cN / dtex or more and 1.5 cN / dtex or less.
  • the single fiber nodule elongation of the acrylic fiber of the present invention is preferably 8% or more and 20% or less, more preferably 15% or less, from the viewpoint of enhancing the anti-pill property.
  • the acrylic fiber of the present invention can be obtained by a wet spinning method or a dry-wet spinning method, but the wet spinning method is desirable in terms of productivity and cost.
  • the method for producing acrylic fibers of the present invention comprises 92% by mass or more and 96.8% by mass or less of acrylonitrile units, 2% by mass or more and 6% by mass or less of vinyl monomer units, and 0.2% of vinyl monomer units containing sulfonic acid groups. It is preferable to use an acrylonitrile-based copolymer containing from mass% to 2.0 mass%.
  • the acrylonitrile copolymer is dissolved in an organic solvent to obtain a spinning dope.
  • the spinning dope is preferably composed of 15% by mass to 30% by mass of an acrylonitrile copolymer and 70% by mass to 85% by mass of an organic solvent. If the concentration of the acrylonitrile copolymer in the spinning dope is 15% by mass or more and 30% by mass or less, the spinning property is favorable from the viewpoint of yarn breakage and productivity.
  • the concentration of the copolymer is more preferably 18% or more and 25% or less from the viewpoint of spinnability.
  • the organic solvent must be an organic solvent such as dimethylacetamide, dimethylformamide, dimethyl sulfoxide. Among them, dimethylacetamide is preferable from the viewpoint of the balance between productivity in fiber production, dyeing clarity of the obtained anti-pill acrylic fiber, and anti-pill performance.
  • the acrylonitrile copolymer is dissolved in an organic solvent at a temperature of 40 ° C. or higher, the amount of undissolved component is small, and accordingly, the use period of the filter medium in a filter equipment such as a filter press can be extended, and the spinnability is impaired. This is preferable because there is not.
  • the dissolution temperature is 95 ° C. or lower, it is preferable because the copolymer is hardly discolored.
  • the temperature of the spinning dope after dissolving the acrylonitrile copolymer in an organic solvent is preferably 40 ° C. or higher and 95 ° C. or lower.
  • the temperature is 40 ° C. or more and 95 ° C. or less, there is no spinnability of the spinning dope, no increase in nozzle pressure due to low viscosity, gelation of the spinning dope, and the spinnability is good.
  • the spinning solution is discharged from a plurality of discharge holes of a spinning nozzle into a coagulation bath having a solvent concentration of 40% by mass to 60% by mass and a temperature of 35 ° C. to 50 ° C. to obtain a coagulated fiber bundle. If the range of the solvent concentration and temperature is within the above ranges, solidification does not become too fast, and the number of recesses on the fiber surface tends to decrease.
  • the jet stretch when discharging from the discharge hole of the spinning nozzle is preferably 0.4 or more and 2.2 or less.
  • the jet stretch is a value obtained by dividing the take-up speed of the coagulated yarn by the discharge linear speed. If the jet stretch is 0.4 or more and 2.2 or less, it is preferable in that the yarn breakage during spinning is small and the spinnability is good. From the viewpoint, the jet stretch is more preferably 0.6 or more and 2.0 or less.
  • the solidified fiber bundle is stretched in hot water at a stretch ratio of 2 to 4 times, provided with an oil agent, dried, and then stretched at a stretch ratio of 1.2 to 3 times by dry heat.
  • the product S of the draw ratio in water and the draw ratio in the dry heat is 4 to 6 times.
  • the draw ratio by dry heat is 1.2 times or more, the concave portion of the fiber surface is extended, the smooth surface is increased, and the glossiness is improved. If it is 3 times or less, the anti-pill property is good, and this is preferable in that yarn breakage due to spinning is reduced. From the viewpoint of reducing the number of concave portions on the fiber surface and improving gloss, the draw ratio with dry heat is more preferably 1.5 or more, and even more preferably 1.7 or more. Moreover, 2 times or less is preferable from the point of process passage property.
  • the product S is 4 times or more and 6 times or less, it is preferable in terms of good passability of spinning and the like and having an appropriate fiber strength. Also, the anti-pill performance tends to be good.
  • the product S is more preferably 4.5 or more and 5.5 times or less.
  • ⁇ Hot water temperature, dry heat drawing fiber temperature> The temperature of hot water when stretching in the hot water is preferably 80 ° C. or higher and 98 ° C. or lower. If it is this range, the cutting
  • the fiber temperature at the time of stretching with dry heat is preferably 150 ° C. or more and 170 ° C. or less. If it is 150 degreeC or more, it will become easy to extend the wrinkle on the fiber surface, and if it is 170 degreeC or less, the discoloration by a heat
  • Examples of means for heating the fiber bundle when stretching by dry heat include contact heating with a heating roll, a hot plate, and non-contact heating with hot air.
  • a heating roll is preferable as a means for heating the fiber bundle in that it can be efficiently heated.
  • what is necessary is just to set suitably with the time when the temperature of a heating roll and a fiber bundle contact a heating roll when heating with a heating roll. It is preferable to heat both sides of the fiber bundle through a plurality of heating rolls.
  • the temperature of a heating roll is 150 degreeC or more and 190 degrees C or less. If the said temperature is 190 degrees C or less, discoloration by the heat
  • the fiber bundle subjected to dry heat drawing is crimped and stored in a container.
  • the degree of swelling of the fiber drawn with hot water is in the range of 80% to 130%. If the degree of swelling is 80% or more and 130% or less, it is preferable in terms of good drying properties and productivity, and wrinkles on the fiber surface tend to be reduced.
  • Heat relaxation treatment is performed so that the thermal shrinkage rate of the fiber is 5% or more and 20% or less to obtain an acrylic fiber.
  • the thermal relaxation condition is defined by the thermal shrinkage rate of the fiber. If the thermal shrinkage of the fiber is 5% or more and 20% or less, it is preferable in terms of knot strength and knot elongation at which anti-pill property is maintained.
  • the heat shrinkage rate is a ratio of shrinkage of the fiber bundle before and after the heat relaxation treatment.
  • the temperature for heat relaxation is 120 ° C or higher and 135 ° C or lower. If the pressure is 120 ° C. or higher, it is preferable in terms of obtaining single fiber strength and single fiber elongation with good card passing properties during spinning, and if it is 135 ° C. or lower, a single fiber having good anti-pill properties is obtained. It is preferable at the point obtained.
  • the acrylic fiber bundle of the present invention obtained by the above production method is cut with a cutter to make short fibers, and then spun.
  • the composition of the spun yarn may be 100% of the acrylic fiber of the present invention, and other fibers, for example, synthetic fibers such as ordinary acrylic fiber, polyester fiber, nylon fiber, rayon fiber or chemical fiber, cotton, wool, silk It is also possible to make a spun yarn by blending with natural fibers such as
  • the content of the acrylic fiber of the present invention contained in the spun yarn is preferably 40% by mass or more. Even if the content is 40% by mass or more, the glossiness and anti-pill performance of the acrylic fiber of the present invention are likely to appear. From this viewpoint, the content is more preferably 60% by mass or more, and further preferably 80% by mass or more.
  • the yarn count of the spun yarn is preferably a cotton count and 40 to 70. If the yarn count is 40 or more, the fabric is easy to soften due to the thin fineness effect of the acrylic fiber of the present invention. Moreover, if it is 70th or less, it will be easy to obtain intensity
  • the CV% of the yarn unevenness of the spun yarn is preferably 11.5 or less. When the CV% is 11.5 or less, the appearance of the knitted fabric is clean and gloss is improved. The CV% is more preferably 11 or less, and even more preferably 10 or less.
  • the spun yarn of the present invention preferably has a cellulosic fiber content of 10% by mass or more and 40% by mass or less. If the content of the cellulosic fiber is 10% by mass or more, the hygroscopic exothermic property is preferable, and if it is 40% by mass or less, the anti-pill property and the heat retaining property are preferable.
  • the content of the spun yarn is preferably 40% by mass or more. If the said content rate is 40 mass% or more, the gloss of a knitted fabric and the effect of an anti-pill property will be easy to be acquired. In view of the above, 50% by mass or more is more preferable, and 60% by mass or more is more preferable.
  • the fabric of the present invention preferably has a basis weight of 150 g / m 2 or more and 230 g / m 2 or less. If the basis weight is 150 g / m 2 or more, the knitted fabric is strong and difficult to tear, and if it is 230 g / m 2 or less, the underwear is light and the soft knitted fabric can be obtained.
  • the knitted fabric of the present invention preferably has an anti-pill performance of 4th grade or higher. If the anti-pilling property is 4th grade or higher, there are few hairballs and the knitted fabric looks beautiful.
  • the anti-pill performance is more preferably 4.5 grade or higher.
  • the knitted fabric of the present invention preferably has a heat retention of 15% to 50%. If the heat retention is 15% or more, warmth can be obtained as underwear, and if it is 50% or less, it is not too hot.
  • the acrylic fiber of this invention is demonstrated using a following example. (Measurement method of fiber surface irregularities)
  • the depth of the unevenness of the acrylic fiber of the present invention is represented by the following centerline average roughness (Ra), maximum height (Ry), 30-point average roughness (Rz), and local summit spacing (S). . These are measured by using a laser microscope.
  • 1 to 4 are diagrams schematically showing the cross-sectional shape of the surface of a single fiber in a cross section perpendicular to the fiber length direction of the single fiber constituting the acrylic fiber of the present invention.
  • the centerline average roughness (Ra) of the surface of the single fiber is, as shown in FIG. 1, extracted from the roughness curve by the reference length L in the direction of the centerline m, and measured from the centerline m of the extracted portion.
  • the absolute values of the deviations up to are summed up to obtain an average value, and this value is expressed in nanometers (nm).
  • the maximum height (Ry) of the surface of the single fiber is extracted by a reference length L in the direction of the center line m from the roughness curve, and the highest peak line and center line in the extracted part
  • the total value (Rp + Rv) of the distance Rp to m and the distance Rv between the lowest valley line and the center line m is obtained, and this value is expressed in nanometers (nm).
  • the 30-point average roughness (Rz) of the surface of a single fiber is obtained by extracting only the reference length from the roughness curve in the direction of the average line, and calculating the longitudinal magnification from the average line of the extracted portion.
  • the distance between the vertices (S) of the convex portions on the surface of the single fiber corresponds to the distance between adjacent local peaks, as shown in FIG. 4, by extracting a reference length L from the roughness curve in the direction of the center line m. The length of the average line is obtained, and the average value between the many local peaks is expressed in nanometers (nm).
  • the hot air of a dryer is applied to 200 or more and 300 or less acrylic fibers of the present invention, and the shrinkage of the fibers is stretched and placed in a tube.
  • the polyethylene tube used shrinks only in the circumferential direction.
  • the polyethylene tube filled with the acrylic fiber of the present invention was cut in a direction substantially perpendicular to the axial direction with an unused razor blade to a length of about 2 mm.
  • One of the cut surfaces is fixed to a table with double-sided tape, and a low-temperature ion sputtering apparatus (manufactured by JEOL Ltd., JFC1100) is used, and it is on the other surface of the cut surface under conditions of 1200 V, 5 mA, 8 minutes.
  • Gold was vapor-deposited on the cut surface of the acrylic fiber of the present invention as the observation surface to prepare a sample.
  • the glossiness evaluation was evaluated as follows. Using 100% of each of the acrylic fibers of Examples 1 and 2 and Comparative Example 1, spun yarns under the same conditions were used, fabrics were prepared under the same conditions, and glossiness was visually evaluated. ⁇ : Good glossiness, X: Poor gloss.
  • Example 1 An acrylonitrile copolymer having a reduced viscosity of 1.8 consisting of 95% acrylonitrile, 4.4% vinyl acetate and 0.6% sodium methallylsulfonate is dissolved in dimethylacetamide, and the copolymer concentration is 24% at 50 ° C. A spinning dope with a viscosity of 200 poise was obtained.
  • This spinning dope is discharged from a plurality of discharge holes having a hole diameter of 0.045 mm into a coagulating liquid having a dimethylacetamide concentration of 56% and a temperature of 41 ° C. to form a fiber, and while washing the solvent in 98 ° C. hot water, 2. 5 times stretching was applied. Subsequently, an oil agent is adhered, dried with a plurality of heat rollers whose surface temperature is set to 150 ° C., further heated with a heat roller of 180 ° C. to a fiber temperature of 160 ° C., stretched twice in air, After applying the shrinkage, it was shaken down to the container.
  • Example 2 Spinning was performed in the same manner as in Example 1 except that the wet heat draw ratio and the dry heat draw ratio were changed. The conditions are shown in Table 1, and the results are shown in Table 2. As a result, the product K of the value of the nodule strength (cN / dtex) and the value of the nodule elongation (%) was 16.6, which was a value at which the anti-pill property was good. In addition, the number of recesses having a depth of 0.1 ⁇ m or more was four, and the gloss was superior to that of the comparative example.
  • Examples 3 to 11 As shown in Table 1, acrylic fibers were produced in the same manner as in Example 1 except that the production conditions of the acrylic fibers were changed. The physical properties of the acrylic fiber are shown in Table 1.
  • the product K is a range showing anti-pilling properties, but it is unsuitable for clothing use because of its fineness and poor texture.
  • Example 12 70% by mass of acrylic fiber of Example 1, Micromodal (manufactured by Lenzing Co., 1.0 dtex) and 30 parts by mass are mixed, and the yarn count is 50, the yarn count is 873 t / m. Manufactured. The physical properties are shown in Table 2.
  • Example 13 A spun yarn of 100% by mass of the acrylic fiber of Example 1, a yarn count of 60, a cotton count, and a twist number of 1139 t / m was produced.
  • the physical properties are shown in Table 2.
  • Example 14 A spun yarn was obtained in the same manner as in Example 13 except that the yarn count was changed as shown in Table 2. The physical properties are shown in Table 2.
  • Example 16 A spun yarn having an acrylic fiber of Example 11 of 100% by mass, a yarn count of 40 and a twist number of 820 t / m was manufactured. The physical properties are shown in Table 2.
  • Comparative Example 5 70% by mass of the acrylic fiber of Comparative Example 1 and 30 parts by mass of Micromodal (manufactured by Lenzing Co., Ltd., 1.0 dtex) are mixed, and the yarn count is 50 and the yarn count is 900 t / m. Manufactured. The physical properties are shown in Table 2. Compared with Example 12, the yarn unevenness was large. Further, when the spun yarn of Example 12 and the spun yarn of Comparative Example 5 were visually compared in a state of being wound around a cone, it was confirmed that the spun yarn of Example 12 was more glossy.
  • Comparative Example 6 A spun yarn of 100% by mass of the acrylic fiber of Comparative Example 1, a yarn count of 60, a cotton count, and a twist number of 1139 t / m was manufactured. The physical properties are shown in Table 2. Compared with Example 13, the yarn unevenness was large.
  • Example 17 Using the spun yarn of Example 15, a flat knitted fabric with a tengu structure was prepared at 14G.
  • the basis weight was 210 g / m 2
  • the anti-pill performance was 4.5 grade
  • the heat retention was 45.1%.
  • Comparative Example 10 Using the spun yarn of Comparative Example 8, a flat knitted fabric with a tengu structure was prepared at 14G.
  • the basis weight was 210 g / m 2
  • the anti-pill performance was 4.5 grade, 44.9%.
  • the gloss was inferior to that of Example 17.

Abstract

The present invention provides: an acrylic fiber having a fineness of 0.5 to 3.5 dtex and having excellent gloss, pilling resistance, and texture; a method for producing said acrylic fiber; and a spun yarn and a knitted fabric including said acrylic fiber. Provided is an acrylic fiber having a filament fineness of 0.5 to 3.5 dtex, wherein the product K of the value of knot strength (cN/dtex) and the value of knot elongation (%) is from 8 to 30 inclusive, and the number of recesses having a depth of 0.1 µm or greater is 10 or fewer. In this method for producing said acrylic fiber, an acrylonitrile-based copolymer including 92 to 96.8 mass% of an acrylonitrile unit, 2 to 6 mass% of a vinyl-based monomer unit, and 0.2 to 2.0 mass% of a sulfonic acid group-containing vinyl monomer unit is dissolved in an organic solvent, to prepare a spinning dope. A coagulated fiber bundle is formed by discharging the spinning dope from discharge holes into a coagulation bath having a solvent concentration of 40 to 60 mass% and a temperature of 35 to 50°C. The coagulated fiber bundle is drawn in hot water at a draw ratio of 2 to 3.8 times, an oil agent is applied, the fiber bundle is dried, and then the fiber bundle is drawn under dry heat at a draw ratio of 1.2 to 3 times. The product S of said draw ratio in hot water and said draw ratio under dry heat is from 4 to 6 times. Further, the fiber bundle is subjected to a thermal relaxation treatment.

Description

光沢抗ピル性アクリル繊維及びその製造方法と前記アクリル繊維を含む紡績糸及び編地Glossy anti-pill acrylic fiber, method for producing the same, spun yarn and knitted fabric containing the acrylic fiber
　本発明は、優れた光沢、柔軟な風合い及び抗ピル性を有するアクリル繊維及びその製造方法と前記アクリル繊維を含む紡績糸及び編地に関する。 The present invention relates to an acrylic fiber having excellent gloss, soft texture and anti-pilling property, a method for producing the same, and a spun yarn and a knitted fabric containing the acrylic fiber.
　アクリル繊維は、柔軟な風合い、保温性、形態安定性、耐候性、染色性等の優れた特徴を有しており、ナイロン繊維、ポリエステル繊維等の合成繊維と同様に、衣料品、インテリア分野に多用されている。しかし、このアクリル繊維からなる繊維製品は、着用中にピリングが発生し易く、編織物の外観や風合いを著しく損ない商品価値を低下させるという問題点を有している。かねてよりアクリル繊維においては、ピリングの発生し難い、いわゆる抗ピル性の改良が求められていた。 Acrylic fibers have excellent characteristics such as soft texture, heat retention, form stability, weather resistance, and dyeability. Like synthetic fibers such as nylon fibers and polyester fibers, acrylic fibers are used in clothing and interior fields. It is used a lot. However, the fiber product made of this acrylic fiber has a problem that pilling is likely to occur during wearing, and the appearance and texture of the knitted fabric are remarkably impaired and the commercial value is lowered. For some time, acrylic fibers have been required to improve so-called anti-pilling property, in which pilling hardly occurs.
　一方、近年では衣料用製品の風合いをよりソフトにするための手段として繊維の細繊度化が進んでおり、細繊度繊維を用いた商品開発が行われているが、一般的に細繊度繊維ほどピリングが発生し易い傾向にあり、抗ピル性改良の要望は益々高まってきているのが現状である。 On the other hand, in recent years, the fineness of fibers has been increasing as a means to make the texture of clothing products softer, and product development using fineness fibers has been conducted. There is a tendency for pilling to occur easily, and the demand for improving anti-pilling properties is increasing.
　また衣料品製品の風合いを改良することにほかに、シルクのような高級感を出すために、光沢性を向上させるという提案がなされている。例えば、特許文献１（特開平１１－２２２７１６号公報）には、単繊維繊度が６～３４ｄｔｅｘの太繊度アクリル繊維において、繊維断面が扁平形状で、繊維表面に一定面積以上の平滑面をもつことで光沢性を向上させたり、特許文献２（特開２０１２－３６５１２号公報）に開示されているように、繊維断面は円形状もしくは円形に近い楕円形の外縁部に内側に凹んだ湾曲部のある形状の光沢繊維が提案されている。これらの繊維は、いずれも単繊維繊度が６ｄｔｅｘ以上の太繊度繊維であったり、扁平やそら豆型の断面であった。 In addition to improving the texture of clothing products, proposals have been made to improve gloss in order to give silky luxury. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 11-222716) discloses that a thick fiber acrylic fiber having a single fiber fineness of 6 to 34 dtex has a flat fiber cross section and a smooth surface of a certain area or more on the fiber surface. As shown in Patent Document 2 (Japanese Patent Laid-Open No. 2012-36512), the cross section of the fiber has a circular or oval outer edge that is nearly circular, and a curved portion that is recessed inward. Some forms of glossy fibers have been proposed. Each of these fibers was a thick fiber having a single fiber fineness of 6 dtex or more, or a flat or broad bean-shaped cross section.
　さらに、特許文献３（特開２００６－１７６９３７号公報）および特許文献４（特開２００８－３８３０９号公報）には、抗ピル性の細繊度アクリル繊維を含む紡績糸、およびその製造方法について提案されている。しかしながら、細繊度アクリル繊維で抗ピル性と光沢性の両方を有するものではなかった。 Further, Patent Document 3 (Japanese Patent Laid-Open No. 2006-176937) and Patent Document 4 (Japanese Patent Laid-Open No. 2008-38309) propose a spun yarn containing an anti-pill fine acrylic fiber and a method for producing the same. ing. However, it was not a fine-fine acrylic fiber having both anti-pilling properties and glossiness.
　特許文献５（特開２０１１－１２３６３号公報）には、炭素繊維前駆体アクリル繊維に関して、繊維表面の凹凸が少なく、単繊維繊度が１．１ｄｔｅｘのアクリル繊維が提案されている。しかしながら、炭素繊維前駆体アクリル繊維の強度を高めているため、結節強度、結節伸度が小さいものである。そのため、炭素繊維前駆体アクリル繊維は紡績工程において、繊維の折損が多いため、紡績糸にはできるものではなかった。 Patent Document 5 (Japanese Patent Application Laid-Open No. 2011-12363) proposes an acrylic fiber having a carbon fiber precursor acrylic fiber with less irregularities on the fiber surface and a single fiber fineness of 1.1 dtex. However, since the strength of the carbon fiber precursor acrylic fiber is increased, the knot strength and the knot elongation are small. For this reason, the carbon fiber precursor acrylic fiber was not able to be formed into a spun yarn because of many fiber breakage in the spinning process.
特開平１１－２２２７１６号公報JP 11-222716 A 特開２０１２－３６５１２号公報JP 2012-36512 A 特開２００６－１７６９３７号公報JP 2006-176937 A 特開２００８－３８３０９号公報JP 2008-38309 A 特開２０１１－１２３６３号公報JP 2011-12363 A
　そこで本発明は、光沢性、抗ピル性及び柔軟な風合いに優れた、０．５ｄｔｅｘ以上３．５ｄｔｅｘ以下のアクリル繊維及びその製造方法と前記アクリル繊維を含む紡績糸及び編地を提供する。 Therefore, the present invention provides an acrylic fiber of 0.5 dtex or more and 3.5 dtex or less excellent in gloss, anti-pill property and soft texture, a method for producing the same, and a spun yarn and a knitted fabric containing the acrylic fiber.
　本発明のアクリル繊維は、単繊維の表面の中心線平均粗さ（Ｒａ）が３ｎｍ以上１２ｎｍ以下であり、単繊維繊度が０．５ｄｔｅｘ以上３．５ｄｔｅｘ以下である。 The acrylic fiber of the present invention has a single fiber surface centerline average roughness (Ra) of 3 nm to 12 nm and a single fiber fineness of 0.5 dtex to 3.5 dtex.
　本発明のアクリル繊維は、結節強度（ｃＮ／ｄｔｅｘ）の値と結節伸度（％）の値との積Ｋが１０以上３０以下であることが好ましい。 In the acrylic fiber of the present invention, the product K of the value of knot strength (cN / dtex) and the value of knot elongation (%) is preferably 10 or more and 30 or less.
　本発明のアクリル繊維は、単繊維の表面の中心線平均粗さ（Ｒａ）が３ｎｍ以上１２ｎｍ以下であり、結節強度（ｃＮ／ｄｔｅｘ）の値と結節伸度（％）の値との積Ｋが１０以上３０以下である。 The acrylic fiber of the present invention has a single fiber surface centerline average roughness (Ra) of 3 nm to 12 nm, and the product K of the value of knot strength (cN / dtex) and the value of knot elongation (%). Is 10 or more and 30 or less.
　本発明のアクリル繊維は、単繊維繊度が０．５ｄｔｅｘ以上３．５ｄｔｅｘ以下であることが好ましい。 The acrylic fiber of the present invention preferably has a single fiber fineness of 0.5 dtex or more and 3.5 dtex or less.
　本発明のアクリル繊維は、単繊維の表面の最大高低差（Ｒｙ）が４０ｎｍ以上１５０ｎｍ以下、３０点平均粗さ（Ｒｚ）が２０ｎｍ以上８０ｎｍ以下および単繊維の表面の凸部の頂点間距離（Ｓ）が８００ｎｍ以上１１００ｎｍ以下であることが好ましい。 In the acrylic fiber of the present invention, the maximum height difference (Ry) of the surface of the single fiber is 40 nm or more and 150 nm or less, the 30-point average roughness (Rz) is 20 nm or more and 80 nm or less, and the distance between the vertices of the convex portion on the surface of the single fiber ( S) is preferably 800 nm or more and 1100 nm or less.
　本発明のアクリル繊維は、繊維軸に垂直な方向の断面において単繊維表面に有する深さ０．１μｍ以上の凹部が１０個以下であることが好ましい。 The acrylic fiber of the present invention preferably has 10 or less recesses having a depth of 0.1 μm or more on the surface of the single fiber in a cross section perpendicular to the fiber axis.
　本発明のアクリル繊維は、アクリロニトリル単位９２質量％以上９６．８質量％以下、ビニル系モノマー単位２質量％以上６質量％以下、およびスルホン酸基含有ビニルモノマー単位０．２質量％以上２．０質量％以下を含むアクリル繊維であって、単繊維引張強度が１．８ｃＮ／ｄｔｅｘ以上３．０ｃＮ／ｄｔｅｘ以下、単繊維結節強度が１．０ｃＮ／ｄｔｅｘ以上１．８ｃＮ／ｄｔｅｘ以下、単繊維結節伸度が８％以上２０％以下であることが好ましい。 The acrylic fiber of the present invention has an acrylonitrile unit of 92% by mass to 96.8% by mass, a vinyl monomer unit of 2% by mass to 6% by mass, and a sulfonic acid group-containing vinyl monomer unit of 0.2% by mass to 2.0%. Acrylic fiber containing less than or equal to mass%, single fiber tensile strength is 1.8 cN / dtex or more and 3.0 cN / dtex or less, single fiber knot strength is 1.0 cN / dtex or more and 1.8 cN / dtex or less, single fiber knot The elongation is preferably 8% or more and 20% or less.
　本発明のアクリル繊維の製造方法は、アクリロニトリル単位を９２質量％以上９６．８質量％以下、スルホン酸基含有ビニルモノマー単位を０．２質量％以上２．０質量％以下を含むアクリロニトリル系共重合体を有機溶媒に溶解して紡糸原液とし、前記紡糸原液を温度が３５℃以上５０℃以下の凝固浴に紡糸ノズルの複数の吐出孔からジェットストレッチが０．４以上２．２以下で吐出して凝固繊維束とし、前記凝固繊維束を８０℃以上９８℃以下の熱水中で延伸倍率２倍以上３．８倍以下で延伸し、油剤付与し、乾燥した後、乾熱延伸工程で繊維温度を１５０℃以上１７０℃以下として乾熱で延伸倍率が１．２倍以上３倍以下で延伸し、前記熱水延伸倍率と前記乾熱延伸倍率の積Ｓが４倍以上６倍以下とするアクリル繊維の製造方法である。 The method for producing an acrylic fiber of the present invention comprises an acrylonitrile copolymer containing 92% by mass or more and 96.8% by mass or less of an acrylonitrile unit and 0.2% by mass or more and 2.0% by mass or less of a sulfonic acid group-containing vinyl monomer unit. The combined solution is dissolved in an organic solvent to form a spinning dope, and the spinning dope is discharged into a coagulation bath having a temperature of 35 ° C. or more and 50 ° C. or less at a jet stretch of 0.4 or more and 2.2 or less from a plurality of discharge holes of a spinning nozzle. The coagulated fiber bundle is stretched at a draw ratio of 2 to 3.8 times in hot water at 80 ° C. or higher and 98 ° C. or lower, oiled, dried, and then dried in a dry heat drawing step. The temperature is set to 150 ° C. or more and 170 ° C. or less and stretched by dry heat at a draw ratio of 1.2 to 3 times, and the product S of the hot water draw ratio and the dry heat draw ratio is set to 4 to 6 times. With acrylic fiber manufacturing method That.
　本発明のアクリル繊維の製造方法は、前記アクリロニトリル系共重合体がビニル系モノマー単位を２質量％以上６質量％以下をさらに含み、前記凝固浴の溶媒濃度が４０質量％以上６０質量％以下であり、乾熱延伸後に熱緩和処理を行うことが好ましい。
　本発明のアクリル繊維の製造方法は、前記熱緩和処理のアニール処理温度が１２０℃以上１３５℃以下であり、繊維緩和率が５％以上２０％以下であることが好ましい。 In the method for producing acrylic fiber according to the present invention, the acrylonitrile-based copolymer further includes 2% by mass to 6% by mass of a vinyl monomer unit, and the solvent concentration of the coagulation bath is 40% by mass to 60% by mass. Yes, it is preferable to perform a thermal relaxation treatment after dry heat stretching.
In the method for producing acrylic fiber of the present invention, it is preferable that the annealing temperature of the thermal relaxation treatment is 120 ° C. or higher and 135 ° C. or lower, and the fiber relaxation rate is 5% or higher and 20% or lower.
　本発明の紡績糸は、前記アクリル繊維を４０質量％以上含み、糸番手が綿番手で４０番手以上７０番手以下である。
　本発明の紡績糸は、セルロース系繊維を１０質量％以上４０質量％以下を含むことが好ましい。 The spun yarn of the present invention contains 40% by mass or more of the acrylic fiber, and the yarn count is 40 to 70.
The spun yarn of the present invention preferably contains 10 to 40% by mass of cellulosic fibers.
　本発明の編地は、前記紡績糸を４０質量％以上含み、目付が１５０ｇ／ｍ2 以上２３０ｇ／ｍ2 以下あり、抗ピル性能が４級以上である。
　本発明の編地は、保温率が、１５％以上５０％以下であることが好ましい。 The knitted fabric of the present invention contains 40% by mass or more of the spun yarn, has a basis weight of 150 g / m 2 or more and 230 g / m 2 or less, and has an anti-pill performance of 4 or more.
The knitted fabric of the present invention preferably has a heat retention rate of 15% or more and 50% or less.
　本発明によれば、特に肌着等のインナー向けの衣料用途において、ソフトな風合い、高級感のある光沢性及び良好な抗ピル性を兼備した繊維製品を得ることが可能なアクリル繊維が提供できる。 According to the present invention, it is possible to provide an acrylic fiber capable of obtaining a textile product having a soft texture, a high-grade glossiness, and a good anti-pilling property, particularly in apparel for innerwear such as underwear.
中心線平均粗さ（Ｒａ）を説明する、単繊維表面の断面図である。It is sectional drawing of the surface of a single fiber explaining a centerline average roughness (Ra). 最大高さ（Ｒｙ）を説明する、単繊維表面の断面図である。It is sectional drawing of the surface of a single fiber explaining maximum height (Ry). ３０点平均粗さ（Ｒｚ）を説明する、単繊維表面の断面図である。It is sectional drawing of the surface of a single fiber explaining 30 point average roughness (Rz). 局部山頂の間隔（Ｓ）を説明する、単繊維表面の断面図である。It is sectional drawing of the surface of a single fiber explaining the space | interval (S) of a local peak.
＜アクリル繊維のポリマー組成＞
　本発明のアクリル繊維を構成する共重合体は、９２質量％以上９６．８質量％以下のアクリロニトリル単位を共重合していることが好ましい。アクリロニトリル単位の共重合率が９２質量％以上であれば、衣料用繊維として必要な繊維強度が得られ易い。
　かかる観点から、アクリロニトリル単位の共重合率は９５質量％以上を含有することがより好ましい。
　また、アクリルニトリル単位の共重合率が９６．８質量％以下であれば、染色性や繊維強度、伸度が得られやすい。 <Acrylic fiber polymer composition>
The copolymer constituting the acrylic fiber of the present invention preferably has 92% by mass or more and 96.8% by mass or less of acrylonitrile units copolymerized. If the copolymerization rate of the acrylonitrile unit is 92% by mass or more, the fiber strength required as a fiber for clothing is easily obtained.
From this viewpoint, the copolymerization rate of acrylonitrile units is more preferably 95% by mass or more.
Further, when the copolymerization ratio of the acrylonitrile unit is 96.8% by mass or less, dyeability, fiber strength, and elongation are easily obtained.
　また、アクリロニトリルと共重合性を有するビニル系モノマー単位の共重合率は３．０質量％以上６．０質量％以下にすることが好ましい。ビニル系モノマー単位の共重合率がこの範囲内であれば、編地製品として十分な物性や染色性を得ることができる。
　さらに、前記共重合体はスルホン酸基含有ビニルモノマーの共重合率を０．２質量％以上２．０質量％以下にすることが好ましい。前記スルホン酸基含有ビニルモノマーの共重合率が０．２質量％以上であれば、染色性が良好になり易すく、２．０質量％以下であればコストの上昇が少なくできる。 Moreover, it is preferable that the copolymerization rate of the vinyl-type monomer unit copolymerizable with acrylonitrile is 3.0 mass% or more and 6.0 mass% or less. If the copolymerization rate of vinyl monomer units is within this range, sufficient physical properties and dyeability can be obtained as a knitted fabric product.
Further, the copolymer preferably has a copolymerization rate of the sulfonic acid group-containing vinyl monomer of 0.2% by mass or more and 2.0% by mass or less. If the copolymerization rate of the sulfonic acid group-containing vinyl monomer is 0.2% by mass or more, the dyeability is easily improved, and if it is 2.0% by mass or less, the increase in cost can be reduced.
　アクリロニトリルと共重合可能なビニル系モノマーとしては、アクリル酸メチル、メタクリル酸メチル、あるいはこれらの（メタ）アクリル酸エステル類、酢酸ビニル、スチレン、アクリル酸アミド、２－ヒドロキシエチルメタクリレート、グリシジルメタクリレート、などが挙げられる。また、スルホン酸基含有ビニルモノマーとしては、アリルスルホン酸、メタリルスルホン酸、スチレンスルホン酸、ビニルスルホン酸、イソプレンスルホン酸、２－アクリルアミド－２－メチルプロパンスルホン酸またはこれらの金属塩類およびアミン塩類等が好ましく用いられるが、本発明はここに挙げたモノマーに限定されるものではない。このようなアクリロニトリル系共重合体を得るための重合方法は、水媒体中で実施する懸濁重合法が望ましい。 Examples of vinyl monomers copolymerizable with acrylonitrile include methyl acrylate, methyl methacrylate, or their (meth) acrylic acid esters, vinyl acetate, styrene, acrylic acid amide, 2-hydroxyethyl methacrylate, glycidyl methacrylate, etc. Is mentioned. Examples of the sulfonic acid group-containing vinyl monomer include allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, or metal salts and amine salts thereof. Etc. are preferably used, but the present invention is not limited to the monomers listed here. The polymerization method for obtaining such an acrylonitrile copolymer is preferably a suspension polymerization method carried out in an aqueous medium.
＜アクリル繊維の単繊維繊度＞
　本発明のアクリル繊維の単繊維繊度は、０．５ｄｔｅｘ以上３．５ｄｔｅｘ以下が好ましい。一般的に、繊維が細くなると染色鮮明性が低下する傾向にあるが、本発明のアクリル繊維は、１．２ｄｔｅｘ以下であっても染色鮮明性を有している。前記単繊維繊度が０．５ｄｔｅｘ以上であれば、染色鮮明性の効果が表れやすく、３．５ｄｔｅｘ以下であれば編地にした時にソフトな風合いが得られ易い。これらの観点から、前記単繊維繊度は、０．７ｄｔｅｘ以上２．０ｄｔｅｘ以下がより好ましく、０．８ｄｔｅｘ以上１．２ｄｔｅｘ以下がさらに好ましい。 <Single fiber fineness of acrylic fiber>
The single fiber fineness of the acrylic fiber of the present invention is preferably 0.5 dtex or more and 3.5 dtex or less. Generally, when the fiber is thin, the dyeing sharpness tends to be lowered. However, the acrylic fiber of the present invention has dyeing sharpness even if it is 1.2 dtex or less. If the single fiber fineness is 0.5 dtex or more, the effect of dyeing clarity is likely to appear, and if it is 3.5 dtex or less, a soft texture is easily obtained when knitted. From these viewpoints, the single fiber fineness is more preferably 0.7 dtex or more and 2.0 dtex or less, and further preferably 0.8 dtex or more and 1.2 dtex or less.
＜積Ｋ＞
　本発明のアクリル繊維は、結節強度（ｃＮ／ｄｔｅｘ）の値と結節伸度（％）の値との積Ｋが１０以上３０以下が好ましい。この積Ｋの値は、抗ピル性の指標として当業者が用いる値である。 <Product K>
The acrylic fiber of the present invention preferably has a product K of 10 to 30 in terms of the value of knot strength (cN / dtex) and the value of knot elongation (%). The value of the product K is a value used by those skilled in the art as an index of anti-pill property.
　前記積Ｋが１０以上であれば、紡績工程で単繊維が細かく切断するフライの発生が少なくなり、３０以下であれば抗ピル性が良好となる。
　かかる観点から、前記積Ｋは１２以上２５以下がより好ましく、１４以上２０以下がさらに好ましい。 If the product K is 10 or more, the occurrence of fly that finely cuts the single fiber in the spinning process is reduced, and if it is 30 or less, the anti-pill property is good.
From this viewpoint, the product K is more preferably 12 or more and 25 or less, and further preferably 14 or more and 20 or less.
＜単繊維表面の中心線平均粗さ（Ｒａ）＞
　本発明のアクリル繊維は、繊維表面に溝が少ないため、光沢性に優れている。本発明のアクリル繊維は、単繊維の表面の中心線平均粗さ（Ｒａ）が３ｎｍ以上１２ｎｍ以下である。前記Ｒａが３ｎｍ以上であれば、紡糸時にロールと繊維の間の摩擦が生じ、ロールでのスリップが発生しにくくなるため好ましく、１２ｎｍ以下であれば光沢が発現し易いため好ましい。かかる観点から、前記Ｒａは、４ｎｍ以上１０ｎｍ以下がより好ましく、５ｎｍ以上９ｎｍ以下がさらに好ましい。 <Center line average roughness (Ra) of single fiber surface>
The acrylic fiber of the present invention has excellent gloss because there are few grooves on the fiber surface. In the acrylic fiber of the present invention, the center line average roughness (Ra) of the surface of the single fiber is 3 nm or more and 12 nm or less. If the Ra is 3 nm or more, friction between the roll and the fiber is generated during spinning, and slippage in the roll is less likely to occur, and if it is 12 nm or less, gloss is easily developed, which is preferable. From this viewpoint, the Ra is more preferably 4 nm or more and 10 nm or less, and further preferably 5 nm or more and 9 nm or less.
＜最大高低差（Ｒｙ）、３０点平均粗さ（Ｒｚ）、凸部の頂点間距離（Ｓ）＞
　本発明のアクリル繊維は、単繊維の表面の最大高低差（Ｒｙ）が４０ｎｍ以上１５０ｎｍ以下、３０点平均粗さ（Ｒｚ）が２０ｎｍ以上８０ｎｍ以下および単繊維の表面の凸部の頂点間距離（Ｓ）が８００ｎｍ以上１１００ｎｍ以下であることが好ましい。 <Maximum height difference (Ry), 30-point average roughness (Rz), distance between vertices of convex portions (S)>
In the acrylic fiber of the present invention, the maximum height difference (Ry) of the surface of the single fiber is 40 nm or more and 150 nm or less, the 30-point average roughness (Rz) is 20 nm or more and 80 nm or less, and the distance between the vertices of the convex portion on the surface of the single fiber ( S) is preferably 800 nm or more and 1100 nm or less.
　前記Ｒｙが４０ｎｍ以上であれば、繊維同士に摩擦が生じ、紡績工程における工程通過性が良い点で好ましく、１５０ｎｍ以下であれば、正反射が生じやすいという点で好ましい。かかる観点から、前記Ｒｙは、５０ｎｍ以上１００ｎｍ以下がより好ましく、５５ｎｍ以上９０ｎｍ以下がさらに好ましい。 When the Ry is 40 nm or more, friction occurs between the fibers and the processability in the spinning process is good, and when the Ry is 150 nm or less, specular reflection is likely to occur. From this viewpoint, the Ry is more preferably 50 nm to 100 nm, and further preferably 55 nm to 90 nm.
　また、前記Ｒｚが２０ｎｍ以上であれば、紡績時の通過性がよいの点で好ましく、８０ｎｍ以下であれば、光沢性が向上する点で好ましい。かかる観点から、前記Ｒｚは、３０ｎｍ以上６５ｎｍ以下がより好ましく、３５ｎｍ以上５０ｎｍ以下がより好ましい。 Further, if the Rz is 20 nm or more, it is preferable in terms of good passability during spinning, and if it is 80 nm or less, it is preferable in terms of improving glossiness. From this viewpoint, the Rz is more preferably 30 nm to 65 nm, and more preferably 35 nm to 50 nm.
　また、前記Ｓが８００ｎｍ以上であれば、紡糸性の点で好ましく、１１００ｎｍ以下であれば、繊維表面の凹凸の数が少なく、乱反射が生じにくい点で好ましい。前記観点から、前記Ｓは、９００ｎｍ以上１０００ｎｍ以下がより好ましい。 If S is 800 nm or more, it is preferable from the viewpoint of spinnability, and if it is 1100 nm or less, it is preferable from the viewpoint that the number of irregularities on the fiber surface is small and irregular reflection hardly occurs. From the viewpoint, the S is more preferably 900 nm or more and 1000 nm or less.
＜繊維表面に有する凹部の数＞
　さらに、本発明のアクリル繊維は、繊維軸に垂直な方向の断面において単繊維表面に有する深さ０．１μｍ以上の凹部が１０個以下であることが好ましい。この凹部の深さは、後述する方法により、繊維軸方向に垂直な断面を観察した時に、繊維表面における０．１μｍ以上の深さの凹部の数が１０個以下であると、光沢が良好になり好ましい。繊維表面に深さが０．１μｍ以上の凹部があると、光りの乱反射が生じる。本発明のアクリル繊維は、繊維断面において、０．１μｍ以上の凹部が１０個以下であれば、光の乱反射を少なくでき、光沢が低下し難くなるため、光沢性が得られ易い。前記観点から、０．１μｍ以上の凹部の数は５個以下がより好ましい。
　繊維表面の凹凸を少なくするには、凝固繊維を湿熱で延伸する際に延伸倍率を低くすることが有効である。 <Number of recesses on fiber surface>
Furthermore, the acrylic fiber of the present invention preferably has 10 or less recesses having a depth of 0.1 μm or more on the surface of the single fiber in a cross section perpendicular to the fiber axis. The depth of the recesses is good when the number of recesses having a depth of 0.1 μm or more on the fiber surface is 10 or less when the cross section perpendicular to the fiber axis direction is observed by a method described later. It is preferable. If there is a recess having a depth of 0.1 μm or more on the fiber surface, diffuse reflection of light occurs. In the acrylic fiber of the present invention, if the number of recesses of 0.1 μm or more is 10 or less in the fiber cross section, the irregular reflection of light can be reduced and the gloss is hardly lowered, so that the gloss is easily obtained. From the above viewpoint, the number of recesses of 0.1 μm or more is more preferably 5 or less.
In order to reduce the unevenness of the fiber surface, it is effective to lower the draw ratio when the coagulated fiber is drawn by wet heat.
　本発明のアクリル繊維の単繊維引張強度は、紡績工程等の加工工程通過性の点で、１．８ｃＮ／ｄｔｅｘ以上であることが好ましく、２．０ｃＮ／ｄｔｅｘ以上がより好ましい。前記引張強度の上限値は、特に制限はないが、３．０ｃＮ／ｄｔｅｘであれば十分である。 The single fiber tensile strength of the acrylic fiber of the present invention is preferably 1.8 cN / dtex or more, more preferably 2.0 cN / dtex or more, from the viewpoint of passing through a processing step such as a spinning step. The upper limit of the tensile strength is not particularly limited, but 3.0 cN / dtex is sufficient.
　本発明のアクリル繊維の単繊維結節強度は、１．０ｃＮ／ｄｔｅｘ以上、１．８ｃＮ／ｄｔｅｘ以下が好ましい。
　前記結節強度が１．０ｃＮ／ｄｔｅｘ以上であれば、紡績工程でのフライの発生が少なくなり、加工工程通過性が良好となり、前記結節強度が１．８ｃＮ／ｄｔｅｘ以下であれば、抗ピル性能が良好となり易い。かかる観点より、前記結節強度は１．２ｃＮ／ｄｔｅｘ以上１．６ｃＮ／ｄｔｅｘ以下がより好ましく、１．４ｃＮ／ｄｔｅｘ以上１．５ｃＮ／ｄｔｅｘ以下がさらに好ましい。 The single fiber knot strength of the acrylic fiber of the present invention is preferably 1.0 cN / dtex or more and 1.8 cN / dtex or less.
If the knot strength is 1.0 cN / dtex or more, the occurrence of fly in the spinning process is reduced and the processing process is good, and if the knot strength is 1.8 cN / dtex or less, the anti-pill performance. Tends to be good. From this viewpoint, the knot strength is more preferably 1.2 cN / dtex or more and 1.6 cN / dtex or less, and further preferably 1.4 cN / dtex or more and 1.5 cN / dtex or less.
　本発明のアクリル繊維の単繊維結節伸度は、抗ピル性を高める観点から、８％以上２０％以下が好ましく、１５％以下がより好ましい。 The single fiber nodule elongation of the acrylic fiber of the present invention is preferably 8% or more and 20% or less, more preferably 15% or less, from the viewpoint of enhancing the anti-pill property.
＜アクリル繊維の製造方法＞
　本発明のアクリル繊維は、湿式紡糸法や乾湿式紡糸法により得ることができるが、生産性やコストの点で、湿式紡糸法が望ましい。 <Method for producing acrylic fiber>
The acrylic fiber of the present invention can be obtained by a wet spinning method or a dry-wet spinning method, but the wet spinning method is desirable in terms of productivity and cost.
＜共重合体組成＞
　本発明のアクリル繊維の製造方法は、アクリロニトリル単位を９２質量％以上９６．８質量％以下、ビニル系モノマー単位を２質量％以上６質量％以下、およびスルホン酸基含有ビニルモノマー単位を０．２質量％以上２．０質量％以下を含むアクリロニトリル系共重合体を使用することが好ましい。 <Copolymer composition>
The method for producing acrylic fibers of the present invention comprises 92% by mass or more and 96.8% by mass or less of acrylonitrile units, 2% by mass or more and 6% by mass or less of vinyl monomer units, and 0.2% of vinyl monomer units containing sulfonic acid groups. It is preferable to use an acrylonitrile-based copolymer containing from mass% to 2.0 mass%.
　前記アクリロニトリル系共重合体を有機溶媒に溶解して紡糸原液とする。
　紡糸原液は、１５質量％以上３０質量％以下のアクリロニトリル系共重合体と、７０質量％以上８５質量％以下の有機溶媒からなることが好ましい。紡糸原液中のアクリロニトリル系共重合体濃度が１５質量％以上３０質量％以下であれば、糸切れや生産性の面から、紡糸性が良好であり好ましい。前記共重合体濃度は、紡糸性の観点から１８％以上２５％以下がより好ましい。 The acrylonitrile copolymer is dissolved in an organic solvent to obtain a spinning dope.
The spinning dope is preferably composed of 15% by mass to 30% by mass of an acrylonitrile copolymer and 70% by mass to 85% by mass of an organic solvent. If the concentration of the acrylonitrile copolymer in the spinning dope is 15% by mass or more and 30% by mass or less, the spinning property is favorable from the viewpoint of yarn breakage and productivity. The concentration of the copolymer is more preferably 18% or more and 25% or less from the viewpoint of spinnability.
　前記有機溶剤としては、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシド等の有機溶剤であることが必要である。中でも、繊維製造における生産性、得られた抗ピル性アクリル繊維の染色鮮明性と、抗ピル性能のバランスの面からジメチルアセトアミドが好ましい。 The organic solvent must be an organic solvent such as dimethylacetamide, dimethylformamide, dimethyl sulfoxide. Among them, dimethylacetamide is preferable from the viewpoint of the balance between productivity in fiber production, dyeing clarity of the obtained anti-pill acrylic fiber, and anti-pill performance.
　アクリロニトリル系共重合体を有機溶媒に溶解温度は、４０℃以上であれば、未溶解分が少なく、それに従いフィルタープレス等の濾過設備における濾材の使用期間が長くでき、また曳糸性を損ねることがないので好ましい。一方、前記溶解温度が９５℃以下であれば、共重合体が変色し難くいので好ましい。 If the acrylonitrile copolymer is dissolved in an organic solvent at a temperature of 40 ° C. or higher, the amount of undissolved component is small, and accordingly, the use period of the filter medium in a filter equipment such as a filter press can be extended, and the spinnability is impaired. This is preferable because there is not. On the other hand, if the dissolution temperature is 95 ° C. or lower, it is preferable because the copolymer is hardly discolored.
　また、アクリロニトリル系共重合体を有機溶媒に溶解した後の紡糸原液の温度は４０℃以上９５℃以下であることが好ましい。４０℃以上９５℃以下であれば紡糸原液の曳糸性や、低粘度によるノズル圧上昇、紡糸原液のゲル化などがなく、紡糸性が良好である。 Further, the temperature of the spinning dope after dissolving the acrylonitrile copolymer in an organic solvent is preferably 40 ° C. or higher and 95 ° C. or lower. When the temperature is 40 ° C. or more and 95 ° C. or less, there is no spinnability of the spinning dope, no increase in nozzle pressure due to low viscosity, gelation of the spinning dope, and the spinnability is good.
＜凝固浴温度＞
　次に、該紡糸原液を溶剤濃度が４０質量％以上６０質量％以下、温度が３５℃以上５０℃以下の凝固浴に紡糸ノズルの複数の吐出孔から吐出して凝固繊維束とする。
　溶剤濃度及び温度の範囲が前記の範囲であれば、凝固が早くなり過ぎず、繊維表面の凹部皺が少なくなり易い。 <Coagulation bath temperature>
Next, the spinning solution is discharged from a plurality of discharge holes of a spinning nozzle into a coagulation bath having a solvent concentration of 40% by mass to 60% by mass and a temperature of 35 ° C. to 50 ° C. to obtain a coagulated fiber bundle.
If the range of the solvent concentration and temperature is within the above ranges, solidification does not become too fast, and the number of recesses on the fiber surface tends to decrease.
＜ジェットストレッチ、熱水延伸倍率、乾熱延伸倍率、延伸倍率積＞
　紡糸ノズルの吐出孔から吐出する際のジェットストレッチは０．４以上２．２以下が好ましい。ジェットストレッチとは、凝固糸の引取り速度を吐出線速度で割った値である。
　該ジェットストレッチが０．４以上２．２以下であれば、紡浴中での糸切れが少なく、紡糸性が良好な点で好ましい。前記観点から、前記ジェットストレッチは０．６以上２．０以下がより好ましい。 <Jet stretch, hot water draw ratio, dry heat draw ratio, draw ratio product>
The jet stretch when discharging from the discharge hole of the spinning nozzle is preferably 0.4 or more and 2.2 or less. The jet stretch is a value obtained by dividing the take-up speed of the coagulated yarn by the discharge linear speed.
If the jet stretch is 0.4 or more and 2.2 or less, it is preferable in that the yarn breakage during spinning is small and the spinnability is good. From the viewpoint, the jet stretch is more preferably 0.6 or more and 2.0 or less.
　さらに、前記凝固繊維束を熱水中で延伸倍率２倍以上４倍以下で延伸し、油剤付与し、乾燥した後、乾熱で延伸倍率１．２倍以上３倍以下で延伸し、前記熱水中での延伸倍率と前記乾熱での延伸倍率の積Ｓが、４倍以上６倍以下とする。 Further, the solidified fiber bundle is stretched in hot water at a stretch ratio of 2 to 4 times, provided with an oil agent, dried, and then stretched at a stretch ratio of 1.2 to 3 times by dry heat. The product S of the draw ratio in water and the draw ratio in the dry heat is 4 to 6 times.
　乾熱での延伸倍率が１．２倍以上であれば、繊維表面の凹部が伸ばされ平滑面が増え、光沢性が向上するので好ましい。３倍以下であれば、抗ピル性が良好となり、紡糸による糸切れが低減する点で好ましい。
　繊維表面の凹部を少なくし、光沢性を高める点で、乾熱での延伸倍率は１．５以上がより好ましく、１．７以上がさらに好ましい。また、工程通過性の点から２倍以下が好ましい。 If the draw ratio by dry heat is 1.2 times or more, the concave portion of the fiber surface is extended, the smooth surface is increased, and the glossiness is improved. If it is 3 times or less, the anti-pill property is good, and this is preferable in that yarn breakage due to spinning is reduced.
From the viewpoint of reducing the number of concave portions on the fiber surface and improving gloss, the draw ratio with dry heat is more preferably 1.5 or more, and even more preferably 1.7 or more. Moreover, 2 times or less is preferable from the point of process passage property.
　また、前記積Ｓが４倍以上６倍以下であれば、紡績等の通過性が良好であり、適切な繊維強度を持つ点で好ましい。また、抗ピル性能が良好になり易い。前記積Ｓは、４．５以上５．５倍以下がより好ましい。 In addition, if the product S is 4 times or more and 6 times or less, it is preferable in terms of good passability of spinning and the like and having an appropriate fiber strength. Also, the anti-pill performance tends to be good. The product S is more preferably 4.5 or more and 5.5 times or less.
＜熱水温度、乾熱延伸の繊維温度＞
　前記熱水中で延伸する際の熱水の温度は、８０℃以上９８℃以下であることが好ましい。この範囲であれば、熱水中での延伸時に繊維の切断が少なくできる。 <Hot water temperature, dry heat drawing fiber temperature>
The temperature of hot water when stretching in the hot water is preferably 80 ° C. or higher and 98 ° C. or lower. If it is this range, the cutting | disconnection of a fiber can be decreased at the time of extending | stretching in hot water.
　また、乾熱で延伸する際の繊維温度は、１５０℃以上１７０℃以下であることが好ましい。１５０℃以上であれば、繊維表面の皺を伸ばしやすくなり、１７０℃以下であれば、熱による変色を少なくでき、乾熱での延伸時に繊維の切断が少なくできる。 Further, the fiber temperature at the time of stretching with dry heat is preferably 150 ° C. or more and 170 ° C. or less. If it is 150 degreeC or more, it will become easy to extend the wrinkle on the fiber surface, and if it is 170 degreeC or less, the discoloration by a heat | fever can be lessened and the cutting | disconnection of a fiber can be lessened at the time of extending | stretching by dry heat.
　乾熱で延伸する際に繊維束を加熱する手段としては、加熱ロール、熱板による接触加熱、熱風で加熱する非接触加熱が挙げられる。中でも、効率的に加熱できる点で、繊維束を加熱する手段は加熱ロールが好ましい。
　また、加熱ロールで加熱する場合は、加熱ロールの温度と繊維束が加熱ロールに接触する時間で適宜設定すればよい。複数の加熱ロールに通して、繊維束の両面を加熱するのが好ましい。 Examples of means for heating the fiber bundle when stretching by dry heat include contact heating with a heating roll, a hot plate, and non-contact heating with hot air. Among them, a heating roll is preferable as a means for heating the fiber bundle in that it can be efficiently heated.
Moreover, what is necessary is just to set suitably with the time when the temperature of a heating roll and a fiber bundle contact a heating roll when heating with a heating roll. It is preferable to heat both sides of the fiber bundle through a plurality of heating rolls.
　加熱ロールの温度は、１５０℃以上１９０℃以下であることが好ましい。前記温度が１９０℃以下であれば、繊維の熱による変色を少なくできる。
　乾熱延伸された繊維束は、捲縮を付与され、コンテナーに収納される。 It is preferable that the temperature of a heating roll is 150 degreeC or more and 190 degrees C or less. If the said temperature is 190 degrees C or less, discoloration by the heat | fever of a fiber can be decreased.
The fiber bundle subjected to dry heat drawing is crimped and stored in a container.
　熱水で延伸された繊維の膨潤度は８０％以上１３０％以下の範囲にあることが好ましい。膨潤度が８０％以上１３０％以下であれば、乾燥性や生産性が良好な点で好ましく、繊維表面の皺が少なくなり易い。 It is preferable that the degree of swelling of the fiber drawn with hot water is in the range of 80% to 130%. If the degree of swelling is 80% or more and 130% or less, it is preferable in terms of good drying properties and productivity, and wrinkles on the fiber surface tend to be reduced.
＜熱緩和処理＞
　最後に繊維の熱収縮率が５％以上２０％以下となるように熱緩和処理を行いアクリル繊維とする。熱緩和条件は繊維の熱収縮率によって規定され、繊維の熱収縮が５％以上２０％以下であれば、抗ピル性が保たれる結節強度及び結節伸度となる点で好ましい。
　前記熱収縮率とは、熱緩和処理前後で繊維束が収縮した比率である。 <Heat relaxation treatment>
Finally, heat relaxation treatment is performed so that the thermal shrinkage rate of the fiber is 5% or more and 20% or less to obtain an acrylic fiber. The thermal relaxation condition is defined by the thermal shrinkage rate of the fiber. If the thermal shrinkage of the fiber is 5% or more and 20% or less, it is preferable in terms of knot strength and knot elongation at which anti-pill property is maintained.
The heat shrinkage rate is a ratio of shrinkage of the fiber bundle before and after the heat relaxation treatment.
　熱緩和する温度は、１２０℃以上１３５℃以下とする。前記圧力が１２０℃以上であれば、紡績時のカード通過性が良好な単繊維強度及び単繊維伸度を得られる点で好ましく、１３５℃以下であれば、抗ピル性が良好な単繊維を得られる点で好ましい。 The temperature for heat relaxation is 120 ° C or higher and 135 ° C or lower. If the pressure is 120 ° C. or higher, it is preferable in terms of obtaining single fiber strength and single fiber elongation with good card passing properties during spinning, and if it is 135 ° C. or lower, a single fiber having good anti-pill properties is obtained. It is preferable at the point obtained.
　以上のような製造方法により得た本発明のアクリル繊維束はカッターで切断して短繊維とされた後、紡績される。紡績糸の構成は、本発明のアクリル繊維を１００％としても良いし、他の繊維、例えば通常のアクリル繊維、ポリエステル繊維、ナイロン繊維、レーヨン繊維等の合成繊維または化学繊維、綿、ウール、絹等の天然繊維と混紡して、紡績糸とすることも可能である。 The acrylic fiber bundle of the present invention obtained by the above production method is cut with a cutter to make short fibers, and then spun. The composition of the spun yarn may be 100% of the acrylic fiber of the present invention, and other fibers, for example, synthetic fibers such as ordinary acrylic fiber, polyester fiber, nylon fiber, rayon fiber or chemical fiber, cotton, wool, silk It is also possible to make a spun yarn by blending with natural fibers such as
＜紡績糸の繊維構成＞
　本発明の紡績糸は、紡績糸中に含まれる本発明のアクリル繊維の含有率を４０質量％以上とすることが好ましい。前記含有率が４０質量％以上であれが、本発明のアクリル繊維の光沢性、抗ピル性能が表れやすい。その観点から、前記含有率は６０質量％以上がより好ましく、８０質量％以上がさらに好ましい。 <Fiber composition of spun yarn>
In the spun yarn of the present invention, the content of the acrylic fiber of the present invention contained in the spun yarn is preferably 40% by mass or more. Even if the content is 40% by mass or more, the glossiness and anti-pill performance of the acrylic fiber of the present invention are likely to appear. From this viewpoint, the content is more preferably 60% by mass or more, and further preferably 80% by mass or more.
＜紡績糸の番手＞
　本発明の紡績糸は、紡績糸の糸番手は綿番手で４０番手以上７０番手以下が好ましい。前記糸番手が４０番手以上であれば、本発明のアクリル繊維の細い繊度の効果により布帛をソフトにし易い。また、７０番手以下であれば、紡績糸を使用する際に必要な強度を得易い。
　紡績糸の糸むらのＣＶ％は１１．５以下が好ましい。前記ＣＶ％が１１．５以下であれば、編地の外観がきれいであり、光沢性が向上する。前記ＣＶ％は１１以下がより好ましく、１０以下がさらに好ましい。 <Count of spun yarn>
In the spun yarn of the present invention, the yarn count of the spun yarn is preferably a cotton count and 40 to 70. If the yarn count is 40 or more, the fabric is easy to soften due to the thin fineness effect of the acrylic fiber of the present invention. Moreover, if it is 70th or less, it will be easy to obtain intensity | strength required when using a spun yarn.
The CV% of the yarn unevenness of the spun yarn is preferably 11.5 or less. When the CV% is 11.5 or less, the appearance of the knitted fabric is clean and gloss is improved. The CV% is more preferably 11 or less, and even more preferably 10 or less.
＜セルロース系繊維の混率＞
　本発明の紡績糸は、セルロース系繊維の含有率が１０質量％以上４０質量％以下であることが好ましい。セルロース系繊維の含有率が１０質量％以上であれば、吸湿発熱性が向上する点で好ましく、４０質量％以下であれば、抗ピル性及び保温性が良好となるという点で好ましい。 <Mixing ratio of cellulosic fibers>
The spun yarn of the present invention preferably has a cellulosic fiber content of 10% by mass or more and 40% by mass or less. If the content of the cellulosic fiber is 10% by mass or more, the hygroscopic exothermic property is preferable, and if it is 40% by mass or less, the anti-pill property and the heat retaining property are preferable.
＜編地の糸構成＞
　本発明の編地は、前記紡績糸の含有率が４０質量％以上であることが好ましい。前記含有率が４０質量％以上であれば、編地の光沢性、抗ピル性の効果を得られ易い。前記観点から、５０質量％以上がより好ましく、６０質量％以上がさらに好ましい。 <Yarn composition of knitted fabric>
In the knitted fabric of the present invention, the content of the spun yarn is preferably 40% by mass or more. If the said content rate is 40 mass% or more, the gloss of a knitted fabric and the effect of an anti-pill property will be easy to be acquired. In view of the above, 50% by mass or more is more preferable, and 60% by mass or more is more preferable.
＜編地の目付＞
　本発明の編地は、目付が１５０ｇ／ｍ2 以上２３０ｇ／ｍ2 以下が好ましい。前記目付が１５０ｇ／ｍ2 以上であれば、編地の強度があり破れにくくなり、２３０ｇ／ｍ2 以下であれば、肌着として軽くてソフトは編地を得ることができる。 <Weight of knitted fabric>
The fabric of the present invention preferably has a basis weight of 150 g / m 2 or more and 230 g / m 2 or less. If the basis weight is 150 g / m 2 or more, the knitted fabric is strong and difficult to tear, and if it is 230 g / m 2 or less, the underwear is light and the soft knitted fabric can be obtained.
＜抗ピル性＞
　本発明の編地は、抗ピル性能が４級以上であることが好ましい。抗ピル性が４級以上であれば、毛玉が少なく編地の見た目がきれいにできる。前記抗ピル性能は４．５級以上がより好ましい。 <Anti-pill property>
The knitted fabric of the present invention preferably has an anti-pill performance of 4th grade or higher. If the anti-pilling property is 4th grade or higher, there are few hairballs and the knitted fabric looks beautiful. The anti-pill performance is more preferably 4.5 grade or higher.
＜保温性＞
　本発明の編地は、保温性が１５％以上５０％以下であることが好ましい。前記保温性が１５％以上であれば、肌着として暖かさを得ることができ、５０％以下であれば、暑すぎることがない。 <Heat retention>
The knitted fabric of the present invention preferably has a heat retention of 15% to 50%. If the heat retention is 15% or more, warmth can be obtained as underwear, and if it is 50% or less, it is not too hot.
　本発明のアクリル繊維について、以下の実施例を用いて説明する。
（繊維表面の凹凸測定方法）
　本発明のアクリル繊維の凹凸の深さは、以下の中心線平均粗さ（Ｒａ）、最大高さ（Ｒｙ）、３０点平均粗さ（Ｒｚ）および局部山頂の間隔（Ｓ）によって表される。これらは、レーザー顕微鏡を用いることによって測定される。
　図１～４は、本発明のアクリル繊維を構成している単繊維の、繊維長さ方向に対して垂直な断面における、単繊維表面の断面形状を模式的に示した図である。 The acrylic fiber of this invention is demonstrated using a following example.
(Measurement method of fiber surface irregularities)
The depth of the unevenness of the acrylic fiber of the present invention is represented by the following centerline average roughness (Ra), maximum height (Ry), 30-point average roughness (Rz), and local summit spacing (S). . These are measured by using a laser microscope.
1 to 4 are diagrams schematically showing the cross-sectional shape of the surface of a single fiber in a cross section perpendicular to the fiber length direction of the single fiber constituting the acrylic fiber of the present invention.
（単繊維の表面の中心線平均粗さ＜Ｒａ＞）
　単繊維の表面の中心線平均粗さ（Ｒａ）とは、図１に示すように、粗さ曲線からその中心線ｍの方向に基準長さＬだけ抜き取り、抜き取り部分の中心線ｍから測定曲線までの偏差の絶対値を合計し、平均した値を求め、この値をナノメートル（ｎｍ）で表したものである。 (Center line average roughness of single fiber <Ra>)
The centerline average roughness (Ra) of the surface of the single fiber is, as shown in FIG. 1, extracted from the roughness curve by the reference length L in the direction of the centerline m, and measured from the centerline m of the extracted portion. The absolute values of the deviations up to are summed up to obtain an average value, and this value is expressed in nanometers (nm).
（単繊維の表面の最大高さ＜Ｒｙ＞）
　単繊維の表面の最大高さ（Ｒｙ）とは、図２に示すように、粗さ曲線からその中心線ｍの方向に基準長さＬだけ抜き取り、抜き取り部分における、最も高い山頂線と中心線ｍとの間隔Ｒｐおよび最も低い谷底線と中心線ｍとの間隔Ｒｖの合計値（Ｒｐ＋Ｒｖ）を求め、この値をナノメートル（ｎｍ）で表したものである。 (Maximum height of single fiber surface <Ry>)
As shown in FIG. 2, the maximum height (Ry) of the surface of the single fiber is extracted by a reference length L in the direction of the center line m from the roughness curve, and the highest peak line and center line in the extracted part The total value (Rp + Rv) of the distance Rp to m and the distance Rv between the lowest valley line and the center line m is obtained, and this value is expressed in nanometers (nm).
（単繊維の表面の３０点平均粗さ＜Ｒｚ＞）
　単繊維の表面の３０点平均粗さ（Ｒｚ）とは、図３に示すように、粗さ曲線からその平均線の方向に基準長さだけを抜き取り、この抜取り部分の平均線から縦倍率の方向に測定した、最も高い山頂から１５番目までの山頂の標高（Ｙｐ）の絶対値の平均値と、最も低い谷底から１５番目までの谷底の標高（Ｙｖ）の絶対値の平均値との和を求め、この値をナノメートル（ｎｍ）で表したものをいう。 (30-point average roughness of single fiber surface <Rz>)
As shown in FIG. 3, the 30-point average roughness (Rz) of the surface of a single fiber is obtained by extracting only the reference length from the roughness curve in the direction of the average line, and calculating the longitudinal magnification from the average line of the extracted portion. The sum of the average absolute value of the elevation (Yp) from the highest peak to the fifteenth peak and the average absolute value of the elevation (Yv) from the lowest valley to the fifteenth peak measured in the direction And this value is expressed in nanometers (nm).
（単繊維の表面の凸部の頂点間距離＜Ｓ＞）
　単繊維の表面の凸部の頂点間距離（Ｓ）とは、図４に示すように、粗さ曲線からその中心線ｍの方向に基準長さＬだけ抜き取り、隣り合う局部山頂間に対応する平均線の長さを求め、この多数の局部山頂間の平均値をナノメートル（ｎｍ）で表したものである。 (Distance between vertices of convex part of single fiber surface <S>)
The distance between the vertices (S) of the convex portions on the surface of the single fiber corresponds to the distance between adjacent local peaks, as shown in FIG. 4, by extracting a reference length L from the roughness curve in the direction of the center line m. The length of the average line is obtained, and the average value between the many local peaks is expressed in nanometers (nm).
（強伸度、結節強伸度）
　ＪＩＳ　Ｌ１０１５に従って測定した。 (Strong elongation, nodular strength)
It measured according to JIS L1015.
（繊維断面の深さ０．１μｍ以上の凹部の数の測定）
　２００本以上３００本以下の本発明のアクリル繊維にドライヤーの熱風を当て、繊維の収縮を伸ばしチューブの中に入れる。ここで、前記ポリエチレンチューブは周方向にのみ縮むものを使用した。 (Measurement of the number of recesses having a fiber cross-section depth of 0.1 μm or more)
The hot air of a dryer is applied to 200 or more and 300 or less acrylic fibers of the present invention, and the shrinkage of the fibers is stretched and placed in a tube. Here, the polyethylene tube used shrinks only in the circumferential direction.
　次に、本発明のアクリル繊維が詰まった前記ポリエチレンチューブを未使用のカミソリの刃で軸方向に略垂直方向に切断し、約２ｍｍの長さにした。
　前記切断した面の一方を両面テープで台に固定し、低温イオンスパッタリング装置（日本電子株式会社製、ＪＦＣ１１００）を使用し、１２００Ｖ、５ｍＡ、８分間の条件で、切断面の他方の面にある観察面とする本発明のアクリル繊維の切断面に金を蒸着させサンプルを作製した。 Next, the polyethylene tube filled with the acrylic fiber of the present invention was cut in a direction substantially perpendicular to the axial direction with an unused razor blade to a length of about 2 mm.
One of the cut surfaces is fixed to a table with double-sided tape, and a low-temperature ion sputtering apparatus (manufactured by JEOL Ltd., JFC1100) is used, and it is on the other surface of the cut surface under conditions of 1200 V, 5 mA, 8 minutes. Gold was vapor-deposited on the cut surface of the acrylic fiber of the present invention as the observation surface to prepare a sample.
　走査型電子顕微鏡（フィリップス社、品番XL-20 ）を使用し、前記サンプルの繊維の断面を倍率５０００倍で撮影したあと、撮影画像より、繊維表面に有する凹部を１つ決め、その凹部の両側にある凸部を結ぶ接線から凹部に垂直におろした線の最長の長さを凹部の深さとし、繊維断面における深さ０．１μｍ以上の凹部の深さとその数を数えた。３個の繊維断面を測定し、その平均値を繊維断面の深さ０．１μｍ以上の凹部の数とした。 Using a scanning electron microscope (Phillips, part number XL-20), after taking a cross-section of the sample fiber at a magnification of 5000 times, determine one concave portion on the fiber surface from the photographed image, and both sides of the concave portion The longest length of a line perpendicular to the concave portion from the tangent line connecting the convex portions is defined as the depth of the concave portion. Three fiber cross sections were measured, and the average value was defined as the number of recesses having a fiber cross section depth of 0.1 μm or more.
（光沢性評価）
　光沢性は以下のようにして評価した。
　実施例１、２及び比較例１のアクリル繊維をそれぞれ１００％使用し、同じ条件の紡績糸とし、同じ条件で布帛を作製し、目視にて光沢性を比較評価した。
　○：光沢性良好、
　×：光沢性悪い。 (Glossiness evaluation)
The glossiness was evaluated as follows.
Using 100% of each of the acrylic fibers of Examples 1 and 2 and Comparative Example 1, spun yarns under the same conditions were used, fabrics were prepared under the same conditions, and glossiness was visually evaluated.
○: Good glossiness,
X: Poor gloss.
（実施例１）
　アクリロニトリル９５％、酢酸ビニル４．４％、メタリルスルホン酸ソーダ０．６％からなる還元粘度１．８のアクリロニトリル系共重合体をジメチルアセトアミドに溶解し、共重合体濃度２４％、５０℃における粘度が２００ポイズの紡糸原液を得た。 (Example 1)
An acrylonitrile copolymer having a reduced viscosity of 1.8 consisting of 95% acrylonitrile, 4.4% vinyl acetate and 0.6% sodium methallylsulfonate is dissolved in dimethylacetamide, and the copolymer concentration is 24% at 50 ° C. A spinning dope with a viscosity of 200 poise was obtained.
　この紡糸原液を孔径０．０４５ｍｍの複数の吐出孔から、ジメチルアセトアミド濃度５６％、温度４１℃の凝固液中に吐出して繊維状とし、９８℃の熱水中で溶媒を洗浄しながら２．５倍の延伸を施した。続いて油剤を付着させ、表面温度が１５０℃に設定した複数の熱ローラーで乾燥し、さらに１８０℃の熱ローラーで加熱して繊維温度を１６０℃とし、空気中で２倍に延伸し、捲縮を付与後、コンテナーに振り落した。 This spinning dope is discharged from a plurality of discharge holes having a hole diameter of 0.045 mm into a coagulating liquid having a dimethylacetamide concentration of 56% and a temperature of 41 ° C. to form a fiber, and while washing the solvent in 98 ° C. hot water, 2. 5 times stretching was applied. Subsequently, an oil agent is adhered, dried with a plurality of heat rollers whose surface temperature is set to 150 ° C., further heated with a heat roller of 180 ° C. to a fiber temperature of 160 ° C., stretched twice in air, After applying the shrinkage, it was shaken down to the container.
　さらに、繊維束の熱収縮率が７％以上９％以下になるように熱緩和処理を行い、単繊維繊度が１．０ｄｔｅｘの繊維を得た。その条件を表１に、その結果を表２に示す。
　この繊維の結節強度（ｃＮ／ｄｔｅｘ）の値と結節伸度（％）の値との積Ｋは１５．９であり、抗ピル性が良好になる値であった。また、深さ０．１μｍ以上の凹部の個数が２個であり、比較例に比べ、光沢性に優れるものであった。 Further, heat relaxation treatment was performed so that the heat shrinkage rate of the fiber bundle was 7% or more and 9% or less, and a fiber having a single fiber fineness of 1.0 dtex was obtained. The conditions are shown in Table 1, and the results are shown in Table 2.
The product K of the value of knot strength (cN / dtex) and the value of knot elongation (%) of this fiber was 15.9, which is a value that makes the anti-pill property good. In addition, the number of recesses having a depth of 0.1 μm or more was two, and the gloss was superior to that of the comparative example.
（実施例２）
　湿熱延伸倍率、乾熱延伸倍率を変更した以外は、実施例１と同様に紡糸を行った。その条件を表１に、その結果を表２に示す。
　その結果、結節強度（ｃＮ／ｄｔｅｘ）の値と結節伸度（％）の値との積Ｋは１６．６であり、抗ピル性が良好になる値であった。また、深さ０．１μｍ以上の凹部の個数が４個であり、比較例に比べ、光沢性に優れるものであった。 (Example 2)
Spinning was performed in the same manner as in Example 1 except that the wet heat draw ratio and the dry heat draw ratio were changed. The conditions are shown in Table 1, and the results are shown in Table 2.
As a result, the product K of the value of the nodule strength (cN / dtex) and the value of the nodule elongation (%) was 16.6, which was a value at which the anti-pill property was good. In addition, the number of recesses having a depth of 0.1 μm or more was four, and the gloss was superior to that of the comparative example.
（実施例３～１１）
　表１に示すとおりに、アクリル繊維の製造条件を変更した以外は、実施例１と同様にアクリル繊維の製造をおこなった。そのアクリル繊維の物性を表１に示す。 (Examples 3 to 11)
As shown in Table 1, acrylic fibers were produced in the same manner as in Example 1 except that the production conditions of the acrylic fibers were changed. The physical properties of the acrylic fiber are shown in Table 1.
（比較例１）
　乾熱延伸をせず、熱水延伸の倍率を高め、総延伸倍率を同じにした以外は実施例１と同様にアクリル繊維の製造を行った。その条件を表１に、その結果を表２に示す。
　その結果、結節強度（ｃＮ／ｄｔｅｘ）の値と結節伸度（％）の値との積Ｋは２５．７であり、抗ピル性はあるものの、本発明のアクリル繊維に比べ良好な値ではなかった。また、深さ０．１μｍ以上の凹部の個数が１５個であり、光沢性は劣るものであった。 (Comparative Example 1)
Acrylic fibers were produced in the same manner as in Example 1 except that the hot-water stretching was not performed, the hot-water stretching ratio was increased, and the total stretching ratio was the same. The conditions are shown in Table 1, and the results are shown in Table 2.
As a result, the product K of the value of nodule strength (cN / dtex) and the value of nodule elongation (%) is 25.7, and although it has anti-pill property, it is not as good as the acrylic fiber of the present invention. There wasn't. Further, the number of recesses having a depth of 0.1 μm or more was 15, and the glossiness was inferior.
（比較例２）
　乾熱延伸をせず、熱水延伸の倍率を高め、総延伸倍率を同じにした以外は実施例３と同様にアクリル繊維の製造を行った。その条件を表１に、その結果を表２に示す。
　その結果、結節強度（ｃＮ／ｄｔｅｘ）の値と結節伸度（％）の値との積Ｋは２０であり、抗ピル性はあるものの、本発明のアクリル繊維に比べ良好な値ではなかった。また、光沢性は劣るものであった。 (Comparative Example 2)
Acrylic fibers were produced in the same manner as in Example 3 except that the hot water stretching was not performed and the hot water stretching ratio was increased and the total stretching ratio was the same. The conditions are shown in Table 1, and the results are shown in Table 2.
As a result, the product K of the value of knot strength (cN / dtex) and the value of knot elongation (%) was 20, and although it had anti-pill property, it was not a good value compared with the acrylic fiber of the present invention. . Moreover, glossiness was inferior.
（比較例３）
　特開２０１３－２０９７７１に記載の炭素繊維前駆体用アクリル繊維を製造する条件でアクリル繊維を製造した。その条件を表１に、その結果を表２に示す。
　炭素繊維前駆体用アクリル繊維は、結節強伸度の積Ｋが低く、紡績時に折損し紡績できない物性であった。 (Comparative Example 3)
An acrylic fiber was produced under the conditions for producing the carbon fiber precursor acrylic fiber described in JP-A-2013-209771. The conditions are shown in Table 1, and the results are shown in Table 2.
The acrylic fiber for carbon fiber precursor had a low product K of knot strength and elongation, and was a physical property that could not be spun because it broke during spinning.
（比較例４）
　特開平１１－２２２７１６に記載の光沢性繊維を製造する条件に従い単繊維繊度２２ｄｔｅｘ、扁平率２２のアクリル繊維を製造した。その条件を表１に、その結果を表２に示す。 (Comparative Example 4)
An acrylic fiber having a single fiber fineness of 22 dtex and a flatness ratio of 22 was produced according to the conditions for producing a glossy fiber described in JP-A-11-222716. The conditions are shown in Table 1, and the results are shown in Table 2.
　積Ｋは抗ピル性を示す範囲であるが、繊度が太く風合いが悪いため、衣料用途には不向きであった。 The product K is a range showing anti-pilling properties, but it is unsuitable for clothing use because of its fineness and poor texture.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（実施例１２）
　実施例１のアクリル繊維を７０質量％とマイクロモダール（レンチング社製、１．０ｄｔｅｘ）と３０質量部とを混綿し、糸番手が綿番手で５０番手、撚り数が８７３ｔ／ｍの紡績糸を製造した。その物性を表２に示す。 Example 12
70% by mass of acrylic fiber of Example 1, Micromodal (manufactured by Lenzing Co., 1.0 dtex) and 30 parts by mass are mixed, and the yarn count is 50, the yarn count is 873 t / m. Manufactured. The physical properties are shown in Table 2.
（実施例１３）
　実施例１のアクリル繊維を１００質量％で、糸番手が、綿番手で６０番手、撚り数が１１３９ｔ／ｍの紡績糸を製造した。その物性を表２に示す。 (Example 13)
A spun yarn of 100% by mass of the acrylic fiber of Example 1, a yarn count of 60, a cotton count, and a twist number of 1139 t / m was produced. The physical properties are shown in Table 2.
（実施例１４、１５）
　糸番手を表２に示す通りに変更した以外は、実施例１３と同様にして紡績糸を得た。その物性を表２に示す。 (Examples 14 and 15)
A spun yarn was obtained in the same manner as in Example 13 except that the yarn count was changed as shown in Table 2. The physical properties are shown in Table 2.
（実施例１６）
　実施例１１のアクリル繊維を１００質量％とし、糸番手が、綿番手で４０番手、撚り数が８２０ｔ／ｍの紡績糸を製造した。その物性を表２に示す。 (Example 16)
A spun yarn having an acrylic fiber of Example 11 of 100% by mass, a yarn count of 40 and a twist number of 820 t / m was manufactured. The physical properties are shown in Table 2.
（比較例５）
　比較例１のアクリル繊維を７０質量％とマイクロモダール（レンチング社製、１．０ｄｔｅｘ）を３０質量部とを混綿し、糸番手が綿番手で５０番手、撚り数が９００ｔ／ｍの紡績糸を製造した。その物性を表２に示す。
　実施例１２と比較して、糸むらが大きいものであった。
　また、実施例１２の紡績糸と比較例５の紡績糸を、コーンに巻かれた状態で目視で比較したところ、実施例１２の紡績糸の方が、光沢があることが確認できた。 (Comparative Example 5)
70% by mass of the acrylic fiber of Comparative Example 1 and 30 parts by mass of Micromodal (manufactured by Lenzing Co., Ltd., 1.0 dtex) are mixed, and the yarn count is 50 and the yarn count is 900 t / m. Manufactured. The physical properties are shown in Table 2.
Compared with Example 12, the yarn unevenness was large.
Further, when the spun yarn of Example 12 and the spun yarn of Comparative Example 5 were visually compared in a state of being wound around a cone, it was confirmed that the spun yarn of Example 12 was more glossy.
（比較例６）
　比較例１のアクリル繊維を１００質量％で、糸番手が、綿番手で６０番手、撚り数が１１３９ｔ／ｍの紡績糸を製造した。その物性を表２に示す。
　実施例１３と比較して、糸むらが大きいものであった。 (Comparative Example 6)
A spun yarn of 100% by mass of the acrylic fiber of Comparative Example 1, a yarn count of 60, a cotton count, and a twist number of 1139 t / m was manufactured. The physical properties are shown in Table 2.
Compared with Example 13, the yarn unevenness was large.
（比較例７、８）
　糸番手を表２に示す通りに変更した以外は、比較例６と同様にして紡績糸を得た。その物性を表２に示す。 (Comparative Examples 7 and 8)
A spun yarn was obtained in the same manner as in Comparative Example 6 except that the yarn count was changed as shown in Table 2. The physical properties are shown in Table 2.
（比較例９）
　比較例２のアクリル繊維を１００質量％とし、糸番手が、綿番手で４０番手、撚り数が８２０ｔ／ｍの紡績糸を製造した。その物性を表２に示す。
　実施例１３～１６の紡績糸とそれぞれ対応する比較例６～９の紡績糸とを、コーンに巻かれた状態を目視で比較したところ、各実施例の紡績糸の方が、光沢があることが確認できた。 (Comparative Example 9)
A spun yarn was produced in which the acrylic fiber of Comparative Example 2 was 100% by mass, the yarn count was 40 cotton count, and the twist number was 820 t / m. The physical properties are shown in Table 2.
When the spun yarns of Examples 13 to 16 and the spun yarns of Comparative Examples 6 to 9 respectively corresponding to the spun yarns were visually compared in the state of being wound around a cone, the spun yarns of each Example were more glossy. Was confirmed.
（実施例１７）
　実施例１５の紡績糸を使用し、１４Ｇで天竺組織の横編地を作成した。目付は２１０ｇ／ｍ2 であり、抗ピル性能は４．５級、保温性は４５．１％であった。 (Example 17)
Using the spun yarn of Example 15, a flat knitted fabric with a tengu structure was prepared at 14G. The basis weight was 210 g / m 2 , the anti-pill performance was 4.5 grade, and the heat retention was 45.1%.
（比較例１０）
　比較例８の紡績糸を使用し、１４Ｇで天竺組織の横編地を作成した。目付は２１０ｇ／ｍ2 であり、抗ピル性能は４．５級、４４．９％であった。
　しかしながら、光沢性は実施例１７と比較して劣るものであった。 (Comparative Example 10)
Using the spun yarn of Comparative Example 8, a flat knitted fabric with a tengu structure was prepared at 14G. The basis weight was 210 g / m 2 , and the anti-pill performance was 4.5 grade, 44.9%.
However, the gloss was inferior to that of Example 17.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

Claims (14)

  1. 　単繊維の表面の中心線平均粗さ（Ｒａ）が３ｎｍ以上１２ｎｍ以下であり、単繊維繊度が０．５ｄｔｅｘ以上３．５ｄｔｅｘ以下であるアクリル繊維。 An acrylic fiber having a center line average roughness (Ra) of 3 nm to 12 nm and a single fiber fineness of 0.5 dtex to 3.5 dtex.
  2. 　単繊維の表面の中心線平均粗さ（Ｒａ）が３ｎｍ以上１２ｎｍ以下であり、結節強度（ｃＮ／ｄｔｅｘ）の値と結節伸度（％）の値との積Ｋが１０以上３０以下であるアクリル繊維。 The center line average roughness (Ra) of the surface of the single fiber is 3 nm or more and 12 nm or less, and the product K of the value of nodule strength (cN / dtex) and the value of nodule elongation (%) is 10 or more and 30 or less. Acrylic fiber.
  3. 　結節強度（ｃＮ／ｄｔｅｘ）の値と結節伸度（％）の値との積Ｋが１０以上３０以下である請求項１に記載のアクリル繊維。 The acrylic fiber according to claim 1, wherein a product K of a value of knot strength (cN / dtex) and a value of knot elongation (%) is 10 or more and 30 or less.
  4. 　単繊維繊度が０．５ｄｔｅｘ以上３．５ｄｔｅｘ以下である請求項２に記載のアクリル繊維。 The acrylic fiber according to claim 2, wherein the single fiber fineness is 0.5 dtex or more and 3.5 dtex or less.
  5. 　単繊維の表面の最大高低差（Ｒｙ）が４０ｎｍ以上１５０ｎｍ以下、３０点平均粗さ（Ｒｚ）が２０ｎｍ以上８０ｎｍ以下および単繊維の表面の凸部の頂点間距離（Ｓ）が８００ｎｍ以上１１００ｎｍ以下である請求項１～４のいずれか一項に記載のアクリル繊維。 The maximum height difference (Ry) of the single fiber surface is 40 nm or more and 150 nm or less, the 30-point average roughness (Rz) is 20 nm or more and 80 nm or less, and the distance (S) between the vertices of the convex portion of the single fiber surface is 800 nm or more and 1100 nm or less. The acrylic fiber according to any one of claims 1 to 4, wherein
  6. 　繊維軸に垂直な方向の断面において単繊維表面に有する深さ０．１μｍ以上の凹部が１０個以下である請求項１～５のいずれか一項に記載のアクリル繊維。 The acrylic fiber according to any one of claims 1 to 5, wherein the number of the concave portions having a depth of 0.1 µm or more on the surface of the single fiber is 10 or less in a cross section perpendicular to the fiber axis.
  7. 　アクリロニトリル単位９２質量％以上９６．８質量％以下、ビニル系モノマー単位２質量％以上６質量％以下、およびスルホン酸基含有ビニルモノマー単位０．２質量％以上２．０質量％以下を含むアクリル繊維であって、単繊維引張強度が１．８ｃＮ／ｄｔｅｘ以上３．０ｃＮ／ｄｔｅｘ以下、単繊維結節強度が１．０ｃＮ／ｄｔｅｘ以上１．８ｃＮ／ｄｔｅｘ以下、単繊維結節伸度が８％以上２０％以下である請求項１～６のいずれか一項に記載のアクリル繊維。 Acrylic fiber containing 92% by mass to 96.8% by mass of acrylonitrile units, 2% by mass to 6% by mass of vinyl monomer units, and 0.2% by mass to 2.0% by mass of sulfonic acid group-containing vinyl monomer units The single fiber tensile strength is 1.8 cN / dtex or more and 3.0 cN / dtex or less, the single fiber knot strength is 1.0 cN / dtex or more and 1.8 cN / dtex or less, and the single fiber knot elongation is 8% or more and 20 The acrylic fiber according to any one of claims 1 to 6, which is not more than%.
  8. 　アクリロニトリル単位を９２質量％以上９６．８質量％以下、およびスルホン酸基含有ビニルモノマー単位０．２質量％以上２．０質量％以下を含むアクリロニトリル系共重合体を有機溶媒に溶解して紡糸原液とし、前記紡糸原液を温度が３５℃以上５０℃以下の凝固浴に紡糸ノズルの吐出孔からジェットストレッチが０．４以上２．２以下で吐出して凝固繊維束とし、前記凝固繊維束を８０℃以上９８℃以下の熱水中で延伸倍率が２倍以上３．８倍以下で延伸し、油剤付与し、乾燥した後、繊維温度が１５０℃以上１７０℃以下として乾熱で延伸倍率が１．２倍以上３倍以下で延伸し、前記熱水中での延伸倍率と前記乾熱での延伸倍率の積Ｓが４倍以上６倍以下であるアクリル繊維の製造方法。 A spinning dope by dissolving an acrylonitrile copolymer containing 92% by mass or more and 96.8% by mass or less of an acrylonitrile unit and 0.2% by mass or more and 2.0% by mass or less of a sulfonic acid group-containing vinyl monomer unit in an organic solvent. The spinning solution is discharged into a coagulation bath having a temperature of 35 ° C. or more and 50 ° C. or less from a discharge hole of a spinning nozzle with a jet stretch of 0.4 or more and 2.2 or less to obtain a coagulated fiber bundle. After stretching at a stretching ratio of 2 to 3.8 times in hot water at 980C to 98C, oiling and drying, the fiber temperature is 150C to 170C and the stretching ratio is 1 with dry heat. A method for producing an acrylic fiber, which is stretched by 2 times or more and 3 times or less, and the product S of the stretching ratio in the hot water and the stretching ratio in the dry heat is 4 times or more and 6 times or less.
  9. 　前記アクリロニトリル系共重合体はビニル系モノマー単位を２質量％以上６質量％以下をさらに含み、前記凝固浴の溶媒濃度が４０質量％以上６０質量％以下であり、乾熱延伸後に熱緩和処理を行う請求項８に記載のアクリル繊維の製造方法。 The acrylonitrile copolymer further includes a vinyl monomer unit in an amount of 2% by mass to 6% by mass, the solvent concentration of the coagulation bath is 40% by mass to 60% by mass, and is subjected to a thermal relaxation treatment after dry heat stretching. The manufacturing method of the acrylic fiber of Claim 8 to perform.
  10. 　前記熱緩和処理温度が、１２０℃以上１３５℃以下であり、繊維緩和率が５％以上２０％以下である請求項８または９に記載のアクリル繊維の製造方法。 The method for producing acrylic fiber according to claim 8 or 9, wherein the thermal relaxation treatment temperature is 120 ° C or higher and 135 ° C or lower, and the fiber relaxation rate is 5% or higher and 20% or lower.
  11. 　請求項１～７のいずれか一項に記載のアクリル繊維を４０質量％以上含み、糸番手が綿番手で４０番手以上７０番手以下である紡績糸。 A spun yarn comprising 40% by mass or more of the acrylic fiber according to any one of claims 1 to 7 and having a yarn count of 40 to 70.
  12. 　セルロース系繊維を１０質量％以上４０質量％以下含んでなる請求項１１に記載の紡績糸。 The spun yarn according to claim 11, comprising 10% by mass or more and 40% by mass or less of cellulose fiber.
  13. 　請求項１１または１２に記載の紡績糸を４０質量％以上含み、目付が１５０ｇ／ｍ2 以上２３０ｇ／ｍ2 以下あり、抗ピル性能が４級以上である編地。 A knitted fabric comprising 40% by mass or more of the spun yarn according to claim 11 or 12, having a basis weight of 150 g / m 2 or more and 230 g / m 2 or less, and an anti-pill performance of grade 4 or more.
  14. 　保温率が、１５％以上５０％以下である、請求項１３に記載の編地。 The knitted fabric according to claim 13, wherein the heat retention rate is 15% or more and 50% or less.
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