Classifications

• • 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
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
• • 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
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
• • 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
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
  • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent

Definitions

• the present invention relates to a conductive polyamide composite fiber that can be dyed with cationic dyes and acid dyes, has conductive performance, and suppresses static electricity charging.
• Conductive fibers are often used for fabrics such as work clothes and protective clothes for flammable hazardous materials handlers, dustproof clothes for clean rooms, carpets, curtains, etc., mainly for the purpose of preventing sparks and dust clinging due to static electricity.
• the conductive fiber is a filament
• it is used in the fabric in a form in which the conductive fiber is inserted in a grid or stripe shape at a pitch of several mm to several cm, and when the conductive fiber is a staple, other Fibers blended with short fibers are used for fabrics.
• Examples of conductive fibers used for such fabrics include metal fibers made of metal itself, metal-plated fibers obtained by plating metal on general fibers, and general fibers coated with a conductive material composite resin by melting or solution coating.
• Conductive coated fibers conductive composite fibers obtained by composite spinning of a kneaded resin composition of a conductive substance and a thermoplastic resin, and the like can be mentioned.
• conductive performance that does not generate sparks, the texture when used as a fabric, corrosion resistance, chemical resistance, stretch resistance, abrasion resistance, washing durability, manufacturing cost, etc.
• conductive Conductive composite fibers using carbon black, titanium oxide particles having a conductive coating, conductive inorganic particles, etc., and using a polyester resin or a polyamide resin as the thermoplastic resin are most preferably used.
• conductive fibers are mixed with fabrics such as cationic dyeable fibers, such as aramid fibers, which are often used for work clothes and protective clothing, and acrylic fibers, which are used for sweaters and fleeces.
• cationic dyeable fibers such as aramid fibers, which are often used for work clothes and protective clothing
• acrylic fibers which are used for sweaters and fleeces.
• the conductive fibers contained in the fabric are not dyed during cationic dyeing, and the conductive fibers are conspicuously visible on the fabric, resulting in a loss of design.
• Patent Document 1 discloses a conductive composite fiber composed of a conductive layer and a non-conductive layer, wherein the conductive layer is made of conductive carbon black or titanium oxide having a conductive coating, and the non-conductive layer is proposed a conductive polyester fiber that can be dyed with a cationic dye by using a modified polyester containing a dicarboxylic acid component containing phosphonium sulfonate as a copolymerization component.
• Patent Documents 2 and 3 propose fabrics containing conductive composite fibers, conductive acrylic fibers, and aramid fibers in which an acrylic copolymer resin is used in the non-conductive layer.
• the conductive fiber using a modified polyester containing a sulfo group and a dicarboxylic acid component containing some salt as a copolymer component was polymerized only with a diol, which is a general polyester material, and a dicarboxylic acid that does not contain a sulfo group. It tends to be inferior in strength to conductive fibers using polyester. Conductive polyester fibers are further weakened by the alkali of the cationic dyeing solution. In addition, there is a problem that the conductive performance tends to decrease in processes such as spinning, warping, knitting, and dyeing. It may get lost. In addition, a problem with conductive acrylic fibers is that the manufacturing method of acrylic fibers is originally very complicated compared to polyester fibers and polyamide fibers. However, it is not suitable for fields that require high conductivity (for example, clean room wear worn during semiconductor manufacturing).
• the present invention has been made to solve the above problems, and has less strength reduction and good conductive performance compared to conductive fibers using unmodified resins.
• Another object of the present invention is to provide a conductive polyamide conjugate fiber which has good dyeability not only with cationic dyes but also with acid dyes.
• the present inventors have found that a terminal amino group of a polyamide resin reacts with a sulfonate-containing triazine derivative to form a polyamide resin in which a sulfonate is introduced into a portion of the terminal amino groups, thereby forming a non-conductive layer of a conductive composite fiber. , and found that a conductive polyamide composite fiber having good dyeability with cationic dyes and acid dyes can be obtained. That is, the present invention provides a non-conductive layer composed of a terminal-modified polyamide resin represented by Formula 1, in which some hydrogen atoms of terminal amino groups of the polyamide resin are substituted with a sulfonate-containing triazine derivative, and a conductive substance.
• a conductive polyamide composite comprising a conductive layer made of a fiber-forming resin, wherein the sulfonate-containing triazine derivative is 0.4 equivalent or more and 1.5 equivalent or less with respect to the terminal amino group amount of the polyamide resin. Fiber.
• PA indicates polyamide.
• R 1 represents an aromatic hydroxy group such as a phenoxy group, cresoxy group, xylenoxy group, naphthoxy group, -NR 2 R 3 -SO 3 X, or polyamide.
• R2 represents a hydrogen atom or a methyl group.
• R 3 represents an aliphatic linear substituent such as ethylene group or n-propylene group, or an aromatic substituent such as phenylene group or methylphenylene group.
• X represents a metal cation such as sodium ion, lithium ion, or an organic cation such as tert-butyl-ammonium ion, benzyltrimethylammonium ion, p-methylphenylammonium ion.
• the conductive substance is preferably one or more selected from conductive carbon black, titanium oxide particles having a conductive coating, and conductive inorganic particles.
• the content ratio of the conductive substance to the fiber-forming resin in the conductive layer is 20% by mass or more and 40% by mass or less in the case of conductive carbon black, and titanium oxide particles having a conductive coating and conductive inorganic particles.
• the content is preferably 60% by mass or more and 80% by mass or less.
• the area ratio of the conductive layer to the entire fiber cross section is 3% or more and 50% or less.
• the present invention is also a fiber structure using the conductive polyamide conjugate fiber at least in part.
• the conductive polyamide composite fiber of the present invention can be industrially manufactured easily and inexpensively, can be dyed with cationic dyes and acid dyes at normal pressure, and has good color development. Therefore, when mixed with aramid material, acrylic material, wool material, silk material, etc., it is possible to dye under the same conditions as other materials, suppressing static electricity charging of the product, and creating a highly designed fabric. can be provided.
• the present invention comprises a non-conductive layer made of a terminal-modified polyamide resin represented by Formula 1, in which some hydrogen atoms of the terminal amino groups of the polyamide resin are substituted with sulfonate-containing triazine derivatives, and a conductive substance. It is a composite fiber comprising a conductive layer made of a fiber-forming resin.
• PA indicates polyamide.
• R 1 represents an aromatic hydroxy group such as a phenoxy group, cresoxy group, xylenoxy group, naphthoxy group, -NR 2 R 3 -SO 3 X, or polyamide.
• R2 represents a hydrogen atom or a methyl group.
• R 3 represents an aliphatic linear substituent such as ethylene group or n-propylene group, or an aromatic substituent such as phenylene group or methylphenylene group.
• X represents a metal cation such as sodium ion, lithium ion, or an organic cation such as tert-butyl-ammonium ion, benzyltrimethylammonium ion, p-methylphenylammonium ion.
• the sulfonate-containing triazine derivative is contained in an amount of 0.4 equivalents or more and 1.5 equivalents or less with respect to the amount of terminal amino groups of the polyamide resin. Within this range, the effects of the present invention are likely to be obtained. Among them, 0.6 equivalent or more is preferable, and 0.8 equivalent or more is more preferable. Also, it is preferably 1.4 equivalents or less, more preferably 1.2 equivalents or less. From the viewpoint of obtaining good dyeability for both the cationic dye and the acid dye, the amount is particularly preferably 0.8 equivalent or more and 1.0 equivalent or less.
• Examples of the compound that reacts with the terminal amino group of the polyamide resin include a sulfonate-containing triazine derivative represented by Formula 2 below.
• R 1 represents an aromatic hydroxy group such as a phenoxy group, cresoxy group, xylenoxy group, naphthoxy group, —NR 2 R 3 —SO 3 X, or polyamide.
• R1 ' represents an aromatic hydroxy group such as a phenoxy group, cresoxy group or naphthoxy group.
• R2 represents a hydrogen atom or a methyl group.
• R 3 represents an aliphatic linear substituent such as ethylene group or n-propylene group, or an aromatic substituent such as phenylene group or methylphenylene group.
• X represents a metal cation such as sodium ion, lithium ion, or an organic cation such as tert-butyl-ammonium ion, benzyltrimethylammonium ion, p-methylphenylammonium ion.
• R 1 ' in formula 2 is a halogen atom such as a chloro group or a bromo group, it reacts with the terminal amino group of the polyamide resin to generate a strong acid such as hydrochloric acid, resulting in decomposition of the polyamide resin, which is not preferable.
• Alkoxy groups such as methoxy, phenoxy, cresoxy, xylenoxy, and naphthoxy are preferred because they do not generate strong acids when reacted with terminal amino groups.
• Aromatic hydroxy groups such as radicals, cresoxy groups, xylenoxy groups and naphthoxy groups are more preferred.
• R 1 in Formulas 1 and 2 is more preferably an aromatic hydroxy group such as a phenoxy group, cresoxy group, xylenoxy group, naphthoxy group, etc. for the same reason as in the preceding paragraph.
• R 1 in formulas 1 and 2 may be -NR 2 R 3 -SO 3 X, and is bound to the terminal amino group of the polyamide resin as shown in formula 3 below. good too.
• R 2 represents a hydrogen atom or a methyl group.
• R 3 represents an aliphatic linear substituent such as ethylene group or n-propylene group, or an aromatic substituent such as phenylene group or methylphenylene group.
• X represents a metal cation such as sodium ion, lithium ion, or an organic cation such as tert-butyl-ammonium ion, benzyltrimethylammonium ion, p-methylphenylammonium ion.
• R 2 in Formula 2 is preferably a hydrogen atom or a methyl group.
• a bulky substituent is not preferred because it lowers the reaction rate when synthesizing the sulfonate-containing triazine derivative of Formula 2.
• R 3 in Formula 2 is preferably an aliphatic linear substituent such as ethylene group or n-propylene group, or an aromatic substituent group such as phenylene group or methylphenylene group.
• Aromatic substituents such as a phenylene group and a methylphenylene group are more preferable because the decrease in resin viscosity after reacting the compound of formula 2 with the polyamide resin is small and the resin effectively reacts with the terminal amino group. .
• X in Formula 2 is preferably a metal cation such as sodium ion or lithium ion, or an organic cation such as tert-butyl-ammonium ion, benzyltrimethylammonium ion or p-methylphenylammonium ion.
• organic cations a decrease in the viscosity of the resin after reacting with Formula 2 and the polyamide resin was observed to be somewhat large, so metal cations such as sodium ions and lithium ions are more preferable.
• the method for synthesizing the sulfonate-containing triazine derivative of formula 2 is not particularly limited, but cyanuric chloride is used as a starting material and is reacted with aminosulfonic acid, followed by reaction with alcohol to obtain cyanuric chloride in cyanuric chloride.
• a method of substituting a chlorine atom with an alkoxy group is preferred because of good reaction efficiency.
• Aminosulfonic acids used in the reaction include, for example, taurine, N-methyltaurine, 3-amino-1-propanesulfonic acid, sulfanilic acid, N-methylsulfanilic acid, aminomethylbenzenesulfonic acid, 2-((2-aminoethyl ) amino) ethylsulfonic acid and the like are preferred. More preferred are sulfanilic acid, N-methylsulfanilic acid and aminomethylbenzenesulfonic acid.
• the alcohol used for the reaction is preferably an organic compound containing an aromatic hydroxy group, such as phenol, cresol, xylenol, naphthol. Phenol is more preferred.
• cyanuric chloride and aminosulfonic acid When cyanuric chloride and aminosulfonic acid are reacted, it is preferable to use an aqueous solvent. Although aminosulfonic acids are water soluble, the reactants become water insoluble, facilitating purification. Cyanuric chloride is sparingly soluble in water but readily soluble in acetone, so a mixed solvent containing water and acetone is more preferable. Further, the reaction of adding an alcohol to substitute a chlorine atom in cyanuric chloride with an alkoxy group is preferably carried out in a basic aqueous solution.
• the molar ratio of aminosulfonic acid is preferably 1 or more and 2 or less when the molar ratio of cyanuric chloride is 1.
• the higher the aminosulfonic acid molar ratio the more formula 5 is produced.
• Formula 5 is highly water-soluble and the recrystallization yield from water is low, so that the synthesis efficiency is good, so the molar ratio of aminosulfonic acid is more preferably 1.0 or more and 1.2 or less.
• the cationic dyeability of the terminal-modified polyamide resin using Formula 4 and the terminal-modified polyamide resin using Formula 5 were comparable, there is no advantage in using Formula 5 in terms of dyeability.
• R1 ' represents an aromatic hydroxy group such as a phenoxy group, cresoxy group, xylenoxy group, naphthoxy group.
• R2 represents a hydrogen atom or a methyl group.
• R 3 represents an aliphatic linear substituent such as ethylene group or n-propylene group, or an aromatic substituent such as phenylene group or methylphenylene group.
• X represents a metal cation such as sodium ion, lithium ion, or an organic cation such as tert-butyl-ammonium ion, benzyltrimethylammonium ion, p-methylphenylammonium ion.
• R1 ' represents an aromatic hydroxy group such as a phenoxy group, cresoxy group, xylenoxy group, naphthoxy group.
• R2 represents a hydrogen atom or a methyl group.
• R 3 is an aliphatic linear substituent such as ethylene group or n-propylene group, or an aromatic substituent group such as phenylene group or methylphenylene group.
• X represents a metal cation such as sodium ion or lithium ion, or an organic cation such as tert-butyl-ammonium ion, benzyltrimethylammonium ion or p-methylphenylammonium ion.
• a method for producing a terminal-modified polyamide resin in which a sulfonate is introduced into a terminal amino group in the present invention a method of melt-kneading a sulfonate-containing triazine derivative and a polyamide resin is preferable.
• the temperature during melt-kneading is preferably 240° C. or higher and 280° C. or lower.
• polyamide 6 As the polyamide resin used in the production of the terminal-modified polyamide resin in which a sulfonate is introduced into the terminal amino group of Formula 1, polyamide 6 (hereinafter sometimes referred to as PA6), polyamide 12, a polymer such as polyamide 66, or these Polyamide resins, etc., which are copolymers of are preferable, and polyamide 6 is particularly preferable when used for clothing applications.
• PA6 polyamide 6
• polyamide 12 a polymer such as polyamide 66, or these Polyamide resins, etc., which are copolymers of are preferable, and polyamide 6 is particularly preferable when used for clothing applications.
• the amount of terminal amino groups in commonly used polyamide resins is about 30 to 40 meq/kg.
• the amount of amino groups within this range is not a problem, but it is preferably 60 meq/kg or more. More preferably, it is 80 meq/kg or more.
• the relative viscosity of the polyamide resin used in the present invention is preferably 2.20 or more and 4.20 or less.
• the operability tends to be poor, such as shortening the life of the mouthpiece. More preferably, it is 2.30 or more and 3.60 or less.
• the kneading ratio of the sulfonate-containing triazine derivative is preferably 0.4 equivalents or more and 1.5 equivalents or less with respect to the amount of terminal amino groups of the polyamide resin. If the amount is less than 0.4 equivalents, the sulfonate is not sufficiently introduced into the terminal amino groups, and if the amount exceeds 1.5 equivalents, the amount of terminal amino groups does not decrease and the reaction efficiency does not increase. . It is more preferably 0.6 equivalents or more and 1.2 equivalents or less, and more preferably 0.8 equivalents or more and 1.0 equivalents or less because good dyeability can be seen with both cationic dyes and acid dyes. .
• the conductive substance contained in the conductive layer is preferably one or more selected from conductive carbon black, titanium oxide having a conductive coating, and conductive inorganic particles.
• the composite conductive fiber has a conductive performance, and when it is mixed with the acrylic fiber to make clothes and worn, it is hardly charged with static electricity. Titanium oxide having a conductive film or conductive inorganic particles is more preferable because of better designability, and titanium oxide having a conductive film is most preferable in consideration of cost.
• Examples of conductive coatings of titanium oxide include metal coatings.
• a metal coating has the drawback of being unstable due to deterioration and alteration due to oxidation or the like.
• Some metal oxides are stable and have electrical conductivity, such as copper oxide, silver oxide, zinc oxide, cadmium oxide, antimony oxide, tin oxide, and manganese oxide.
• electrical conductivity such as copper oxide, silver oxide, zinc oxide, cadmium oxide, antimony oxide, tin oxide, and manganese oxide.
• Combinations of the main component and the second component include, for example, copper oxide/copper, zinc oxide/aluminum oxide, tin oxide/antimony oxide, zinc oxide/zinc oxide, aluminum oxide/aluminum, tin oxide/tin, antimony oxide/antimony, etc. is preferred.
• the conductive coating of titanium oxide particles having a conductive coating can be obtained, for example, by a vacuum deposition method, by attaching a metal compound (for example, an organic acid salt) and baking it to an oxide, or by partially reducing it. can be formed.
• a metal compound for example, an organic acid salt
• the conductive substance preferably has a specific resistance of 9.9 ⁇ 10 4 ⁇ cm or less, more preferably 9.9 ⁇ 10 2 ⁇ cm or less in powder form.
• the specific resistance of the conductive material is measured by filling a cylinder with a diameter of 1 cm with 10 g of a sample, applying a pressure of 200 kg from the top with a piston, and applying a direct current (0.1 to 100 V).
• thermoplastic polymer that becomes fibrous when melt-spun.
• examples include polyamides, polyesters, polyolefins, polycarbonates and the like.
• the content ratio of the conductive substance to the fiber-forming resin in the conductive layer is 20% by mass or more and 40% by mass or less in the case of conductive carbon black, and in the case of titanium oxide particles or conductive inorganic particles having a conductive coating. , 60% by mass or more and 80% by mass or less. If the content ratio is within the above range, the conductive performance is good.
• the ratio of the conductive layer to the entire fiber cross section in the fiber cross section is preferably 3% or more and 50% or less in terms of area ratio. If the ratio of the conductive layer exceeds 50%, the strength tends to be greatly reduced, making it difficult to take up the yarn. Moreover, when the ratio of the conductive layer is less than 3%, the conductivity tends to be insufficient, and it tends to be difficult to exhibit the conductive performance. More preferably, it is 4% or more and 40% or less.
• the cross-sectional shape of the fiber is not particularly limited because the ratio of the conductive layer greatly affects the conductivity. , a side-by-side structure, a hamburger type structure, and the like. Since the exposed area of the conductive layer also affects the conductivity, it is more preferable that the sheath has a core-sheath structure of the conductive layer.
• the fiber-forming resin containing the conductive substance of the conductive layer in the present invention can be obtained by mixing the fiber-forming resin used for the conductive layer and the conductive substance.
• the method of mixing the resin used in the conductive layer of the conductive polyamide composite fiber of the present invention with conductive substances such as conductive carbon black, titanium oxide having a conductive coating, and conductive inorganic particles is not particularly limited. Instead, they can be mixed by a known method such as a twin-screw kneading method.
• the conductive polyamide conjugate fiber of the present invention can be produced by conjugate spinning using a fiber-forming resin containing a conductive substance for the conductive layer and the terminal-modified polyamide resin for the non-conductive layer.
• a fiber-forming resin containing a conductive substance and a terminal-modified polyamide resin are melted in an extruder, and each resin is discharged from a spinneret while being weighed using a gear pump, cooled, and then wound up. , and a melt spinning method are suitable.
• the spinning temperature is preferably above the melting point of each resin and below 300°C.
• Winding methods include, for example, a method of winding an undrawn yarn once at a low speed of about 400 to 1,200 m/min and then heat-stretching it using a twisting machine to obtain a drawn yarn (conventional method); A method of winding at a high speed of ⁇ 5,000 m / min to obtain a semi-drawn yarn (POY method), and a first roller (GR1) of 800 to 1,200 m / min and a speed of about 3,000 to 4,500 m / min.
• a method of obtaining a directly drawn yarn by performing hot drawing between GR1 and GR2 using a second roller (GR2) (direct drawing method) is preferably exemplified.
• the draw ratio is not particularly limited, it is usually preferably 2 to 4 times.
• the fineness and the number of components of the conductive polyamide conjugate fiber of the present invention are not particularly limited, but for clothing applications, the total fineness is preferably 18 to 500 dtex, and the number of components is preferably about 1 to 96 f, more preferably the total fineness. is 20 to 400 dtex, and the number of constituent lines is 1 to 72f.
• the conductive polyamide composite fiber of the present invention can be used as a filament yarn as it is, or as a yarn obtained by blending cut staple yarn with other staple yarn, for fabrics such as woven and knitted fabrics. Fabrics such as woven and knitted fabrics can be suitably used for clothing such as general clothing, sportswear, work clothing and protective clothing, bedding, vehicle interior materials, and the like. In addition, as an example of a suitable method of use, when used for general clothing, sportswear, work clothes, protective clothing, etc., for example, blended yarn (core yarn) of functional yarn and cotton etc. ), the use of the polyamide composite fiber of the present invention as a fiber structure made of a fabric using yarn as a covering yarn (sheath yarn).
• the polyamide conjugate fiber of the present invention may be used alone, or a yarn obtained by covering or twisting the polyamide conjugate fiber of the present invention with another polyamide yarn or the like may be used. Also good.
• the conjugate fiber of the present invention When used for a woven or knitted fabric, it may be used partially or entirely. As for the specific usage ratio when used partially, the conjugate fiber of the present invention is preferably mixed at a mixing ratio of 0.1% by mass or more, more preferably at a mixing ratio of 0.3% by mass or more.
• Resin Viscosity Measurement A Ubbelohde viscometer was used to measure the relative viscosity of the polyamide resin. A solution in which a polyamide resin was dissolved at a concentration of 0.01 g/mL in 96.0% by mass sulfuric acid was measured at 25° C. for the time required for the solution to fall from the top to the bottom of the measurement mark. It implemented 3 times and made the average value tave . The time for 96.0% by mass sulfuric acid to fall from the top of the measurement mark to the bottom at 25°C was measured three times, and the average value was taken as t0 . Relative viscosity was calculated using the following formula.
• the breaking strength and breaking elongation of the conductive polyamide composite fiber are measured according to JIS L 1013, using an AGS-1KNG Autograph (registered trademark) tensile tester manufactured by Shimadzu Corporation. The strength and elongation were obtained by measuring the strength and elongation when the sample was stretched and broken under the conditions of a sample thread length of 20 cm and a tensile speed of 20 cm/min.
• the wire resistance value is obtained by taking 10 cm of the conductive polyamide composite fiber, adhering aluminum foil to both ends with a conductive adhesive, and measuring the resistance value ( ⁇ ) using a high resistance meter 4339B manufactured by Agilent. (cm) to obtain a linear resistance value ( ⁇ /cm).
• the obtained tubular knitted fabric was treated with an aqueous solution of 2 g/L sodium hydrogen carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 g/L polyoxyethylene alkyl ether (manufactured by Kao Corporation) at 70° C. for 20 minutes.
• the scouring was performed under the conditions of
• the tubular knitted fabric of the product of the present invention is referred to as this sample
• the tubular knitted fabric of polyamide control yarn is referred to as PA control
• PE control tubular knitted fabric of normal pressure cationic polyester control
• Cationic staining and acid staining were performed using the degummed present sample, the PA control sample and the PE control sample.
• the samples before and after dyeing were checked for color (L * , a * , b * ) before and after dyeing using a color meter (ZE-2000 colorimetric color difference meter manufactured by Nippon Denshoku Industries Co., Ltd.).
• a plurality of E * (ab) values were determined by the following formula, and the staining rate was calculated from the determined E * (ab) values to evaluate the stainability.
• the dyeing rate is 0.8 or more and 1.0 or less.
• ⁇ The dyeing rate is 0.7 or more and less than 0.8.
• ⁇ The dyeing rate is 0.4 or more and less than 0.7.
• x The staining rate is less than 0.4.
• organic compound 1 Sodium-4-(4,6-diphenoxy-1,3,5-triazinyl-2-amino)benzenesulfonate (hereinafter referred to as organic compound 1) was synthesized by the following method. 18.5 g of cyanuric chloride (manufactured by Sigma-Aldrich) was dissolved in 40 ml of acetone (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and poured into 60 ml of ice water while vigorously stirring with a stirrer.
• cyanuric chloride manufactured by Sigma-Aldrich
• acetone manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
• a 100 ml aqueous solution of 17.3 g of sodium carbonate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 5.3 g of sodium carbonate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added in a short period of time to react with each other under ice cooling. Further, a 20 ml aqueous solution of 5.3 g of sodium carbonate was gradually added to keep the pH at 7-8. After reacting for 2 hours, the precipitate deposited was separated by filtration and thoroughly washed with water. After washing with acetone and drying under reduced pressure at room temperature, 27.1 g of a white solid was obtained.
• organic compound 2 Sodium-2-(4,6-diphenoxy-1,3,5-triazinyl-2-amino)ethanesulfonate (hereinafter referred to as organic compound 2) was synthesized by the following method.
• organic compound 2 instead of sulfanilic acid, 12.5 g of taurine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was reacted to obtain 15.0 g of a white solid (organic compound 2).
• NMR measurement of the obtained organic compound 2 confirmed a phenol proton peak at 7.0 to 7.5 ppm. A methyl proton peak of taurine was confirmed at 2.5 to 3.5 ppm.
• the mixture was supplied to a twin-screw extruder kneader (manufactured by Shibaura Kikai Co., Ltd.) and melt-kneaded at 260°C.
• the strand-shaped melt was cooled with water and pelletized by a pelletizer to obtain 3.5 kg of resin composition (1).
• the relative viscosity of the resin composition (1) obtained here was measured, it was 2.44.
• Example 1 The resin composition (1) and polyethylene (referred to as C-PE) having 75% by mass of titanium oxide particles coated with antimony oxide and tin oxide are used as spinning raw materials and compounded at a temperature of 240 ° C. using an extruder type compound spinning machine. spinning was performed. The resin composition (1) was melted separately so that the sheath part and the C-PE became the core part, and then spun from a core-sheath type spinning nozzle at a temperature of 240 ° C., cooled and oiled at a spinning speed of 1,000. It was wound up at 400 m/min. Thereafter, the fiber was hot drawn at 60° C. to 2.8 times using a drawing machine and heat set at 150° C.
• C-PE polyethylene
• the core-sheath ratio of this core-sheath type composite fiber is 1:20 (area ratio).
• the resulting fiber had a breaking strength of 3.5 cN/dtex, a breaking elongation of 32.6%, a wire resistance of 3.8 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.83, and an acid dyeability of 0. 0.83.
• Example 2 Spinning was carried out in the same manner as in Example 1 except that the resin composition (1) was used as the resin composition (2) to obtain a core-sheath type conjugate fiber that was a drawn yarn of 22 dtex/6 f.
• the resulting fiber had a breaking strength of 3.6 cN/dtex, a breaking elongation of 34.7%, a wire resistance of 4.0 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.80, and an acid dyeability of 0. 0.84.
• Example 3 Spinning was carried out in the same manner as in Example 1 except that the resin composition (1) was used as the resin composition (3) to obtain a core-sheath type conjugate fiber that was a drawn yarn of 22 dtex/6 f.
• the resulting fiber had a breaking strength of 3.5 cN/dtex, a breaking elongation of 35.6%, a wire resistance of 3.6 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.85, and an acid dyeability of 0. 0.81.
• Example 4 Spinning was carried out in the same manner as in Example 1 except that the resin composition (1) was used as the resin composition (4) to obtain a core-sheath type conjugate fiber that was a drawn yarn of 22 dtex/6 f.
• the resulting fiber had a breaking strength of 3.4 cN/dtex, a breaking elongation of 34.9%, a wire resistance of 4.1 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.89, and an acid dyeability of 0. .71.
• Example 5 Spinning was carried out in the same manner as in Example 1 except that the resin composition (1) was used as the resin composition (5) to obtain a core-sheath type conjugate fiber that was a drawn yarn of 22 dtex/6 f.
• the resulting fiber had a breaking strength of 3.2 cN/dtex, a breaking elongation of 32.5%, a wire resistance of 3.5 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.90, and an acid dyeability of 0. .43.
• Example 6 Spinning was carried out in the same manner as in Example 1 except that the resin composition (1) was changed to the resin composition (6) to obtain a core-sheath type conjugate fiber that was a drawn yarn of 22 dtex/6 f.
• the resulting fiber had a breaking strength of 3.6 cN/dtex, a breaking elongation of 36.7%, a wire resistance of 2.8 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.48, and an acid dyeability of 0. .90.
• Example 7 Spinning was carried out in the same manner as in Example 1 except that the resin composition (1) was changed to the resin composition (7) to obtain a core-sheath type conjugate fiber that was a drawn yarn of 22 dtex/6 f.
• the obtained fiber had a breaking strength of 3.1 cN/dtex, a breaking elongation of 33.7%, a wire resistance of 5.1 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.91, and an acid dyeability of 0. 0.92.
• Example 8 Spinning was carried out in the same manner as in Example 1 except that the resin composition (1) was changed to the resin composition (8) to obtain a core-sheath type conjugate fiber that was a drawn yarn of 22 dtex/6 f.
• the resulting fiber had a breaking strength of 3.0 cN/dtex, a breaking elongation of 32.6%, a wire resistance of 5.2 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.82, and an acid dyeability of 0. 0.86.
• Example 9 Spinning was carried out in the same manner as in Example 1 except that the resin composition (1) was changed to the resin composition (9) to obtain a core-sheath type conjugate fiber that was a drawn yarn of 22 dtex/6 f.
• the resulting fiber had a breaking strength of 2.9 cN/dtex, a breaking elongation of 35.2%, a wire resistance of 6.4 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.91, and an acid dyeability of 0. 0.73.
• Example 1 Spinning was carried out in the same manner as in Example 1, except that the resin composition (1) was used as the resin composition (10) to obtain a core-sheath type composite fiber.
• the resulting fiber had a breaking strength of 3.0 cN/dtex, a breaking elongation of 31.2%, a wire resistance of 4.5 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.94, and an acid dyeability of 0. .32.
• Example 2 Spinning was carried out in the same manner as in Example 1, except that the resin composition (1) was changed to the resin composition (11) to obtain a core-sheath type composite fiber.
• the resulting fiber had a breaking strength of 3.3 cN/dtex, a breaking elongation of 33.3%, a wire resistance of 3.0 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.36, and an acid dyeability of 0. 0.92.
• Example 3 Spinning was carried out in the same manner as in Example 1, except that the resin composition (1) was polyamide 6 (manufactured by Chusheng Industrial Co., Ltd., relative viscosity: 2.43, terminal amino group content: 40 meq/kg). , to obtain a core-sheath type composite fiber.
• the resulting fiber had a breaking strength of 3.3 cN/dtex, a breaking elongation of 35.3%, a wire resistance of 2.7 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 0.30, and an acid dyeability of 1. 0.00.
• Resin composition (1) is a polyester obtained by copolymerizing metal sulfonate group-containing isophthalic acid and polyalkylene glycol (manufactured by KB Seiren, intrinsic viscosity: 0.54), spinning temperature is 280 ° C., spinning speed is 1,400 m / min. It was wound up in the same manner as in Example 1 except that Thereafter, the fiber was hot-drawn at 95° C. to 2.7 times using a drawing machine, and heat-set at 150° C. with a plate heater to obtain a core-sheath type conjugate fiber as drawn yarn of 22 dtex/6 f.
• the resulting fiber had a breaking strength of 2.9 cN/dtex, a breaking elongation of 32.5%, a wire resistance of 2.6 ⁇ 10 9 ⁇ /cm, a cationic dyeability of 1.00, and an acid dyeability of 0. .27.
• Tables 1 and 2 show the physical properties and evaluation results of the core resins and sheath resins used in Examples and Comparative Examples, and the obtained core-sheath type composite fibers.
• the added amount with respect to the terminal amino group amount of the sheath resin is the content of the sulfonate group-containing triazine derivative in the sheath resin.
• the fibers obtained from Examples 1 to 7 in which the content of the sulfonate-containing triazine derivative is 0.4 equivalents or more and 1.5 equivalents or less with respect to the terminal amino group amount of the polyamide resin are Cationic dyeability and acid dyeability were good.
• the content of the sulfonate-containing triazine derivative is 0.6 equivalent or more and 1.0 equivalent or less with respect to the terminal amino group amount of the polyamide resin obtained from Examples 1, 2, 3, 7 and 8.
• the resulting fibers were particularly good in cationic dyeability and acid dyeability.
• the conductive composite fiber of the present invention is a conductive polyamide composite fiber that can be subjected to normal pressure cationic dyeing and acid dyeing, has good color development, and can suppress static electricity charging, and is suitable for mixing with acrylic fiber and polyamide fiber. is.

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