Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
  • C08G69/14—Lactams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • 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
  • D01D5/08—Melt spinning methods
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/02—Material containing basic nitrogen
  • D06P3/04—Material containing basic nitrogen containing amide groups
  • D06P3/24—Polyamides; Polyurethanes
  • D06P3/241—Polyamides; Polyurethanes using acid dyes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • 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
  • D01F1/10—Other agents for modifying properties
• • 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
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides

Definitions

• the present invention relates to a polyamide-based fiber having excellent color-developing property, a method for producing the same, and a fiber structure.
• Polyamide-based resin is a crystalline linear polymer having an amide bond (-CONH-) as a repeating unit in the molecular chain.
• Polyamide 9, polyamide 10, polyamide 11, polyamide 12, and the like are present as grade resins having excellent chemical resistance and cold resistance, and polyamide elastomer and the like are present as grade resins having elasticity.
• Patent Document 1 International Publication No. 2017/146018
• a polyamide elastomer composition having a base concentration of 2.0 ⁇ 10 -5 eq / g or more is disclosed. This polyamide elastomer composition is used as a molded product, a fiber, a button for clothing, a wire fastener, and the like.
• Patent Document 2 Japanese Unexamined Patent Publication No. 2010-189773 describes a conjugate fiber having a two-component split type structure of a component containing a polyamide-based elastomer and a component containing a polyester-based resin, and is contained in the fiber.
• the conjugated fiber is disclosed, wherein the content of the polyamide-based elastomer is 40 to 80% by weight.
• This conjugated fiber has excellent dyeability, and it is possible to obtain a fabric having a good cool contact feeling and a good touch.
• Patent Document 1 in order to improve dyeability and dyeing fastness, it is necessary to add a phosphite compound and adjust the terminal amine group at the time of melt polymerization, which is a characteristic texture of the polyamide elastomer fiber. Not only is it reduced, but it also affects the cost increase due to the deterioration of spinnability and the complexity of the process. Further, in Patent Document 2, although dyeing property is obtained by combining with polyester, there is a problem that the texture and functionality (flexibility, hydrolysis resistance, etc.) characteristic of the polyamide elastomer are impaired.
• an object of the present invention is to provide a polyamide fiber, a method for producing the same, and a fiber structure, which are excellent in color development and can be used without impairing the characteristics of the polyamide resin.
• the present inventors have made a resin composition by combining an amino group-containing color development improving agent with a polyamide resin for fiberization, and this amino group-containing color development improvement.
• We have found that by setting the concentration of terminal amino groups present in the fiber to a specific value by using an agent, it is possible to obtain a polyamide-based fiber having excellent color-developing property and maintaining the characteristics of a polyamide-based resin. was completed.
• the present invention can be configured in the following aspects.
• Aspect 1 It is formed from a polyamide-based resin composition composed of a polyamide-based resin and an amino group-containing color-developing agent (a polyamide-based resin composition containing a polyamide-based resin and an amino group-containing color-developing agent), and has a terminal amino group concentration of 5. .0 to 40.0 ⁇ eq / g (preferably 10.0 to 35.0 ⁇ eq / g, more preferably 12.0 to 30.0 ⁇ eq / g), polyamide-based fibers.
• the polyamide resin contains a polyamide elastomer.
• the amino group-containing color-developing agent is composed of a polyamide oligomer (the amino group-containing color-improving agent contains a polyamide oligomer).
• the polyamide fiber according to the fourth aspect wherein the number average molecular weight of the polyamide oligomer is 500 to 10000 (preferably 500 to 9000, more preferably 1000 to 6000).
• the terminal amino group concentration of the amino group-containing color development improver is 100 to 2000 ⁇ eq / g (preferably 125 to 2000 ⁇ eq / g, more preferably 200 to 1000 ⁇ eq / g). Polyamide-based fiber.
• the mass ratio of the polyamide resin and the amino group-containing color-developing agent is 99/1 to 70/30 (preferably 98/2 to 98) as the former / latter.
• Polyamide-based fiber which is 75/25, more preferably 95/5 to 80/20).
• a fiber structure comprising the polyamide-based fiber according to any one of aspects 1 to 8.
• a manufacturing method including at least a melt-kneading step of obtaining a melt of the above-mentioned material and a spinning step of spinning the melt-kneaded product into fibers.
• the polyamide-based fiber of the present invention improves the color-developing property of the fiber while taking advantage of the characteristics of the polyamide-based resin constituting the polyamide-based fiber by controlling the terminal amino group concentration to a specific value with an amino group-containing color-developing agent. Can be made to.
• the polyamide fiber of the present invention is spun from a polyamide resin composition composed of a polyamide resin and an amino group-containing color development improver.
• the polyamide resin has at least a repeating unit in which divalent hydrocarbon groups which may have a substituent are connected via an amide bond, and is represented by the following formulas (1) to (3), for example. Has at least one of the repeating units.
• R1, R2, and R3 are the same or different hydrocarbon groups having 1 to 22 carbon atoms, and m is an integer of 0 or 1.
• Formula (1) is a repeating unit derived from a diamine compound
• formula (2) is a repeating unit derived from a dicarboxylic acid compound
• formula (3) is a repeating unit derived from lactam or ⁇ aminocarboxylic acid. ..
• hydrocarbon group having 1 to 22 carbon atoms examples include a linear or branched saturated aliphatic hydrocarbon group having 1 to 22 carbon atoms (preferably 6 to 20, more preferably 9 to 18) and 6 carbon atoms.
• a linear or branched saturated aliphatic hydrocarbon group having 1 to 22 carbon atoms preferably 6 to 20, more preferably 9 to 18
• 6 carbon atoms preferably 6 to 20, more preferably 6 to 18
• Examples thereof include linear or branched aromatic hydrocarbon groups. Substituents may be present in these hydrocarbon groups as long as the effects of the present invention are not impaired.
• a polyamide-based resin having a repeating unit containing a linear or branched saturated aliphatic hydrocarbon group having 2 to 22 carbon atoms is preferable, and particularly from the viewpoint of imparting high functionality.
• a polyamide resin having a repeating unit containing a saturated aliphatic hydrocarbon group having a linear or branched chain having 6 to 20 carbon atoms (preferably 9 to 18 carbon atoms) is preferable.
• Preferred polyamide-based resins include polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 6/11, polyamide 6/12, polyamide 9, polyamide 10, polyamide 11, polyamide 12, and polyamide MXD6.
• polyamide resin having two CHs having a long carbon number such as polyamide 9, polyamide 10, polyamide 11, and polyamide 12 (polyamide-based polyamide resin) Is preferable.
• the polyamide resin may contain not only a non-elastomer but also a polyamide elastomer.
• Polyamide-based elastomers are preferable because they can give the fibers a unique texture.
• the polyamide-based elastomer may be a polyether block polyamide, a polyester block polyamide, or a polyester ether block polyamide having the polyamide-based resin component as a hard segment and a polyether block or a polyester block as a soft segment.
• the polyether block may be a linear or branched saturated aliphatic polyether having 2 to 10 carbon atoms, preferably a segment having 2 to 6 carbon atoms between ether bonds, for example, polyethylene glycol. , Polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol and the like.
• the ratio (mass ratio) between the hard segment and the soft segment may be, for example, about 50/50 to 95/5, preferably about 60/30 to 92/8, although it is not particularly limited as long as it has spinnability. , More preferably about 70/30 to 90/10.
• the polyamide-based elastomer may have, for example, an aliphatic polyamide having 6 to 22 carbon atoms as a hard segment, and preferably an aliphatic polyamide having a prime number of 9 to 20 as a hard segment.
• the aliphatic polyamide means a polyamide in which the hydrocarbon group in the repeating units of the above formulas (1) to (3) is a saturated aliphatic hydrocarbon group.
• polyamide 6, polyamide 6/6, polyamide 6/11, polyamide 6/12, polyamide 9, polyamide 11, or polyamide 12 is used as a hard segment, and polyethylene glycol, polypropylene glycol, etc. It may be a polyether block polyamide having polytetramethylene glycol or the like as a soft segment.
• the amino group-containing color development improver has at least an amino group and is used together with a polyamide resin to impart a predetermined terminal amino group concentration to the polyamide fiber.
• the amino group-containing color-developing agent may have a terminal amino group concentration of, for example, 100 to 2000 ⁇ eq / g, preferably 125 to 2000 ⁇ eq / g, and more preferably 200 to 1000 ⁇ eq / g. Good.
• the amino group-containing color development improver can be combined in an appropriate ratio according to the type of the amino group-containing color development improver as long as the characteristics of the polyamide resin exhibited in the polyamide fiber are not impaired.
• the mass ratio of the polyamide resin and the amino group-containing color-developing agent may be 99/1 to 70/30 as the former / latter, preferably 98, from the viewpoint of color development and compatibility. It may be / 2 to 75/25, more preferably 95/5 to 80/20.
• the proportion of the polyamide resin (particularly the polyamide elastomer resin) in the polyamide fiber (particularly the polyamide elastomer fiber) may be, for example, 70 to 99% by mass, preferably 75 to 98% by mass. It may be preferably 80 to 95% by mass.
• amino group-containing color development improver examples include amino group-containing compounds such as polyamide oligomers and diverse amines from the viewpoint of improving the color development of polyamide fibers without impairing the characteristics of the polyamide resin.
• the polyamide oligomer is preferably composed of any of the repeating units represented by the formulas (1) to (3) described in the polyamide resin.
• the hydrocarbon group having 1 to 22 carbon atoms used in the repeating unit represented by the formulas (1) to (3) include 1 to 22 carbon atoms (preferably 6 to 20, more preferably 9 to 18).
• Examples thereof include linear or branched aromatic hydrocarbon groups of up to 22 (preferably 6 to 20, more preferably 6 to 18). Substituents may be present in these hydrocarbon groups as long as the effects of the present invention are not impaired.
• Preferred polyamide oligomers include polyamide 6 oligomers, polyamide 4/6 oligomers, polyamide 6/6 oligomers, polyamide 6/10 oligomers, polyamide 6/11 oligomers, polyamide 6/12 oligomers, polyamide 9 oligomers, polyamide 10 oligomers, and polyamide 11 Examples thereof include oligomers and polyamide 12 oligomers.
• the hydrocarbon group of the repeating unit of the polyamide oligomer and the polyamide resin preferably has the same number of single elements.
• the hydrocarbon group of the repeating unit in the polyamide oligomer is The carbon number may be within the range of ⁇ 3 single elements in the repeating unit of the polyamide resin, preferably within the range of ⁇ 2 single elements in the repeating unit of the polyamide resin, and more preferably the polyamide resin. It may be within the range of the number of single elements ⁇ 1 in the repeating unit of.
• the polyamide-based resin is a polyamide-based elastomer, it is preferable that the hydrocarbon groups of the repeating units of the polyamide-based resin component in the hard segment have the above-mentioned relationship.
• the number average molecular weight of the polyamide oligomer may be, for example, 500 to 10000, preferably 500 to 9000, and more preferably 1000 to 6000.
• the molecular weight of the polyamide oligomer is a value measured by the method described in Examples described later.
• the versatile amine has a structure having 3 to 12 amino groups without being limited to a monomer or a polymer, and is a linear aliphatic, alicyclic or aromatic multidiversified amine (diamine, triamine). , Tetraamine, etc.).
• the polyamide-based resin composition used in the present invention may contain various commonly used additives, if necessary.
• Additives include, for example, heat stabilizers, antioxidants, light stabilizers, UV absorbers, antistatic agents, colorants (eg color pigments), smoothing agents, plasticizers, antibacterial agents, antifungal agents and deodorants. Examples include additives such as agents.
• the polyamide-based resin composition used in the present invention may contain other thermoplastic resins as long as the effects of the present invention are not impaired.
• the polyamide resin composition used in the present invention preferably has a melt viscosity at 240 ° C. of 600 to 3000 poise from the viewpoint of improving fibrosis. If the melt viscosity exceeds 3000 poise, the high-speed spinnability at the time of fiberization may decrease. Further, if it is less than 600 poise, the yarn may be easily broken during spinning and the productivity may be poor, and the strength of the obtained fiber may be low.
• the melt viscosity of the polyamide resin composition is more preferably 800 to 2000 pablye.
• the polyamide-based resin composition used in the present invention preferably has good compatibility between the polyamide-based resin and the amino group-containing color-developing agent.
• a DSC curve measured by differential scanning calorimetry (DSC) It is preferable that the shape of the melting peak indicated by is a single peak. Whether or not the shape of the melting peak is a single peak can be determined by examining the DDSC curve obtained by differentiating the DSC curve.
• the DDSC curve is a curve obtained by firstly differentiating the DSC curve with respect to time, and indicates the slope of the DSC curve.
• the value of the DDSC curve becomes zero when the slope of the DSC curve becomes zero, the value of the DDSC curve becomes zero at the maximum value or the minimum value of the DSC curve. That is, in the melting peak indicated by the DSC curve, when there is only one point where the value of the DDSC curve becomes zero, it can be determined that the shape of the melting peak is a single peak.
• the polyamide fiber of the present invention can be obtained by a known method as long as it can be spun, and may be spun by melt spinning of a polyamide resin composition, for example.
• melt spinning include a spinning / drawing method, a straight drawing method, and a POY (partially oriented yarn) -DTY (draw-textured yarn) method.
• the polyamide-based resin composition may be fiberized by a melt blow method, an electrospinning method, or the like.
• a method for producing a polyamide fiber includes a melt kneading step in which a polyamide resin composition is melt-kneaded to obtain a melt having a predetermined melt viscosity, and a spinning step in which the melt-kneaded product is spun into fibers. You may have it.
• an amino group-containing color-developing agent may be added to the polyamide-based resin for melt-kneading, or a polyamide-based resin composition (master) containing the amino group-containing color-developing agent once.
• a batch) may be formed, and the polyamide resin and the masterbatch may be kneaded and melt-spun to form fibers.
• the melt viscosity of the polyamide-based resin composition can be adjusted to a viscosity suitable for spinning by using an amino group-containing color-developing agent, and spinning is performed more than when spinning with the polyamide-based resin alone. It is possible to improve the sex.
• the polyamide fiber of the present invention since it is excellent in color development, it may further include a dyeing step of the obtained fiber.
• the dyeing step can be performed by a known method depending on the dyeing agent used.
• the dyeing agent examples include acid dyes, acid mordant dyes, metal complex hydrochloric acid dyes, and disperse dyes. Of these, acid dyes, acid mordant dyes, and metal complex hydrochloric acid dyes are preferable from the viewpoint of color development and spinnability.
• Acid dyes are dyes containing sulfonic acid groups, carboxyl groups, hydroxy groups and the like as soluble groups, and are azo-based, triphenylmethane-based, anthraquinone-based, oxygen anthracene-based, phthalocyanine-based, indigoid-based, nitroso-based and pyrazolone. Acid dyes such as systems can be mentioned.
• Acid mordant dyes are dyes that can mainly form metal complex chlorides (for example, coordination bonds with chromium atoms) while having color-developing properties due to acid dyes, and are azo-based, triphenylmethane-based, anthraquinone-based, and oxygen anthracene-based dyes. , Phthalocyanine-based, indigoid-based, nitroso-based and pyrazolone-based acid mordant dyes.
• Metal complex hydrochloric acid dyes are roughly classified into 1: 1 type dyes in which one metal atom and one dye molecule are bonded, and 1: 2 type dyes in which two dye molecules are bonded to one metal atom. Examples thereof include metal complex hydrochloric acid dyes such as triphenylmethane-based, anthraquinone-based, oxygen anthracene-based, phthalocyanine-based, indigoid-based, nitroso-based and pyrazolone-based.
• the polyamide fiber of the present invention has a terminal amino group concentration of 5.0 to 40.0 ⁇ eq / g, preferably 10.0 to 35.0 ⁇ eq / g, and more preferably 12.0 to 30.0 ⁇ eq / g. It may be.
• the concentration of the terminal amino group present in the fiber can be increased by utilizing the amino group-containing color development improver.
• the properties of the polyamide resin for example, washing fastness
• the polyamide fiber of the present invention may be a monofilament or a multifilament. Further, although composite fibers (for example, core sheath type, sea island type, side-by-side type, etc.) may be used, even non-composite fibers can exhibit good color development.
• composite fibers for example, core sheath type, sea island type, side-by-side type, etc.
• the cross-sectional shape of the polyamide fiber of the present invention may be a known or conventional shape, may be a circular cross-section which is a solid cross-sectional shape, or may have a deformed cross-section (for example, a flat shape, an ellipse shape, a triangle shape, or the like). It may be a square cross section). Further, it may have a hollow cross-sectional shape or the like.
• the fineness of the polyamide fiber of the present invention is not particularly limited, and for example, the single fiber fineness may be in the range of about 0.1 to 1000 dtex, preferably 1 to 100 dtex, and more preferably 2 to 50 dtex, depending on the application. ..
• the single fiber fineness may be 1 to 10 dtex or 1 to 5 dtex.
• the polyamide fiber of the present invention preferably has a fiber strength of 1.0 cN / dtex or more at room temperature, for example, 1.0 to 10 cN / dtex, and more preferably 2.0 to 10 cN / dtex or more.
• the fiber strength is a value measured according to the JIS L 1013 test method.
• the polyamide fiber of the present invention is excellent in color development, and in particular, it is excellent in color development in dark color dyeing such as dark blue, dark brown, and black.
• the polyamide fiber of the present invention may have, for example, an L * value of 20 or less, preferably 19 or less, and more preferably 18 or less in dark color dyeing.
• the L * value is a value measured by the method described in Examples described later.
• polyamide fiber of the present invention is also good in washing fastness, and can show grade 4 or higher in the washing fastness test defined in JIS L 0844, for example.
• polyamide fiber of the present invention is also good in light fastness, and can show grade 3 or higher in the light fastness test defined in JIS L 0842, for example.
• the polyamide fiber of the present invention uses a polyamide elastomer as the base resin, a polyamide fiber having a particularly excellent texture can be obtained.
• the texture means that the fiber has excellent grip (difficulty in slipping).
• the present invention includes a fiber structure containing the above-mentioned polyamide-based fiber.
• the fiber structure may be a one-dimensional structure such as continuous fibers (monofilaments, multifilaments), short fibers (cut fibers), threads, strings, ropes, etc., or a woven fabric containing the polyamide fibers. , Knitted fabric, non-woven fabric, or the like.
• the fiber structure may be composed of only polyamide fibers, or may be composed of a combination of polyamide fibers and other fibers.
• melt viscosity in order to reproduce the melt viscosity during spinning, pellets were extruded by adding an amino group-containing color development improver to a polyamide resin composition, and "Capillograph 1C PMD-C" manufactured by Toyo Seiki Seisakusho Co., Ltd. was measured at 240 ° C. and a shear rate of 1000 sec -1.
• the terminal carboxyl group concentration (COOH) was measured as follows. Approximately 0.5 g of a sample of a polyamide fiber or amino group-containing color improving agent is dissolved in 50 mL of benzyl alcohol, phenolphthalein is added as an indicator to the obtained sample solution, and the solution is N / 20 potassium hydroxide / methanol solution. By titration, the terminal carboxyl group concentration COOH ( ⁇ eq / g) was measured.
• the breaking strength (initial tensile resistance) was determined under the conditions of a trial length of 20 cm, an initial load of 0.1 g / d, and a tensile speed of 10 cm / min, and an average value of 5 points or more was adopted.
• Example 1 (1) Preparation of Polyamide 12 Oligomer
• the autoclave was replaced with nitrogen, 1.000 g of lauryl lactam and 38 g of dodecanediamine were added together with a small amount of water and a small amount of phosphoric acid, and the obtained mixture was stirred under heating.
• the reaction system was gradually pressure regulated by the nitrogen gas while heated, 17.5kgf / cm 2 maintained at (1.7 ⁇ 10 6 Pa) at 270 ° C., was continued for about 4 hours heating and stirring. Then, the reaction system was gradually returned to normal pressure, and while circulating a very small amount of nitrogen gas, it took about 1 hour to reduce the pressure and the water in the system was discharged.
• the polyamide 12 oligomer was taken out in a molten state while cooling the system under normal pressure. The obtained polyamide 12 oligomer was further cooled to obtain a slightly brittle solid.
• the number average molecular weight of the polyamide 12 oligomer was as low as about 5400, and the content of the terminal amino group was 350 ⁇ eq / g. This polyamide 12 oligomer was used as an amino group-containing color development improver.
• a polyamide-based elastomer fiber was produced according to the following method.
• a polyamide 12 elastomer (“VESTAMID E47-S1” manufactured by Dycel Evonik) was used, and the above-mentioned polyamide 12 oligomer was added as an amino group-containing color development improver so as to have a weight ratio of 9%. It was melted by an extruder and discharged from a spinning nozzle at 250 ° C.
• the yarn discharged from the spinning nozzle is cooled by a horizontal spray type cooling air device having a length of 1.0 m, and then continuously installed at a position 1.3 m from directly below the spinneret, having a length of 1.0 m and an inner diameter of 30 mm. It was introduced into a tube heater (inner wall temperature: 130 ° C.) and stretched in the tube heater. Then, a spinning oil was applied to the fibers coming out of the tube heater, and the fibers were subsequently wound up via a roller at a take-up speed of 3000 m / min to obtain 84 dtex / 24 filament polyamide 12 elastomer fibers. The terminal amino group concentration of the fiber was 17.6 ⁇ eq / g.
• a tubular knitted fabric with a grain size of 200 g / m 2 was prepared using this fiber and refined, and then dyed with a dye Kayanol Milling Black TLB (4% owf) at a bath ratio of 1:50 and a time of 80 ° C. for 40 minutes. , Various measurements were performed.
• Example 2 Polyamide 12 elastomer fibers were obtained by spinning in the same manner as in Example 1 except that the polyamide 12 oligomer was added so as to have a weight ratio of 20%. The terminal amino group concentration of the fiber was 38.5 ⁇ eq / g. Using this fiber, a tubular knitted fabric was prepared in the same manner as in Example 1, dyed, and various measurements were performed.
• Example 3 Polyamide 12 elastomer fibers were obtained by spinning in the same manner as in Example 1 except that the polyamide 12 oligomer was added so as to have a weight ratio of 6%.
• the terminal amino group concentration of the fiber was 12.1 ⁇ eq / g.
• a tubular knitted fabric was prepared in the same manner as in Example 1, dyed, and various measurements were performed.
• Example 1 Spinning was performed in the same manner as in Example 1 except that the polyamide 12 oligomer was not added to obtain a polyamide 12 elastomer fiber.
• the terminal amino group concentration of the fiber was 4.0 ⁇ eq / g.
• a tubular knitted fabric was prepared in the same manner as in Example 1, dyed, and various measurements were performed.
• Table 1 shows the performance of the obtained polyamide 12 elastomer fiber.
• Comparative Example 1 the polyamide-based elastomer is fibroticized without using an amino group-containing color-developing agent, and the spinnability is not sufficient.
• the obtained fibers have insufficient color development, and their washing fastness and light fastness are also poor as compared with Examples 1 to 3.
• Comparative Example 2 as a result of increasing the amount of the amino group-containing color development improving agent added in order to increase the terminal amino group concentration, the spinnability is not sufficient. Further, the obtained fibers have lower strength, and are also inferior in washing fastness and light fastness as compared with Examples 1 to 3. Further, as a result of increasing the proportion of the amino group-containing color development improver, the elastomer component in the fiber is reduced, and as a result, the texture of the fiber is inferior as compared with Examples 1 to 3.
• the polyamide-based fiber of the present invention can improve the color-developing property while making the best use of the characteristics of the polyamide-based resin, it can be used as a fiber structure such as a cloth or rope formed from the polyamide-based fiber, for example, various clothing.

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• 2020
  • 2020-11-11 WO PCT/JP2020/042138 patent/WO2021095783A1/ja not_active Ceased
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• 2022
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