WO2024071390A1 - Fibre biodégradable, produit fibreux et article vestimentaire - Google Patents

Fibre biodégradable, produit fibreux et article vestimentaire Download PDF

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Publication number
WO2024071390A1
WO2024071390A1 PCT/JP2023/035676 JP2023035676W WO2024071390A1 WO 2024071390 A1 WO2024071390 A1 WO 2024071390A1 JP 2023035676 W JP2023035676 W JP 2023035676W WO 2024071390 A1 WO2024071390 A1 WO 2024071390A1
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mol
structural units
nylon
structural unit
formula
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PCT/JP2023/035676
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English (en)
Japanese (ja)
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崇士 正木
史典 小林
晴紀 目代
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株式会社クレハ
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    • 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
    • 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
    • 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
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides

Definitions

  • the present invention relates to biodegradable fibers, textile products, and clothing items.
  • Nylon fibers are processed into woven, knitted, braided, and nonwoven fabrics, and are used in a wide range of applications, including clothing, fashion accessories, interior goods, and bedding. Fiber products used for these purposes can generate fiber debris due to friction during use and washing. This fiber debris can flow into the ocean and become microplastics, causing environmental pollution.
  • Patent Document 1 discloses fibers made of polylactic acid
  • Patent Document 2 discloses fibers made of nylon 4.
  • nylon 4 is difficult to produce fibers by melt spinning because the resin decomposition temperature and melting point are close to each other.
  • Patent Document 2 discloses wet spinning nylon 4 using a spinning dope containing at least a first acid with an acid dissociation constant of 2.80 or more and a second acid with an acid dissociation constant larger than that of the first acid.
  • Fibers made from polyester (polylactic acid) as described in Patent Document 1 cannot achieve the same abrasion resistance or texture as nylon fibers.
  • nylon 4 as described in Patent Document 2
  • wet spinning as described in Patent Document 2 is expensive and not suitable for mass production.
  • nylon 4 easily absorbs water. For this reason, fibers spun from nylon 4 tend to lose strength through washing, and cannot withstand repeated use when processed into woven fabrics, knitted fabrics, braided fabrics, nonwoven fabrics, etc.
  • the present invention was made in consideration of the above problems, and aims to provide a nylon fiber that can be spun without wet spinning, a biodegradable fiber for woven fabrics, knitted fabrics, braided fabrics, or nonwoven fabrics that is biodegradable and reduces the loss of strength due to washing, and textile processed products and clothing items that use the biodegradable fiber.
  • a nylon resin having a structural unit represented by the following formula (1) and other nylon structural units The nylon resin has a ratio of the structural unit represented by the following formula (1) to all structural units of 1 mol % or more and less than 40 mol %: Biodegradable fibers for woven, knitted, braided or nonwoven fabrics. (In formula (1), x is an integer of 1 or more and 3 or less.)
  • the nylon resin is a random copolymer in which the structural unit represented by the formula (1) and the structural units of the other nylons are randomly arranged.
  • the structural unit represented by the formula (1) includes a structural unit in which x is 3; A biodegradable fiber according to [1] or [2].
  • the structural units of the other nylons include nylon 6 structural units or nylon 12 structural units.
  • the structural units of the other nylons include an adipic acid structural unit or a sebacic acid structural unit and a hexamethylenediamine structural unit.
  • the tensile strength measured at 25°C and 50% relative humidity is 2.5 cN/dtex or more.
  • a textile product comprising a woven fabric, knitted fabric, braided fabric or nonwoven fabric formed from the biodegradable fiber according to any one of [1] to [8].
  • a clothing item comprising the textile product according to [9].
  • the present invention provides a nylon fiber that can be spun without wet spinning, a biodegradable fiber for woven fabrics, knitted fabrics, braided fabrics, or nonwoven fabrics that is biodegradable and reduces the loss of strength due to washing, and textile processed products and clothing items that use the biodegradable fiber.
  • One embodiment of the present invention relates to a biodegradable fiber containing nylon resin.
  • nylon resin The nylon resin has a structural unit represented by the following formula (1) and other nylon structural units.
  • the proportion of the structural unit represented by the following formula (1) to all structural units of the nylon resin is 1 mol % or more and less than 40 mol %.
  • x is an integer of 1 to 3.
  • the alkylene group in formula (1) may be linear or branched.
  • the structural unit represented by formula (1) may contain only structural units in which x is the same number, or may contain multiple types of structural units in which x is a different number.
  • the nylon resin is a copolymer having a structural unit represented by formula (1) and other nylon structural units.
  • the structural unit represented by formula (1) imparts biodegradability to the fiber, while the ratio of the structural unit represented by formula (1) within a specified range suppresses the decrease in strength of the fiber due to water absorption. Due to these effects, it is believed that the fiber containing the nylon has both biodegradability and sufficient resistance to washing. Furthermore, depending on the composition and randomness of the copolymer, the strength is less likely to decrease even when subjected to hot water treatment at high temperatures, and therefore resistance to hot water in which the fiber is immersed during dyeing can also be increased.
  • the ratio of the structural units represented by formula (1) to all structural units of the nylon resin is set to 1 mol% or more and less than 40 mol%.
  • the ratio of the structural units represented by formula (1) to all structural units of the nylon resin is preferably 3 mol% or more and 35 mol% or less, more preferably 5 mol% or more and 20 mol% or less, even more preferably 5 mol% or more and 17 mol% or less, even more preferably 5 mol% or more and 14 mol% or less, and particularly preferably 5 mol% or more and less than 10 mol%.
  • the ratio of other nylon structural units to the total structural units of the nylon resin is preferably more than 60 mol% and not more than 99 mol%, more preferably 65 mol% to 97 mol%, even more preferably 80 mol% to 95 mol%, even more preferably 86 mol% to 95 mol%, and particularly preferably 83 mol% to 95 mol%.
  • the structural units of the other nylons may be structural units represented by formula (2) formed by ring-opening polymerization of lactam compounds or polymerization of amino acids, or structural units represented by formula (3) and formula (4) derived from the polyamines and polycarboxylic acids, respectively, when a moiety formed by condensation of a polyamine and a polycarboxylic acid is contained in the nylon resin.
  • the structural units of the other nylons may include only one of these, or may include a plurality of these.
  • y is an integer of 4 or more and 11 or less.
  • the alkylene group in formula (2) may be linear or branched.
  • structural units of other nylons may contain structural units represented by formula (2), they may contain only structural units in which y is the same number, or may contain multiple types of structural units in which y is different numbers.
  • a is an integer of 1 or more and 10 or less.
  • the alkylene group in formula (3) may be linear or branched.
  • structural units of other nylons may contain structural units represented by formula (3), they may contain only structural units in which a is the same number, or may contain multiple types of structural units in which a is different numbers.
  • b is an integer of 1 to 12.
  • the alkylene group in formula (4) may be linear or branched.
  • the structural units of other nylons may contain structural units represented by formula (4), they may contain only structural units in which b is the same number, or may contain multiple types of structural units in which b is a different number.
  • the structural units of the other nylons preferably include structural units represented by formula (2) in which x is 4 or more and 7 or less, and preferably include structural units in which x is 5 (hereinafter also referred to as "nylon 6 structural units").
  • the ratio of nylon 6 structural units to the structural units of the other nylons is preferably 50 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, and even more preferably 85 mol% or more and 100 mol% or less.
  • the structural units of the other nylon preferably include structural units represented by formula (2) in which y is 5 or more and 11 or less, and preferably include structural units in which y is 11 (hereinafter also referred to as "nylon 12 structural units").
  • the ratio of nylon 12 structural units to the structural units of the other nylon is preferably 50 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, and even more preferably 85 mol% or more and 100 mol% or less.
  • the structural units of the other nylons include a structural unit represented by formula (3) and a structural unit represented by formula (4), it is preferable that the structural units include a structural unit represented by formula (3) in which a is 3 to 10, and a structural unit represented by formula (4) in which b is 4 to 6.
  • the structural unit represented by formula (3) includes a structural unit in which a is 4 (hereinafter also referred to as an "adipic acid structural unit") or a structural unit in which a is 10 (hereinafter also referred to as a sebacic acid structural unit), and it is more preferable that the structural unit represented by formula (4) includes a structural unit in which b is 6 (hereinafter also referred to as a "hexamethylenediamine structural unit").
  • the structural units of the other nylons can be a combination of an adipic acid structural unit and a hexamethylenediamine structural unit (nylon 66), a combination of a sebacic acid structural unit and a hexamethylenediamine structural unit (nylon 612), etc.
  • the total ratio of adipic acid structural units, sebacic acid structural units and hexamethylenediamine structural units to other nylon structural units is preferably 50 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, and even more preferably 85 mol% or more and 100 mol% or less.
  • the structural units derived from the polyamine and the polycarboxylic acid may be structural units derived from the aromatic polyamine and the aromatic polycarboxylic acid when the nylon resin contains a site formed by condensation of an aromatic polyamine such as p-phenylenediamine or m-phenylenediamine, or an aromatic polycarboxylic acid such as terephthalic acid or isophthalic acid.
  • the ratio of the structural units derived from the aromatic polyamine and the aromatic polycarboxylic acid to the total structural units of the nylon resin is preferably 0 mol% or more and 20 mol% or less, more preferably 0 mol% or more and 10 mol% or less, even more preferably 0 mol% or more and 5 mol% or less, and particularly preferably 0 mol% or more and 1 mol% or less.
  • the nylon resin may be a copolymer consisting of only the structural unit represented by formula (1) and other nylon structural units, or may be a copolymer containing further other structural units.
  • the other structural units include structural units derived from a polymerization initiator and structural units other than nylon.
  • the ratio of the other structural units to the total structural units of the nylon resin is preferably 0 mol% or more and 50 mol% or less, more preferably 0 mol% or more and 30 mol% or less, and even more preferably 0 mol% or more and 15 mol% or less.
  • the structural units of other nylons can reduce the thermal decomposition of the nylon resin. Therefore, the nylon resin, which is a copolymer with the structural units of other nylons, can be spun by a normal melt spinning method instead of wet spinning. Furthermore, the structural units of other nylons can reduce the thermal decomposition of the nylon resin, thereby suppressing the inclusion of monomers that decompose during melt processing (particularly monomers that are raw materials for the structural units represented by formula (1)). Therefore, the nylon resin can suppress environmental pollution caused by the elution of decomposed monomers from the molded product.
  • the type and proportion of each structural unit contained in the nylon resin can be calculated from the integral value of the signal attributed to each structural unit appearing in the spectrum obtained by 1 H-NMR measurement or 13 C-NMR measurement.
  • the nylon resin may be a random copolymer or a block copolymer, but is preferably a random copolymer from the viewpoint of enhancing biodegradability. Whether or not it is a random copolymer can be determined from the measurement of the melting point or glass transition temperature by a differential scanning calorimeter (DSC), the infrared absorption spectrum (IR spectrum), the spectrum obtained by 13C -NMR measurement, etc.
  • DSC differential scanning calorimeter
  • IR spectrum infrared absorption spectrum
  • 13C -NMR measurement etc.
  • the nylon resin exhibits better biodegradability as the randomness of the structural units increases.
  • the structural units represented by formula (1) and the structural units of other nylons do not form blocks of only the same structural units in succession, and the higher the ratio of adjacently linked different structural units, the higher the biodegradability.
  • the nylon resin has a difference (hereinafter also referred to as " 1H theoretical randomness") between the randomness calculated from the ratio of each structural unit obtained by 1H -NMR measurement assuming that each structural unit is an ideal random arrangement, and the randomness calculated from the ratio of the carbonyl carbon of the amino group linking different structural units to the total peak integral value of the carbonyl carbon obtained by 13C -NMR measurement (hereinafter also referred to as " 13C randomness”), which is preferably 0.10 or less, more preferably 0.05 or less.
  • the lower limit of the randomness difference ⁇ is not particularly limited, but can be 0.00 or more.
  • the 13 C randomness is a value calculated by the following formula 1.
  • Formula 1 (Sum of peak integral values derived from the carbonyl carbon peaks of the amide groups connecting the structural unit represented by formula (1) and other nylon structural units)/(Sum of peak integral values derived from all carbonyl carbon peaks)
  • the 1H theoretical randomness is the ratio of carbonyl carbons of amino groups linking different structural units to the total number of carbonyl carbons when all structural units in the nylon resin are stochastically randomly selected and arranged, and is calculated from the ratio of each structural unit obtained by 1H -NMR measurement using the following formula 2.
  • Formula 2 (abundance ratio of structural units represented by formula (1)) ⁇ (abundance ratio of structural units of other nylons) ⁇ 2
  • the difference in randomness ⁇ can be adjusted by the type of catalyst and polymerization temperature, etc. For example, by using a Grignard reagent as a catalyst, which increases the reactivity of monomers, the difference in reactivity between monomers can be reduced, thereby reducing the difference in randomness ⁇ . Furthermore, if the polymerization temperature is high, monomers that become structural units of other nylons are consumed preferentially, and if the polymerization temperature is low, monomers that become NA4 structural units are consumed preferentially, which tends to result in sites rich in that monomer. Therefore, by setting the polymerization temperature within an appropriate range according to the combination of monomers, the difference in reactivity between monomers can be reduced, thereby reducing the difference in randomness ⁇ .
  • the nylon resin can biodegrade not only the structural unit represented by formula (1) that is inherently biodegradable, but also other nylon structural units that are not biodegradable by themselves.
  • the degree of biodegradation of the nylon resin calculated from the amount of carbon dioxide generated when the nylon resin is immersed for one month in seawater containing microorganisms contained in seabed sediments, can be made greater than the theoretical value of the degree of biodegradation when all the structural units represented by formula (1) are decomposed.
  • the nylon resin may be linear or branched. From the viewpoint of improving the moldability and strength of the filament, it is preferable that the nylon resin is linear. If a monobranched or bibranched polymerization initiator is used during polymerization, which will be described later, a linear nylon resin can be obtained.
  • the melting point of the nylon resin is preferably 220°C or less, more preferably 160°C to 215°C, and even more preferably 180°C to 210°C. Note that by increasing the melting point within this range, the resistance to dyeing can also be further improved.
  • the melting point of the nylon resin can be measured by DSC. Note that when the difference ⁇ in the degree of randomness is large (i.e., when blocks of any of the structural units are formed), two or more melting points may be observed by NMR for the nylon resin, but it is preferable that only one melting point be observed by NMR for the nylon resin.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the nylon resin are not particularly limited.
  • the Mw of the nylon resin may be 10,000 or more, 30,000 or more, or 50,000 or more.
  • the Mw of the nylon resin may be 1,000,000 or less, 500,000 or less, 300,000 or less, 200,000 or less, or 100,000 or less.
  • the Mw of the nylon resin is the Mw calculated as polymethyl methacrylate resin (PMMA) and can be determined by a known technique such as gel permeation chromatography (GPC).
  • the polydispersity (Mw/Mn) of the nylon resin is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less.
  • the lower limit of Mw/Mn is not particularly limited, but can be 1.0 or more.
  • the smaller the Mw/Mn the less low molecular weight oligomers there are, so that changes in characteristics due to elution of oligomers during use and environmental pollution due to eluted oligomers can be suppressed. Furthermore, the smaller the Mw/Mn, the higher the mechanical strength of the filament can be.
  • the nylon resin is a random copolymer, for example, it can be synthesized by ring-opening and copolymerizing a monomer (first monomer) that will become the structural unit represented by formula (1) with a monomer (second monomer) that will become another structural unit of nylon in the presence of a basic catalyst and a polymerization initiator.
  • the first monomer glycine, ⁇ -alanine, ⁇ -alanine, ⁇ -lactam (2-azetidinone), and 2-pyrrolidone can be used.
  • lactam compounds having 5 to 12 carbon atoms such as ⁇ -valerolactam (2-piperidone), ⁇ -caprolactam, ⁇ -octalactam, and ⁇ -laurolactam, as well as salts of adipic acid and hexamethylenediamine and salts of sebacic acid and hexamethylenediamine can be used.
  • the basic catalyst may be any compound capable of generating anion species in each monomer.
  • Examples of basic catalysts include Grignard reagents such as ethyl magnesium bromide (EtMgBr), ethyl magnesium chloride (EtMgCl), butyl magnesium chloride (BuMgCl), methyl magnesium chloride (MeMgCl), and methyl magnesium iodide (MeMgI); alkali metals such as lithium, sodium, and potassium, and their hydrides, oxides, hydroxides, carbonates, carboxylates, alkylates, and alkoxides; and alkaline earth metals such as calcium, their hydrides, oxides, hydroxides, carbonates, carboxylates, alkylates, and alkoxides.
  • Grignard reagents such as ethyl magnesium bromide (EtMgBr), ethyl magnesium chloride (EtMgCl), butyl magnesium chloride (BuM
  • alkylates of alkali metals examples include potassium salt of 2-pyrrolidone and potassium tert-butoxide.
  • the potassium salt of 2-pyrrolidone may act as both a monomer and a basic catalyst.
  • Grignard reagents are preferred because they require small amounts and are less likely to cause environmental pollution due to residues, can be polymerized at relatively low temperatures, and can easily reduce the difference ⁇ in the degree of randomness.
  • the amount of basic catalyst used is not particularly limited, but is preferably 0.01 mol% to 20 mol% of the total amount of raw material monomers, more preferably 0.03 mol% to 15 mol%, and even more preferably 0.05 mol% to 10 mol%.
  • the amount of basic catalyst used can be 0.05 mol% to 5 mol%, 0.15 mol% to 2.5 mol%, or even 1 mol% to 1.5 mol% of the total amount of raw material monomers, from the viewpoint of balancing the reaction rate and catalyst cost.
  • quaternary ammonium salts such as tetramethylammonium chloride, quaternary phosphonium salts such as tetrabutylphosphonium bromide, and crown ethers may be used in combination as co-catalysts.
  • quaternary ammonium salts such as tetramethylammonium chloride
  • quaternary phosphonium salts such as tetrabutylphosphonium bromide
  • crown ethers may be used in combination as co-catalysts.
  • polymerization initiators examples include ester compounds or derivatives thereof, imide compounds, and carbon dioxide. From the viewpoint of improving the moldability of nylon, ester compounds or derivatives thereof, and imide compounds are preferred.
  • the polymerization initiator may be a monobranched compound, or a bi- or tri-branched compound. From the viewpoint of achieving both improved processability during molding and improved strength and toughness of the molded product, bi-branched compounds are preferred, and mono-branched compounds are particularly preferred.
  • Examples of mono-branched polymerization initiators include tert-butyl acetate, isopropyl myristate, N-acetyl- ⁇ -caprolactam, 1-acetyl-2-pyrrolidone, and N-benzoyl-2-pyrrolidone.
  • Examples of bi- or tri-branched polymerization initiators include diisopropyl adipate and adipoyldipyrrolidone.
  • the amount of polymerization initiator used is not particularly limited, but is preferably 0.01 mol% to 1.5 mol% relative to the total amount of raw material monomers, more preferably 0.03 mol% to 1.0 mol%, even more preferably 0.05 mol% to 0.75 mol%, and particularly preferably 0.2 mol% to 0.3 mol%. If the amount of polymerization initiator used is within the above range, a nylon resin with a high molecular weight can be obtained.
  • the polymerization temperature can be, for example, 25°C or higher and 250°C or lower.
  • the polymerization temperature is preferably 50°C or higher and 180°C or lower, and more preferably 80°C or higher and lower than 150°C.
  • the method for synthesizing the nylon resin is not limited to this, and for example, ⁇ -aminobutyric acid (GABA) may be reacted with a lactam compound or ⁇ -aminocarboxylic acid having 5 to 12 carbon atoms.
  • GABA ⁇ -aminobutyric acid
  • filaments can be prepared by melt extruding a resin composition containing the nylon resin described above and spinning it into a monofilament.
  • the resin composition may contain other resins, plasticizers, nucleating agents, antioxidants, UV absorbers, dyes, pigments, heat stabilizers, light stabilizers, fillers (glass fiber, etc.), internal release agents, matting agents, conductivity imparting agents, charge control agents, antistatic agents, lubricants, and other processing aids and other known additives.
  • the ratio of the above-mentioned nylon resin to the total mass of the resin components in the above-mentioned resin composition is preferably 70% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less.
  • melt extrusion is preferably carried out at a temperature higher than the melting point of the nylon resin and lower than the thermal decomposition temperature.
  • the temperature range in which melt extrusion is possible can be expanded, making molding easier.
  • melt extrusion can be carried out at a temperature of 180°C or higher and 270°C or lower.
  • the resin composition melt-extruded into fibers is preferably cooled in a water bath.
  • the bath temperature can be set to 0°C or higher and 10°C or lower.
  • the monofilament thus obtained can be stretched appropriately to obtain a filament.
  • the stretching ratio is preferably 3 times or more, more preferably 3.5 times or more, even more preferably 4 times or more, and particularly preferably 5 times or more. If the degree of molecular orientation before stretching is sufficiently high, the stretching ratio is preferably 4 times or less, more preferably 3 times or less, and even more preferably 2.5 times or less. By setting the stretching ratio within the above range, it is possible to obtain a monofilament with a tensile strength suitable for woven fabrics, knitted fabrics, braided fabrics, or nonwoven fabrics.
  • the stretching may be performed in multiple stages. A relaxation treatment may also be performed after stretching.
  • the weight average molecular weight of the filament is preferably 30,000 or more, more preferably 35,000 or more, even more preferably 40,000 or more, and particularly preferably 50,000 or more. From the viewpoint of the processability of the filament, the weight average molecular weight of the filament may be 80,000 or less.
  • the diameter of the filament is not particularly limited.
  • the filament diameter is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the diameter is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 5 ⁇ m or more.
  • the fineness is preferably 2000 dtex or less to provide flexibility, more preferably 1500 dtex or less, and even more preferably 1000 dtex or less. To provide abrasion resistance, the fineness is preferably 10 dtex or more, more preferably 20 dtex or less, and even more preferably 30 dtex or more.
  • the fibers obtained in this way have high tensile strength both on land and in water, and are less likely to lose strength due to water absorption.
  • the filament may have a tensile strength of 2.5 cN/dtex or more, preferably 3 cN/dtex or more, and more preferably 4 cN/dtex or more, measured at 25°C and a relative humidity of 50%.
  • the filament may have a tensile strength of 2 cN/dtex or more, preferably 2.5 cN/dtex or more, and more preferably 3 cN/dtex or more, measured at 25°C after immersing in pure water at 25°C for 3 hours and then removing it from the pure water without drying.
  • the filament may have a tensile strength retention of 80% or more, preferably 85% or more, and more preferably 90% or more, measured at 25°C and a relative humidity of 50% after immersing in hot water at 95°C for 30 minutes and drying it until the moisture content is 1 wt% or less.
  • the upper limit of these tensile strengths is not particularly limited, but may be 10 cN/dtex or less.
  • the above fibers also have good biodegradability.
  • the filament can have a tensile strength of 2.5 cN/dtex or more, preferably 3 cN/dtex or more, and more preferably 4 cN/dtex or more, when immersed in seawater at 25°C for 3 hours, removed from the seawater and measured at 25°C without drying.
  • the above tensile strength was determined by dividing the strength at which the filament broke by the diameter of the filament when a 300 mm long filament was used as the test sample, the gripping distance was 150 mm, and the crosshead speed of the testing machine was set to 150 mm/min.
  • the seawater used in the above measurements may have a NaCl concentration of 3% or more and 4% or less.
  • the seawater used in the above measurements may be seawater actually collected from the ocean, or it may be commercially available artificial seawater such as MARINE ART (registered trademark) SF-1 manufactured by Osaka Yaken Co., Ltd.
  • the filament is stored at 25°C at the interface between seawater and sediment for one month, then left to dry for three days at 25°C in a dry room with a dew point of -40°C or lower, and the reduction rate of the tensile strength measured at 25°C and 50% relative humidity compared to the tensile strength measured at 25°C and 50% relative humidity before the storage is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more.
  • the reduction rate is preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less.
  • the above-mentioned interface between seawater and sediments refers to the environment within 5 cm from the interface between seawater and sediments as defined in ISO 19679.
  • the above-mentioned sediments can be sea sand collected from the ocean.
  • the above-mentioned filaments can be used for various applications as textile processed products obtained by weaving, knitting, or incorporating them by known methods to form woven, knitted, or braided fabrics, or by processing them into nonwoven fabrics by known methods such as dry, wet, spunbond, and meltblowing.
  • the above-mentioned textile processed products can be used for a wide range of applications, such as clothing items such as outerwear, innerwear, and legwear, clothing accessories such as shoes, umbrellas, and bags, interior items such as curtains, and bedding items such as duvet covers and sheets.
  • the above-mentioned filaments are not likely to lose strength even when washed, so they are suitable for use in applications that require repeated washing, such as clothing items, interior items, and bedding items.
  • the polymer was pulverized, it was washed in the order of pure water, acetic acid solution, pure water, and pure water to remove unreacted monomers and catalyst. It was then dried under reduced pressure to remove moisture, and polymer powder for spinning was obtained.
  • the polymer powder obtained above was fed into a small twin-screw extruder, melt-extruded into a fiber form, and cooled and solidified by passing through a cold bath to produce an undrawn monofilament. This monofilament was then appropriately drawn to obtain filament 1.
  • filament 13 A multifilament was prepared from polymer 2 in the same manner as for preparation of filament 1, except that the nozzle of the small twin-screw extruder was changed to that for multifilament, and the multifilament was stretched to prepare filament 13 (number of single fibers: 36, fineness: 235 dtex).
  • polymerization conditions for polymer 1 to polymer 12 used in the production of filament 1 to filament 12, and the stretch ratios for filament 1 to filament 12 are shown in Table 1. Note that “NA4/6” for the polymer type indicates nylon 4/6, “NA4" for nylon 4, and “NA6” for nylon 6.
  • the amounts of initiator and catalyst added are the amounts blended relative to the total moles of monomers, while the monomer “pyrrolidone” indicates the amount of 2-pyrrolidone, and "caprolactam” indicates the amount of ⁇ -caprolactam.
  • the ratio of the integral value of the peak of methylene protons derived from nylon 4 structural units to the integral value of the peak of methylene protons derived from nylon 6 units was calculated. From the integral value ratio of these peaks, the ratio of nylon 4 structural units was calculated, which was designated as the "NA4 ratio".
  • NA4 ratio the degree of randomness ((NA4 ratio) ⁇ (NA6 ratio) ⁇ 2) was calculated on the assumption that each polymer was an ideal random arrangement of nylon 4 structural units and nylon 6 structural units, and this was defined as the " 1H theoretical randomness.”
  • 13 C-NMR Measurement 13 C-NMR spectrum was obtained using a nuclear magnetic resonance spectrometer (JASCO Corporation, JNM-ECZ600R/S1). Specifically, 10 mg of sample for each polymer was dissolved in 1 ml of a mixed solvent of trifluoroethanol (TFE)/deuterated chloroform (CDCl 3 ) at a volume ratio of 1/1. Then, measurement was performed using tetramethylsilane (TMS) as a standard.
  • TFE trifluoroethanol
  • CDCl 3 deuterated chloroform
  • DSC Measurement DSC curves were obtained by differential scanning calorimetry (DSC method) using a differential scanning calorimeter (DSC3 + , manufactured by Mettler Toledo). Specifically, 10 mg of a sample for each polymer was weighed into an aluminum pan and heated at a rate of 20°C/min in a range from 25°C to 280°C under a nitrogen atmosphere to obtain a DSC curve. The peak top temperature of the endothermic peak based on the melting behavior in this DSC curve was taken as the "melting point" of each polymer.
  • GPC analysis was performed using a gel permeation chromatography (GPC) analyzer (HLC-8420GPC, manufactured by Tosoh Corporation). Specifically, 10 mg of sample was dissolved for each filament in hexafluoroisopropanol (HFIP) in which sodium trifluoroacetate was dissolved at a concentration of 5 mM to obtain a 10 mL solution, and then the solution was filtered through a membrane filter to obtain a sample solution. 100 ⁇ L of this sample solution was injected into the analyzer, and measurements were performed under the following conditions.
  • GPC gel permeation chromatography
  • Tables 2 and 3 show the NA4 ratio, 1H theoretical randomness, 13C randomness, the difference ⁇ between the 1H theoretical randomness and the 13C randomness, the melting point, the weight average molecular weight Mw, the number average molecular weight Mn, Mw/Mn, the PA4 ratio of each polymer on a mass basis converted from the molar ratio of PA4, and biodegradability ( O2 standard) for polymers 1 to 12 and filaments 1 to 13.
  • the tensile strength was measured in indoor, underwater and biodegradable environments using a tensile testing machine (Tensilon RTF-1210, manufactured by A&D Co., Ltd.). Specifically, each filament with a length (grab distance) of 300 mm was used as a test sample, the crosshead speed of the testing machine was set to 150 mm/min, and the load at which the filament broke was taken as the tensile strength. The value obtained by dividing this by the diameter of the filament was taken as the tensile strength in each environment.
  • the environmental conditions were as follows: Indoor environment: Measured at 25°C and a relative humidity of 50% Underwater environment: Immersed in pure water at 25°C for 3 hours, then measured at 25°C without drying Dyeing treatment environment: Immersed in hot water at 95°C for 30 minutes, then dried to a moisture content of 1 wt% or less, and measured at 25°C and a relative humidity of 50% Biodegradation environment: Stored at the interface between seawater and sediment at 25°C for one month, then left to dry for 3 days at 25°C in a dry room with a dew point of -40°C or less, and then measured at 25°C and a relative humidity of 50% Note that seawater (NaCl concentration: 3.1-3.4%) and sea sand collected from the Pacific coast were used as the seawater and sediment, respectively.
  • the difference between the tensile strength in an indoor environment and the tensile strength in a biodegradable environment was calculated, and the ratio of this difference to the tensile strength in an indoor environment ((tensile strength in an indoor environment - tensile strength in a biodegradable environment) / tensile strength in an indoor environment x 100) was calculated to obtain the "strength reduction rate after biodegradation.”
  • a strength reduction rate of 10% or more in a biodegradable environment was determined to have "biodegradability (strength standard)."
  • Table 4 shows the tensile strength of filaments 1 to 13 in an indoor environment, an underwater environment, and a biodegradable environment, the rate of strength reduction after biodegradation, the rate of tensile strength retention after dyeing treatment, and the results of the biodegradability assessment. Note that filaments 6 to 8 became significantly embrittled in water and were unable to maintain their shape. As a result, it was not possible to measure the tensile strength in an underwater environment or a biodegradable environment.
  • Filament 13 also showed sufficiently high strength even after dyeing compared to a commercially available nylon 6 multifilament for textiles (manufactured by Toray; number of single threads: 34, fineness: 210 dtex; indoor environmental strength: 3.7 cN/dtex).
  • the biodegradable fiber according to the present invention is expected to contribute to the reduction of environmental pollution because of its biodegradability.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polyamides (AREA)

Abstract

L'invention concerne des fibres de nylon qui peuvent être filées sans filage à l'état humide et qui sont des fibres biodégradables qui doivent être utilisées dans un tissu tissé, un tissu tricoté, un article tressé ou un tissu non tissé et suppriment une baisse de résistance provoquée par le blanchissage tout en étant biodégradables. Des fibres biodégradables qui doivent être utilisées dans un tissu tissé, un tissu tricoté, un article tressé ou un tissu non tissé et contiennent une résine de nylon qui a une unité structurale représentée par la formule (1) et une autre unité structurale en nylon, la proportion de l'unité structurale représentée par la formule (1) par rapport à toutes les unités structurales de la résine de nylon étant d'au moins 1 % en moles et inférieure à 40 % en moles. (Dans la formule (1), x est un nombre entier de 1 à 3, inclus.)
PCT/JP2023/035676 2022-09-30 2023-09-29 Fibre biodégradable, produit fibreux et article vestimentaire WO2024071390A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120077819A (ko) * 2010-12-31 2012-07-10 코오롱인더스트리 주식회사 폴리아미드 수지의 제조 방법 및 폴리아미드 수지
KR20130101909A (ko) * 2012-03-06 2013-09-16 한양대학교 에리카산학협력단 폴리아미드 공중합체의 제조 방법
US20150065650A1 (en) * 2013-08-29 2015-03-05 Nylon Corporation Of America, Inc. Biodegradable nylon and method for the manufacture thereof
KR20150042487A (ko) * 2013-10-11 2015-04-21 코오롱인더스트리 주식회사 폴리아마이드의 제조방법 및 이를 이용하여 제조된 폴리아마이드

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120077819A (ko) * 2010-12-31 2012-07-10 코오롱인더스트리 주식회사 폴리아미드 수지의 제조 방법 및 폴리아미드 수지
KR20130101909A (ko) * 2012-03-06 2013-09-16 한양대학교 에리카산학협력단 폴리아미드 공중합체의 제조 방법
US20150065650A1 (en) * 2013-08-29 2015-03-05 Nylon Corporation Of America, Inc. Biodegradable nylon and method for the manufacture thereof
KR20150042487A (ko) * 2013-10-11 2015-04-21 코오롱인더스트리 주식회사 폴리아마이드의 제조방법 및 이를 이용하여 제조된 폴리아마이드

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