WO2024058076A1 - Fibres à base de p3hb3hh colorées, agrégat de fibres les comprenant, et leurs procédés de fabrication - Google Patents

Fibres à base de p3hb3hh colorées, agrégat de fibres les comprenant, et leurs procédés de fabrication Download PDF

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WO2024058076A1
WO2024058076A1 PCT/JP2023/032906 JP2023032906W WO2024058076A1 WO 2024058076 A1 WO2024058076 A1 WO 2024058076A1 JP 2023032906 W JP2023032906 W JP 2023032906W WO 2024058076 A1 WO2024058076 A1 WO 2024058076A1
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fibers
p3hb3hh
fiber
dyed
dyeing
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PCT/JP2023/032906
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English (en)
Japanese (ja)
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大関達郎
藤田正人
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株式会社カネカ
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • D06P1/16—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 dispersed, e.g. acetate, dyestuffs
    • 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
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/54—Polyesters using dispersed dyestuffs

Definitions

  • the present invention relates to dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fibers, fiber aggregates containing the same, and methods for producing them.
  • polyester fibers composed of aromatic polyesters such as polyethylene terephthalate have been widely used in various textile products such as clothing, carpets, and pile fabrics.
  • biodegradable aliphatic polyester fibers that decompose in the natural environment have been used.
  • Patent Document 1 describes a fiber structure containing polylactic acid fibers.
  • Patent Document 2 describes a fabric containing an aliphatic polyester multifilament having a melting point of 130° C. or higher.
  • Polyester fibers are usually dyed under pressure at 130°C, or if a carrier is used, they are often dyed at 100°C under normal pressure.
  • Patent Documents 1 and 2 also dye aliphatic polyester fibers using a disperse dye at a temperature of 90° C. or higher, which poses a problem in that the energy required for dyeing is high. In the following, when there is no mention of pressure, normal pressure is meant.
  • the present invention aims to dye poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)-based fibers with good dyeability while reducing the energy required for dyeing.
  • a method for producing a dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)-based fiber, and a dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)-based fiber A method for producing a fiber aggregate containing fibers, a dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fiber, and a fiber aggregate containing the same are provided.
  • One or more embodiments of the invention include dyeing poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)-based fibers using a dye at a temperature of 85° C. or less.
  • the present invention relates to a method for producing dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fibers.
  • One or more embodiments of the present invention provide a method of making a fiber assembly comprising dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)-based fibers, the method comprising:
  • the present invention relates to a method for producing a fiber aggregate, comprising a step of dyeing (co-3-hydroxyhexanoate) based fibers with a dye, the dyeing being carried out at a temperature of 85° C. or lower.
  • the maximum temperature T2 of the dyeing process calculated based on a thermomechanical analysis (TMA) curve measured from 30 to 180°C is 88°C or less, and the T2 is: Corresponds to the intersection of the straight line A passing through the two points of 30°C and 40°C on the TMA curve and the tangent line B whose tangent point is the point on the TMA curve that shows a heat shrinkage rate of 25% compared to the heat shrinkage rate at 120°C.
  • TMA thermomechanical analysis
  • One or more embodiments of the present invention relate to a fiber assembly comprising the dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)-based fibers.
  • poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)-based fibers can be dyed with good dyeability while reducing the energy required for dyeing.
  • a fiber assembly includes dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fibers that have good dyeability while reducing the energy required for dyeing. can be obtained.
  • TMA curve obtained by thermomechanical analysis of an example of dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fiber.
  • P3HB3HH-based fibers obtained by low-temperature dyeing and fiber aggregates containing the same have excellent soil degradability and ocean degradability, and are resistant to hydrolysis. In addition, the color fastness to washing is also good.
  • ⁇ when a numerical range is indicated by " ⁇ ", the numerical range includes both end values (upper limit and lower limit).
  • a numerical range of "X to Y” is a range that includes both end values of X and Y.
  • a numerical range that is a combination of the upper and lower limits of different numerical ranges as appropriate is included.
  • biodegradability refers to properties that can be differentiated to the molecular level through the action of microorganisms and eventually become water and carbon dioxide
  • marine degradability refers to properties that can be differentiated to the molecular level by the action of microorganisms in the ocean, It means the property of being differentiated down to the molecular level and eventually becoming water and carbon dioxide.
  • Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is widely used as a biodegradable bioplastic that is degradable in the ocean, and P3HB3HH fibers and fiber aggregates containing them are also highly degradable in soil. It can also have ocean degradability.
  • Dyed P3HB3HH fiber and its manufacturing method Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fibers dyed with dyes, that is, containing dyes, will be referred to as "dyed P3HB3HH fibers" and simply P3HB3HH.
  • P3HB3HH type fiber it means a P3HB3HH type fiber that does not contain dye.
  • Dyed P3HB3HH fibers can be produced by dyeing P3HB3HH fibers with a dye at a temperature of 85° C. or lower. That is, the dyed P3HB3HH fiber is a P3HB3HH fiber dyed at a temperature of 85° C. or lower. P3HB3HH fibers dyed at a low temperature of 85° C. or lower can be confirmed by TMA (thermo-mechanical analysis), as described below. Further, the residual shrinkage rate when dyed P3HB3HH fibers are heat treated at a specific temperature can be estimated from the TMA heat shrinkage curve.
  • TMA thermo-mechanical analysis
  • the P3HB3HH-based fiber preferably contains P3HB3HH in an amount of 80% by weight or more, more preferably 85% by weight or more, even more preferably 90% by weight or more, and even more preferably 95% by weight or more.
  • the monomer composition of P3HB3HH is not limited, but from the viewpoint of excellent strength and low-temperature dyeing properties, 50 to 98 mol% of 3-hydroxybutyrate (3HB) and 2 to 50 mol of 3-hydroxyhexanoate (3HH). %, and more preferably 50 to 97 mol% of 3HB and 3 to 50 mol% of 3HH.
  • One kind of P3HB3HH may be used alone, or two or more kinds having different molar contents of 3HB may be used in combination.
  • P3HB3HH is not particularly limited and can be produced by a known method, but from the viewpoint of easily obtaining P3HB3HH with high marine degradability, it is preferably produced by a production method using microorganisms.
  • a production method using microorganisms known methods can be used.
  • the microorganism is not particularly limited as long as it has the ability to produce P3HB3HH.
  • microorganisms capable of producing P3HB3HH include Aeromonas caviae, Cupriavidus necator, Ralstonia eutropha, and Alcaligenes ratus. enes latus), etc.
  • P3HB3HH In addition, in order to increase the productivity of P3HB3HH, the Alcaligenes eutrophus AC32 strain (FERM BP-6038) into which genes for the P3HB3HH synthase group were introduced (J. Bateriol., 179, p4821-4830) (1997) ) etc. may be used. Furthermore, as P3HB3HH, a commercially available product such as biodegradable polymer GP (Green Planet) (registered trademark) manufactured by Kaneka Corporation may be used.
  • biodegradable polymer GP Green Planet
  • the weight average molecular weight of P3HB3HH is not particularly limited, but from the viewpoint of moldability and strength, it is preferably 100,000 to 3,000,000, more preferably 150,000 to 1,500,000.
  • the weight average molecular weight refers to that measured from polystyrene equivalent molecular weight distribution using gel permeation chromatography (GPC) using chloroform as an eluent.
  • GPC gel permeation chromatography
  • a column suitable for measuring the molecular weight may be used as a column in the GPC.
  • the melt flow rate (MFR) of P3HB3HH is not particularly limited, but according to JIS K 7210-1:2014, the melt flow rate (MFR) measured under the conditions of a temperature of 165°C and a load of 5 kg (49 N) is 0.1. It may be ⁇ 100 g/10 minutes, it may be 1-50 g/10 minutes, it may be 10-40 g/10 minutes. When the melt flow rate is within the above-mentioned range, the fluidity of the molten resin will be within an appropriate range, and fiberization will be good. Note that, if fiberization is possible, the melt flow rate (MFR) of P3HB3HH may exceed 100 g/10 minutes.
  • the P3HB3HH fiber may contain a crystal nucleating agent from the viewpoint of fiber properties and productivity.
  • the crystal nucleating agent is not particularly limited as long as it is a compound that has the effect of promoting crystallization of P3HB3HH.
  • sugar alcohol compounds, polyvinyl alcohol, chitin, chitosan, etc. are preferred, sugar alcohol compounds are more preferred, and pentaerythritol is even more preferred.
  • One type of crystal nucleating agent may be used alone, or two or more types may be used in combination.
  • the content of the crystal nucleating agent in the P3HB3HH fiber is not particularly limited, but for example, it is preferably 0.05 to 12 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of P3HB3HH.
  • the amount is preferably 0.5 to 8 parts by weight, more preferably 0.5 to 8 parts by weight, and particularly preferably 1 to 5 parts by weight.
  • the content of the crystal nucleating agent is 0.05 part by weight or more, the crystallization promoting effect tends to be improved and the productivity of fibers tends to be improved.
  • the content of the crystal nucleating agent is set to 12 parts by weight or less, it is easy to suppress a decrease in the viscosity of P3HB3HH, a decrease in fiber physical properties, etc. during processing while maintaining a sufficient effect of accelerating the crystallization rate.
  • the P3HB3HH fiber may contain a lubricant from the viewpoint of productivity and fiber properties.
  • the lubricant is not particularly limited as long as it is a compound that has the effect of imparting lubricity to P3HB3HH. Examples include fatty acid amide, alkylene fatty acid amide, glycerin monofatty acid ester, organic acid monoglyceride, sorbitan fatty acid ester, polyglycerin fatty acid ester, and higher alcohol fatty acid ester.
  • fatty acid amides include monoamides and bisamides of fatty acids.
  • the fatty acid (fatty acid moiety) constituting the fatty acid amide preferably has a carbon number of 12 to 30, and more preferably has a carbon number of 12 to 30, from the viewpoint of giving the resin composition a suitably high melting point and suppressing deterioration of processability during melt processing. Preferably it is 18-22.
  • fatty acid amides include behenic acid amide, erucic acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, and ethylene bis oleic acid amide.
  • Examples include biserucic acid amide.
  • Examples of glycerin fatty acid esters include monoesters of fatty acids and glycerin, diesters of fatty acids and glycerin, and triesters of fatty acids and glycerin.
  • glycerin triesters include glycerin diacetomonoesters such as glycerin diacetomonolaurate, glycerin diacetomonooleate, glycerin diacetomonostearate, glycerin diacetomonocaprylate, and glycerin diacetomonodecanoate.
  • glycerin diacetomonoesters such as glycerin diacetomonolaurate, glycerin diacetomonooleate, glycerin diacetomonostearate, glycerin diacetomonocaprylate, and glycerin diacetomonodecanoate.
  • One type of lubricant may be used alone, or two or more types may be used in combination.
  • the content of the lubricant in the P3HB3HH fiber is not particularly limited, but for example, it is preferably 0.05 to 12 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of P3HB3HH. , more preferably 0.5 to 8 parts by weight, particularly preferably 1 to 5 parts by weight.
  • a lubricant content of 0.05 parts by weight or more friction between P3HB3HH and the metal surface inside the extruder or spinning machine during fiberization is suppressed, and decomposition of P3HB3HH due to shear heat generation is suppressed, and the nozzle It is also easy to prevent the fibers extruded from sticking to each other.
  • the P3HB3HH fibers may contain plasticizers, inorganic fillers, organic fillers (cellulose, etc.), antioxidants, ultraviolet absorbers, antistatic agents, etc. within the range that does not impede the effects of the present invention. It may also contain other additive components. The amount of other additive components added may be 5 parts by weight or less, or 1 part by weight or less with respect to 100 parts by weight of P3HB3HH.
  • the P3HB3HH-based fibers may contain resin components other than P3HB3HH (other resin components), if necessary, within a range that does not impede the effects of the present invention.
  • resin components include resin components other than P3HB3HH (other resin components), if necessary, within a range that does not impede the effects of the present invention.
  • biodegradable resins are preferred.
  • other biodegradable resins include petroleum-derived resins such as polylactic acid, polycaprolactone, polybutylene adipate terephthalate, polybutylene succinate adipate, and polybutylene succinate, and natural polymers such as starch and cellulose. Can be mentioned.
  • the content of other resin components is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less, based on the total amount (100% by weight) of the resin components.
  • One type of other resin components can be used alone, or two or more types can be used in combination.
  • P3HB3HH-based fibers can be obtained, for example, by fiberizing a resin composition containing P3HB3HH.
  • the resin composition is not particularly limited, but preferably contains 80% by weight or more of P3HB3HH, more preferably 85% by weight or more, and even more preferably 90% by weight or more.
  • the upper limit may be 100% by weight, but may be, for example, 98% by weight or less or 95% by weight or less.
  • the resin composition is not particularly limited, from the viewpoint of productivity and fiber properties, it is preferable that the resin composition further contains a crystal nucleating agent.
  • a crystal nucleating agent those mentioned above can be used as appropriate, and pentaerythritol is particularly preferred.
  • One type of crystal nucleating agent may be used alone, or two or more types may be used in combination.
  • the content of the crystal nucleating agent in the resin composition is not particularly limited, but for example, it is preferably 0.05 to 12 parts by weight, and preferably 0.1 to 10 parts by weight, based on 100 parts by weight of P3HB3HH.
  • the amount is more preferably 0.5 to 8 parts by weight, and particularly preferably 1 to 5 parts by weight.
  • the content of the crystal nucleating agent is 0.05 part by weight or more, the crystallization promoting effect tends to be improved and the productivity of fibers tends to be improved.
  • by setting the content of the crystal nucleating agent to 12 parts by weight or less while maintaining a sufficient effect of accelerating the crystallization rate, it is easy to suppress a decrease in the viscosity of the resin composition and a decrease in fiber physical properties during processing.
  • the resin composition is not particularly limited, it is preferable from the viewpoint of productivity that it further contains a lubricant.
  • a lubricant those mentioned above can be used as appropriate, and fatty acid amides are particularly preferred.
  • the content of the lubricant in the resin composition is not particularly limited, but for example, it is preferably 0.05 to 12 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of P3HB3HH.
  • the amount is preferably 0.5 to 8 parts by weight, more preferably 0.5 to 8 parts by weight, and particularly preferably 1 to 5 parts by weight.
  • the resin composition may optionally contain a plasticizer, an inorganic filler, an organic filler (cellulose, etc.), an antioxidant, an ultraviolet absorber, an antistatic agent, etc., within a range that does not impede the effects of the present invention. It may also contain other additive components.
  • the amount of other additive components added may be 5 parts by weight or less, or 1 part by weight or less with respect to 100 parts by weight of P3HB3HH.
  • the above resin composition may contain resin components other than P3HB3HH (other resin components), if necessary, within a range that does not impede the effects of the present invention.
  • resin components biodegradable resins are preferred.
  • other biodegradable resins include petroleum-derived resins such as polylactic acid, polycaprolactone, polybutylene adipate terephthalate, polybutylene succinate adipate, and polybutylene succinate, and natural polymers such as starch and cellulose. It will be done.
  • the content of other resin components is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less, based on the total amount (100% by weight) of the resin components.
  • One type of other resin components can be used alone, or two or more types can be used in combination.
  • P3HB3HH fibers can be obtained by melt spinning the resin composition.
  • a pellet-shaped resin composition obtained by melt-kneading the above resin composition is melted using a melt extruder, and the molten resin composition is continuously extruded from a nozzle to form fibers.
  • Spun filaments (undrawn filaments) can be produced.
  • the melt spinning temperature is not particularly limited as long as it is higher than the melting point of the resin composition and lower than the thermal decomposition temperature, but for example, when the melting point of the resin composition is Tm, it is [Tm+5°C] to [Tm+40°C]. It may be [Tm+10°C] to [Tm+30°C].
  • the temperature may be 145 to 180°C, 150 to 180°C, or 150 to 170°C.
  • the melt spinning temperature By setting the melt spinning temperature to 145° C. or higher, the resin composition can be sufficiently dissolved, so that spinning can be easily stabilized. Further, by setting the spinning temperature to 180° C. or lower, thermal decomposition of P3HB3HH is suppressed, the spinning is easily stabilized, and the physical properties of the resulting fiber tend to be further improved.
  • the melt spinning temperature refers to a temperature in the highest temperature range among the temperatures applied while the resin composition is fiberized.
  • the resin composition is not particularly limited, but for example, from the viewpoint of moldability and fiber strength, the weight average molecular weight is preferably 100,000 to 3,000,000, and preferably 150,000 to 1,500,000. It is more preferable that
  • the environmental temperature when extruding the molten resin composition from the spinneret is not particularly limited, and when the glass transition temperature of the resin composition is Tg, it may be [Tg + 5 ° C] to [Tg + 50 ° C], [ [Tg+10°C] to [Tg+40°C]. More specifically, the temperature can be adjusted as appropriate within the range of, for example, 5 to 40°C. It is preferable to apply rectified air to the fibers (spun filaments) extruded from the spinneret. The rectified air is also called quench air, and has the function of stabilizing the flow of yarn. It is also possible to cool the spun filaments by using cooled gas as quench air.
  • the temperature of the quench air is preferably 5 to 40°C, more preferably 10 to 30°C. When the temperature is 5°C or higher, it is easy to suppress generation of residual stress in the fibers. When the temperature is 40° C. or lower, the resin is sufficiently solidified, and it is easy to prevent the fibers from sticking.
  • the wind speed of the quench air is not particularly limited, but is preferably 0.1 to 3.0 m/sec, for example. When it is 0.1 m/sec or more, the rectifying effect is easily exhibited, and when it is 3.0 m/sec or less, the quenching wind is not too strong and the yarns are not disturbed, causing sticking of fibers to each other and yarn breakage. It is restrained from doing so.
  • the glass transition temperature, crystallization temperature, melting point, and thermal decomposition temperature of the resin or resin composition can be measured as described in the Examples.
  • the spun filaments can be drawn to obtain drawn filaments (multifilaments).
  • drawn filaments multifilaments
  • Stretching is not particularly limited, and may be carried out by a two-step spinning/drawing method or by a direct spinning/drawing method. In the two-stage spinning and drawing method, drawing is performed after the spun filament is wound up. In the direct spinning/drawing method, spinning and drawing are performed continuously without winding the spun filaments. Further, the stretching step may be performed in multiple stages by combining a plurality of roll pairs. The surface temperatures and speeds of the multiple rolls may be the same or different.
  • the stretching temperature is not particularly limited, but may be, for example, 30 to 100°C, or 40 to 90°C.
  • the stretching ratio may be, for example, 1.5 to 20 times. When the stretching ratio is 1.5 times or more, the strength of the fiber can be further increased. Before stretching, an oil agent may be applied to the spun filaments as necessary.
  • the single fiber tensile strength of the drawn filament is preferably 0.5 to 10 cN/dtex, more preferably 0.7 to 10 cN/dtex, and still more preferably 1.0 to 10 cN/dtex.
  • the single fiber tensile strength of the drawn filament can be measured based on JIS L 1013:2021.
  • a dyed P3HB3HH fiber may be obtained by dyeing the drawn filament as described below.
  • P3HB3HH short fibers can be obtained by crimping the drawn filaments and then cutting them into a predetermined length.
  • the crimping process is not particularly limited, and can be performed by, for example, a known crimping method such as a gear crimp method or a stuffing box method.
  • the obtained P3HB3HH fiber has crimps, specifically mechanical crimps.
  • the crimping process may be performed using a stuffing box after preheating the drawn filament.
  • the drawn filament may be preheated by, for example, wet heat treatment or dry heat treatment.
  • the moist heat treatment can be performed using, for example, steam.
  • the dry heat treatment may be performed using, for example, a hot air oven or an electric heater.
  • the preheating temperature of the drawn filament is preferably 60 to 120°C, more preferably 60 to 110°C, even more preferably 70 to 100°C, even more preferably 80 to 90°C.
  • the stuffing box pressure is more preferably 0.001 to 0.08 MPa, even more preferably 0.001 to 0.06 MPa, even more preferably 0.001 to 0.04 MPa.
  • the fiber length of the P3HB3HH short fibers is not particularly limited, but for example, from the viewpoint of suitability for use in spun yarn, it may be 20 to 176 mm, 25 to 138 mm, or 28 to 110 mm. good.
  • the P3HB3HH fiber has a single fiber fineness of preferably 0.1 to 100 dtex, more preferably 0.5 to 50 dtex, even more preferably 1.0 to 25 dtex, and 1. Even more preferably it is .0 to 15 dtex.
  • the P3HB3HH short fibers preferably have a tensile strength of 0.3 to 6.0 cN/dtex, more preferably 0.5 to 6.0 cN/dtex, and even more preferably It is 1.0 to 6.0 cN/dtex.
  • the tensile strength of P3HB3HH short fibers can be measured based on JIS L 1015:2021.
  • the weight average molecular weight of the P3HB3HH fiber is not particularly limited, but is preferably 100,000 to 3,000,000, more preferably 120,000 to 3,000,000, and even more preferably 150,000 to 3,000,000. ,000 to 1,500,000, more preferably 200,000 to 500,000.
  • the weight average molecular weight of a fiber can be measured as a polystyrene equivalent molecular weight using gel permeation chromatography (GPC) using chloroform as an eluent.
  • the P3HB3HH fiber preferably has a hot water shrinkage rate at 85°C of 15% or less, more preferably 10% or less, and even more preferably 5% or less. It is particularly preferably 3% or less.
  • the hot water shrinkage rate of a fiber is defined as the length of the fiber before the hot water treatment and the length of the fiber after the hot water treatment when the fiber is immersed in hot water at a predetermined temperature for 60 minutes. The length can be measured and calculated using the following formula (1).
  • the hot water may be a dye solution. When measuring the length of a fiber, the fiber is held at both ends with tweezers and stretched into a straight line.
  • Hot water shrinkage rate (%) (L0-L1)/L0 ⁇ 100 (1)
  • L0 is the length of the fiber before hot water treatment
  • L1 is the length of the fiber after hot water treatment.
  • the P3HB3HH fiber preferably has a hot water shrinkage rate at 80°C of 10% or less, more preferably 5% or less, and even more preferably 3% or less. It is.
  • Dyed P3HB3HH fibers can be obtained by immersing P3HB3HH fibers in a dye solution containing a dye at a temperature of 85° C. or lower. By dyeing at a temperature of 85° C. or lower, the energy required for dyeing can be reduced.
  • the dye may be a synthetic dye or a natural dye. Synthetic dyes are not particularly limited, and include, for example, disperse dyes, direct dyes, vat dyes, and metal-containing dyes (also referred to as metal complex dyes). One or more commercially available dyes can be appropriately selected and used depending on the desired color and the like.
  • the dyeing solution may contain a carrier from the viewpoint of improving low-temperature dyeability, and may not contain a carrier from the viewpoint of reducing the environmental load due to waste liquid treatment.
  • dyed P3HB3HH fibers can be obtained by dyeing P3HB3HH fibers using a disperse dye without using a carrier at a temperature of 85° C. or lower.
  • the dye concentration of the dye solution may be appropriately set depending on the desired hue and is not particularly limited.
  • the dye concentration may be 0.0001 to 4% by weight (% o.w.f.) based on the weight of the P3HB3HH fiber from the viewpoint of hue, cost, and color fastness.
  • the bath ratio is not particularly limited, but may be 1:10 or more, and from the viewpoint of reducing costs and environmental impact due to waste liquid treatment, it is preferably 1:30 or less, and 1:20 or less. More preferred.
  • the dyeing temperature (temperature of the dyeing solution) may be 85°C or lower and is not particularly limited, but from the viewpoint of dyeability, it is preferably 30°C or higher, more preferably 40°C or higher, and 50°C or higher. It is more preferable that the temperature is at least °C. Furthermore, from the viewpoint of more effectively reducing the energy required for dyeing, the dyeing temperature (temperature of the dyeing solution) is preferably 80°C or lower, more preferably 75°C or lower, and 70°C or lower. The temperature is even more preferably 65°C or lower, even more preferably 60°C or lower, and particularly preferably 60°C or lower.
  • the staining time is not particularly limited, but for example, from the viewpoint of productivity and suppression of staining spots, it may be 30 to 120 minutes or 60 to 120 minutes.
  • P3HB3HH fibers may be dyed (yarn dyed) in the form of fibers or spun yarns, or may be dyed (piece dyed) in the form of cloth. Piece dyeing is preferable from the viewpoint of reducing costs. Since P3HB3HH fibers have good low-temperature dyeability at temperatures of 85° C. or lower, they can be piece-dyed even in the case of fabrics that use cellulose fibers in combination.
  • the dyed P3HB3HH fiber has a maximum dyeing temperature T2 of 88°C or lower, which is calculated based on a thermomechanical analysis (TMA) curve that measures the thermal shrinkage rate from 30 to 180°C, and the T2 is 30°C on the TMA curve.
  • TMA thermomechanical analysis
  • the present inventors determined that when P3HB3HH fibers were dyed to produce dyed P3HB3HH fibers, the dyeing temperature T1 in the manufacturing process and the heat shrinkage rate of the obtained dyed P3HB3HH fibers from 30 to 180°C were measured.
  • the maximum temperature T2 of the dyeing process calculated based on the mechanical analysis (TMA) curve satisfies the following relational expression (I), that is, the relational expression (II), and more specifically, the following relational expression (III). I found something that satisfies me.
  • T2 of the dyed P3HB3HH fiber is preferably 85°C or lower, more preferably 80°C or lower, and even more preferably 75°C or lower.
  • the temperature is preferably 70°C or lower, even more preferably.
  • T2 of the dyed P3HB3HH fiber is preferably 53°C or higher, more preferably 55°C or higher, and even more preferably 60°C or higher.
  • the single fiber fineness of the dyed P3HB3HH fiber is not particularly limited, and can be appropriately set depending on the purpose, use, etc.
  • the single fiber fineness is preferably 0.1 to 100 dtex, more preferably 0.5 to 50 dtex, and 1.0 to 25 dtex. More preferably, it is 1.0 to 15 dtex, and even more preferably 1.0 to 15 dtex.
  • single fiber fineness can be measured by an autobibroscopy method.
  • the dyed P3HB3HH fibers may be filaments or short fibers.
  • the dyed P3HB3HH filament has a single fiber tensile strength of preferably 0.5 to 10 cN/dtex, more preferably 0.7 to 10 cN/dtex, and still more preferably 1.0 to 10 cN/dtex. It is. Thereby, the physical properties of the fiber aggregate using dyed P3HB3HH filaments can be improved.
  • the single fiber tensile strength of the dyed P3HB3HH filament can be measured based on JIS L 1013:2021.
  • the dyed P3HB3HH short fibers preferably have a tensile strength of 0.3 to 6.0 cN/dtex, more preferably 0.5 to 6.0 cN/dtex, and even more preferably is 1.0 to 6.0 cN/dtex.
  • the tensile strength of dyed P3HB3HH short fibers can be measured based on JIS L 1015:2021.
  • dyed P3HB3HH fibers have a knitted fabric made of 100% by mass of dyed P3HB3HH fibers as a measurement sample, and the dyeing fastness determined by the discoloration grade specified in JIS L 0844 No. A-2: 2011.
  • the degree is preferably 3rd class or higher, more preferably 3-4th class or higher, and even more preferably 4th class or higher.
  • dyed P3HB3HH fibers are measured using a knitted fabric consisting of 100% by mass of dyed P3HB3HH fibers, and the color fastness determined by the contamination grade specified in JIS L 0844 No. A-2: 2011. is preferably 3rd grade or higher, more preferably 3-4th grade or higher.
  • the dyed P3HB3HH fiber preferably has a weight average molecular weight of 100,000 to 3,000,000, more preferably 120,000 to 3,000,000. Yes, more preferably 150,000 to 1,500,000, even more preferably 200,000 to 500,000.
  • dyed P3HB3HH fibers preferably have a weight loss rate (decomposition rate) of 5% or more after being buried in soil at a temperature of 25°C or higher for 10 days, and 8% or more. It is more preferable that the amount is at least 12%, and even more preferably 12% or more.
  • the dyed P3HB3HH fiber preferably has a weight loss rate (decomposition rate) of 3% or more after being immersed in seawater at a temperature of 19° C. or higher for 4 weeks. , more preferably 4% or more, and still more preferably 5% or more.
  • dyed P3HB3HH fibers must have a weight average molecular weight retention rate of 60% or more after being left in a high humidity environment of 80°C and 90% RH (relative humidity) for 82 hours. is preferable, more preferably 65% or more, and still more preferably 70% or more.
  • the dyed P3HB3HH fibers preferably have a number average molecular weight retention rate of 60% or more after being left in a high humidity environment of 80° C. and 90% RH for 82 hours, and 65%. It is more preferably at least 70%, even more preferably at least 70%.
  • the dyed P3HB3HH fiber preferably has a z-average molecular weight retention rate of 60% or more after being left in a high humidity environment of 80° C. and 90% RH for 82 hours, preferably 65%. It is more preferably at least 70%, even more preferably at least 70%.
  • the dyed P3HB3HH fiber preferably has a hot water shrinkage rate at 85°C of 15% or less, more preferably 10% or less, still more preferably 5% or less, and particularly Preferably it is 3% or less.
  • the dyed P3HB3HH fiber preferably has a hot water shrinkage rate at 80° C. of 10% or less, more preferably 5% or less, and even more preferably 3% or less.
  • the dyed P3HB3HH fiber preferably has a dry heat shrinkage rate at 85° C. of 15% or less, more preferably 10% or less, still more preferably 5% or less, and particularly Preferably it is 3% or less.
  • the dry heat shrinkage rate of a fiber is defined as the length of the fiber before the dry heat treatment and the length of the fiber after the dry heat treatment when the fiber is left in a circulating air dryer at a predetermined temperature for 60 minutes and subjected to dry heat treatment. It can be calculated using the following formula (2).
  • Dry heat shrinkage rate (%) (L2-L3)/L2 ⁇ 100 (2)
  • L2 is the length of the fiber before the dry heat treatment
  • L3 is the length of the fiber after the dry heat treatment.
  • the dyed P3HB3HH fiber preferably has a dry heat shrinkage rate at 80° C. of 10% or less, more preferably 5% or less, and still more preferably 3% or less.
  • the dyed P3HB3HH fiber preferably has a residual dry heat shrinkage rate at 85°C of 15% or less, more preferably 10.5% or less, and still more preferably 5% or less. It is even more preferably 3% or less, particularly preferably 1.5% or less.
  • the residual dry heat shrinkage rate of dyed P3HB3HH fibers can be measured by thermomechanical analysis (TMA).
  • the dyed P3HB3HH fiber preferably has a residual dry heat shrinkage rate at 80° C. of 10% or less, more preferably 7% or less, and even more preferably 5% or less, Even more preferably it is 3% or less, particularly preferably 1.5% or less.
  • the fiber aggregate may be manufactured using dyed P3HB3HH fibers, but from the perspective of reducing costs, in the fiber aggregate containing P3HB3HH fibers, the P3HB3HH fibers may be manufactured using a dye at a temperature of 85°C or lower. Preferably, it is produced by dyeing.
  • the P3HB3HH fibers in the fiber assembly containing the P3HB3HH fibers can be dyed in the same manner as the P3HB3HH fibers described above, and the explanation will be omitted here.
  • the fiber aggregate may contain dyed P3HB3HH fibers, and the content of dyed P3HB3HH fibers is not particularly limited.
  • the fiber aggregate preferably contains 10% by weight or more of dyed P3HB3HH fibers, more preferably 20% by weight or more, still more preferably 30% by weight or more, from the viewpoint of increasing biodegradability such as marine degradability. Still more preferably 40% by weight or more, even more preferably 50% by weight or more, even more preferably 60% by weight or more, even more preferably 70% by weight or more, even more preferably 80% by weight or more, Even more preferably it contains 90% by weight or more, even more preferably 95% by weight or more.
  • the fiber aggregate may be composed of 100% by weight of dyed P3HB3HH fibers.
  • the fiber aggregate may contain other fibers in addition to the dyed P3HB3HH fibers.
  • Other fibers are not particularly limited, and include synthetic fibers, natural fibers, recycled fibers, and the like. From the viewpoint of biodegradability, the other fibers are preferably biodegradable fibers.
  • biodegradable synthetic fibers include synthetic fibers containing aliphatic polyesters other than P3HB3HH, and examples of aliphatic polyesters other than P3HB3HH include polylactic acid, polycaprolactone, polybutylene adipate terephthalate, and polybutylene succinate. Examples include adipate and polybutylene succinate.
  • natural fibers include natural cellulose fibers and natural animal fibers.
  • Examples of natural cellulose fibers include cotton fibers, kapok fibers, flax fibers, hemp fibers, ramie fibers, jute fibers, Manila hemp fibers, and kenaf fibers.
  • Examples of natural animal fibers include wool fibers, mohair fibers, cashmere fibers, camel fibers, alpaca fibers, and angora fibers.
  • Examples of regenerated fibers include regenerated cellulose fibers such as rayon, polynosic, cupro, and lyocell, and regenerated protein fibers such as regenerated collagen fibers.
  • the fiber assembly may, for example, contain 10-95% by weight of dyed P3HB3HH fibers and 5-90% by weight of other fibers, 20-90% by weight of dyed P3HB3HH fibers and 10-80% by weight of other fibers, 30-80% by weight of dyed P3HB3HH fibers and 20-70% by weight of other fibers, 40-70% by weight of dyed P3HB3HH fibers and 30-60% by weight of other fibers, or 50-70% by weight of dyed P3HB3HH fibers and 30-50% by weight of other fibers.
  • the form of the fiber aggregate is not particularly limited, and examples include thread, cloth, and nonwoven fabric.
  • the yarn may be a multifilament or a spun yarn.
  • the cloth may be knitted or woven.
  • Fabrics include plain weave, oblique weave, satin weave, variable plain weave, variable oblique weave, variable satin weave, variable weave, patterned weave, single layer weave, double weave, multiple weave, warp pile weave, weft pile weave, and Examples include twine weave.
  • Knitted fabrics also referred to as knits
  • Knitted fabrics include circular knitting, weft knitting, warp knitting, pile knitting, etc., as well as flat knitting, jersey knitting, rib knitting, smooth knitting (double-sided knitting), rubber knitting, pearl knitting, and denby knitting. Examples include tissue, cord tissue, atlas tissue, chain tissue, and insertion tissue.
  • the jersey knit and ribbed knit have an excellent texture as a product.
  • the nonwoven fabric may be a long fiber nonwoven fabric or a short fiber nonwoven fabric.
  • the fiber aggregate can be used for various textile products.
  • textile products include clothing, daily necessities, interior goods, and the like.
  • clothing include jackets, underwear, sweaters, vests, pants, gloves, socks, mufflers, hats, and the like.
  • daily necessities include bedding, pillows, cushions, stuffed animals, and hygiene materials.
  • Examples of the interior include curtains, carpets, etc.
  • other fibers may be dyed or may not be dyed. It may be set as appropriate depending on the purpose, use, etc. Further, the dyed P3HB3HH fiber and other fibers may be dyed in the same color or may be dyed in different colors.
  • Fiber aggregates such as spun yarn and cloth containing dyed P3HB3HH fibers and cellulose fibers have excellent ocean degradability and moisture absorption and quick drying properties, so they can be suitably used for daily necessities such as clothing and bedding products.
  • the cellulose fibers may be natural cellulose fibers or regenerated cellulose fibers. As the natural cellulose fibers and regenerated cellulose fibers, those mentioned above can be used as appropriate.
  • the fiber aggregate may contain 10 to 95% by weight of dyed P3HB3HH fibers, 5 to 90% by weight of cellulose fibers, and 20 to 90% by weight of dyed P3HB3HH fibers, from the viewpoint of excellent marine degradability and moisture absorption and quick drying properties.
  • % may contain 10 to 80% by weight of cellulose fibers, 30 to 80% by weight of dyed P3HB3HH fibers, 20 to 70% by weight of cellulose fibers, 40 to 70% by weight of dyed P3HB3HH fibers, It may contain 30 to 60% by weight of cellulose fibers, 50 to 70% by weight of dyed P3HB3HH fibers, and 30 to 50% by weight of cellulose fibers.
  • the weight loss rate (decomposition rate) after immersing a fiber aggregate containing dyed P3HB3HH fibers and cellulose fibers in seawater at a temperature of 19°C or higher for 4 weeks is It is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more.
  • the cellulose fibers in the fiber assembly may be dyed with a dye at a temperature of 85° C. or lower. By performing dyeing at a temperature of 85° C. or lower, the energy required for dyeing can be reduced.
  • Natural dyes or synthetic dyes may be used for dyeing cellulose fibers. Examples of synthetic dyes include reactive dyes, direct dyes, vat dyes, basic dyes, naphthol dyes, sulfur dyes, and special disperse dyes.
  • the dyeing of cellulose fibers is not particularly limited, and can be carried out in the same manner as usual dyeing of cellulose fibers.
  • the fiber aggregate preferably has a color fastness of grade 3 or higher, as determined by the discoloration/fading grade specified in JIS L 0844 A-2: 2011, and is grade 3-4 or higher. It is more preferable that it is, and it is still more preferable that it is 4th grade or higher.
  • the fiber aggregate preferably has a color fastness of grade 3 or higher as determined by the contamination grade specified in JIS L 0844 No. A-2: 2011, and preferably has a color fastness of grade 3-4 or higher. It is more preferable that there be.
  • the spun yarn preferably has a tensile strength of 100 gf or more, more preferably 150 gf or more, even more preferably 200 gf or more, and even more preferably 250 gf or more. Further, from the viewpoint of process stability during fabric manufacturing, the tensile strength of the spun yarn may be 500 gf or less.
  • the thickness of the spun yarn is not particularly limited, but when used for clothing, it may be 2 to 50 or 5 to 40 in English cotton count.
  • the weight per unit area (fabric weight) of the fiber aggregate is not particularly limited and may be determined as appropriate depending on the use and purpose, and may be, for example, 10 to 2000 g/m 2 .
  • the fabric weight may be 100 to 800 g/m 2
  • the fabric weight may be 10 to 100 g/m 2
  • the fabric weight may be 100 to 2000 g/m 2 2 is fine.
  • Dyed P3HB3HH fibers and fiber aggregates and textile products using them biodegrade if left in an environment where microorganisms exist, so they do not require special disposal and are environmentally friendly.
  • shrinkage rate during dyeing of fiber The length of the fibers in the dyed object before dyeing and the length of the fibers in the dyed object after dyeing were measured, and the shrinkage rate of the fibers during dyeing was calculated using the following formula (3).
  • the fiber When measuring the length of the fiber, the fiber was held at both ends with tweezers and stretched into a straight line.
  • the shrinkage rate of the fibers in the spun yarn during dyeing was measured by untwisting the spun yarn and taking out only the P3HB3HH short fibers.
  • Shrinkage rate during staining (%) (Ls0-Ls1)/Ls0 ⁇ 100 (3)
  • Ls0 is the length of the P3HB3HH fiber in the dyed object before dyeing
  • Ls1 is the length of the dyed P3HB3HH fiber in the dyed object after dyeing.
  • thermomechanical analyzer TMA-7100 manufactured by Hitachi High-Technology Co., Ltd. .
  • TMA-7100 manufactured by Hitachi High-Technology Co., Ltd. .
  • TMA curve the horizontal axis shows the temperature, and the left vertical axis shows the dimensional change rate.
  • the maximum dyeing temperature (maximum processing temperature experienced during dyeing) T2 of the dyed P3HB3HH short fibers was calculated by the following procedure. (1) A straight line connecting 30°C and 40°C of the TMA curve was drawn to define straight line A. (2) When the thermal shrinkage rate at 120° C. on the TMA curve is assumed to be 100%, a tangent line with a point showing a thermal contraction rate of 25% as a tangent point was drawn to define tangent line B. (3) The temperature corresponding to the intersection of straight line A and tangent line B was determined, and was determined as the maximum temperature for dyeing process T2. FIG.
  • TMA curve obtained by thermomechanical analysis of a dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fiber of one example (Example 3).
  • a straight line connecting 30°C and 40°C of the TMA curve was drawn to define straight line A(1).
  • the temperature corresponding to the intersection point (5) of the straight line A (1) and the tangent line B (4) was determined and set as the maximum temperature T2 for the dyeing process.
  • dyeability The dyeability of the measurement sample (fiber or fiber aggregate) was visually evaluated based on the following criteria. Note that dyeability is one of the indicators for evaluating dyeability, and indicates how much dye has been adsorbed by the fiber. A: Sufficiently colored B: Colored C: Not colored
  • Example 2 dyed P3HB3HH short fibers were knitted with a flat knitting machine into a knit (rib knit) with a basis weight of about 300 g/m 2 , and Examples 3 to 5 and Comparative Example 2
  • a knit (rib knit) with a basis weight of approximately 300 g/m 2 was knitted from the dyed spun yarn using a flat knitting machine, and in the case of Example 6, the dyed knit was used as the measurement sample as it was.
  • ⁇ 4 a knit (rib knit) with a basis weight of approximately 300 g/m 2 was knitted from the dyed spun yarn using a flat knitting machine, and in the case of Example 6, the dyed knit was used as the measurement sample as it was.
  • the measurement sample (fiber) was placed in a mesh bag and immersed in seawater (Takasago, Hyogo Prefecture) for decomposition.
  • the water temperature during the test period varied between 19 and 25°C.
  • the weight (W0) was measured.
  • the decomposition rate of the measurement sample in seawater was calculated using the following formula (4).
  • Decomposition rate in seawater (%) (W0-W1)/W0 ⁇ 100 (4)
  • W0 is the dry weight of the measurement sample before being immersed in seawater
  • W1 is the dry weight of the measurement sample after being immersed in seawater for a predetermined time.
  • Decomposition rate in soil (%) (W2-W3)/W2 ⁇ 100 (5)
  • W2 is the dry weight of the measurement sample before being buried in the soil
  • W3 is the dry weight of the measurement sample after being buried in the soil for a predetermined time.
  • the tensile strength and elongation rate of the spun yarn were measured according to JIS L 1095:2010, and the tensile strength and elongation rate of the multifilament were measured according to JIS L 1095:2010.
  • Mw retention rate (%) Mwa/Mwb ⁇ 100 (6)
  • Mn retention rate (%) Mna/Mnb ⁇ 100 (7)
  • Mz retention rate (%) Mza/Mzb ⁇ 100 (8)
  • Mwa is the weight average molecular weight of the measurement sample after the accelerated test
  • Mwb is the weight average molecular weight of the measurement sample before the acceleration test
  • Mna is the number average molecular weight of the measurement sample after the accelerated test
  • Mnb is the number average molecular weight of the measurement sample before the acceleration test.
  • Mza is the z-average molecular weight of the measurement sample after the accelerated test
  • Mzb is the z-average molecular weight of the measurement sample before the acceleration test.
  • the resulting pellet-shaped resin composition had a glass transition temperature of 2°C, a crystallization temperature of 100°C, a melting point of 146°C, a thermal decomposition temperature of 180°C, and a weight average molecular weight of 350,000.
  • the glass transition temperature, crystallization temperature, melting point, and thermal decomposition temperature of the pelletized resin composition were measured using a differential scanning calorimeter (manufactured by TA Instruments, model number "DSC25”) within the measurement temperature range of 0 to 0.
  • the weight average molecular weight of the pellet-shaped resin composition was measured by differential scanning calorimetry under the conditions of 180°C, a temperature increase rate of 10°C/min, and a cooling rate of 10°C/min, using chloroform as an eluent. It was measured from polystyrene equivalent molecular weight distribution using gel permeation chromatography (GPC).
  • the obtained resin composition pellet was melted using a kneading extruder (single-screw extruder, screw diameter 25 mm).
  • the obtained melt was discharged from a spinning nozzle (temperature: 175° C., shape of discharge hole: circular, diameter of discharge hole: 0.3 mm, number of discharge holes: 368) to obtain a spun filament.
  • the flow rate of the melt was adjusted to 3.6 kg/h using a gear pump.
  • air at 20° C. was blown onto the spun filaments discharged from the circumferential direction at a speed of 0.7 m/s.
  • the cooled spun filament is taken up by a first take-up roll section (speed: 536 m/min) and transported in order by the first to fourth transport roll sections (speed: 562 m/min), and then the first winding is carried out. It was wound up with a take-up roll (speed: 546 m/min) and stored at room temperature (5 to 35°C) for 18 hours to obtain an undrawn filament with a single fiber fineness of 5.47 dtex.
  • the spun filament (undrawn filament) is taken up from the first take-up roll part by a second take-up roll part (speed: 50 m/min, roll temperature: 30°C), and the drawing roll part (115 m/min, roll Temperature: 90°C), conveyed by a take-off roll section (heat treatment roll section) (speed: 115 m/min, roll temperature: 90°C), and wound by a second winding roll section (speed: 106 m/min).
  • a drawn filament having a fineness of 2.53 dtex, a tensile strength of 2.58 cN/dtex, and a hot water shrinkage rate (80° C.) of 11.5% was obtained.
  • the stretching ratio was 2.3 times.
  • a roll part comprised of two rolls each having the same speed and the same temperature was used as the take-up roll part and the conveyance roll part.
  • the obtained P3HB3HH short fibers had a single fiber fineness of 2.5 dtex, a single fiber tensile strength of 1.51 cN/dtex, an 80°C hot water shrinkage rate of 11.5%, a melting point of 146°C, and a softening point of 125°C. there were.
  • the melting point and softening point of the P3HB3HH short fibers were determined using a differential scanning calorimeter (manufactured by TA Instruments, model number "DSC25”) at a temperature range of 0 to 180°C, a heating rate of 10°C/min, and a cooling rate of 10°C. It was measured by differential scanning calorimetry under the conditions of °C/min.
  • Example 1 The P3HB3HH multifilament obtained in Production Example 1 was used as an object to be dyed, and a dyeing solution (solution temperature: 60° The object to be dyed was placed in a bath (bath ratio 1:20) and dyed at 60°C for 60 minutes, then washed with water and hot water (40-50°C warm water). I got the filament. Note that the dyeing solution did not contain a dispersing agent, a leveling agent, and an auxiliary dye (carrier). Further, as treatments after dyeing, soaping using a surfactant and reduction cleaning using caustic soda, hydrosulfite, and a surfactant were not performed.
  • Example 2 Dyeing was carried out in the same manner as in Example 1 except that the P3HB3HH short fibers of Production Example 2 were used as the dyed material to obtain P3HB3HH short fibers dyed in blue.
  • Example 3 Dyeing was carried out in the same manner as in Example 1, except that the spun yarn A made of P3HB3HH short fibers of Production Example 3 was used as the object to be dyed, and a spun yarn made of P3HB3HH short fibers dyed blue was obtained.
  • Example 4 A spun yarn made of P3HB3HH short fibers dyed blue was obtained in the same manner as in Example 3, except that the temperature of the dyeing solution was adjusted to 80° C. and dyeing was carried out at 80° C. for 60 minutes.
  • Example 5 A spun yarn made of P3HB3HH short fibers dyed blue was obtained in the same manner as in Example 3, except that the temperature of the dyeing solution was adjusted to 85° C. and dyeing was carried out at 85° C. for 60 minutes.
  • Example 6 Dyeing was carried out in the same manner as in Example 1, except that spun yarn B containing the P3HB3HH short fibers and Lyocell fibers of Production Example 4 was used as the material to be dyed, and the P3HB3HH short fibers were dyed blue, and the Lyocell fibers were not dyed. No spun yarn was obtained.
  • Example 7 In the same manner as in Example 6, a spun yarn was obtained in which the P3HB3HH short fibers were dyed and the Lyocell fibers were not dyed.
  • the obtained spun yarn in which only the P3HB3HH short fibers were dyed blue, was used as a material to be dyed, and 1% by weight of blue reactive dye (Sumifix (registered trademark) Br.Blue R 150% gran. , manufactured by Sumika Chemtex), 40 g/L of sodium sulfate, and 15 g/L of sodium carbonate (bath ratio 1:20), and dyeing at 60°C for 60 minutes. Lyocell fibers were dyed with this method to obtain a spun yarn dyed entirely blue.
  • Example 8 Dyeing was carried out in the same manner as in Example 1, except that knit A of Production Example 5 was used as the object to be dyed, to obtain a knit in which P3HB3HH short fibers were dyed blue.
  • Example 9 Dyeing was carried out in the same manner as in Example 1, except that knit B of Production Example 6 was used as the dyed material, to obtain a knit in which only the P3HB3HH short fibers were dyed blue and the Lyocell fibers were not dyed.
  • Example 10 In the same manner as in Example 9, a knit was obtained in which the P3HB3HH short fibers were dyed and the Lyocell fibers were not dyed. Lyocell fibers were dyed in the same manner as in Example 7, except that a knit in which only the obtained P3HB3HH short fibers were dyed blue was used to obtain a knit dyed entirely in blue.
  • Example 1 Same as Example 1 except that 100% polylactic acid fiber spun yarn (100% polylactic acid spun yarn Terramac (registered trademark) manufactured by Unitika Co., Ltd., English cotton count 21/1) was used as the material to be dyed. Dispersion staining was performed.
  • 100% polylactic acid fiber spun yarn 100% polylactic acid spun yarn Terramac (registered trademark) manufactured by Unitika Co., Ltd., English cotton count 21/1) was used as the material to be dyed. Dispersion staining was performed.
  • Example 3 Dyeing was carried out in the same manner as in Example 3, except that the dyeing temperature was 95° C., to obtain a spun yarn made of P3HB3HH short fibers dyed blue.
  • Example 4 Dyeing was carried out in the same manner as in Example 3 except that the dyeing temperature was 100° C. to obtain a spun yarn made of P3HB3HH short fibers dyed blue.
  • the dyeing temperature T1 when dyeing P3HB3HH fibers and the maximum temperature T2 for dyeing processing calculated based on the TMA curve obtained by thermomechanical analysis of dyed P3HB3HH fibers are:
  • II T1+3°C ⁇ T2 ⁇ T1-2°C
  • Comparative Example 1 has a high L value and is insufficiently dyed. Furthermore, in any of the P3HB3HH fibers (short fibers) of Example 2, the spun yarns made of 100% by weight of P3HB3HH short fibers of Examples 3 to 5, and the knit made of 100% by weight of P3HB3HH short fibers of Example 8. The color fastness to washing was good.
  • the spun yarn of Comparative Example 4 dyed at 100° C. has a larger fiber diameter than the heat-shrinkable P3HB3HH staple fiber, and has an inferior texture.
  • P3HB3HH fibers are excellent in both seawater decomposition and soil decomposition. Furthermore, it can be seen that when P3HB3HH fibers are used in combination with cellulose fibers, the sea degradability is also excellent.
  • P3HB3HH fibers and fiber aggregates containing them are resistant to hydrolysis, and even when left in a high humidity environment of 80°C and 90% RH for 82 hours, the strength (tensile strength) ) and the decrease in molecular weight is suppressed.
  • PLA fibers have poor durability (hydrolysis) and cannot maintain their strength and shape when left in a high humidity environment of 80° C. and 90% RH for 82 hours.
  • a method for producing a fiber aggregate containing dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fibers comprising: Including the process of dyeing poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)-based fibers with a dye, A method for producing a fiber aggregate, characterized in that the dyeing is carried out at a temperature of 85° C. or lower.
  • the dye includes at least one selected from the group consisting of synthetic dyes and natural dyes.
  • the synthetic dye includes at least one selected from the group consisting of disperse dyes and direct dyes.
  • the fiber aggregate further includes cellulose fibers, and includes a step of dyeing the cellulose fibers with a dye at a temperature of 85° C. or lower, according to any one of [5] to [9].
  • T2 of the dyeing process calculated based on the thermomechanical analysis (TMA) curve that measured the heat shrinkage rate from 30 to 180°C is 88°C or less, and the T2 is equal to 30°C and 40°C of the TMA curve. This is the temperature corresponding to the intersection of a straight line A passing through two points of °C and a tangent line B whose tangent point is a point on the TMA curve showing a heat shrinkage rate of 25% with respect to the heat shrinkage rate at 120°C.
  • Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fiber [12] A fiber assembly comprising the dyed poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) fiber according to [11].

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Abstract

La présente invention aborde le problème de la coloration, avec une excellente adhérence de coloration, de fibres à base de poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) tout en réduisant la quantité d'énergie requise pour la coloration.　La présente invention concerne des fibres à base de poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) colorées, un agrégat de fibres, et des procédés de fabrication de ceux-ci, lesdits procédés étant caractérisés en ce qu'ils comprennent une étape de coloration de fibres à base de poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), et caractérisés en outre en ce que la coloration est effectuée à une température inférieure ou égale à 85 °C à l'aide d'un colorant.
PCT/JP2023/032906 2022-09-14 2023-09-08 Fibres à base de p3hb3hh colorées, agrégat de fibres les comprenant, et leurs procédés de fabrication WO2024058076A1 (fr)

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JP2004091962A (ja) * 2002-08-30 2004-03-25 Unitika Textiles Ltd 生分解性仮撚紡績糸及び織編物
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JP2022114186A (ja) * 2021-01-26 2022-08-05 株式会社カネカ 生分解性短繊維不織布

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JPS50121581A (fr) * 1974-03-01 1975-09-23
JP2004091962A (ja) * 2002-08-30 2004-03-25 Unitika Textiles Ltd 生分解性仮撚紡績糸及び織編物
JP2005226183A (ja) * 2004-02-12 2005-08-25 Nisshinbo Ind Inc 生分解性プラスチックを含む繊維製品
JP2022114186A (ja) * 2021-01-26 2022-08-05 株式会社カネカ 生分解性短繊維不織布

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