WO2014077402A1 - Procédé de production d'un monofilament biodégradable - Google Patents

Procédé de production d'un monofilament biodégradable Download PDF

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Publication number
WO2014077402A1
WO2014077402A1 PCT/JP2013/081111 JP2013081111W WO2014077402A1 WO 2014077402 A1 WO2014077402 A1 WO 2014077402A1 JP 2013081111 W JP2013081111 W JP 2013081111W WO 2014077402 A1 WO2014077402 A1 WO 2014077402A1
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WIPO (PCT)
Prior art keywords
resin
biodegradable
monofilament
stretching
temperature
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PCT/JP2013/081111
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English (en)
Japanese (ja)
Inventor
紀生 尾澤
健一郎 島田
寺島　久明
明美 坪沼
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株式会社クレハ
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Priority to JP2014547067A priority Critical patent/JPWO2014077402A1/ja
Publication of WO2014077402A1 publication Critical patent/WO2014077402A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
    • 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
    • D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a method for producing a biodegradable monofilament containing a polyglycolic acid resin.
  • polyamides, polyesters, polyolefins, and the like have been conventionally used as filament materials used for agricultural materials, marine products, industrial materials, and the like. Since filaments made of these resins hardly decompose in a natural environment, if they are left as they are after use, they remain semipermanently in the natural world, often causing environmental problems. For this reason, application of biodegradable resins such as polyglycolic acid resins has been studied.
  • Patent Document 1 a polyglycolic acid resin having a residual monomer amount of less than 0.5 parts by mass is melt-spun and rapidly cooled in a liquid bath at 10 ° C. or lower.
  • Patent Document 2 discloses that a polyglycolic acid resin having a residual monomer amount of 0.5 parts by mass or more is melt-spun and rapidly cooled in a refrigerant at 10 ° C. or less, and then 60 A method for producing a polyglycolic acid resin filament is disclosed, in which amorphous stretching is performed in a medium at ⁇ 83 ° C., and further, if necessary, second-stage stretching and thermal relaxation are performed. It is also described that the resulting polyglycolic acid resin filament is a biodegradable filament having high tensile strength, knot strength and moderate elongation.
  • polyglycolic acid resin filaments described in Patent Documents 1 and 2 are not necessarily high in durability against impact, and depending on the application, polyglycolic acid resin filaments with higher durability against impact are required. .
  • the present invention has been made in view of the above-described problems of the prior art, and aims to provide a method for producing a biodegradable filament containing a polyglycolic acid resin and having excellent durability against impact. To do.
  • the present inventors have performed primary stretching on an unstretched yarn obtained by melt spinning a biodegradable resin containing a polyglycolic acid resin, Furthermore, it discovered that the durability with respect to the impact of the biodegradable monofilament obtained by performing secondary extending
  • the method for producing the biodegradable monofilament of the present invention includes: A step of melt spinning a biodegradable resin containing 35% by mass or more of a polyglycolic acid resin to obtain an undrawn yarn; A step of primarily stretching the unstretched yarn in the length direction to obtain a monofilament; A step of subjecting the monofilament after the primary stretching to a lengthwise direction and a secondary stretching of 1.02 to 1.6 times at a glass transition temperature of the polyglycolic acid resin + 22 ° C. or lower; It is a method including.
  • the biodegradable resin may further contain an aliphatic-aromatic copolymer polyester.
  • the undrawn yarn is primarily drawn at a glass transition temperature of the polyglycolic acid resin + 10 ° C. or more at a temperature of 2.0 to 6.0 times.
  • the temperature during the first stretching is more preferably a glass transition temperature of the polyglycolic acid resin + 22 ° C. or higher.
  • the method for producing a biodegradable monofilament of the present invention comprises a step of spinning a biodegradable resin containing 35% by mass or more of a polyglycolic acid resin to obtain an undrawn yarn (spinning step), A step of primary stretching in the length direction to obtain a monofilament (primary stretching step), and the monofilament after the primary stretching in the length direction at a glass transition temperature of the polyglycolic acid resin + 22 ° C. or lower And a step of secondary stretching (secondary stretching step) by 1.02 to 1.6 times.
  • the PGA resin has the following formula (1): — [O—CH 2 —C ( ⁇ O)] — (1)
  • a glycolic acid homopolymer consisting only of glycolic acid repeating units represented by the formula hereinafter referred to as “PGA homopolymer”, including a ring-opened polymer of glycolide which is a bimolecular cyclic ester of glycolic acid).
  • PGA copolymer a polyglycolic acid copolymer containing glycolic acid repeating units.
  • Such PGA-type resin may be used individually by 1 type, or may use 2 or more types together.
  • the PGA homopolymer can be synthesized by dehydration polycondensation of glycolic acid, dealcoholization polycondensation of glycolic acid alkyl ester, ring-opening polymerization of glycolide, etc., among which it is preferable to synthesize by ring-opening polymerization of glycolide. .
  • Such ring-opening polymerization can be carried out by either bulk polymerization or solution polymerization.
  • the PGA copolymer can be synthesized by using a comonomer in combination in such a polycondensation reaction or ring-opening polymerization reaction.
  • comonomers include ethylene oxalate (ie, 1,4-dioxane-2,3-dione), lactides, lactones (eg, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -pivalolactone, ⁇ - Butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone, etc.), carbonates (eg, trimethylene carbonate, etc.), ethers (eg, 1,3-dioxane, etc.), ether esters ( For example, cyclic monomers such as dioxanone), amides (such as ⁇ -caprolactam); hydroxycarboxylic acids such as lactic acid, 3-hydroxypropanoic acid, 3-hydroxybuta
  • Catalysts used when the PGA resin is produced by ring-opening polymerization of glycolide include tin compounds such as tin halides and tin organic carboxylates; titanium compounds such as alkoxy titanates; aluminum compounds such as alkoxy aluminums Known ring-opening polymerization catalysts such as zirconium compounds such as zirconium acetylacetone; antimony compounds such as antimony halides and antimony oxides;
  • the PGA-based resin can be produced by a conventionally known polymerization method.
  • the polymerization temperature is preferably 120 to 300 ° C, more preferably 130 to 250 ° C, particularly preferably 140 to 220 ° C, and 150 to 200. C is most preferred.
  • the polymerization temperature is less than the lower limit, the polymerization tends not to proceed sufficiently.
  • the polymerization temperature exceeds the upper limit, the produced resin tends to be thermally decomposed.
  • the polymerization time of the PGA resin is preferably 2 minutes to 50 hours, more preferably 3 minutes to 30 hours, and particularly preferably 5 minutes to 18 hours.
  • the polymerization time is less than the lower limit, the polymerization does not proceed sufficiently, whereas when the upper limit is exceeded, the generated resin tends to be colored.
  • the content of the glycolic acid repeating unit represented by the formula (1) is preferably 55% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. 90 mass% or more is particularly preferable, and 100 mass% is most preferable.
  • the effects as a PGA resin such as biodegradability, hydrolyzability, biocompatibility, mechanical strength, and heat resistance tend to be reduced.
  • the weight average molecular weight of such a PGA resin is preferably 30,000 to 800,000, more preferably 50,000 to 500,000, and particularly preferably 80,000 to 300,000.
  • the weight average molecular weight of the PGA resin is less than the lower limit, the mechanical strength of the resulting biodegradable monofilament tends to decrease.
  • the upper limit is exceeded, the molten PGA resin may be discharged. It tends to be difficult.
  • the weight average molecular weight is a polymethylmethacrylate conversion value measured by gel permeation chromatography (GPC).
  • the melt viscosity (temperature: 240 ° C., shear rate: 122 sec-1) of the PGA resin is preferably 1 to 10,000 Pa ⁇ s, more preferably 50 to 6000 Pa ⁇ s, and still more preferably 100 to 5000 Pa ⁇ s. 300 to 4000 Pa ⁇ s is particularly preferable. If the melt viscosity is less than the lower limit, the mechanical strength of the resulting biodegradable monofilament tends to be reduced. On the other hand, if the melt viscosity exceeds the upper limit, it tends to be difficult to discharge the molten PGA resin. .
  • the glass transition temperature Tg of the PGA resin is preferably 30 to 50 ° C., more preferably 35 to 45 ° C.
  • the glass transition temperature Tg (unit: ° C.) of the PGA resin was obtained by heating the PGA resin from 0 ° C. to 270 ° C. at a temperature rising rate of 20 ° C./min using a differential scanning calorimeter. It is obtained from the DSC curve.
  • the PGA resin may be used alone or in combination with other biodegradable resins.
  • the durability of the resulting biodegradable monofilament with respect to impact tends to be improved.
  • biodegradable resins examples include polyhydroxyalkanoic acid esters other than PGA resins (eg, polyhydroxybutyrate (PHB resin), polymalic acid, polyhydroxyvalerate, poly- ⁇ -caprolactone (PCL resin).
  • PHB resin polyhydroxybutyrate
  • PCL resin poly- ⁇ -caprolactone
  • Polyether esters eg, polydioxanone
  • copolymers of aliphatic dicarboxylic acids and aliphatic diols eg, polybutylene succinate (PBS resin), polyethylene succinate (PES resin), polyethylene adipate (PEA resin)
  • PBS resin polybutylene succinate
  • PES resin polyethylene succinate
  • PET resin polyethylene adipate
  • PBAT resin polybutylene adipate-butylene tele Tareto copolymer
  • PBST resin polybutylene succinate - aliphatic such butylene terephthalate coater rates copolymer (PBST resin) - such as aromatic copolymerized polyester.
  • biodegradable resins may be used alone or in combination of two or more.
  • aliphatic-aromatic copolyesters are preferred, and PBAT resins are more preferred from the viewpoint of improving the durability against impact of the resulting biodegradable monofilament.
  • the weight average molecular weight of such other biodegradable resins is preferably 10,000 to 800,000, more preferably 20,000 to 600,000, and particularly preferably 40,000 to 400,000.
  • the weight average molecular weight of the other biodegradable resin is less than the lower limit, the mechanical strength of the resulting biodegradable monofilament tends to decrease, whereas when the upper limit is exceeded, the biodegradable resin in the molten state is reduced. It tends to be difficult to discharge.
  • the weight average molecular weight is a polymethylmethacrylate conversion value measured by gel permeation chromatography (GPC).
  • the melt viscosity (temperature: 200 ° C., shear rate: 122 sec-1) of other biodegradable resins is preferably 1 to 10,000 Pa ⁇ s, more preferably 10 to 6000 Pa ⁇ s, and more preferably 50 to 4000 Pa ⁇ s. More preferred is 100 to 2000 Pa ⁇ s. If the melt viscosity is less than the lower limit, the mechanical strength of the resulting biodegradable monofilament tends to decrease, whereas if the upper limit is exceeded, it tends to be difficult to discharge the melted biodegradable resin. is there.
  • the biodegradable resin used in the present invention contains 35% by mass or more of PGA resin.
  • PGA resin may consist of 100% by mass of PGA-based resin, 35% by mass to less than 100% by mass of PGA-based resin, and more than 0% by mass and 65% by mass or less of the other resins. And a mixture thereof.
  • the content of the PGA resin is less than the lower limit, the mechanical strength of the resulting biodegradable monofilament is lowered.
  • biodegradable resin according to the present invention containing 35% by mass or more of PGA-based resin
  • the biodegradable resin according to the present invention can be added to the biodegradable resin according to the present invention within the range not impairing the object of the present invention.
  • Thermoplastic resins and various additives for example, plasticizers, heat stabilizers, light stabilizers, moisture proofing agents, waterproofing agents, water repellents, lubricants, mold release agents, coupling agents, oxygen absorbers, pigments, dyes
  • the manufacturing method of the biodegradable monofilament of this invention is demonstrated.
  • the biodegradable monofilament manufacturing method of the present invention is a method including a spinning step, a primary stretching step, and a secondary stretching step.
  • a spinning step a spinning step
  • a primary stretching step a primary stretching step
  • a secondary stretching step a secondary stretching step
  • a biodegradable resin containing 35% by mass or more of a PGA-based resin is melted (preferably melt-kneaded) using an extruder or the like.
  • the melting temperature is preferably 200 to 300 ° C, more preferably 230 to 280 ° C, and particularly preferably 240 to 270 ° C.
  • the melting temperature is less than the lower limit, the fluidity of the biodegradable resin according to the present invention is reduced, the biodegradable resin is not discharged from the nozzle, and it tends to be difficult to mold the biodegradable resin monofilament,
  • the upper limit is exceeded, the biodegradable resin according to the present invention tends to be colored or thermally decomposed.
  • Such a melting process can be performed using an agitator or a continuous kneader in addition to the extruder, but the process can be performed in a short time and a smooth transition to the subsequent discharge process is possible. From the viewpoint of being, it is preferable to use an extruder.
  • the biodegradable resin according to the present invention thus melted is discharged from a single-layer nozzle, and then cooled (preferably quenched in a liquid bath at 10 ° C. or lower, more preferably 5 ° C. or lower).
  • An undrawn yarn is obtained by taking it up with a roller or the like.
  • the temperature of the single layer nozzle is preferably 210 to 280 ° C, more preferably 230 to 270 ° C, and particularly preferably 240 to 260 ° C.
  • the fluidity of the biodegradable resin according to the present invention is lowered, the biodegradable resin is not discharged from the nozzle, and the biodegradable resin monofilament tends to be difficult to mold.
  • the upper limit is exceeded, the biodegradable resin according to the present invention tends to be thermally decomposed.
  • the pore diameter of the single-layer nozzle is appropriately selected according to the intended use of the resulting biodegradable monofilament, and is not particularly limited, but is preferably 2 to 15 mm ⁇ , and more preferably 4 to 10 mm ⁇ .
  • the undrawn yarn obtained in the spinning step is primarily drawn in the length direction (take-off direction) to obtain a monofilament.
  • a biodegradable monofilament excellent in mechanical strength can be obtained.
  • the primary stretching temperature T 1 is preferably Tg + 10 ° C. or higher of the PGA resin, that is, T 1 ⁇ Tg + 10 ° C., assuming that the glass transition temperature of the PGA resin is Tg, It is more preferable to satisfy T 1 ⁇ Tg + 15 ° C., and it is particularly preferable to satisfy T 1 ⁇ Tg + 22 ° C.
  • T 1 ⁇ Tg + 40 °C the primary stretching temperature
  • the glass transition temperature Tg (unit: ° C.) of the PGA resin is such that the PGA resin is heated from 0 ° C. to 270 ° C. at a heating rate of 20 ° C./min using a differential scanning calorimeter. It is obtained from the obtained DSC curve.
  • the primary draw ratio is preferably 2.0 to 6.0 times. If the primary draw ratio is less than the lower limit, the mechanical strength of the biodegradable monofilament finally obtained tends to be low. On the other hand, if the upper limit is exceeded, the secondary draw becomes difficult and finally obtained. The biodegradable monofilaments that are produced tend to be less durable against impact.
  • a desired biodegradable monofilament can be obtained by secondary-stretching the monofilament subjected to primary stretching in this way in the length direction (take-off direction) under predetermined conditions.
  • secondary stretching a biodegradable monofilament excellent in durability against impact can be obtained.
  • the secondary stretching temperature T 2 is preferably a temperature of Tg + 22 ° C. or lower of the PGA-based resin, that is, satisfies T 2 ⁇ Tg + 22 ° C.
  • the secondary stretching temperature T 2 preferably satisfies T 2 ⁇ Tg + 20 ° C., more preferably satisfies T 2 ⁇ Tg + 15 ° C., and T 2 ⁇ It is more preferable that Tg + 10 ° C. is satisfied, T 2 ⁇ Tg + 5 ° C.
  • T 2 ⁇ Tg is more preferable, T 2 ⁇ Tg is further more preferable, T 2 ⁇ Tg ⁇ 5 ° C. is particularly preferable, and T 2 ⁇ Most preferably, Tg ⁇ 10 ° C. is satisfied.
  • the lower limit of the secondary stretching temperature preferably satisfies T 2 ⁇ Tg ⁇ 20 ° C. When the secondary stretching temperature is less than the lower limit, secondary stretching becomes difficult, and the durability of the biodegradable monofilament finally obtained tends to be low.
  • the secondary drawing is be carried out in the primary stretching temperature T 1 of the following temperatures, i.e., secondary stretching temperature T 2 preferably satisfies the T 2 ⁇ T 1.
  • the secondary stretching temperature preferably satisfies T 2 ⁇ T 1 ⁇ 5 ° C., more preferably satisfies T 2 ⁇ T 1 ⁇ 10 ° C., and satisfies T 2 ⁇ T 1 ⁇ 15 ° C. Is more preferable, T 2 ⁇ T 1 ⁇ 20 ° C. is more preferable, T 2 ⁇ T 1 ⁇ 25 ° C. is more preferable, and T 2 ⁇ T 1 ⁇ 30 ° C. is most preferable. preferable.
  • the temperature is usually higher than the temperature during the primary stretching (that is, T 2 > T 1 ).
  • the secondary stretching is performed.
  • the secondary stretching is performed at a temperature equal to or lower than the temperature during the primary stretching, thereby ensuring excellent durability against the impact of the obtained monofilament.
  • the secondary stretching ratio is 1.02 to 1.6 times.
  • the durability of the biodegradable monofilament finally obtained is not improved compared to the case where the secondary stretching is not performed, and when the upper limit is exceeded, The monofilament breaks.
  • the biodegradable monofilament thus obtained has not only excellent mechanical strength but also excellent durability against impact. Therefore, the biodegradable monofilament produced by the method of the present invention can be used for applications that require durability against impacts, such as mowing cords for brush cutters.
  • the effect of secondary stretching according to the present invention does not depend on the thickness of the biodegradable monofilament. Therefore, in the present invention, the diameter of the obtained biodegradable monofilament can be appropriately selected depending on the application. For example, when used as a mowing cord of a brush cutter, 1.4 to 3 mm is preferable.
  • the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.
  • the glass transition temperature of PGA-type resin was measured with the following method.
  • Example 1 Pellet PGA resin (manufactured by Kureha Co., Ltd., glass transition temperature: 38 ° C., weight average molecular weight: 190,000, melt viscosity (temperature 270 ° C., shear rate 122 sec-1): 350 Pa ⁇ s, melting point: 220 ° C.)
  • the raw material hopper was charged into a single screw extruder with a cylinder diameter of 35 mm ⁇ and melted at 230 to 250 ° C.
  • the cylinder temperature of the extruder was set to 230 to 250 ° C., and the adapter temperature and gear pump temperature were both set to 250 ° C.
  • the molten PGA resin was discharged at 110 g / min from a single-layer nozzle (hole diameter 8 mm ⁇ ) set at 250 ° C. using a gear pump, and was taken out at a take-up speed of 4 m / min while rapidly cooling in a 5 ° C. water bath. Thereafter, the obtained unstretched PGA resin yarn was primarily stretched in the take-off direction (length direction) at a draw ratio of 4.0 times while being heated in a 60 ° C. (Pg resin Tg + 22 ° C.) hot water bath. The monofilament was further stretched at 23 ° C. (PGA resin Tg ⁇ 15 ° C.) in the take-up direction (length direction) at a draw ratio of 1.2 times to obtain a biodegradable monofilament having a diameter of 2.3 mm.
  • Example 2 A biodegradable monofilament having a diameter of 2.3 mm was prepared in the same manner as in Example 1 except that the monofilament after the primary stretching was heat-treated at 150 ° C. in a dry heat bath and then subjected to the secondary stretching. Durability was evaluated. The results are shown in Table 1.
  • Example 3 A biodegradable monofilament having a diameter of 2.4 mm or 2.2 mm was produced in the same manner as in Example 2 except that the secondary draw ratio was changed to 1.02 times or 1.5 times, and durability against impact was evaluated. did. The results are shown in Table 1.
  • Example 6 A biodegradable monofilament having a diameter of 2.3 mm was produced in the same manner as in Example 2 except that the temperature during secondary stretching was changed to 40 ° C. (Pg resin Tg + 2 ° C.) or 60 ° C. (PGA resin Tg + 22 ° C.). The durability against impact was evaluated. The results are shown in Table 1.
  • Example 7 A biodegradable monofilament having a diameter of 2.4 mm was produced in the same manner as in Example 2 except that the primary draw ratio was changed to 3.0, and durability against impact was evaluated. The results are shown in Table 1.
  • Example 8 Pellet PGA resin (manufactured by Kureha Co., Ltd., glass transition temperature: 38 ° C., weight average molecular weight: 190,000, melt viscosity (temperature: 270 ° C., shear rate: 122 sec-1): 350 Pa ⁇ s, melting point: 220 ° C.) 50 Part by mass and polybutylene adipate-butylene terephthalate copolymer ("Ecoflex FBELND C1200" manufactured by BASF, glass transition temperature: -30 ° C, weight average molecular weight: 74000, melt viscosity (temperature 200 ° C, shear rate 122 sec-1 ): 240 Pa ⁇ s, melting point: 115 ° C.
  • PBAT resin 50 parts by mass, and 0.3 parts by mass of xylene diisocyanate (Mitsui) with respect to 100 parts by mass of the obtained mixture.
  • Chemical "Takenate 500" was added as a reactive compatibilizer.
  • TEM-26SS twin-screw kneading extruder
  • a biodegradable monofilament having a diameter of 2.3 mm was prepared in the same manner as in Example 1 except that this pellet-like PGA-PBAT resin composition was used in place of the PGA resin, and durability against impact was evaluated. The results are shown in Table 2.
  • Example 9 A biodegradability of 2.4 mm in diameter was performed in the same manner as in Example 8 except that the monofilament after primary stretching was heat-treated at 150 ° C. in a dry heat bath and then subjected to secondary stretching at a stretching ratio of 1.1 times. Monofilaments were prepared and evaluated for durability against impact. The results are shown in Table 2.
  • Example 10 A biodegradable monofilament having a diameter of 2.2 mm was produced in the same manner as in Example 9 except that the secondary draw ratio was changed to 1.5, and durability against impact was evaluated. The results are shown in Table 2.
  • Example 11 A biodegradable monofilament having a diameter of 2.5 mm was produced in the same manner as in Example 9 except that the primary draw ratio was changed to 3.0, and durability against impact was evaluated. The results are shown in Table 2.
  • Example 12 A biodegradable monofilament having a diameter of 2.4 mm or 2.3 mm was produced in the same manner as in Example 11 except that the secondary draw ratio was changed to 1.2 times or 1.5 times, and durability against impact was evaluated. did. The results are shown in Table 2.
  • Example 14 to 15 A biodegradable monofilament having a diameter of 2.5 mm was prepared in the same manner as in Example 11 except that the temperature during secondary stretching was changed to 40 ° C. (Pg resin Tg + 2 ° C.) or 60 ° C. (PGA resin Tg + 22 ° C.). The durability against impact was evaluated. The results are shown in Table 2.
  • Example 16 A biodegradable monofilament having a diameter of 2.4 mm was prepared in the same manner as in Example 12 except that the temperature during secondary stretching was changed to 40 ° C. (Pg resin Tg + 2 ° C.) or 60 ° C. (PGA resin Tg + 22 ° C.). The durability against impact was evaluated. The results are shown in Table 2.
  • Example 18 A biodegradable monofilament having a diameter of 2.4 mm or 2.5 mm was produced in the same manner as in Example 9 or 11 except that the temperature of primary stretching was changed to 75 ° C. (Tg of PGA resin + 37 ° C.), and durability against impacts Sex was evaluated. The results are shown in Table 2.
  • Example 20 A biodegradable monofilament having a diameter of 2.5 mm was produced in the same manner as in Example 11 except that 40 parts by mass of PGA resin and 60 parts by mass of PBAT resin were mixed, and durability against impact was evaluated. The results are shown in Table 2.
  • Example 21 A biodegradable monofilament having a diameter of 2.5 mm was prepared in the same manner as in Example 11 except that 60 parts by mass of PGA resin and 40 parts by mass of PBAT resin were mixed, and durability against impact was evaluated. The results are shown in Table 2.
  • Example 6 A biodegradable monofilament having a diameter of 2.5 mm was prepared in the same manner as in Example 9 except that secondary stretching was not performed, and durability against impact was evaluated. The results are shown in Table 2.
  • Example 7 A biodegradable monofilament having a diameter of 2.5 mm was prepared in the same manner as in Example 11 except that only the PBAT resin was used instead of the PGA-PBAT resin composition, and the durability against impact was evaluated. The results are shown in Table 2.
  • monofilaments subjected only to primary stretching are biodegradable monofilaments of the present invention (Examples 1 to 7 and Examples 8 to 8) further subjected to predetermined secondary stretching. Compared to 9), the durability against impact was inferior.
  • monofilaments (Comparative Examples 3 to 5) subjected to secondary stretching at a temperature exceeding a predetermined temperature (which is also a temperature exceeding the temperature during primary stretching) have a predetermined temperature (below the temperature during primary stretching).
  • the biodegradable monofilaments of the present invention Examples 1 to 2, 5 to 6) subjected to secondary stretching in the above-described manner.
  • the monofilament not containing the PGA resin (Comparative Example 7) was compared with the biodegradable monofilament of the present invention containing the PGA resin (Examples 11 and 20 to 21). The durability against impact was inferior.
  • the method for producing a biodegradable filament of the present invention is useful as a monofilament used for applications requiring biodegradability and durability against impact, for example, a mowing cord for a brush cutter in place of a nylon cord.

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Abstract

L'invention concerne un procédé de production d'un monofilament biodégradable, caractérisé en ce qu'il comprend : une étape permettant d'obtenir un fil non tiré par filage par fusion d'une résine biodégradable contenant 35 % en masse ou plus d'une résine d'acide polyglycolique ; une étape permettant d'obtenir un monofilament par étirement principal du fil non tiré dans le sens de la longueur ; et une étape d'étirement secondaire du monofilament ayant subi un étirement principal 1,02-1,6 fois dans le sens de la longueur à une température supérieure à la température de transition vitreuse de la résine d'acide polyglycolique à 22 °C ou moins.
PCT/JP2013/081111 2012-11-19 2013-11-19 Procédé de production d'un monofilament biodégradable WO2014077402A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017132076A (ja) * 2016-01-26 2017-08-03 一成 増谷 溶融積層型３ｄプリンタ用光沢性フィラメント

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000027030A (ja) * 1998-07-03 2000-01-25 Unitika Ltd ポリ乳酸モノフィラメントとその製造方法
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