WO2012157359A1 - Textile de polyester aliphatique biodégradable ayant une excellente adhérence microbienne - Google Patents

Textile de polyester aliphatique biodégradable ayant une excellente adhérence microbienne Download PDF

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Publication number
WO2012157359A1
WO2012157359A1 PCT/JP2012/059349 JP2012059349W WO2012157359A1 WO 2012157359 A1 WO2012157359 A1 WO 2012157359A1 JP 2012059349 W JP2012059349 W JP 2012059349W WO 2012157359 A1 WO2012157359 A1 WO 2012157359A1
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fabric
pga
water
aliphatic polyester
biodegradable aliphatic
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PCT/JP2012/059349
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English (en)
Japanese (ja)
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▲高▼橋健夫
吉岡聡子
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株式会社クレハ
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Publication of WO2012157359A1 publication Critical patent/WO2012157359A1/fr

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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/009—Condensation or reaction polymers
    • D04H3/011—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/103—Textile-type packing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to a non-woven fabric or the like containing a biodegradable aliphatic polyester fiber having good bioadhesiveness to aquatic organisms such as microorganisms such as useful bacteria and algae.
  • a porous substrate such as a nonwoven fabric, a woven fabric, a knitted fabric, a braid, a net, a foam, and an inorganic porous material is used.
  • Patent Document 1 JP-A-9-276897
  • Patent Document 2 JP-A-9-276897
  • Patent Document 3 JP-A-9-276897
  • Patent Document 2 JP Laid-Open No. 2004-82014
  • Patent Document 3 discloses a method of fixing a porous material having a cation exchange capacity to the surface of a constituent fiber of a nonwoven fabric.
  • the water treatment material that has been treated on the surface of the porous substrate has a high production cost, the production process is complicated, and the porous substrate and the porous material are different depending on the situation such as the water area and the type of useful bacteria. It was also necessary to study various combinations with quality materials.
  • aliphatic polyesters such as polyglycolic acid and polylactic acid have been attracting attention as biodegradable polymer materials with low environmental impact because they are decomposed by microorganisms or enzymes existing in nature such as soil and sea. Since these biodegradable aliphatic polyesters have biodegradable absorbability, they are used as medical polymer materials such as surgical sutures and artificial skin. Further, for example, in JP-A-6-264343 (Patent Document 3), the main repeating unit is represented by the general formula —O—CHR—CO— (wherein R represents H or an alkyl group having 1 to 3 carbon atoms).
  • a biodegradable agricultural fiber assembly comprising an aliphatic polyester is disclosed, and Japanese Patent Application Laid-Open No. 2000-45164 (Patent Document 4) discloses a biodegradable multi-sheet comprising a polylactic acid-based long-fiber nonwoven fabric. ing.
  • biodegradable aliphatic polyester examples include polyglycolic acid composed of glycolic acid repeating units (hereinafter sometimes referred to as “PGA”) and polylactic acid composed of lactic acid repeating units (hereinafter sometimes referred to as “PLA”).
  • PGA glycolic acid repeating units
  • PLA polylactic acid composed of lactic acid repeating units
  • Hydroxycarboxylic acid polyesters such as poly ⁇ -caprolactone, lactone polyesters such as poly ⁇ -caprolactone, diol / dicarboxylic acid polyesters such as polyethylene succinate and polybutylene succinate, and copolymers thereof such as glycolic acid repeating units Copolymers composed of lactic acid repeating units are known.
  • PLA can be obtained by using L-lactic acid as a raw material at low cost by fermentation from corn, straw, etc.
  • the resulting poly L-lactic acid is characterized by high rigidity and good transparency.
  • PGA has excellent hydrolytic and biodegradable properties, as well as excellent mechanical strength such as heat resistance and tensile strength, and gas barrier properties when used as a film or sheet. For this reason, PGA is expected to be used as agricultural materials, various packaging (container) materials and medical polymer materials, and has been developed for use alone or in combination with other resin materials.
  • a water treatment material that uses a conventional porous substrate alone or a water treatment material that has been surface-treated with a porous material. Therefore, it can be used as a water treatment material without the need for surface treatment with a porous material, has good bioadhesiveness to microorganisms such as useful bacteria and algae underwater organisms, and has biodegradability. If a fabric such as a non-woven fabric formed from a material is provided, a method for improving water quality that is low in production cost, simple in production process, easy to maintain, excellent in resource saving and energy saving, and low in environmental load Therefore, the development of such a fabric has been expected.
  • JP-A-9-276897 Japanese Patent Laid-Open No. 2004-82014 JP-A-6-264343 JP 2000-45164 A
  • An object of the present invention is to provide a fabric containing a biodegradable aliphatic polyester fiber that has excellent bioadhesiveness to aquatic organisms such as microorganisms such as useful bacteria and algae and excellent water purification performance.
  • the inventors of the present invention have a specific combination of basis weight, fiber diameter, and porosity for a fabric containing biodegradable aliphatic polyester fibers. The inventors have found that the problems can be solved and completed the present invention.
  • the basis weight is 1 to 500 g / m 2
  • the fiber diameter is 300 nm to 100 ⁇ m
  • the porosity is 50 to 95%.
  • a fabric containing biodegradable aliphatic polyester fibers is provided.
  • the fabric containing the biodegradable aliphatic polyester fiber of the following (1) and (2) is provided as an embodiment.
  • the water treatment material containing the said fabric is provided.
  • the basis weight is 1 to 500 g / m 2
  • the fiber diameter is 300 nm to 100 ⁇ m
  • the porosity is 50 to 95%. Because it is a fabric containing biodegradable aliphatic polyester fibers, it has good bioadhesion to aquatic organisms such as microorganisms such as useful bacteria and algae, has excellent water purification performance, and secondary environmental pollution occurs. It is possible to provide a fabric containing biodegradable aliphatic polyester fiber that is excellent in resource saving and energy saving, and a water treatment material containing the fabric.
  • Biodegradable Aliphatic Polyester As a biodegradable aliphatic polyester constituting the fabric containing the biodegradable aliphatic polyester fiber of the present invention (hereinafter sometimes referred to as “biodegradable aliphatic polyester fabric”), In addition to glycolic acid and glycolic acid containing glycolide (GL), a bimolecular cyclic ester of glycolic acid; lactic acid and lactic acid containing lactide, a bimolecular cyclic ester of lactic acid; ethylene oxalate (ie, 1 , 4-dioxane-2,3-dione), lactones (eg, ⁇ -propiolactone, ⁇ -butyrolactone, pivalolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone) Etc.), carbonates (eg trimethylene carbonate, etc.), ethers (eg 1,3 Dioxane
  • the biodegradable aliphatic polyester which has 50 mass% or more of the glycolic acid or lactic acid repeating unit represented by these, polylactone, polyhydroxybutyrate, polyethylene succinate, polybutylene succinate, etc. are mentioned. Of these, biodegradable aliphatic polyesters having 50% by mass or more of glycolic acid or lactic acid repeating units are preferable.
  • PGA that is, a homopolymer of glycolic acid, or a copolymer having a glycolic acid repeating unit of 50% by mass or more; a homopolymer of poly L-lactic acid or poly D-lactic acid, L-lactic acid or D -PLA having a repeating unit of lactic acid of 50% by mass or more, or a mixture thereof, and more preferably a mixture of PGA and PLA; Particularly preferred is PGA or PLA from the viewpoint of excellent bioadhesiveness, decomposability, heat resistance, and mechanical strength.
  • biodegradable aliphatic polyesters can be synthesized, for example, by dehydration polycondensation of ⁇ -hydroxycarboxylic acids such as glycolic acid and lactic acid known per se.
  • a method of synthesizing a bimolecular cyclic ester of ⁇ -hydroxycarboxylic acid and subjecting the cyclic ester to ring-opening polymerization is employed.
  • PLA is obtained by ring-opening polymerization of lactide, which is a bimolecular cyclic ester of lactic acid.
  • PGA is obtained by ring-opening polymerization of glycolide, which is a bimolecular cyclic ester of glycolic acid.
  • PLA can be synthesized by the above-described method, and commercially available products include, for example, “Lacia” (registered trademark) series (such as Lacia H-100, H-280, H-400, H-440) ( “Ingeo” (registered trademark) (manufactured by Natureworks), such as 3001D, 3051D, 4032D, 4042D, 6201D, 6251D, 7000D, and 7032D, Ecoplastic U'z S-09, S-12 "Ecoplastic U'z series” (manufactured by Toyota Motor Corporation), "Viro Indiana (registered trademark)” (manufactured by Toyobo Co., Ltd.), etc. From the viewpoint of sex, it is preferably selected.
  • biodegradable aliphatic polyester will be further described mainly using PGA as an example, but PLA and other biodegradable aliphatic polyesters can also take a form for carrying out the invention according to PGA. .
  • PGA Polyglycolic acid
  • PGA particularly preferably used as a raw material for the biodegradable aliphatic polyester fabric of the present invention is a homopolymer of glycolic acid consisting of glycolic acid repeating units represented by the formula: (—O—CH 2 —CO—)
  • a PGA copolymer containing 50% by mass or more of the glycolic acid repeating unit is included.
  • Examples of comonomers that give a PGA copolymer together with glycolic acid monomers such as glycolide include ethylene oxalate (ie, 1,4-dioxane-2,3-dione), lactides, lactones, carbonates, ethers.
  • the glycolic acid repeating unit in the PGA as a raw material of the fabric containing the PGA fiber of the present invention is 50% by mass or more, preferably 70% by mass or more.
  • the PGA homopolymer is preferably 85% by mass or more, more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 99% by mass or more. If the proportion of glycolic acid repeating units is too small, the strength and degradability expected for PGA will be poor.
  • the repeating unit other than the glycolic acid repeating unit is 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 5% by mass or less, and particularly preferably 2% by mass or less. Most preferably, it is used in a proportion of 1% by mass or less, and may not contain any repeating unit other than the glycolic acid repeating unit.
  • the PGA used as a raw material for the PGA fabric of the present invention is obtained by polymerizing 50 to 100% by mass of glycolide and 50 to 0% by mass of the other comonomer described above in order to efficiently produce a desired high molecular weight polymer.
  • PGA is preferred.
  • the other comonomer may be a cyclic monomer between two molecules, or may be a mixture of both instead of a cyclic monomer, but in order to obtain a PGA fabric intended by the present invention, a cyclic monomer is used. preferable.
  • PGA obtained by ring-opening polymerization of 50 to 100% by mass of glycolide and 50 to 0% by mass of other cyclic monomers will be described in detail.
  • glycolide that forms PGA by ring-opening polymerization is a bimolecular cyclic ester of glycolic acid, which is a kind of hydroxycarboxylic acid.
  • the manufacturing method of glycolide is not specifically limited, Generally, it can obtain by thermally depolymerizing a glycolic acid oligomer.
  • a thermal depolymerization method for glycolic acid oligomers for example, a melt depolymerization method, a solid phase depolymerization method, a solution depolymerization method or the like can be employed, and glycolide obtained as a cyclic condensate of chloroacetate is also used. be able to.
  • glycolide containing glycolic acid can be used up to 20% by mass of the glycolide amount.
  • the PGA used as the raw material of the PGA fabric of the present invention may be formed by ring-opening polymerization of only glycolide, but may also be formed by simultaneously ring-opening polymerization using another cyclic monomer as a copolymerization component. Good.
  • the proportion of glycolide is 50% by mass or more, preferably 70% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more, and particularly preferably 98% by mass. % Or more, and most preferably 99% by mass or more of a substantially PGA homopolymer.
  • hydroxycarboxylic acids include L-lactic acid, D-lactic acid, ⁇ -hydroxybutyric acid, ⁇ -hydroxyisobutyric acid, ⁇ - Hydroxyvaleric acid, ⁇ -hydroxycaproic acid, ⁇ -hydroxyisocaproic acid, ⁇ -hydroxyheptanoic acid, ⁇ -hydroxyoctanoic acid, ⁇ -hydroxydecanoic acid, ⁇ -hydroxymyristic acid, ⁇ -hydroxystearic acid, and these Examples include alkyl-substituted products.
  • Another particularly preferable cyclic monomer is lactide, which is a bimolecular cyclic ester of lactic acid, and may be any of L-form, D-form, racemate, and a mixture thereof.
  • the other cyclic monomer is 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 5% by mass or less, particularly preferably 2% by mass or less, and most preferably 1% by mass. Used in the following proportions.
  • the melting point of PGA (copolymer) is lowered to lower the processing temperature, and the crystallization speed is controlled to improve extrusion processability and stretch processability. You can do it.
  • the use ratio of these cyclic monomers is too large, the crystallinity of the formed PGA (copolymer) is impaired, and heat resistance, gas barrier properties, mechanical strength, and the like are lowered.
  • PGA is formed from glycolide 100 mass%
  • another cyclic monomer is 0 mass%, and this PGA is also included in the scope of the present invention.
  • the ring-opening polymerization or ring-opening copolymerization of glycolide (hereinafter sometimes collectively referred to as “ring-opening (co) polymerization”) is preferably carried out in the presence of a small amount of a catalyst.
  • the catalyst is not particularly limited.
  • a tin-based compound such as tin halide (for example, tin dichloride, tin tetrachloride) and organic carboxylate (for example, tin octoate such as tin 2-ethylhexanoate).
  • Titanium compounds such as alkoxy titanates; aluminum compounds such as alkoxy aluminum; zirconium compounds such as zirconium acetylacetone; antimony compounds such as antimony halide and antimony oxide;
  • the amount of the catalyst used is preferably about 1 to 1000 ppm, more preferably about 3 to 300 ppm in terms of mass ratio with respect to the cyclic ester.
  • Ring-opening (co) polymerization of glycolide is a molecular weight regulator for controlling higher molecular weights such as molecular weight and melt viscosity of PGA to be produced, and higher alcohols such as lauryl alcohol, other alcohols, and protic compounds such as water.
  • Can be used as Glycolide usually contains trace amounts of water and hydroxycarboxylic acid compounds composed of glycolic acid and linear glycolic acid oligomers as impurities, and these compounds also act on the polymerization reaction.
  • the concentration of these impurities is quantified as a molar concentration by, for example, neutralizing titration of the amount of carboxylic acid in these compounds, and based on this quantified value, alcohols or
  • the molecular weight and the like of the produced PGA can be adjusted by adding water and controlling the molar concentration of all protic compounds with respect to glycolide.
  • the ring-opening (co) polymerization of glycolide may be bulk polymerization or solution polymerization, but in many cases, bulk polymerization is employed.
  • bulk polymerization equipment for bulk polymerization, such as an extruder type, a vertical type with paddle blades, a vertical type with helical ribbon blades, a horizontal type such as an extruder type and a kneader type, an ampoule type, a plate type and a tubular type.
  • the device can be selected as appropriate.
  • various reaction tanks can be used for solution polymerization.
  • the polymerization temperature can be appropriately set according to the purpose within a range from 120 ° C. to 300 ° C. which is a substantial polymerization start temperature.
  • the polymerization temperature is preferably 130 to 270 ° C., more preferably 140 to 260 ° C., and particularly preferably 150 to 250 ° C. If the polymerization temperature is too low, the molecular weight distribution of the produced PGA tends to be wide. If the polymerization temperature is too high, the produced PGA is susceptible to thermal decomposition.
  • the polymerization time is in the range of 3 minutes to 50 hours, preferably 5 minutes to 30 hours. If the polymerization time is too short, the polymerization does not proceed sufficiently and a predetermined molecular weight cannot be realized. If the polymerization time is too long, the produced PGA tends to be colored.
  • solid phase polymerization may be further performed if desired.
  • the solid phase polymerization means an operation of performing heat treatment while maintaining a solid state by heating at a temperature lower than the melting point (Tm) of PGA described later.
  • Tm melting point
  • the solid phase polymerization is preferably performed for 1 to 100 hours, more preferably 2 to 50 hours, particularly preferably 3 to 30 hours.
  • PGA fabric of the present invention in addition to PGA, other aliphatic polyesters, polyglycols such as polyethylene glycol and polypropylene glycol, modified polyvinyl alcohol, polyurethane, Other resins such as polyamides such as poly-L-lysine, plasticizers, antioxidants, heat stabilizers, end-capping agents, UV absorbers, lubricants, mold release agents, waxes, colorants, crystallization promotion Additives that are usually blended such as an agent, a hydrogen ion concentration regulator, and fillers such as reinforcing fibers can be blended as necessary.
  • additives such as an agent, a hydrogen ion concentration regulator, and fillers such as reinforcing fibers can be blended as necessary.
  • the compounding amount of these additives and the like is usually 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and 5 parts by mass or less or 1 part by mass or less with respect to 100 parts by mass of PGA.
  • the amount may be fine.
  • a carboxyl group end-capping agent it is preferable to add a carboxyl group end-capping agent to PGA because the long-term storage stability of the resulting PGA fabric is improved. That is, by adding a carboxyl group end-capping agent, the hydrolysis resistance of the PGA fabric is improved, and a decrease in molecular weight during storage can be further suppressed.
  • a carboxyl group terminal blocker a compound having a carboxyl group terminal blocker and known as a water resistance improver for aliphatic polyesters can be used.
  • carboxyl group end-capping agents include carbodiimide compounds such as N, N-2,6-diisopropylphenylcarbodiimide; 2,2′-m-phenylenebis (2-oxazoline), 2,2′-p-phenylene Oxazoline compounds such as bis (2-oxazoline), 2-phenyl-2-oxazoline and styrene / isopropenyl-2-oxazoline; oxazine compounds such as 2-methoxy-5,6-dihydro-4H-1,3-oxazine; And epoxy compounds such as N-glycidylphthalimide, cyclohexene oxide, and tris (2,3-epoxypropyl) isocyanurate.
  • carbodiimide compounds such as N, N-2,6-diisopropylphenylcarbodiimide
  • carboxyl group end-capping agents are preferred, and any of aromatic, alicyclic, and aliphatic carbodiimide compounds are used, but aromatic carbodiimide compounds are particularly preferred, and particularly high purity. Gives water resistance improvement effect.
  • the carboxyl group end-capping agent is usually used in a proportion of 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of PGA.
  • Thermal stabilizers include cyclic neopentanetetrayl bis (2,6-di-tert-butyl-4-methylphenyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-tert-butylphenyl) ) Phosphite having a pentaerythritol skeleton structure such as phosphite or cyclic neopentanetetraylbis (octadecyl) phosphite; mono- or di-stearyl acid phosphate or a mixture thereof, preferably having 8 to 8 carbon atoms Phosphoric acid alkyl ester or phosphorous acid alkyl ester having 24 alkyl groups; carbonate carbonate such as calcium carbonate and strontium carbonate; bis [2- (2-hydroxybenzyl) phosphite, cyclic neopentanetetrayl bis (2,6-di-ter
  • the heat stabilizer is usually 3 parts by mass or less, preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.5 part by mass, and particularly preferably 0.01 to 0. It is used at a ratio of 1 part by mass (100 to 1000 ppm).
  • the weight average molecular weight (Mw) of the PGA contained in the PGA fabric of the present invention is 20,000 or more, preferably within the range of 2 to 1.5 million, more preferably 5 to 1,000,000, still more preferably 7 Those within the range of ⁇ 800,000, particularly preferably within the range of 100,000 to 500,000 are selected.
  • the weight average molecular weight (Mw) of PGA is determined using a gel permeation chromatography (GPC) analyzer. Specifically, a PGA sample is dissolved in hexafluoroisopropanol (HFIP) in which sodium trifluoroacetate is dissolved at a predetermined concentration, and then filtered through a membrane filter to obtain a sample solution. The weight average molecular weight (Mw) is calculated from the result of measuring the molecular weight after injection into the analyzer.
  • HFIP hexafluoroisopropanol
  • the PGA contained in the PGA fabric of the present invention has a molecular weight distribution (Mw / Mn) represented by a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the PGA of 1.5.
  • Mw / Mn molecular weight distribution
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the molecular weight distribution is preferably 1.6 to 3.7, more preferably 1.7 to 3.5.
  • the molecular weight distribution (Mw / Mn) can be determined using a GPC analyzer in the same manner as the weight average molecular weight (Mw).
  • the weight average molecular weight (Mw) of PLA contained in the fabric containing the PLA fiber of the present invention is preferably 5 to 1,200,000, more preferably 6 to 100.
  • the molecular weight distribution (Mw / Mn) is preferably 1.5 to 4.0, more preferably 1.7 to 3.5.
  • the melt viscosity of PGA contained in the PGA fabric of the present invention is usually in the range of 30 to 5000 Pa ⁇ s, preferably 50 to 3000 Pa ⁇ s, more preferably 100 to 2000 Pa ⁇ s. If the melt viscosity of PGA is too large, it may be difficult to obtain PGA fibers, and a PGA fabric having the desired characteristics may not be obtained. If the melt viscosity of PGA is too small, the strength of the PGA fiber and the PGA fabric may be insufficient.
  • the melt viscosity of PGA is measured under the conditions of a temperature of 270 ° C. and a shear rate of 122 sec ⁇ 1 .
  • the PLA contained in the PLA fabric of the present invention has a melt viscosity of preferably 50 to 3000 Pa ⁇ s, more preferably 100 to 2000 Pa ⁇ s (under conditions of a temperature of 210 ° C. and a shear rate of 122 sec ⁇ 1 . Measurement).
  • the melting point (Tm) of PGA contained in the PGA fabric of the present invention is usually 197 to 245 ° C., and can be adjusted by the weight average molecular weight (Mw), molecular weight distribution, type and content ratio of copolymerization component, and the like.
  • the melting point (Tm) of PGA is preferably 200 to 240 ° C., more preferably 205 to 235 ° C., and particularly preferably 210 to 230 ° C.
  • the melting point (Tm) of the homopolymer of PGA is usually about 220 ° C. If the melting point (Tm) is too low, the heat resistance and strength may be insufficient.
  • the melting point (Tm) of PGA is determined in a nitrogen atmosphere using a differential scanning calorimeter (DSC). Specifically, the endotherm accompanying crystal melting is detected in the temperature rising process in which the sample PGA is heated from room temperature to a temperature near melting point (Tm) + 60 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere. It means peak temperature. When a plurality of absorption peaks are observed, the peak having the largest endothermic peak area is defined as the melting point (Tm).
  • the melting point (Tm) of PLA contained in the PLA fabric of the present invention is preferably in the range of 145 to 185 ° C., more preferably 150 to 182 ° C., and further preferably 155 to 180 ° C.
  • the glass transition temperature (Tg) of PGA contained in the PGA fabric of the present invention is usually 25 to 60 ° C., preferably 30 to 50 ° C., more preferably 35 to 45 ° C.
  • the glass transition temperature (Tg) of PGA can be adjusted by the weight average molecular weight (Mw), the molecular weight distribution, the type and content ratio of the copolymerization component, and the like.
  • the glass transition temperature (Tg) of PGA is determined in a nitrogen atmosphere using a differential scanning calorimeter (DSC), similarly to the measurement of the melting point (Tm).
  • the sample PGA is detected from the glass state to the rubber state detected in the temperature rising process in which the sample PGA is heated from room temperature to a temperature near the melting point (Tm) + 60 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere.
  • the intermediate point between the start temperature and the end temperature of the transition to is the glass transition point (Tg).
  • Tg glass transition point
  • the glass transition temperature (Tg) is too low, the surface of the obtained PGA fabric is excessively softened, and it may be difficult to control the porosity of the fabric within a predetermined range. If the glass transition temperature (Tg) is too high, moldability may be deteriorated.
  • the glass transition temperature (Tg) of PLA contained in the PLA fabric of the present invention is preferably in the range of 45 to 75 ° C, more preferably 50 to 70 ° C, and further preferably 55 to 65 ° C.
  • the biodegradable aliphatic polyester fabric of the present invention is a fabric mainly composed of biodegradable aliphatic polyester fiber, and 50 mass of biodegradable aliphatic polyester fiber. % Or more of the fabric.
  • fibers other than the biodegradable aliphatic polyester fiber are 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass. % Or less, and may not contain fibers other than biodegradable aliphatic polyester fibers.
  • fibers other than biodegradable aliphatic polyester fibers include well-known fibers such as polyethylene terephthalate (PET) fibers, polyamide fibers, and acrylic fibers, low-temperature fusible fibers, and the like. A fabric formed in advance from these fibers may be used.
  • the biodegradable aliphatic polyester fabric of the present invention is preferably a PGA fabric, a PLA fabric, or a mixed fabric of PGA and PLA.
  • the biodegradable aliphatic polyester fabric of the present invention includes a woven fabric, a knitted fabric, a nonwoven fabric, a cotton-like body or a mat, and is preferably a nonwoven fabric or a woven fabric, particularly preferably a nonwoven fabric.
  • Nonwoven fabrics include melt blown nonwoven fabrics, spunbonded nonwoven fabrics, needle punched nonwoven fabrics, three-dimensional entangled nonwoven fabrics by water flow or air flow, and may be nonwoven fabrics manufactured by a papermaking method.
  • a melt blown nonwoven fabric or a spunbonded nonwoven fabric is preferred, and a melt blown nonwoven fabric is particularly preferred because the desired fiber diameter and porosity can be easily obtained.
  • the biodegradable aliphatic polyester fabric of the present invention has (a) a basis weight of 1 to 500 g / m 2 , (b) a fiber diameter of 300 nm to 100 ⁇ m, and (c) a porosity of 50 to 95%. It is a biodegradable aliphatic polyester fabric characterized by being.
  • the biodegradable aliphatic polyester fabric of the present invention has a weight per unit area (a) in the range of 1 to 500 g / m 2 , preferably 2 to 400 g / m 2 , more preferably 3 to 300 g / m 2 . m 2 , more preferably in the range of 4 to 200 g / m 2 .
  • the basis weight of a nonwoven fabric or the like is measured according to JIS L1096. If the fabric weight is less than 1 g / m 2 , the strength of the fabric may be insufficient, the usable period in water may be shortened, and frequent replacement and installation may be required.
  • the fabric weight is greater than 500 g / m 2 , the fabric may be too heavy and handleability may be insufficient, or it may take a long time to biodegrade or hydrolyze the fabric after a certain period of use.
  • the biodegradable aliphatic polyester fabric of the present invention has (b) a fiber diameter in the range of 300 nm to 100 ⁇ m, preferably 500 nm to 70 ⁇ m, more preferably 800 nm to 50 ⁇ m, still more preferably 1. It is in the range of ⁇ 30 ⁇ m.
  • the fiber diameter of the fabric such as the nonwoven fabric is less than 300 nm, the fabric is densified and cannot have the desired water purification ability, or microorganisms such as useful bacteria cannot enter the void of the fabric. Bioadhesion may be insufficient.
  • the fiber diameter is more than 100 ⁇ m
  • the cloth such as a nonwoven fabric becomes excessively rough
  • the contact frequency between water and PGA fibers decreases
  • the water purification performance decreases
  • microorganisms such as useful bacteria are present in the gaps of the cloth.
  • the bioadhesiveness becomes insufficient.
  • the fiber diameter was measured by sampling 10 points so as not to overlap in the width direction and longitudinal direction of the fabric, measuring 10 fiber diameters from an electron micrograph magnified 1000 times, and calculating an average value of a total of 100 points.
  • the average fiber diameter was taken as the fiber diameter of the fabric.
  • the biodegradable aliphatic polyester fabric of the present invention has (c) a porosity in the range of 50 to 95%, preferably 60 to 94%, more preferably 70 to 93%. More preferably, it is in the range of 80 to 92%. If the porosity of the fabric such as the nonwoven fabric is less than 50%, the fabric becomes excessively dense and the space volume in the fabric is reduced. Therefore, microorganisms such as useful bacteria in the fabric are reduced, and the water quality is reduced. The purification performance may be reduced. When the porosity of the fabric is more than 95%, the strength of the fabric is lowered and the shape cannot be maintained when water purification is performed, or microorganisms such as useful bacteria pass through the voids of the fabric.
  • Bioadhesion may be insufficient.
  • the porosity is determined by measuring the mass of a sample fabric cut out to a size of 50 mm ⁇ 50 mm (W1), dipping it in a perfluoropolyester test solution (trade name “Galwick” manufactured by Porous Materials) for 5 minutes, The mass after taking out the sample fabric from the test solution and draining it for 1 minute was measured (W2), and calculated from the following formula.
  • Porosity (%) (((W2-W1) / ⁇ 2 ) / ((W2-W1) / ⁇ 2 + W1 / ⁇ 1 )) ⁇ 100
  • ⁇ 1 density of biodegradable aliphatic polyester (in the case of PGA, 1.53 g / cm 3 )
  • the thickness of the biodegradable aliphatic polyester fabric of the present invention is not particularly limited, but is preferably in the range of 50 to 1000 ⁇ m, more preferably 80 to 700 ⁇ m, and still more preferably 100 to 500 ⁇ m. If the thickness of the fabric is too small, the strength of the water treatment material may be insufficient and the usage period may be too short. If the thickness of the fabric is too large, the adhesion of microorganisms may be insufficient. The thickness of a fabric such as a nonwoven fabric is measured at a load of 0.7 kPa according to JIS L1096.
  • Temperature rising crystallization temperature ( TC1 ) In the biodegradable aliphatic polyester fabric of the present invention, the temperature-programmed crystallization temperature (T C1 ) of PGA contained in the PGA fabric is PGA glass transition temperature + 10 ° C. or higher, PGA glass transition temperature + 65 ° C. or lower. May be seen in range.
  • a specific range of the temperature rising crystallization temperature (T C1 ) is a temperature in the range of 50 to 110 ° C.
  • the temperature rising crystallization temperature (T C1 ) is determined in a nitrogen atmosphere using a differential scanning calorimeter (DSC), similarly to the measurement of the melting point (Tm) and the like.
  • DSC differential scanning calorimeter
  • an exothermic peak accompanying crystallization is detected during the temperature rising process in which the sample PGA is heated from room temperature to the melting point (Tm) + 60 ° C. in a nitrogen atmosphere at a temperature rising rate of 20 ° C./min. Means the temperature of the exothermic peak in the case.
  • the temperature rising crystallization temperature (T C1 ) can be adjusted by appropriately selecting the degree of polymerization (weight average molecular weight (Mw)), the molecular weight distribution, and the type and amount of polymerization components.
  • the temperature rising crystallization temperature (T C1 ) of PGA does not exist.
  • PGA non-woven fabric was heat-treated in the spunbonded nonwoven fabric, heating crystallization temperature (T C1) may not exist.
  • the temperature rising crystallization temperature (T C1 ) of PLA contained in the PLA fabric of the present invention is preferably 65 to 135 ° C., but the temperature rising crystallization temperature (T C1 ) may not exist.
  • Heating crystallization heat ( ⁇ H TC1 )
  • the biodegradable aliphatic polyester fabric such as the PGA fabric of the present invention is calculated as the calorific value associated with the crystallization of the biodegradable aliphatic polyester contained in the fabric, which is detected in the temperature rising process by a differential scanning calorimeter.
  • the temperature rise crystallization heat ( ⁇ H TC1 ) is preferably 10 J / g or more.
  • the temperature rise crystallization heat ( ⁇ H TC1 ) is the exothermic peak area in the vicinity of the temperature rise crystallization temperature (T C1 ) [usually, the area within the temperature rise crystallization temperature (T C1 ) ⁇ 20 ° C.]. It is calculated by integrating.
  • a fabric containing a biodegradable aliphatic polyester having a temperature rising crystallization heat ( ⁇ H TC1 ) of 10 J / g or more is a fabric in which the amorphous part is present in a predetermined amount or more and the degree of the amorphous part is large. Adhesion performance of microorganisms such as useful bacteria and aquatic organisms such as algae is improved, and water purification performance is improved.
  • T C1 temperature rising crystallization temperature
  • the temperature rising crystallization heat ( ⁇ H TC1 ) does not exist and is 0 J / g.
  • the temperature increase crystallization heat amount ( ⁇ H TC1 ) of the biodegradable aliphatic polyester contained in the biodegradable aliphatic polyester fabric of the present invention is more preferably 15 J / g or more, still more preferably 20 J / g or more, particularly preferably. Is 25 J / g or more.
  • the upper limit is usually 40 J / g, and in many cases 35 J / g.
  • the biodegradable aliphatic polyester fabric of the present invention having good bioadhesiveness can be used as a water treatment material to be described later, and by fixing the fabric to the sea or the bottom of the sea, a scaffold for algae growth It can be used as a scaffold for forming an algae bed where the algae decomposes and disappears when the algae has settled on the rocks.
  • a biodegradable aliphatic polyester fabric such as the PGA fabric of the present invention is particularly useful as a water treatment material.
  • water treatment material by continuously contacting water existing in natural or artificial water areas such as rivers, lakes, ponds, dams, seas, industrial and agricultural waterways, and water use facilities such as pools and hot springs, It is used for water purification.
  • the biodegradable aliphatic polyester fabric of the present invention retains microorganisms such as useful bacteria by attaching microorganisms such as useful bacteria to the fiber surface, or by attaching aquatic organisms such as algae to the fiber surface, By growing microorganisms such as useful bacteria, it is possible to remove harmful substances by treating nutrient sources such as phosphorus and nitrogen present in the water to be treated, or by decomposing unnecessary organic substances. Stable water purification performance can be exhibited.
  • the water treatment material may be used solely by the biodegradable aliphatic polyester fabric of the present invention, or may be used by attaching the biodegradable aliphatic polyester fabric of the present invention to a frame material or a support.
  • the biodegradable aliphatic polyester fabric of the present invention When the biodegradable aliphatic polyester fabric of the present invention is used as a water treatment material, for example, the fabric itself has excellent water purification performance without performing a surface treatment such as attaching a porous material such as zeolite. Can show.
  • the water purification performance can be measured and evaluated by the following method.
  • the container is allowed to stand in an environment at a temperature of 23 ° C., and the river water at the start of the rest (hereinafter sometimes referred to as “raw water”).
  • raw water the river water at the start of the rest
  • the quality of the treated water (turbidity and chromaticity of water) every time a predetermined period of time elapses are measured for the supernatant.
  • the fabric test piece uses what sterilized by irradiating ultraviolet rays after alcohol spraying beforehand.
  • the turbidity of water is measured using a turbidity meter 2020 manufactured by Kasahara Chemical Co., Ltd. Using formazine as a standard substance, the turbidity [NTU: Nephelometric Turbidity Unit] is determined from the intensity ratio of transmitted light and scattered light. The higher the concentration of the turbid component in the water, the higher the turbidity. Therefore, if the turbidity is low, the water quality is purified.
  • NTU Nephelometric Turbidity Unit
  • Water chromaticity is measured using a chromaticity sensor CR-30 manufactured by Kasahara Chemical Industry Co., Ltd. Based on JIS K0102, the degree of yellowish-yellowish brown color of soluble substances and colloidal substances contained in water is measured at a wavelength of 390 nm by spectrophotometric analysis. In general, the higher the concentration of the organic component in the water, the higher the chromaticity. Therefore, the lower the chromaticity, the better the water quality.
  • the biodegradable aliphatic polyester fabric of the present invention is used as a water treatment material, for example, the surface of the porous decomposable material such as zeolite is adhered, and the fabric itself can be used as an excellent useful bacteria. It can show the adhesion performance of microorganisms.
  • the adhesion performance of microorganisms such as useful bacteria of the biodegradable aliphatic polyester fabric can be evaluated by measuring the adhesion performance of bacteria by the following test method. That is, in the measurement of the number of bacteria in water, 1 ml of river water is collected to determine the number of viable bacteria. The number of viable bacteria is counted by culturing at a temperature of 37 ° C.
  • biodegradable aliphatic polyester fabric of the present invention is excellent in adhesion performance of microorganisms such as useful bacteria is the fabric subjected to the test on the sixth day from the start of the test in the water purification performance test. In addition, it can be confirmed that bacteria are attached. Preferably, if more bacteria adhere to the fabric than water, it can be evaluated that the adhesion performance of microorganisms such as useful bacteria is excellent.
  • the biodegradable aliphatic polyester fabric of the present invention has (a) a basis weight of 1 to 500 g / m 2 , (b) a fiber diameter of 300 nm to 100 ⁇ m, And (c) as long as a fabric having a porosity of 50 to 95% can be produced, the production method is not particularly limited, and a commonly known woven fabric, knitted fabric, nonwoven fabric, cotton-like body or A manufacturing method such as a mat can be employed.
  • the biodegradable aliphatic polyester fabric of the present invention is preferably a non-woven fabric or a woven fabric, and particularly preferably a non-woven fabric.
  • a melt blow method a spun bond method, a needle punch method, a three-dimensional entanglement method using a water flow or an air flow, etc.
  • a known method for producing a nonwoven fabric can be employed.
  • the biodegradable aliphatic polyester fabric of the present invention contains fibers other than the biodegradable aliphatic polyester fiber, a composite fiber having a core-sheath structure or the like is used, or the biodegradable material spun
  • the biodegradable aliphatic polyester of the present invention is produced from an aliphatic polyester fiber and a fiber other than the biodegradable aliphatic polyester fiber by a method known per se, such as producing a nonwoven fabric or laminating a fabric. Fabrics can be manufactured.
  • the melt blow method or the spun bond method is preferable because the desired fiber diameter and porosity can be easily obtained.
  • the melt blow method is more preferable.
  • the manufactured nonwoven fabric containing the biodegradable aliphatic polyester fiber may be heat-treated for a predetermined time at a required temperature using a heat treatment machine to obtain a heat treated nonwoven fabric.
  • the heat treatment temperature and treatment time are not necessarily constant depending on the melting point and content of the fibers contained in the nonwoven fabric, but in order not to reduce the porosity of the nonwoven fabric, it is preferable to be less than the melting point,
  • Heat treatment is preferably performed at a temperature of 70 to 200 ° C. for 1 second to 60 minutes, more preferably at a temperature of 80 to 180 ° C. for 3 seconds to 40 minutes, and even more preferably at a temperature of 90 to 150 ° C. for 5 seconds to 30 What is necessary is just to heat-process for minutes.
  • the present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the examples.
  • the measuring method of the physical property or characteristic of PGA which is a PGA nonwoven fabric or its material in an Example and a comparative example is as follows.
  • Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured using a gel permeation chromatography (GPC) analyzer under the following conditions. 10 mg of PGA sample is dissolved in hexafluoroisopropanol (HFIP) in which sodium trifluoroacetate is dissolved at a concentration of 5 mM to make 10 ml, then filtered through a membrane filter to obtain a sample solution, and 10 ⁇ l of this sample solution is analyzed by GPC analysis. The molecular weight was determined by injecting into the apparatus and measuring under the following measurement conditions.
  • HFIP hexafluoroisopropanol
  • Temperature rising crystallization temperature (T c1 ) and temperature rising crystallization heat ( ⁇ H TC1 ) Temperature rising process when 10 mg of sample is heated from room temperature to a temperature in the vicinity of melting point (Tm) + 60 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere using the differential scanning calorimeter. in exothermic peak due to crystallization and a temperature of the heated crystallization temperature of the heat generating peak when the detected (T c1). Further, the heat generation crystallization heat amount ( ⁇ H TC1 ) was calculated by integrating the exothermic peak areas within the temperature increase crystallization temperature (T C1 ) ⁇ 20 ° C. range.
  • Fabric weight of nonwoven fabric was measured according to JIS L1096.
  • Fiber diameter of the nonwoven fabric The fiber diameter of the nonwoven fabric was sampled at 10 points so as not to overlap in the width direction and the longitudinal direction of the nonwoven fabric, and 10 fiber diameters were measured from an electron micrograph magnified 1000 times, The average value of a total of 100 points was defined as the average fiber diameter, and the fiber diameter of the nonwoven fabric.
  • Thickness of the nonwoven fabric The thickness of the nonwoven fabric was measured at a load of 0.7 kPa according to JIS L1096.
  • Porosity of the nonwoven fabric was determined by measuring the mass of the sample nonwoven fabric cut into a size of 50 mm ⁇ 50 mm (W1), and using this as a perfluoropolyester test solution (trade name “Porous Materials” It was immersed in (Galwick ”) for 5 minutes, then the sample nonwoven fabric was taken out from the test solution, and the mass after draining for 1 minute was measured (W2) and calculated by the following formula.
  • Porosity (%) (((W2-W1) / ⁇ 2 ) / ((W2-W1) / ⁇ 2 + W1 / ⁇ 1 )) ⁇ 100
  • the turbidity of water was measured using a turbidimeter 2020 model manufactured by Kasahara Chemical Co., Ltd. Using formazine as a standard substance, turbidity [NTU: Nephelometric Turbidity Unit] was determined from the intensity ratio of transmitted light and scattered light.
  • the chromaticity of water was measured using a chromaticity sensor CR-30 manufactured by Kasahara Chemical Co., Ltd. Based on JIS K0102, the degree of yellowish or yellowish brown color of soluble substances and colloidal substances contained in water was measured at a wavelength of 390 nm by absorptiometry.
  • Bioadhesion (fungus adhesion performance) The bioadhesiveness of the nonwoven fabric was evaluated by measuring the adhesion performance of the bacteria by the following test method. That is, in the measurement of the number of bacteria in water, 1 ml of river water was collected, and the number of viable bacteria in raw water and on the sixth day from the start of the test was determined. The number of viable bacteria was counted by culturing at a temperature of 37 ° C. for 2 days by a pour plate method using a standard agar medium.
  • the number of bacteria in the nonwoven fabric is measured in advance using alcohol-sprayed, ultraviolet-irradiated, sterilized nonwoven fabric, and sterilized physiological saline so that the amount is 10 times the mass of the nonwoven fabric on the sixth day from the start of the test.
  • the number of viable bacteria per 1 g of the nonwoven fabric was determined using water as a sample solution after washing with a stomacher.
  • the number of viable bacteria was counted by culturing at a temperature of 37 ° C. for 2 days by a pour plate method using a standard agar medium.
  • Example 1 Manufacture of non-woven fabric
  • Pellet PGA manufactured by Kureha Corporation, Mw: 2.1 ⁇ 10 5 , Mw / Mn: 2.3, melt viscosity (measured at a temperature of 270 ° C. and a shear rate of 122 sec ⁇ 1 ): 610 Pa ⁇ s, melting point: 220 (° C., glass transition temperature: 43 ° C.) was melted by an extruder, discharged from a die having a spinneret, and stretched fibers were collected on a belt conveyor to prepare a melt blown nonwoven fabric.
  • the amount of lamination was controlled by adjusting the discharge amount and the speed of the belt conveyor to prepare a PGA nonwoven fabric having a basis weight of 15 g / m 2 and a thickness of 130 ⁇ m.
  • the average fiber diameter of the nonwoven fabric was 4.4 ⁇ m, and the porosity was 90.8%.
  • T c1 of PGA contained in this nonwoven fabric, 86 ° C., [Delta] H TC1 was 33J / g.
  • the nonwoven fabric test piece having a volume of 7.8 cm 3 (area cm 2 ) was immersed in a glass container containing 1500 cm 3 of river water. Next, cover the mouth of the container with gauze to prevent the inflow of bacteria and the like from the outside, while gently stirring the river water in the container with a stirrer, leave the container in an environment at a temperature of 23 ° C., Water quality (turbidity, chromaticity) was investigated every predetermined period.
  • Example 2 In the state which fixed the melt blown nonwoven fabric manufactured in Example 1, it heat-processed by putting in the gear oven set to the temperature of 100 degreeC for 30 minutes.
  • This nonwoven fabric had a basis weight of 15 g / m 2 , a thickness of 120 ⁇ m, an average fiber diameter of 4.5 ⁇ m, and a porosity of 90.0%.
  • PGA contained in this nonwoven fabric Tc1 was not detected.
  • water purification performance and bioadhesion tests were conducted.
  • Example 3 Instead of the melt blown nonwoven fabric produced in Example 1, using the pellet-like PGA used in Example 1, by changing the configuration of the die, and controlling the stacking amount by adjusting the discharge amount and the belt conveyor speed, A PGA meltblown nonwoven fabric having a basis weight of 106 g / m 2 , a thickness of 450 ⁇ m, an average fiber diameter of 7.8 ⁇ m, and a porosity of 91.6% was prepared. T c1 of PGA contained in this nonwoven fabric, 77 ° C., [Delta] H TC1 was 33J / g. Using this melt-blown nonwoven fabric as a test piece, water purification performance and bioadhesion tests were conducted.
  • Table 1 shows the turbidity and chromaticity measurement results of raw water and water on the 6th, 16th and 45th days from the start of the test. In addition, after the 6th day, it has confirmed visually that the brown precipitate settled and the one part adhered to the nonwoven fabric.
  • Example 4 instead of the melt blown nonwoven fabric produced in Example 1, a spunbond nonwoven fabric of PGA having a basis weight of 88 g / m 2 , a thickness of 390 ⁇ m, an average fiber diameter of 16.4 ⁇ m, and a porosity of 87.3% was prepared. As for PGA contained in this nonwoven fabric, Tc1 was not detected. Using this spunbond nonwoven fabric as a test piece, water purification performance and bioadhesion tests were conducted. Table 1 shows the turbidity and chromaticity measurement results of raw water and water on the 6th, 16th and 45th days from the start of the test. In addition, after the 6th day, it has confirmed visually that the brown precipitate settled and the one part adhered to the nonwoven fabric.
  • Example 1 In place of the melt blown nonwoven fabric produced in Example 1, water purification performance and bioadhesion tests were conducted using a nonwoven fabric [manufactured by Kureha Co., Ltd., Dustman (registered trademark)] consisting of 30% by mass of pulp and 70% by mass of PET as a test piece. went.
  • This nonwoven fabric had a basis weight of 17 g / m 2 , a thickness of 70 ⁇ m, an average fiber diameter of 12.0 ⁇ m, and a porosity of 77.5%.
  • Example 2 In place of the melt blown nonwoven fabric produced in Example 1, water purification performance and bioadhesion tests were conducted using a nonwoven fabric made of 100% by weight of cotton yarn (manufactured by Cainz Co., Ltd., a large towel for tableware wiping) as a test piece.
  • This nonwoven fabric had a basis weight of 147 g / m 2 , a thickness of 400 ⁇ m, an average fiber diameter of 8.1 ⁇ m, and a porosity of 75.2%.
  • Table 1 shows the turbidity and chromaticity measurement results of raw water and water on the 6th, 16th and 45th days from the start of the test. On the 16th day, it was visually confirmed that white, black, brown and yellow stains were floating in the water and adhered to the entire nonwoven fabric, and a strange odor was felt.
  • Example 3 instead of the melt-blown nonwoven fabric produced in Example 1, water-purifying performance and bioadhesion tests were conducted using a mat-like nonwoven fabric made of 100% by mass of PET (manufactured by Cainz Co., Ltd., upper filter filtration mat) as a test piece.
  • This nonwoven fabric had a basis weight of 198 g / m 2 , a thickness of 16000 ⁇ m, an average fiber diameter of 31.9 ⁇ m, and a porosity of 82.9%.
  • Table 1 shows the turbidity and chromaticity measurement results of raw water and water on the 6th, 16th and 45th days from the start of the test. In addition, on the 16th day, it was confirmed visually that it was clouded as a whole, there were few precipitates, and there was little adhesion to a nonwoven fabric.
  • Examples 1 to 4 in which (a) the basis weight is 1 to 500 g / m 2 , (b) the fiber diameter is 300 nm to 100 ⁇ m, and (c) the porosity is 50 to 95%.
  • the PGA non-woven fabric of the present invention significantly decreases the turbidity and chromaticity of the river water by immersing it in river water having a turbidity of 16.2 NTU and a chromaticity of 46.3 degrees. On the day, the turbidity was 1 NTU or less and the chromaticity was 10 degrees or less, and it was found that the water had excellent water purification performance.
  • the biodegradable aliphatic polyester fabric of the present invention has good adhesion and fixability of useful bacteria and the like existing in water. As a result, purification of water by these bacteria proceeds, It was found that it has the function of purifying water by reducing the turbidity and chromaticity of river water. Moreover, although a detailed mechanism is unknown, it is guessed that PGA nonwoven fabric itself was hydrolyzed in water, glycolic acid eluted, this became a nutrient source of the bacterium, and the bacterium grew.
  • the biodegradable aliphatic polyester fabric of the present invention has a sufficient ability to exert a water purification effect by microorganisms due to its excellent hydrolysis and biodegradability. Furthermore, since the biodegradable aliphatic polyester fabric of the present invention is excellent in hydrolysis and biodegradability, it was found that maintenance disappears because it disappears after a certain period of time when the water purification treatment has proceeded. .
  • the nonwoven fabric composed of 100% by mass of PET of Comparative Example 3 has better water purification performance than Comparative Examples 1 and 2, but less turbidity and chromaticity than Examples 1 to 4, and the whole It was found that the water purification performance is not sufficient from the fact that it is cloudy.
  • the nonwoven fabric of Comparative Example 1 was immersed in river water for 6 days, the bacteria that were present in the river water adhered to the nonwoven fabric only at a concentration that did not reach the concentration in water. It was speculated that the purification of water could not be expected to progress due to the bacteria attached to.
  • the present invention provides a raw material characterized in that (a) the basis weight is 1 to 500 g / m 2 , (b) the fiber diameter is 300 nm to 100 ⁇ m, and (c) the porosity is 50 to 95%.
  • the basis weight is 1 to 500 g / m 2
  • the fiber diameter is 300 nm to 100 ⁇ m
  • the porosity is 50 to 95%.
  • biodegradable aliphatic polyester fabric of the present invention having good bioadhesiveness is fixed to the sea or the bottom of the sea, so that it acts as a scaffold for the growth of algae, and the algae has been established on the rocks. It can also be used as a scaffolding material for the formation of algae beds that decomposes and disappears in stages.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Microbiology (AREA)
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  • Environmental & Geological Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
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Abstract

L'invention porte sur un textile, tel qu'un non-tissé, et sur un matériau de traitement d'eau comprenant le textile. Le textile, qui contient une fibre de polyester aliphatique biodégradable constituée de poly(acide glycolique), de poly(acide lactique) ou d'un mélange de ceux-ci, est caractérisé en ce qu'il présente (a) une masse surfacique de 1 à 500 g/m², (b) une taille de fibre de 300 nm à 100 µm et (c) une porosité de 50 à 95 %.
PCT/JP2012/059349 2011-05-18 2012-04-05 Textile de polyester aliphatique biodégradable ayant une excellente adhérence microbienne WO2012157359A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013125607A1 (fr) * 2012-02-21 2013-08-29 学校法人同志社 Substrat de régénération tissulaire
JP2015016436A (ja) * 2013-07-11 2015-01-29 水ｉｎｇ株式会社 生物学的脱窒素方法及び装置
CN112384650A (zh) * 2018-07-09 2021-02-19 国立研究开发法人物质·材料研究机构 无纺布、无纺布的制造方法和静电纺丝用组合物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10325064A (ja) * 1997-05-26 1998-12-08 Unitika Ltd 伸縮性に優れた生分解性不織布及びその製造方法
WO2000057989A1 (fr) * 1999-03-30 2000-10-05 Chisso Corporation Cartouche filtrante
JP2005009052A (ja) * 2003-06-20 2005-01-13 Kureha Gosen Kk 生分解性ポリエステル繊維を含む構造体、及びその製造方法
WO2006028244A1 (fr) * 2004-09-07 2006-03-16 Teijin Limited Objet poreux bioabsorbable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10325064A (ja) * 1997-05-26 1998-12-08 Unitika Ltd 伸縮性に優れた生分解性不織布及びその製造方法
WO2000057989A1 (fr) * 1999-03-30 2000-10-05 Chisso Corporation Cartouche filtrante
JP2005009052A (ja) * 2003-06-20 2005-01-13 Kureha Gosen Kk 生分解性ポリエステル繊維を含む構造体、及びその製造方法
WO2006028244A1 (fr) * 2004-09-07 2006-03-16 Teijin Limited Objet poreux bioabsorbable

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013125607A1 (fr) * 2012-02-21 2013-08-29 学校法人同志社 Substrat de régénération tissulaire
JP2015016436A (ja) * 2013-07-11 2015-01-29 水ｉｎｇ株式会社 生物学的脱窒素方法及び装置
CN112384650A (zh) * 2018-07-09 2021-02-19 国立研究开发法人物质·材料研究机构 无纺布、无纺布的制造方法和静电纺丝用组合物

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