JP4481302B2 - ポリグリコール酸系樹脂フィラメントおよびその製造方法 - Google Patents
ポリグリコール酸系樹脂フィラメントおよびその製造方法 Download PDFInfo
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- JP4481302B2 JP4481302B2 JP2006511216A JP2006511216A JP4481302B2 JP 4481302 B2 JP4481302 B2 JP 4481302B2 JP 2006511216 A JP2006511216 A JP 2006511216A JP 2006511216 A JP2006511216 A JP 2006511216A JP 4481302 B2 JP4481302 B2 JP 4481302B2
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- polyglycolic acid
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- acid resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 73
- 239000011347 resin Substances 0.000 title claims abstract description 73
- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 71
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000002074 melt spinning Methods 0.000 claims description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- -1 cyclic ester Chemical class 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000011162 core material Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000012792 core layer Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000012773 agricultural material Substances 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012770 industrial material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- ZNLAHAOCFKBYRH-UHFFFAOYSA-N 1,4-dioxane-2,3-dione Chemical compound O=C1OCCOC1=O ZNLAHAOCFKBYRH-UHFFFAOYSA-N 0.000 description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 231100000209 biodegradability test Toxicity 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 description 1
- ULKFLOVGORAZDI-UHFFFAOYSA-N 3,3-dimethyloxetan-2-one Chemical compound CC1(C)COC1=O ULKFLOVGORAZDI-UHFFFAOYSA-N 0.000 description 1
- FHUDZSGRYLAEKR-UHFFFAOYSA-N 3-hydroxybutanoic acid;4-hydroxybutanoic acid Chemical compound CC(O)CC(O)=O.OCCCC(O)=O FHUDZSGRYLAEKR-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- YHTLGFCVBKENTE-UHFFFAOYSA-N 4-methyloxan-2-one Chemical compound CC1CCOC(=O)C1 YHTLGFCVBKENTE-UHFFFAOYSA-N 0.000 description 1
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical class OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920009537 polybutylene succinate adipate Polymers 0.000 description 1
- 239000004630 polybutylene succinate adipate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- D—TEXTILES; PAPER
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
- D01D5/0885—Cooling filaments, threads or the like, leaving the spinnerettes by means of a liquid
-
- 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
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/444—Yarns or threads for use in sports applications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/223—Stretching in a liquid bath
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/228—Stretching in two or more steps, with or without intermediate steps
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Biological Depolymerization Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
式:−(−O−CH2−CO−)−
で表わされるグリコール酸繰り返し単位のみからなるグリコール酸の単独重合体(グリコール酸の2分子間環状エステルであるグリコリド(GL)の開環重合物を含む)に加えて、上記グリコール酸繰り返し単位を55重量%以上含むポリグリコール酸共重合体を含むものである。
本発明のフィラメント製造方法を適用するに先立って、PGA樹脂を熱安定剤と混練し、ペレット化しておくことが好ましい。
本発明のPGA樹脂フィラメントの糸径(直径)は、特に限定されるものではないが、モノフィラメントとしては、好ましくは30μm〜3mm、更に好ましくは50μm〜2mmの範囲内である。また、マルチフィラメントとしては、構成する単糸(直径)が、好ましくは0.1μm〜30μm、更に好ましくは0.5μm〜20μmの範囲内である。
サンプル約300mgを約6gのDMSO(ジメチルスルホキシド)中150℃で約10分加熱し溶解させ、室温まで冷却した後、ろ過を行う。そのろ液に内部標準物質の4−クロロベンゾフェノンとアセトンを一定量添加する。その溶液を2μl採取し、GC装置に注入し残留モノマー(グリコリド)量の測定を行った。
装置:島津GC−2010
カラム:TC−17(0.25mmφ×30m)、
カラム温度:150℃で5分保持後、20℃/分で270℃まで昇温して、270℃で3分間保持、
気化室温度:200℃、
検出器:FID(水素炎イオン化検出器)、
温度:300℃。
ポリマーサンプルを120℃の乾燥空気を接触させて、水分含有量を50ppm以下にまで低減させた。溶融粘度測定は、キャピラリー(1mmφ×10mmL)を装着した東洋精機「キャピログラフ1−C」を用いて測定した。設定温度240℃に加熱した装置に、サンプル約20gを導入し、5分間保持した後、剪断速度121sec−1での溶融粘度を測定した。
ポリマーサンプルを分子量測定で使用する溶媒に溶解させるために、非晶質のポリマーを得る。すなわち、十分乾燥したポリマー約5gをアルミニウム板に挟み、275℃のヒートプレス機にのせて90秒加熱した後、2MPaで1分間加圧保持した後、直ちに水が循環しているプレス機に移し冷却した。このようにして、透明な非晶質のプレスシートを作製した。
装置:昭和電工(株)製「Shodex−104」
カラム:HFIP−606M、2本(直列接続)およびプレカラム、
カラム温度:40℃、
溶離液:5mMのトリフルオロ酢酸ナトリウムを溶解させたHFIP溶液、
流速:0.6ml/分、
検出器:RI(Refractive Index:示差屈折率)検出器、
分子量較正:分子量の異なる標準ポリメタクリル酸メチル5種を用いた。
JISL1013に準拠し、オリエンテック(株)社製「テンシロンUTM−III−100型」引張試験機を用い、23℃65RH%の室内で、試長300mm、引張速度300mm/分、測定数n=5にて引張強度、引張伸度および引張弾性率を、それぞれ測定した。また、結節強度および伸度は試料のつかみ間の中央に結節を作り、同様の引張条件に付し、切断時の強さおよび伸度を測定した。
金属メッシュにフィラメントサンプルを挟み込み、金属性のかごの中に入れ、これを小名浜港護岸壁海中に沈め、経時的に引き上げて残留強度および伸度を測定した。
市販ポリカプロラクトン系生分解性樹脂(ダイセル化学工業(株)製「セルグリーンP−H7」を原料とし、径35mmの押出機および径2mm×6ホールの単層ノズルを用いて、押出機温度150℃、ノズル温度140℃で溶融紡出後、20℃の水浴中に導入して急冷しつつ引取速度10m/分の条件で紡糸して未延伸糸を作成し、引続き40℃の温水中で5.0倍に延伸して、直径0.31mmのモノフィラメントを得た。
ポリグリコール酸重合体(PGA)(呉羽化学工業(株)製;残留モノマー:0.8重量%、溶融粘度:2560Pa・s)を径35mmの押出機および径1.3mm×6ホールの単層ノズルを用いて、押出機温度250℃、ノズル温度230℃で溶融紡出後、エアギャップ10cmをおいて、20℃の水浴中に導入して急冷しつつ引取速度8.4m/分の条件で紡糸して未延伸糸を得た。得られた未延伸糸は結晶化し不透明であった。この未延伸糸を次に、送出し速度2m/分で80℃グリセリン浴中に導入し、5.2倍に延伸して直径0.3mmのモノフィラメントを得た。
PGA(呉羽化学工業(株)製;残留モノマー:0.18重量%、溶融粘度:2786Pa・s)を、比較例2と同じ押出機およびノズルを用い、同様に押出機温度260℃およびノズル温度230℃の条件で溶融紡出後、エアギャップ6.5cmをおいて5℃の水浴中に導入して急冷しつつ引取速度4.5m/分の条件で紡糸し、次いで80℃のグリセリン浴中に導入し、6.0倍に延伸して直径0.26mmのモノフィラメントを得た。
実施例1と同一原料、条件で紡糸後、引続き80℃のグリセリン浴中で6.25倍に延伸し、直径0.26mmのモノフィラメントを得た。
グリセリン延伸浴温度を85℃と上昇した以外は、実施例1と同一条件で直径0.26mmのモノフィラメントを得た。得られたモノフィラメントは、延伸糸全体が白化し、低い引張強度を示し、結節強度、結節伸度を測るまでもなかった。
市販生分解性釣糸(ポリブチレンサクシネートアジペート(東レ(株)製「フィールドメート」、8ポンド、直径0.31mm)を用いて実施例3と同様に海水生分解性試験を行った。結果をまとめて次表2に示す。
ポリグリコール酸重合体(PGA)(呉羽化学工業(株)製:残留モノマー0.37%、溶融粘度:3049Pa・s)を、比較例2の押出機及び単層ノズルを用いて、押出温度275℃、ノズル温度265℃で溶融紡出後、エアギャップ15cmをおいて6℃の水浴中に導入して急冷しつつ引取速度5m/分の条件で紡糸し、次いで80℃のグリセリン浴中に導入し、6.0倍に延伸して、直径0.24mmのモノフィラメントを得た。
実施例4で得られたモノフィラメントを、更に90℃のグリセリン浴中に導入して1.15倍の第2段延伸(延伸倍率:計6.9倍)を行い、直径0.21mmのモノフィラメントを得た。
Claims (15)
- 残留モノマー量が0.5重量%未満のポリグリコール酸系樹脂からなり、引張強度が750MPa以上、且つ結節強度が600MPa以上であることを特徴とするポリグリコール酸系樹脂フィラメント。
- 結節強度が650MPa以上である請求項1に記載のフィラメント。
- 引張強度が800MPa以上である請求項1または2に記載のフィラメント。
- 残留モノマー量が0.2重量%未満のポリグリコール酸系樹脂からなる請求項1〜3のいずれかに記載のフィラメント。
- 引張破断伸度が10〜50%である請求項1〜3のいずれかに記載のフィラメント。
- 引張破断伸度が15〜40%である請求項5に記載のフィラメント。
- 引張破断伸度が20%を超え30%未満である請求項5に記載のフィラメント。
- 引張弾性率が12GPa以上である請求項1〜7のいずれかに記載のフィラメント。
- 残留モノマー量が0.5重量%未満のポリグリコール酸系樹脂を溶融紡出後、10℃以下の液浴中で急冷した後、60〜83℃の液浴中で延伸することを特徴とするポリグリコール酸系樹脂フィラメントの製造方法。
- 前記延伸後、その延伸温度より高い温度で、且つ延伸倍率が1.8倍以下で第2段の延伸を行う請求項9に記載のフィラメントの製造方法。
- 前記延伸後、その延伸温度より差が約40℃以下の範囲で高い温度で、第2段の延伸を行う請求項9または10に記載のフィラメントの製造方法。
- 前記延伸後、その延伸温度より差が約12℃以下の範囲で高い温度で、第2段の延伸を行う請求項9または10に記載のフィラメントの製造方法。
- ポリグリコール酸系樹脂を溶融紡出後、10℃以下の液浴中で急冷した後、60〜83℃の液浴中で第1段延伸し、続いて第1段延伸の温度より差が12℃以下の範囲で高い温度、且つ1.8倍以下の延伸倍率で第2段延伸することを特徴とするポリグリコール酸系樹脂フィラメントの製造方法。
- 残留モノマー量が0.2重量%未満のポリグリコール酸系樹脂を溶融紡出する請求項9〜13のいずれかに記載のフィラメントの製造方法。
- 請求項1〜8のいずれかに記載のフィラメントからなる釣糸。
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JP4664167B2 (ja) * | 2005-09-16 | 2011-04-06 | 株式会社クレハ | 生分解性の制御された生分解性樹脂フィラメント及びその製造方法 |
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EP2642002A4 (en) * | 2010-11-15 | 2014-04-30 | Kureha Corp | UNRISED YARN WITH POLYGLYCOLIC ACID RESIN, SLICED YARN WITH POLYGLYCOLIC ACID RESIN AND METHOD FOR THE PRODUCTION OF BOTH |
US20140377555A1 (en) * | 2012-03-01 | 2014-12-25 | Kureha Corporation | Water-disintegrable composite fiber and method of producing the same |
EP2843090A4 (en) * | 2012-04-27 | 2015-10-28 | Kureha Corp | BRIEF POLYGLYCOLIC ACID RESIN FIBERS AND BOROON TREATMENT LIQUID |
US9534163B2 (en) | 2012-04-27 | 2017-01-03 | Kureha Corporation | Polyglycolic acid resin short fibers for use in well treatment fluid |
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US8808596B2 (en) | 2014-08-19 |
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