JP3791177B2 - Vinyl chloride fiber and method for producing the same - Google Patents
Vinyl chloride fiber and method for producing the same Download PDFInfo
- Publication number
- JP3791177B2 JP3791177B2 JP07761798A JP7761798A JP3791177B2 JP 3791177 B2 JP3791177 B2 JP 3791177B2 JP 07761798 A JP07761798 A JP 07761798A JP 7761798 A JP7761798 A JP 7761798A JP 3791177 B2 JP3791177 B2 JP 3791177B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- weight
- parts
- heat stabilizer
- chloride resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920006312 vinyl chloride fiber Polymers 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 138
- 229920005989 resin Polymers 0.000 claims description 132
- 239000011347 resin Substances 0.000 claims description 132
- 239000000314 lubricant Substances 0.000 claims description 102
- 239000012760 heat stabilizer Substances 0.000 claims description 87
- 239000000835 fiber Substances 0.000 claims description 74
- 239000000203 mixture Substances 0.000 claims description 62
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 47
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 47
- 238000002074 melt spinning Methods 0.000 claims description 39
- 239000011342 resin composition Substances 0.000 claims description 27
- 238000009987 spinning Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000004698 Polyethylene Substances 0.000 claims description 20
- 229920000573 polyethylene Polymers 0.000 claims description 20
- 239000000344 soap Substances 0.000 claims description 19
- 229910052793 cadmium Inorganic materials 0.000 claims description 18
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 18
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 229920006026 co-polymeric resin Polymers 0.000 claims description 14
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 claims description 14
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 13
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- QUGNZNCOLVCQKW-UHFFFAOYSA-M S[Sn] Chemical compound S[Sn] QUGNZNCOLVCQKW-UHFFFAOYSA-M 0.000 claims description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 12
- AJDTZVRPEPFODZ-PAMPIZDHSA-J [Sn+4].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O Chemical compound [Sn+4].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O AJDTZVRPEPFODZ-PAMPIZDHSA-J 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 5
- 229960001545 hydrotalcite Drugs 0.000 claims description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000004386 Erythritol Substances 0.000 claims 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 2
- 229940009714 erythritol Drugs 0.000 claims 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims 2
- 235000019414 erythritol Nutrition 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 230000001788 irregular Effects 0.000 claims 1
- 239000004753 textile Substances 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000002474 experimental method Methods 0.000 description 39
- 210000004209 hair Anatomy 0.000 description 39
- 150000001875 compounds Chemical class 0.000 description 23
- 239000000155 melt Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000004014 plasticizer Substances 0.000 description 11
- 238000013329 compounding Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 238000005034 decoration Methods 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 6
- 230000035807 sensation Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004801 Chlorinated PVC Substances 0.000 description 4
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- 229910002975 Cd Pb Inorganic materials 0.000 description 3
- ZIXVIWRPMFITIT-UHFFFAOYSA-N cadmium lead Chemical compound [Cd].[Pb] ZIXVIWRPMFITIT-UHFFFAOYSA-N 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002952 polymeric resin Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 239000003017 thermal stabilizer Substances 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229940043348 myristyl alcohol Drugs 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229940012831 stearyl alcohol Drugs 0.000 description 2
- 230000009182 swimming Effects 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BMASLOOHTMQIGP-ZOKJKDLISA-H (z)-but-2-enedioate;butyltin(3+) Chemical compound CCCC[Sn+3].CCCC[Sn+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O BMASLOOHTMQIGP-ZOKJKDLISA-H 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- PKZGKWFUCLURJO-GRHBHMESSA-L (z)-but-2-enedioate;dimethyltin(2+) Chemical compound C[Sn+2]C.[O-]C(=O)\C=C/C([O-])=O PKZGKWFUCLURJO-GRHBHMESSA-L 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical group C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 1
- BCBHWVAFKCCWBG-UHFFFAOYSA-N chloroethene;ethenyl propanoate Chemical compound ClC=C.CCC(=O)OC=C BCBHWVAFKCCWBG-UHFFFAOYSA-N 0.000 description 1
- OTBMOTROYGWSNQ-UHFFFAOYSA-N chloroethene;ethyl prop-2-enoate Chemical compound ClC=C.CCOC(=O)C=C OTBMOTROYGWSNQ-UHFFFAOYSA-N 0.000 description 1
- GRFFKYTUNTWAGG-UHFFFAOYSA-N chloroethene;prop-2-enenitrile Chemical compound ClC=C.C=CC#N GRFFKYTUNTWAGG-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- JMZPFWOGSIXUME-UHFFFAOYSA-N hex-5-enyl prop-2-enoate Chemical compound C=CCCCCOC(=O)C=C JMZPFWOGSIXUME-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002942 palmitic acid derivatives Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005671 poly(vinyl chloride-propylene) Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、かつら、ヘア・ピース、ブレード、エクステンションヘアー、アクセサリーヘアーなどの頭髪装飾用に用いられる人工毛髪、或いはドールヘアー等の人形用頭髪繊維などとして使用される塩化ビニル系繊維、およびその製造方法に関するものである。
【０００２】
【従来の技術】
塩化ビニル系樹脂を紡糸して繊維状にしてなる塩化ビニル系繊維は、その優れた強度、伸度、カール保持性、スタイル性などの故に、頭髪装飾用などの人工毛髪用繊維として、あるいはドールヘアーなどの人形用頭髪繊維として多量に使用されている。
【０００３】
従来、頭髪装飾用などの人工毛髪用繊維として、細繊度（断面積が小さく、細い繊維）の繊維を工業的に製造するには、一般的に塩化ビニル系樹脂に対する溶媒を使用する湿式紡糸法、または乾式紡糸法によって、細い繊度の塩化ビニル系繊維を製造する方法が工業的に実施されている。しかしながら、該方法は、溶媒を使用するが故に脱溶媒工程を必要とし、過大な設備投資が必要であり、その設備の維持管理にも多数の人手を必要とするという問題点がある。また、溶媒に対する溶解性を向上するべく、アクリロニトリルなどのコモノマーを共重合する為、繊維の初期着色性に弱点があり、乾燥工程での熱によって黄色味の強い毛髪になり易いという問題点、あるいは繊維のカール保持性が充分でないなどの問題点がある。
【０００４】
一方、溶媒を使用しない紡糸方法としては溶融紡糸法が知られているが、この方法によって、人毛に極めて類似した半艶表面（艶の評価については、実施例に評価基準を示した。）、触感の頭髪装飾用などの細繊度の人工毛髪用繊維を得る為には、１ケの断面積が極めて小さいノズル孔（０.５ｍｍ2以下）から溶融・流出させ、紡糸ドラフト比を小さくする（Ｄｒ比：２５以下）のが好ましい。すなわち、逆に大きな断面積のノズル孔から溶融・流出させて、細繊度の塩化ビニル系繊維とすると、必然的に紡糸ドラフト比を大きくする必要があり、溶融紡糸時に未延伸糸が極端に引き伸ばされることになるため、この未延伸糸に延伸・熱処理を施してなる繊維(延伸糸)表面が、平滑になり、光沢が出て、サラサラ触感がなくなるなど頭髪装飾用などの人工毛髪用繊維としては不十分な繊維となる傾向があった。故に、頭髪装飾用などの人工毛髪用繊維として品質的に優れた繊維を得る為には、できる限り１ケの断面積が小さいノズル孔から溶融・流出させ、紡糸ドラフト比を小さくするのが好ましい。
【０００５】
しかしながら、従来は１ケの断面積が極めて小さいノズル孔から流出させる場合には、ノズルにかかる圧力が高くなり、押出機の設計圧力をオーバーしてしまうという問題や、その圧力を定格以下とするべく、押出量を低くすると、溶融紡糸生産性が低下するという問題、あるいは溶融粘度を低くする為に、溶融紡糸温度を高く設定すると、熱分解を発生したり、ロングラン性が劣るような傾向があった。
【０００６】
故に、これらの問題を解決するべく、従来から様々な提案がなされているが、十分な解決には至っていない。例えば、特公昭５１-２１０９号公報では、塩素化塩化ビニル樹脂とメチルメタクリレート系樹脂を使用することにより、曳糸性を向上するという提案があるが、比較的大きな断面から小さな断面へと引き伸ばして、細繊度とする為、繊維表面が平滑になり光沢が発生しやすく、人毛に類似した半艶表面からかけ離れるたものになるばかりでなく、サラサラとした触感がなくなり、毛髪用繊維として不十分であった。また、組成物の溶融粘度を低下するべく、カドミウムや鉛を使用したＣｄ-Ｐｂ系の熱安定剤、滑剤を使用する方法が工業的に実施されている。しかしこれらの配合剤を使用すると、ノズル圧力の問題や溶融紡糸生産性の問題などは解決できるものの、初期着色が大きく、黄色味の強い毛髪になりやすい。また、これらの配合剤は毒性が高く、製造上問題があるばかりでなく、頭髪装飾用として皮膚に触れる為に安全衛生上の問題がある。また、これらの頭髪装飾用品などが廃棄される場合、一般ゴミに混入して環境を汚染するという問題もある。
【０００７】
【発明が解決しようとする課題】
本発明の第１の目的は、従来公知のＣｄ-Ｐｂ系の熱安定剤、滑剤を使用しなくても、初期着色性を大幅に改善しつつ、人毛に極めて類似した半艶表面、触感、柔軟性を保持し、また優れた強度、伸度、収縮性を保持した細繊度の塩化ビニル系繊維を提供することにあり、第２の目的は、従来公知の錫系安定剤を使用した塩化ビニル系繊維の品質課題であるプラチック的触感、キラキラ感のある表面性、ゴワゴワとした指巻き触感、熱収縮性などを改善し、安全に、かつ安定的に生産できる細繊度の塩化ビニル系繊維およびその製造方法を提供することにある。さらに第３の目的は、１ヶのノズル断面積が極めて小さいノズル孔から溶融紡糸する際の諸問題点を解決し、ノズル圧力と溶融紡糸生産性を高度にバランスし、さらに、溶融紡糸温度と熱分解・ロングラン性のバランスをレベルアップした細繊度の塩化ビニル系繊維の製造方法を提供することにある。
【０００８】
【課題を解決する為の手段】
本発明者らは、上記課題を解決するべく、組成物の配合系、ノズル孔断面積、溶融紡糸条件などについて、鋭意研究を重ねた結果、塩化ビニル系樹脂と塩素化塩化ビニル系樹脂からなる塩化ビニル系混合物にエチレン−酢酸ビニル系樹脂、熱安定剤、および滑剤を特定範囲で配合した場合には、Ｃｄ−Ｐｂ系の熱安定剤、滑剤等を使用しなくても人毛に極めて類似した半艶表面、触感等を保持し、前記品質問題を解決した細繊度の繊維を溶融紡糸生産性を低下させることなく安定的に得られることを見出し、本発明を完成するに至った。
【０００９】
すなわち本発明は、塩化ビニル系樹脂１００〜６０重量％と塩素化塩化ビニル系樹脂０〜４０重量％からなる塩化ビニル系混合物１００重量部に対して、（ａ）エチレン−酢酸ビニル系樹脂を１〜３５重量部と、（ｂ）熱安定剤０.２〜５.０重量部と、（ｃ）滑剤０.２〜５.０重量部とを配合してなる塩化ビニル系樹脂組成物からなる塩化ビニル系繊維であり、前記熱安定剤(ｂ)は錫系熱安定剤、Ｃａ-Ｚｎ系熱安定剤、ハイドロタルサイト系熱安定剤、およびゼオライト系熱安定剤からなる群の内から選択される少なくとも１種を用いることができ、また前記滑剤(ｃ)はカドミウムや鉛を含有しない金属石鹸系滑剤、ポリエチレン系滑剤、高級脂肪酸系滑剤、ペンタエリスリトール系滑剤、高級アルコール系滑剤、およびモンタン酸ワックス系滑剤からなる群の内から選択される少なくとも１種を用いることができる。
【００１０】
また塩化ビニル系樹脂９０〜７５重量％と塩素化塩化ビニル系樹脂１０〜２５重量％からなる塩化ビニル系混合物１００重量部に対して、（ａ）エチレン−酢酸ビニル系樹脂を１〜３５重量部と、（ｂ）メルカプト錫系熱安定剤、マレエート錫系熱安定剤、およびラウレート錫系熱安定剤からなる群の内から選択される少なくとも１種の熱安定剤を０.２〜５.０重量部と、（ｃ）カドミウムや鉛を含有しない金属石鹸系滑剤、ポリエチレン系滑剤、およびペンタエリスリトール系滑剤からなる群の内から選択される少なくとも１種の滑剤を０.２〜５.０重量部とを配合してなる塩化ビニル系樹脂組成物を用いることができ、さらに、塩化ビニル系樹脂１００重量部に対して、（ａ）エチレン−酢酸ビニル系樹脂を１〜３５重量部と、（ｂ）メルカプト錫系熱安定剤、マレエート錫系熱安定剤、およびラウレート錫系熱安定剤からなる群の内から選択される少なくとも１種の熱安定剤を０.２〜５.０重量部と、（ｃ）カドミウムや鉛を含有しない金属石鹸系滑剤、ポリエチレン系滑剤、およびペンタエリスリトール系滑剤からなる群の内から選択される少なくとも１種の滑剤を０.２〜５.０重量部とを配合してなる塩化ビニル系樹脂組成物を用いることもできる。
本発明にかかる塩化ビニル系樹脂は塩化ビニル単独樹脂、エチレン-塩化ビニル共重合樹脂、および酢酸ビニル−塩化ビニル共重合樹脂からなる群の内から選択される少なくとも１種の樹脂であり、かつ塩素化塩化ビニル系樹脂は、重合度３５０〜１１００の原料塩化ビニル樹脂を用いて、塩素含有量６０〜７０重量％にしたものを用いることが好ましい。
【００１１】
一方、本発明の製造方法は、塩化ビニル系樹脂１００〜６０重量％と塩素化塩化ビニル系樹脂０〜４０重量％からなる塩化ビニル系混合物１００重量部に対して、（ａ）エチレン−酢酸ビニル系樹脂を１〜３５重量部と、（ｂ）熱安定剤０.２〜５.０重量部と、（ｃ）滑剤０.２〜５.０重量部とを配合してなる塩化ビニル系樹脂組成物を溶融紡糸して塩化ビニル系繊維とするものである。
【００１２】
前記熱安定剤(ｂ)は錫系熱安定剤、Ｃａ-Ｚｎ系熱安定剤、ハイドロタルサイト系熱安定剤、およびゼオライト系熱安定剤からなる群の内から選択される少なくとも１種を用いることができ、また、前記滑剤(ｃ)はカドミウムや鉛を含有しない金属石鹸系滑剤、ポリエチレン系滑剤、高級脂肪酸系滑剤、ペンタエリスリトール系滑剤、高級アルコール系滑剤、およびモンタン酸ワックス系滑剤からなる群の内から選択される少なくとも１種を用いることができる。
【００１３】
また塩化ビニル系樹脂９０〜７５重量％と塩素化塩化ビニル系樹脂１０〜２５重量％からなる塩化ビニル系混合物１００重量部に対して、（ａ）エチレン−酢酸ビニル系樹脂を１〜３５重量部と（ｂ）メルカプト錫系熱安定剤、マレエート錫系熱安定剤、およびラウレート錫系熱安定剤からなる群の内から選択される少なくとも１種の熱安定剤を０.２〜５.０重量部と、（ｃ）カドミウムや鉛を含有しない金属石鹸系滑剤、ポリエチレン系滑剤、およびペンタエリスリトール系滑剤からなる群の内から選択される少なくとも１種の滑剤を０.２〜５.０重量部とを配合してなる塩化ビニル系樹脂組成物を溶融紡糸して塩化ビニル系繊維とすることができ、さらに、塩化ビニル系樹脂１００重量部に対して、（ａ）エチレン−酢酸ビニル系樹脂を１〜３５重量部と、（ｂ）メルカプト錫系熱安定剤、マレエート錫系熱安定剤、およびラウレート錫系熱安定剤からなる群の内から選択される少なくとも１種の熱安定剤を０.２〜５.０重量部と、（ｃ）カドミウムや鉛を含有しない金属石鹸系滑剤、ポリエチレン系滑剤、およびペンタエリスリトール系滑剤からなる群の内から選択される少なくとも１種の滑剤を０.２〜５.０重量部を配合してなる塩化ビニル系樹脂組成物を溶融紡糸して塩化ビニル系繊維とすることもできる。
【００１４】
本発明の製造方法は、本発明の塩化ビニル系樹脂組成物を溶融紡糸するに際し、１ケのノズル孔の断面積が０．５ｍｍ2以下のノズル孔から溶融・流出せしめることができる。
また、前記溶融紡糸するに際し、１ケのノズル孔の断面積が０.５ｍｍ2以下のノズル孔から溶融・流出せしめ、３００デニール以下の未延伸糸を製造し、次いで、この未延伸糸に延伸処理、熱処理を施して、１００デニール以下の繊維とすることもできる。
【００１５】
さらに、本発明の塩化ビニル系樹脂組成物をノズル圧力５００Ｋｇ/ｃｍ2以下、樹脂温度１９５℃以下で、ノズル孔から溶融・流出せしめると同時に、紡糸ドラフト比を２５以下の条件下で、未延伸糸を引取る方法も用いることができ、溶融紡糸のダイ先端部に使用するノズルに存在するノズル孔が、５０〜３００ケであり、該ノズル孔が、円状、楕円状、長方形状、または正方形状に配列され、隣接するノズル孔の中心間（異形断面形状にあっては、該断面の重心間）の距離が、少なくとも、０.８ｍｍ以上となる様に配列されているノズルを用いることもできる。
【００１６】
【発明の実施の形態】
本発明に使用する塩化ビニル系樹脂とは、従来公知の塩化ビニルの単独重合物であるホモポリマー樹脂、または従来公知の各種の共重合樹脂であり、特に限定されるものではない。該共重合樹脂としては、従来公知の共重合樹脂を使用でき、塩化ビニル−酢酸ビニル共重合樹脂、塩化ビニル−プロピオン酸ビニル共重合樹脂などの塩化ビニルとビニルエステル類との共重合樹脂、塩化ビニル−アクリル酸ブチル共重合樹脂、塩化ビニル−アクリル酸２エチルヘキシル共重合樹脂などの塩化ビニルとアクリル酸エステル類との共重合樹脂、塩化ビニル−エチレン共重合樹脂、塩化ビニル−プロピレン共重合樹脂などの塩化ビニルとオレフィン類との共重合樹脂、塩化ビニル−アクリロニトル共重合樹脂などが代表的に例示される。特に好ましくは、塩化ビニル単独樹脂、エチレン−塩化ビニル共重合樹脂、酢酸ビニル−塩化ビニル共重合樹脂などを使用するのが良い。該共重合樹脂に於いて、コモノマーの含有量は特に限定されず、成形加工性、糸特性などの要求品質に応じて決めることができる。特に好ましくは、コモノマーの含有量は、２〜３０％である。
【００１７】
本発明に使用する塩化ビニル系樹脂の粘度平均重合度は、４５０〜１８００であることが望ましい。４５０未満であると、繊維の特性、特に熱収縮率、カール保持性、艶状態などが劣る傾向があり好ましくない。逆に、１８００を越えると、溶融粘度が高くなる為、ノズル圧力が高くなり、安全な製造が困難になる。
これら成形加工性と繊維特性とのバランスから、塩化ビニル単独樹脂を使用する場合は、粘度平均重合度が６５０〜１４５０の領域が特に好ましく、共重合樹脂を使用する場合は、コモノマーの含有量にも依存するが、粘度平均重合度は、１０００〜１７００の領域が特に好ましい。
【００１８】
また本発明に使用する塩化ビニル系樹脂は、乳化重合、塊状重合または懸濁重合などによって製造したものを使用できるが、繊維の初期着色性などを勘案して、懸濁重合によって製造したものを使用するのが好ましい。
本発明に使用する塩素化塩化ビニル系樹脂とは、塩化ビニル系樹脂を原料とし、これに塩素を付加反応せしめ、塩素含有量を５８〜７２重量％、好ましくは６０〜７０重量％に高めたものを使用するのが好ましいが、主たる目的として、繊維の熱収縮率を低下せしめる為に使用することができる。また該塩素化塩化ビニル系樹脂は、粘度平均重合度（原料塩化ビニル系樹脂の粘度平均重合度）が３００〜１１００であることが好ましい。該粘度平均重合度が３００未満であると、繊維の熱収縮率を低下せしめる効果が小さくなるので収縮率のやや高い繊維となる。逆に、該粘度平均重合度が１１００を越えると、溶融粘度が高くなり、紡糸時のノズル圧力が高くなるため、安全操業が困難になるばかりでなく、溶融紡糸時の糸の破断（糸切れ）の頻度が著しくなり、安定操業が困難になる傾向がある。より好ましくは、粘度平均重合度は、３５０〜１１００のものが良く、特には５００〜９００のものが良い。また、前記塩素含有量については、５８重量％未満であると繊維の熱収縮率を低下せしめる効果が小さくなり、逆に７２重量％を越えると、溶融粘度が高くなって安定操業が困難となる傾向があり好ましくない。
【００１９】
該塩素化塩化ビニル系樹脂の原料となる塩化ビニル系樹脂は、前述の塩化ビニル系樹脂と同様であるが、塩化ビニル単独樹脂またはエチレン−塩化ビニル共重合樹脂を原料として使用している場合が、特に好ましい。
本発明に於いては、塩化ビニル系樹脂と塩素化塩化ビニル系樹脂の使用比率は、（塩化ビニル／塩素化塩化ビニル）＝（１００〜６０重量％／０〜４０重量％）の塩化ビニル系混合物とすることが好ましい。前記塩化ビニルが６０重量％未満であると塩素化塩化ビニル系樹脂が過剰となるため、溶融粘度が高くなり、溶融紡糸時のノズル圧力が高くなって、安全操業が困難になる傾向があり好ましくない。尚、塩化ビニル系樹脂の比率が高い場合には、熱収縮率の高い繊維になる傾向があり、目的に応じて、使用比率は適宜調整して用いることができる。
【００２０】
本発明に於いては、主たる目的として、繊維の柔軟性を高め、柔らかで、しなやかで、かつ、サラサラとした触感の繊維とする為に、塩化ビニル系混合物１００重量部に対して、エチレン−酢酸ビニル系樹脂（以下、ＥＶＡ系樹脂と略記する。）を１〜３５重量部添加配合して使用するのが好ましく、触感などの点においては３〜３５重量部がさらに好ましい。また該樹脂は、副次的には、該組成物のゲル化・溶融性を調節し、均一で適度な溶融状態を醸し出し、適度なノズル圧力を可能とする効果がある。
【００２１】
前記ＥＶＡ系樹脂の使用量が１重量部未満となると、繊維柔軟性改良効果が希薄になるばかりでなく、ゲル化・溶融性調節機能が低下し、ノズル圧力が上昇したりする傾向がある。逆に３５重量部を越えると、組成物のゲル化・溶融性調節機能が低下し、不均一なゲル化・溶融状態になるため、未延伸糸内に「ブツ」状物（未溶融粒子、または、剪断応力によって崩壊しなかった粒子）が多くなって溶融紡糸時あるいは延伸・熱処理時の糸切れ頻度が多くなる傾向があり好ましくない。
【００２２】
本発明でいうＥＶＡ系樹脂とは、従来公知の酢酸ビニル含有量が２０〜６５重量％のエチレン−酢酸ビニル共重合樹脂、さらに極性基としてカルボニル基を導入してなるエチレン−酢酸ビニル系共重合樹脂からなるＥＶＡ樹脂またはこれらのＥＶＡ樹脂に塩化ビニルをグラフト重合してなるＥＶＡ−塩化ビニルグラフトポリマー樹脂を意味する。ＥＶＡ−塩化ビニルグラフトポリマー樹脂は、水性媒体中で塩化ビニルを懸濁重合または乳化重合する際、ＥＶＡ樹脂を重合系に添加して重合を進めることによって容易に得られる。該樹脂は、溶媒による分別により、ＥＶＡ樹脂成分、ポリ塩化ビニル樹脂成分、およびＥＶＡ樹脂成分に塩化ビニルが化学的に結合してなるＥＶＡ−塩化ビニルグラフトポリマー成分の混合物である。
【００２３】
本発明に使用するＥＶＡ樹脂の酢酸ビニル含有量は、２０〜６５重量％のものを使用するのが好ましい。酢酸ビニル含有量が２０重量％未満あるいは６５重量％を越えると組成物系との相溶性が低下し、組成物のゲル化・溶融性調節機能が低下し、不均一なゲル化・溶融状態になり、未延伸糸内に「ブツ」状物が多くなって、溶融紡糸時あるいは延伸・熱処理時の糸切れ頻度が多くなる傾向があり好ましくない。また、酢酸ビニル含有量が２０重量％未満であると、繊維柔軟性改良効果が不十分となり、逆に、酢酸ビニル含有量が６５重量％を越えると、均一混合しなかった組成物中のＥＶＡ樹脂成分が溶融紡糸時に溶解し、 加熱筒あるいはノズル先端部からメルトダウンして、未延伸糸を得ることが困難となるなどの問題がある。
【００２４】
また、該樹脂の分子量の目安となるメルトインデックス(ＭＩ：ｇｒ／１０分）は、１〜２６０程度の範囲が望ましい。該メルトインデックスが１未満であるとＥＶＡ樹脂成分の溶融粘度が高くなり、溶融紡糸時のノズル圧力が高くなる傾向がある。また逆にメルトインデックスが２６０を越えると、該樹脂の粘度が低下し、塩化ビニル系混合物成分の溶融が不十分となり、均一溶融が不十分となって未延伸糸内に「ブツ」状として残存し易くなるため、紡糸時の糸切れ頻度が多くなりやすく好ましくない。
【００２５】
本発明に使用できるＥＶＡ−塩化ビニルグラフトポリマー樹脂は、ＥＶＡ成分含有量が３〜４５重量％の範囲のものが特に好ましい。該含有量が３重量％未満であると、繊維柔軟性改良効果が不十分となり、逆に４５重量％を越えると、組成物のゲル化・溶融性調節機能が低下し、不均一なゲル化・溶融状態になるため、未延伸糸内に「ブツ」状物が多くなって、溶融紡糸時あるいは延伸・熱処理時の糸切れ頻度が多くなる傾向がある。
【００２６】
本発明に使用する熱安定剤は従来公知のものが使用できるが、中でも錫系熱安定剤、Ｃａ-Ｚｎ系熱安定剤、ハイドロタルサイト系熱安定剤、ゼオライト系熱安定剤から選択される１種または２種以上の熱安定剤を０.２〜５.０重量部使用するのが好ましい。該熱安定剤は、成形時の熱分解、ロングラン性、繊維の色調を改良する為に使用するもので、特に好ましくは、紡糸時のノズル周囲に発生するスケール（以下、ノズル目脂と略記する。）発生量の比較的少ない錫系熱安定剤が良く、中でもメルカプト錫系熱安定剤、マレエート錫系熱安定剤、ラウレート錫系熱安定剤から１種または２種以上を使用するのが良い。例えば、ジメチルスズメルカプト、ジブチルスズメルカプト、ジオクチルスズメルカプトなどのメルカプト錫系熱安定剤、ジメチルスズマレエート、ジブチルスズマレエート、ジオクチルスズマレエート、ジオクチルスズマレエートポリマーなどのマレエート錫系熱安定剤、ジメチルスズラウレート、ジブチルスズラウレート、ジオクチルスズラウレートなどのラウレート錫系熱安定剤が例示される。
【００２７】
繊維の初期着色を抑制し、顔料を含まないナチュラル組成物の白色度を高める為には、メルカプト錫系熱安定剤を塩化ビニル系混合物１００重量部に対して、少なくとも０.１〜１.４重量部使用し、他の熱安定剤と併用して合計が、塩化ビニル系混合物１００重量部に対して、０.２〜５.０重量部の範囲とするのが特に好ましい。該熱安定剤の使用量は、０.２〜５.０重量部であるが、０.２重量部未満となると、成形時の熱分解防止効果が低下する傾向がある。逆に、５.０重量部を越えると、紡糸時のノズル目脂発生が多くなり、紡糸時の流出変動発生が大となりやすく、好ましくない。
【００２８】
本発明に使用する滑剤は、カドミウムや鉛を含有しない従来公知のものを用いることができるが、特に金属石鹸系滑剤、ポリエチレン系滑剤、高級脂肪酸系滑剤、ペンタエリスリトール系滑剤、高級アルコール系滑剤、モンタン酸ワックス系滑剤から選択される１種または２種以上を塩化ビニル系混合物１００重量部に対して、０.２〜５.０重量部使用するのが好ましい。該滑剤は、組成物の溶融状態、ならびに組成物と金属面との接着状態を制御する為に使用するもので、繊維の表面状態、触感、糸切れ頻度、ノズル目脂発生頻度、ノズル圧力などに大きく影響する。
【００２９】
比較的サラサラとした触感を得る為には、金属石鹸系滑剤を使用するのが好ましい。また特に、衛生上の観点から、カドミウム、鉛以外の金属石鹸が良い。例えば、Ｎａ，Ｍｇ，Ａｌ，Ｃａ，Ｂａなどのステアレート、ラウレート、パルミテート、オレエートなどの金属石鹸が例示される。また、ノズル目脂発生頻度を低減し、ノズル圧力を低く抑える為には、ポリエチレン系滑剤を使用するのが好ましく、従来公知のポリエチレン系滑剤を使用できるが、特に好ましくは、平均分子量が１５００〜４０００であり、密度が０.９１〜０.９７の非酸化タイプまたはごくわずかに極性を附加したタイプのポリエチレン系滑剤が特に好ましい。該ポリエチレン系滑剤は０.２〜１.３重量部の範囲で使用するのが特に好ましい。
【００３０】
本発明に於いては、高級脂肪酸系滑剤、ペンタエリスリトール系滑剤、高級アルコール系滑剤、モンタン酸ワックス系滑剤は、主として組成物の溶融状態を制御する為に使用するのが好ましい。高級脂肪酸系滑剤としては、例えば、ステアリン酸、パルミチン酸、ミリスチン酸、ラウリン酸、カプリン酸などの飽和脂肪酸、オレイン酸などの不飽和脂肪酸、またはこれらの混合物などが例示される。ペンタエリスリトール系滑剤としては、ペンタエリスリトールまたはジペンタエリスリトールと高級脂肪酸とのモノエステル、ジエステル、トリエステル、テトラエステル、またはこれらの混合物などが例示される。高級アルコール系滑剤としては、ステアリルアルコール、パルミチルアルコール、ミリスチルアルコール、ラウリルアルコール、オレイルアルコールなどが例示される。さらに、モンタン酸ワックス系滑剤としては、モンタン酸とステアリルアルコール、パルミチルアルコール、ミリスチルアルコール、ラウリルアルコール、オレイルアルコールなどの高級アルコールとのエステル類が例示される。
【００３１】
該滑剤系の特に好ましい使用量の領域は、塩化ビニル系混合物１００重量部に対して、カドミウムや鉛を含有しない金属石鹸系滑剤であれば０.５〜３.０重量部、ポリエチレン系滑剤であれば０.２〜１.８重量部、ペンタエリスリトール系滑剤であれば０.２〜１.０重量部併用するのが特に好ましい。
本発明に於ける塩化ビニル系樹脂組成物は、塩化ビニル系樹脂１００〜６０重量％と塩素化塩化ビニル系樹脂０〜４０重量％からなる塩化ビニル系混合物１００重量部に対して、（ａ）ＥＶＡ系樹脂を１〜３５重量部と（ｂ）熱安定剤０.２〜５.０重量部と（ｃ）滑剤０.２〜５.０重量部を配合してなるものの他、塩化ビニル系樹脂９０〜７５重量％と塩素化塩化ビニル系樹脂１０〜２５重量％からなる塩化ビニル系混合物１００重量部に対して、（ａ）ＥＶＡ系樹脂を１〜３５重量部と（ｂ）メルカプト錫系熱安定剤、マレエート錫系熱安定剤、ラウレート錫系熱安定剤から選択される１種または２種以上の熱安定剤を０.２〜５.０重量部、と（ｃ）カドミウム、鉛を含有しない金属石鹸系滑剤、ポリエチレン系滑剤、ペンタエリスリトール系滑剤から選択される１種または２種以上の滑剤を０.２〜５.０重量部を配合してなる塩化ビニル系樹脂組成物を用いることができる。
【００３２】
前記樹脂組成物は、糸切れの発生が少なく、安定した製造ができ、品質とのバランスがとれる点で好ましい。
また、塩化ビニル系樹脂１００重量部に対して、（ａ）ＥＶＡ系樹脂を１〜３５重量部と（ｂ）メルカプト錫系熱安定剤、マレエート錫系熱安定剤、ラウレート錫系熱安定剤から選択 される１種または２種以上の熱安定剤を０.２〜５.０重量部と（ｃ）カドミウム、鉛を含有しない金属石鹸系滑剤、ポリエチレン系滑剤、ペンタエリスリトール系滑剤から選択される１種または２種以上の滑剤を０.２〜５.０重量部を配合してなる塩化ビニル系樹脂組成物も用いることができる。
【００３３】
前記樹脂組成物は、繊維の熱収縮率がやや高くなる傾向にあるが、製造は、より安定する利点があり、収縮率が高いものを好む用途には好ましい。
本発明に於いては、目的に応じて、塩化ビニル系組成物に使用される公知の配合剤、例えば、加工助剤、強化剤、紫外線吸収剤、酸化防止剤、可塑剤、帯電防止剤、充填剤、難燃剤、顔料などを使用することができる。また、場合によっては、発泡剤、架橋剤、粘着性付与剤、親水性付与剤、導電性付与剤、香料など特殊な配合剤を適宜使用することも可能である。
【００３４】
前記加工助剤としては、例えば、メチルメタクリレートを主成分とするアクリル系加工助剤、または熱可塑性ポリエステルを主成分とするポリエステル系加工助剤などが挙げられる。該加工助剤の使用量としては、塩化ビニル系混合物１００重量部に対して、０.２〜１２重量部程度が好ましい。また、これらの加工助剤は単独でも使用できるし、２種以上を併用しても良い。
【００３５】
本発明に使用する充填剤としては、例えば炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、酸化アルミニウム、水酸化マグネシウム、水酸化アルミニウム、タルク、マイカ、クレーなどが挙げられる。該充填剤の使用量としては、塩化ビニル系混合物１００重量部に対して、０.２〜５.０重量部程度が好ましい。また、これらの充填剤は単独でも使用できるし、２種以上を併用しても良い。
【００３６】
本発明に使用する可塑剤としては、例えば、ジブチルフタレート、ジ-２-エチルヘキシルフタレート、ジイソノニルフタレートなどのフタル酸系可塑剤、オクチルトリメリテートなどのトリメリット酸系可塑剤、オクチルピロメリテートなどのピロメリット酸系可塑剤、ポリエステル系可塑剤、エポキシ系可塑剤などを使用できる。該可塑剤の使用量としては、塩化ビニル系混合物１００重量部に対して、０.２〜５.０重量部程度が好ましい。また、これらの可塑剤は単独でも使用できるし、２種以上を併用しても良い。
【００３７】
本発明に使用する塩化ビニル系樹脂組成物は、従来公知の混合機、例えばヘンシェルミキサー、スーパーミキサー、リボンブレンダーなどを使用して混合してなるパウダーコンパウンド、またはこれを溶融混合してなるペレットコンパウンドとして使用することができる。該パウダーコンパウンドの製造は、従来公知の通常の条件で製造でき、ホットブレンドでもコールドブレンドでも良い。特に好ましくは、組成物中の揮発分を減少する為に、ブレンド時のカット温度を１０５〜１５５℃迄上げてなるホットブレンドを使用するのが良い。該ペレットコンパウンドは、通常の塩化ビニル系ペレットコンパウンドの製造と同様にして製造できる。例えば、単軸押出機、異方向２軸押出機、コニカル２軸押出機、同方向２軸押出機、コニーダー、プラネタリーギアー押出機、ロール混練り機などの混練り機を使用してペレットコンパウンドとすることができる。該ペレットコンパウンドを製造する際の条件は、特に限定はされないが、樹脂温度を１８５℃以下になる様に設定することが好ましい。また、該ペレットコンパウンド中に混入し得る掃除用具の金属片などの異物を取り除く為に、目開きの細かいステンレスメッシュなどを混練り機内に設置したり、コールドカットの際に混入し得る「切り粉」などを除去する手段を採用したり、ホットカットを行なうなどの方法は自在に可能であるが、特に好ましくは、「切り粉」混入の少ないホットカット法を使用するのが良い。
【００３８】
前記塩化ビニル系樹脂組成物を繊維状の未延伸糸にする際には、従来公知の押出機を使用できる。例えば単軸押出機、異方向２軸押出機、コニカル２軸押出機などを使用できるが、特に好ましくは、口径が３５〜８５ｍｍφ程度の単軸押出機または口径が３５〜５０ｍｍφ程度のコニカル押出機を使用するのが良い。口径が過大になると、押出量が多くなり、ノズル圧力が過大になったり、未延伸糸の流出速度が早過ぎて、巻取りが困難になる傾向があり好ましくない。
【００３９】
本発明に於いては、１ケのノズル孔の断面積が、０.５ｍｍ2以下のノズルをダイ先端部に取り付けて溶融紡糸を行なうのが好ましい。該断面積が、０.５ｍｍ2を越えるノズルを使用すると、未延伸糸の繊度が太くなり、細繊度の繊維を得る為には、延伸処理の際に延伸倍率を大きくをする必要がある。その為、延伸処理を施した後の細繊度の繊維(延伸糸)に光沢が出て、半艶〜七部艶状態を維持することが困難となる。また、繊維の触感がザラザラとしたり、キラキラ感が出たり、あるいはプラスチック的な滑り触感になる傾向があり好まくない。
【００４０】
該ノズルに存在するノズル孔の配列、位置関係は、巻取りの容易さに大きく関係する。特に好ましい配列数は、１〜５列であり、これ以上になるとダイ内の溶融物の流動速度差が大きくなり、流出速度分布が拡がり、未延伸糸の「泳ぎ」が大きくなる傾向があり好ましくない。また、該ノズル孔の配列形状は、円状、楕円状、または４角以上の多角形状であることが望ましい。三角形状であると、ダイ内の溶融物の流動速度差が大きくなり、流出速度分布が拡がり、未延伸糸の「泳ぎ」が大きくなる傾向となり好ましくない。さらに、１ケのノズルに存在するノズル孔の数は、５０〜３００であることが好ましい。ノズル孔の数が少な過ぎると生産性が低下し、逆に多過ぎると、「糸切れ」などのトラブル発生確率が高くなり好ましくない。
本発明に於いては、隣接するノズル孔の中心間（異形断面にあっては、該断面の重心間）の距離が、少なくとも、０.８ｍｍ以上となる様に配置するのが好ましい。該距離が、０.８ｍｍ未満であると溶融紡糸する際、未延伸糸同志の接触頻度が多くなり、糸切れの原因になり好ましくない。また、該距離が長過ぎるとノズルそのものが大きなものとなって重くなったり、ノズルに配置する孔数が少なくなり加工生産性が低下したりして好ましくない。特に好ましい範囲は、０.８〜３.８ｍｍの範囲である。
【００４１】
本発明に於いては、未延伸糸の繊度を３００デニール以下にしておくことが好ましい。該未延伸糸の繊度が３００デニールを越えると、細繊度の繊維を得る為には、延伸処理の際に延伸倍率を大きくをする必要があるので、延伸処理を施した後の細繊度の繊維(延伸糸)に光沢が出て、半艶〜七部艶状態を維持することが困難となる。また、プラスチック的な滑り触感になる傾向がある。また、溶融紡糸の際、ノズル圧力は５００Ｋｇ/ｃｍ2以下で紡糸するのが好ましい。ノズル圧力が５００Ｋｇ/ｃｍ2を越えると、押出機のスラスト部にかかる負荷が過大になり、押出機に不具合を発生し易くなり好ましくない。ノズル圧力は、スクリュー回転数あるいはフィード量を変更して、押出量を制御することでコントロールするのが品質に影響が少なく好ましい。しかしながら、押出量を減少すると生産性が低下する為、このバランスから、４８０〜３００Ｋｇ/ｃｍ2の範囲が特に好ましい。 ノズル圧力を低下するには、金属面との滑り効果の高い滑剤を使用したり、多量の溶融粘度低下剤、例えば、可塑剤、高分子可塑剤などを使用することが可能であるが、この様な手段によって、ノズル圧力を２００Ｋｇ/ｃｍ2以下にすると組成物のゲル化・溶融状態が極めて不均一になり、糸切れ頻度が多くなり、製造が困難になると共に、艶状態、触感などの品質が不十分な繊維となる傾向がある。故に前記した様な押し出し量の制御による圧力コントロールが好ましい。
【００４２】
溶融紡糸の際、ノズル孔から溶融・流出したストランドは、３００デニール以下の未延伸糸に引き伸ばされるが、その際のドラフト比は、２５以下であることが特に好ましい。該ドラフト比が２５を越えると、未延伸糸の時点で表面が過剰に引き伸ばされている為、延伸処理を施した後の細繊度の繊維に光沢が出て、半艶〜七部艶状態を維持することが困難となる傾向がある。また、プラスチック的な滑り触感になる傾向がある。また、樹脂温度は１９５℃以下で紡糸することが好ましい。１９５℃を越えた温度で紡糸すると繊維の着色傾向が顕著となり、黄色味の強い繊維となりやすく好ましくない。その為、シリンダー温度を１５０〜１８５℃程度とし、ダイ温度を１６０〜１９０℃程度とすることが特に好ましい。
【００４３】
以上の様に、本発明に於いては、溶融紡糸の際、１ケのノズル孔の断面積が、０.５ｍｍ2以下のノズルを使用して、かつ、３００デニール以下の未延伸糸を製造するのが好ましい。特に、樹脂温度は１９５℃以下、ドラフト比を２５以下、ノズル圧力を５００Ｋｇ/ｃｍ2以下、ノズル孔数は、５０〜３００とし、ノズル配列形状は、円状、楕円状、または４角以上の多角形状とし、ノズル配列数は１〜５として行なうのが特に優れた方法である。
【００４４】
前記溶融紡糸で得られた未延伸糸に公知の方法で延伸処理・熱処理を施して、１００デニール以下の細繊度の繊維（延伸糸）とすることができる。頭髪装飾用の繊維としては、２５〜１００デニールの範囲が特に好ましく、また、人形用頭髪の繊維としては、１０〜６５デニールの範囲が特に好ましい。
延伸処理条件としては、延伸処理温度７０〜１５０℃の雰囲気下で、延伸倍率は、２００〜４５０％程度延伸することが特に好ましい。延伸処理温度が７０℃未満であると繊維の強度が低くなると共に、糸切れを発生し易く、逆に１５０℃を越えると繊維の触感がプラスチック的な滑り触感になり好ましくない。また、延伸倍率が２００％未満であると繊維の強度発現が不十分となり、４５０％を越えると延伸処理時に、糸切れを発生し易く好ましくない。
【００４５】
さらに、延伸処理を施した繊維に熱処理を施して、２〜７５％の緩和率で繊維を緩和処理することにより、熱収縮率を低下させることができる。また、繊維表面の凹凸を整えて、人毛に類似した触感、半艶〜七部艶表面とする為にも該緩和処理が好ましい。該緩和率の範囲を外れると人工毛髪用繊維として、あるいは人形用頭髪繊維として、品質が低下する傾向があり好ましくない。該熱処理は、延伸処理と連動して実施することもできるし、切り離して実施することもできるが、条件としては、雰囲気温度８０〜１５０℃で実施することが特に好ましい。また本発明に於いては、従来公知の溶融紡糸に関わる技術、例えば、各種ノズル断面形状に関わる技術、加熱筒に関わる技術、延伸処理に関わる技術、熱処理に関わる技術などは、自在に組み合わせて使用することが可能である。
【００４６】
【実施例】
次に、実施例をあげて、本発明の詳細な態様を明らかにするが、本発明はこれらの実施例のみに限定されるものではない。
尚、表中の組成物表示等は、次のように略記する。
塩化ビニル樹脂：「ＰＶＣ」、塩素化塩化ビニル系樹脂：「ＣＰＶＣ」、酢酸ビニル：「ＶＡｃ」、粘度平均重合度：「Ｍ」、メルトインデックス：「ＭＩ」。また表２、４〜６、８〜９における、組成物での配合剤の数値は、ＰＶＣとＣＰＶＣの合計＝１００重量部に対する各配合剤の重量部を表すものである。
【００４７】
[実験１〜５(ＰＶＣ/ＣＰＶＣの配合比率)]
塩化ビニル系混合物１００重量部が４Ｋｇになる様に計量し、次いで、表２に示す配合剤をそれぞれ計量して、２０Ｌのヘンシェルミキサーに投入し、撹拌しながら、内容物の温度が１１５℃になる迄、撹拌・混合した。その後、冷却水をヘンシェルミキサーのジャケットに流しながら撹拌・混合を続け、内容物の温度が７５℃になる迄、冷却して、塩化ビニル系パウダーコンパウンドを得た。該パウダーコンパウンドを表１（紡糸条件１）に示す条件にて、溶融紡糸・延伸・熱処理実験に供した。
【００４８】
【表１】
溶融紡糸実験は、定常状態になってから、スクリュー回転数と押出量の関係を求め、押出量が７.０Ｋｇ/Ｈｒｓになる様にスクリュー回転数を決定した。ノズル圧力、樹脂温度は、 ダイ圧計、樹脂温度センサーをそれぞれノズル部に設置して測定した。
鉛直方向に、ノズルから溶融・流出したストランドを加熱紡糸筒に導入し、ここで該ストランドを瞬間的に加熱溶解し、ノズル直下約３ｍの位置に設置した引取機にて、未延伸糸を一定速度で巻き取った。この際、該未延伸糸の繊度が約１６５〜１８５デニールになる様に引取速度を調節した。この未延伸糸を製造する段階で、糸切れの発生状況を目視観察し、次の様に評価した。
【００５０】
[溶融紡糸時の糸切れ発生状況]
◎：全く糸切れが発生しない。
○：１時間に３回以内発生する。
△：１時間に４〜１５回発生する。
また、この未延伸糸の着色状態を目視観察にて、次の様に評価した。
【００５１】
[未延伸糸の着色状態]
◎：乳白色で黄色味がない。
○：乳白色であるが、わずかに黄色味がある。
△：かなり強い黄色味がある。
該未延伸糸を延伸・熱処理機に導入し、延伸処理、次いで、熱緩和処理を行い、延伸糸を製造した。この際、熱緩和処理は、２５％緩和に固定し、延伸処理は、最終の延伸糸の繊度が、６５〜６８デニールになる様に延伸倍率を若干調整した。この延伸・熱処理時に発生する糸切れの発生状況を目視観察し、次の様に評価した。
【００５２】
[延伸・熱処理時の糸切れ発生状況]
◎：全く糸切れが発生しない。
○：１時間に３回以内発生する。
△：１時間に４〜１５回発生する。
また、この延伸糸の表面艶・光沢を目視観察し、次の様に評価した。
【００５３】
[延伸糸の艶状態]
◎(半艶状態)：表面が平滑で、わずかに鈍い光沢がある。
○(七部艶状態)：表面が平滑で、鈍い光沢がある。
●(完全艶消状態)：表面がザラザラで、光沢がない。
△(八分艶状態)：表面がザラザラで、局部的に光沢があり、キラキラ感がある。
×(艶有状態)：表面が平滑で、全面的に光沢があり、輝き感がある。
さらに、この延伸糸を手で触り、その手触り触感を、次の様に評価した。
【００５４】
[延伸糸の触感]
◎：表面が平滑で、サラサラとした触感がある。
○：表面が平滑で、かすかに湿った触感があるが、サラサラ感がある。
△(ザラザラ感)：表面がザラザラで、ザラザラとした触感がある。
●(プラスチック感)：表面が平滑で、プラスチック的触感があり、滑り触感がある。
またさらに、この延伸糸を指に数回巻き付け、その際の反発力、触感、柔軟性を、次の様に評価した。
【００５５】
[延伸糸のしなやかさ]
◎：指にやわらかく、しなやかに巻き取ることができる。
○：かすかに反発触感があるが、しなやかに巻き取ることができる。
△：全体的に硬い感触で、かなり強い反発触感がある。
該延伸糸を引張試験、熱収縮試験に供し、強度および熱収縮率を求めた。尚、延伸糸の熱収縮率の測定は、１００℃の雰囲気温度で、２５分熱収縮させ、計算は、次の様に行なった。
（熱処理前の延伸糸長−熱処理後の延伸糸長）/熱処理前の延伸糸長さ×１００＝熱収縮率(％)
これらの評価結果を表２に示す。
【００５６】
【表２】
実験１〜５の比較から判る様に、塩素化塩化ビニル樹脂の配合比率が、４０重量％を越えるとノズル圧力が５００Ｋｇ/ｃｍ2以上になり、押出機の設計圧力を超える状態になり、安全な生産が困難となる。また、スクリュー回転数を低下すると、押出量が低下し、生産性が低下する傾向にある。また、塩素化塩化ビニル樹脂の配合比率が、４０重量％を越えると、溶融紡糸時の糸切れが頻繁に発生したり、未延伸糸の着色状態がやや黄色味を呈してくる傾向があり、さらに、延伸糸の艶も消え過ぎになり、触感もザラザラとした触感になり、かつ、繊維のしなやかさが劣る傾向となる。これらの実験から、塩化ビニル系樹脂と塩素化塩化ビニル系樹脂の配合比率は、前者が１００〜６０重量％で、後者が０〜４０重量％の範囲が最適であることが判る。
【００５８】
[実験６〜１１(ＥＶＡ系樹脂の添加効果)]
実験１〜５と同様、塩化ビニル系混合物１００重量部が４Ｋｇになる様に計量し、次いで、ＥＶＡ系樹脂の添加量を変更して、表４に示す配合剤をそれぞれ計量して、２０Ｌのヘンシェルミキサーに投入し、撹拌しながら、内容物の温度が１３５℃になる迄、撹拌・混合した。その後、冷却水をヘンシェルミキサーのジャケットに流しながら撹拌・混合を続け、内容物の温度が７０℃になる迄、冷却して、塩化ビニル系パウダーコンパウンドを得た。該パウダーコンパウンドを表３（紡糸条件２）に示した紡糸条件,延伸条件,熱緩和処理条件にて、溶融紡糸・延伸・熱処理実験に供した。
【００５９】
【表３】
溶融紡糸実験は、定常状態になってから、フィード量、スクリュー回転数と押出量の関係を求め、押出量が７.０Ｋｇ/Ｈｒｓになる様に、フィード量、スクリュー回転数を決定した。ノズル圧力、樹脂温度は、ダイ圧計、樹脂温度センサーをノズル部に設置して測定した。
鉛直方向に、ノズルから溶融・流出したストランドを加熱紡糸筒に導入し、ここで該ストランドを瞬間的に加熱溶解し、ノズル直下、約３ｍの位置に設置した引取機にて、未延伸糸を一定速度で巻き取った。この際、該未延伸糸の繊度が約１５４〜１７６デニールになる様に引取速度を調節した。また、その他の紡糸条件などは、実験１〜５に示した方法と同様に行い、評価方法なども実験１〜５に示した方法と全く同様に行なった。これらの評価結果を表４に示す。
【００６１】
【表４】
実験６〜１１の比較から判る様に、ＥＶＡ系樹脂の添加量が１重量部未満になると、延伸糸のしなやかさが不足し、ゴワゴワとした触感の繊維となる。また、熱収縮率もやや高くなる傾向がある。また、 ＥＶＡ系樹脂の添加量が３５重量部を越えると、組成の不均一化(ＣＰＶＣ成分の溶融が不均一となる)が起こり、溶融紡糸時あるいは延伸処理時の糸切れが頻繁になる。さらに、ノズル圧力も高くなる傾向があり、繊維の触感もザラザラとした触感になる。これらの実験から、ＥＶＡ系樹脂の添加量は、塩化ビニル系混合物１００重量部に対して、１〜３５重量部の範囲が最適であり、触感などの点では３〜３５重量部の範囲がさらに好ましいことが判る。
【００６３】
[実験１２〜１６(熱安定剤の添加・併用効果)]
実験１〜５と同様、塩化ビニル系混合物１００重量部が４Ｋｇになる様に計量し、次いで、熱安定剤の種類・添加量を変更して、表５に示す配合剤をそれぞれ計量して、２０Ｌのヘンシェルミキサーに投入し、撹拌しながら、内容物の温度が１３５℃になる迄、撹拌・混合した。その後、冷却水をヘンシェルミキサーのジャケットに流しながら撹拌・混合を続け、内容物の温度が７５℃になる迄、冷却して、塩化ビニル系パウダーコンパウンドを得た。尚、ＥＶＡ系樹脂は、酢酸ビニル含有量２５重量％、メルトインデックス５のＥＶＡ樹脂に塩化ビニルをグラフト重合し、ＥＶＡ含量を４０％に調節したＥＶＡ-塩化ビニルグラフト樹脂を使用した。該パウダーコンパウンドを実験６〜１１に示した紡糸条件、延伸条件,熱緩和処理条件と同様の条件にて、溶融紡糸・延伸・熱処理実験に供した。また、実験６〜１１に示した試験方法、評価方法にて、未延伸糸、延伸糸の評価を全く同様に行なった。これらの評価結果を表５に示す。
【００６４】
【表５】
実験１２〜１６の比較から判る様に、熱安定剤の添加量が適量であれば、未延伸糸の初期着色も良好であるが、ブチル錫マレエートを過剰に使用すると、繊維の熱収縮率が極端に高くなり、品質の不十分な繊維となる。また、ゼオライトの様な無機粉末状の熱安定剤を過剰に使用すると、ゴワゴワとした触感の繊維となるばかりでなく、糸切れが著しくなり、繊維の強度も低下する。これらの実験から、熱安定剤の添加量は、塩化ビニル系混合物１００重量部に対して、０.２〜５.０重量部の範囲が最適であることが判る。
【００６６】
[実験１７〜２１(ノズル断面積の効果)]
実験１〜５と同様、塩化ビニル系混合物１００重量部が４Ｋｇになる様に計量し、次いで、表６に示す配合剤をそれぞれ計量して、２０Ｌのヘンシェルミキサーに投入し、撹拌しながら、内容物の温度が１２５℃になる迄、撹拌・混合した。その後、冷却水をヘンシェルミキサーのジャケットに流しながら撹拌・混合を続け、内容物の温度が７５℃になる迄、冷却して、塩化ビニル系パウダーコンパウンドを得た。尚、ＥＶＡ系樹脂は、酢酸ビニル含有量６５重量％、メルトインデックス１５のＥＶＡ樹脂に塩化ビニルをグラフト重合し、ＥＶＡ含量を２５％に調節したＥＶＡ-塩化ビニルグラフト樹脂を使用した。該パウダーコンパウンドを実験１〜５に示した紡糸条件、延伸条件,熱緩和処理条件と同様の条件にて、溶融紡糸・延伸・熱処理実験に供した。この際、表６に示したノズル孔断面積および孔数のノズルに変更して紡糸実験を行なった。また、押出量は、７.８Ｋｇ/Ｈｒｓとし、これに合わせて、引取速度、延伸倍率を調節した。さらに、実験１〜５に示した試験方法、評価方法にて、未延伸糸、延伸糸の評価を全く同様に行なった。評価結果を表６に示す。
【００６７】
【表６】
実験１７〜２１の比較から判る様に、１ケのノズル孔の断面積が０.５ｍｍ2以下であれば、紡糸する際の各種性能、延伸処理・加熱処理時の性能、繊維の性能が高度にバランスされた状態になる。一方、１ケのノズル孔の断面積が０.５ｍｍ2を越えると、延伸糸の艶が出てきて、キラキラした目視感になり、触感もプラスチック的な滑り触感になり、品質的に不十分な繊維となる。また、１ケのノズル孔の断面積が大きくなると、溶融紡糸時のドラフト比が高くなり、延伸時の糸切れ頻度が増加するし、繊維の熱収縮率が高くなる傾向がある。
【００６９】
[実験２２〜２６(未延伸糸の繊度の効果)]
実験１〜５と同様、塩化ビニル系混合物１００重量部が４Ｋｇになる様に計量し、次いで、表８に示す配合剤をそれぞれ計量して、２０Ｌのヘンシェルミキサーに投入し、撹拌しながら、内容物の温度が１３５℃になる迄、撹拌・混合した。その後、冷却水をヘンシェルミキサーのジャケットに流しながら撹拌・混合を続け、内容物の温度が７５℃になる迄、冷却して、塩化ビニル系パウダーコンパウンドを得た。尚、ＥＶＡ系樹脂は、酢酸ビニル含有量３５重量％、メルトインデックス１０のＥＶＡ樹脂に塩化ビニルをグラフト重合し、ＥＶＡ含量を３５％に調節したＥＶＡ-ＶＣＬグラフト樹脂を使用した。該パウダーコンパウンドを表７に示す（ペレット化条件）にて、ペレットコンパウンドとした後、溶融紡糸実験に供した。
【００７０】
【表７】
該ペレットコンパウンドを実験１〜５に示した紡糸条件,延伸条件,熱緩和処理条件と同様の条件にて、溶融紡糸・延伸・熱処理実験に供した。この際、引取速度を変更して、未延伸糸の繊度が表８になる様に設定した。また、実験１〜５に示した試験方法、評価方法にて、未延伸糸、延伸糸の評価を全く同様に行なった。評価結果を表８に示す。
【００７２】
【表８】
実験２２〜２６の比較から判る様に、未延伸糸の繊度が３００デニールを越えると、６５〜７０デニールの延伸糸を得る為には、延伸処理に於いて、過剰に延伸する必要がある。その為、延伸処理を施す際、糸切れ頻度が多くなるばかりでなく、延伸糸の触感が、プラスチック的な滑り触感になり、艶がでてきて品質的に不十分な繊維となる。一方、未延伸糸の繊度が３００デニール以下であれば、これらの品質が高度にバランスされ、人毛に極めて類似した人工毛髪用繊維として優れたものを得ることができる。
【００７４】
[実験２７〜３１(延伸糸の繊度の効果)]
塩化ビニル系混合物１００重量部が４Ｋｇになる様に計量し、次いで、表９に示す配合剤をそれぞれ計量して、２０Ｌのヘンシェルミキサーに投入し、撹拌しながら、内容物の温度が１１５℃になる迄、撹拌・混合した。その後、冷却水をヘンシェルミキサーのジャケットに流しながら撹拌・混合を続け、内容物の温度が７５℃になる迄、冷却して、塩化ビニル系パウダーコンパウンドを得た。尚、ＥＶＡ系樹脂は、酢酸ビニル含有量３５重量％、メルトインデックス１０のＥＶＡ樹脂に塩化ビニルをグラフト重合し、ＥＶＡ含量を３５％に調節したＥＶＡ-ＶＣＬグラフト樹脂を使用した。該パウダーコンパウンドを実験１〜５に示した紡糸条件,延伸条件,熱緩和処理条件と同様の条件にて、溶融紡糸・延伸・熱処理実験に供した。この際、延伸倍率を変更して、延伸糸の繊度が表９になる様に設定した。また、実験１〜５に示した試験方法、評価方法にて、未延伸糸、延伸糸の評価を全く同様に行なった。評価結果を表９に示す。
【００７５】
【表９】
実験２７〜３１の比較から判る様に、延伸糸の繊度が１００デニールを越えると、延伸糸の触感がゴワゴワとした、硬い触感となり、また、しなやかさが劣る為、人工毛髪用繊維として品質的に不十分な繊維となる。一方、延伸糸の繊度を１００デニール以下とすれば、これらの品質が高度にバランスされて、人毛に極めて類似した人工毛髪用繊維として優れたものを得ることができる。
【００７７】
【発明の効果】
以上のように、本発明の塩化ビニル系樹脂組成物を用いれば、品質に優れ、人毛に極めて類似した七部〜半艶表面でサラサラとした手触り触感を兼ね備えた塩化ビニル繊維を得られ、また、本発明の製造方法を用いれば、目的の塩化ビニル系繊維を、高い紡糸生産性を維持しながら、安全に製造することができる。本発明の塩化ビニル系繊維は、頭髪装飾用などの人工毛髪用繊維として、あるいはドールヘアーなどの人形用頭髪繊維として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to artificial hair used for hair decoration such as wigs, hair pieces, blades, extension hairs, accessory hairs, or vinyl chloride fibers used as doll hair fibers such as doll hairs, and the production thereof It is about the method.
[0002]
[Prior art]
Vinyl chloride fibers made by spinning vinyl chloride resin into fibers are used as artificial hair fibers for hair decoration or dolls because of their excellent strength, elongation, curl retention, style, etc. It is used in large quantities as hair fibers for dolls such as hair.
[0003]
Conventionally, in order to industrially produce fibers with fineness (small cross-sectional area, thin fibers) as artificial hair fibers for hair decoration, etc., a wet spinning method that generally uses a solvent for vinyl chloride resin Alternatively, a method of producing a vinyl chloride fiber having a fine fineness by a dry spinning method has been industrially carried out. However, this method has a problem that it requires a desolvation step because it uses a solvent, requires an excessive investment in equipment, and requires a lot of manpower to maintain and manage the equipment. In addition, in order to improve the solubility in a solvent, a comonomer such as acrylonitrile is copolymerized, so there is a weak point in the initial colorability of the fiber, and the problem is that it tends to become a strong yellowish hair by heat in the drying process, or There are problems such as insufficient curl retention of the fiber.
[0004]
On the other hand, a melt spinning method is known as a spinning method that does not use a solvent. By this method, a semi-glossy surface that is very similar to human hair (the evaluation criteria are shown in the Examples for the evaluation of gloss). In order to obtain fibers for artificial hair with fineness, such as for tactile hair decoration, a nozzle hole with a very small cross-sectional area (0.5 mm) 2 It is preferable that the spinning draft ratio is reduced (Dr ratio: 25 or less). That is, conversely, if a vinyl chloride fiber having a fineness is melted and discharged from a nozzle hole having a large cross-sectional area, it is inevitably necessary to increase the spinning draft ratio, and the undrawn yarn is extremely stretched during melt spinning. Therefore, the surface of the fiber (drawn yarn) formed by drawing and heat-treating this undrawn yarn becomes smooth, glossy, and has no smooth touch. Tended to be inadequate fiber. Therefore, in order to obtain a fiber excellent in quality as an artificial hair fiber for hair decoration or the like, it is preferable to melt and flow out from a nozzle hole having a cross-sectional area as small as possible to reduce the spinning draft ratio. .
[0005]
However, in the past, when flowing out from a nozzle hole having a very small cross-sectional area, the pressure applied to the nozzle becomes high, and the design pressure of the extruder is exceeded, and the pressure is set below the rating. Therefore, if the extrusion amount is low, the melt spinning productivity is lowered, or if the melt spinning temperature is set high in order to reduce the melt viscosity, thermal decomposition tends to occur or the long run property tends to be inferior. there were.
[0006]
Therefore, various proposals have been made so far to solve these problems, but they have not been sufficiently solved. For example, in Japanese Examined Patent Publication No. 51-2109, there is a proposal to improve the spinnability by using a chlorinated vinyl chloride resin and a methyl methacrylate resin, but it is stretched from a relatively large cross section to a small cross section. Because of its fineness, the surface of the fiber is smooth and gloss is likely to occur, and it is not only a material that is far away from a semi-glossy surface similar to human hair. It was enough. Further, in order to lower the melt viscosity of the composition, a method of using a Cd—Pb heat stabilizer and a lubricant using cadmium or lead is industrially implemented. However, when these compounding agents are used, the problem of nozzle pressure, melt spinning productivity, and the like can be solved, but the initial coloration is large and the hair tends to have a strong yellowish color. In addition, these compounding agents are highly toxic and have manufacturing problems, as well as safety and health problems for touching the skin for hair decoration. In addition, when these hair ornaments are discarded, there is also a problem that they are mixed with general garbage and pollute the environment.
[0007]
[Problems to be solved by the invention]
The first object of the present invention is to provide a semi-glossy surface that is very similar to human hair, without touching the conventionally known Cd—Pb-based heat stabilizers and lubricants, while greatly improving the initial colorability. The purpose of the present invention is to provide a fine vinyl chloride fiber having flexibility and excellent strength, elongation and shrinkage, and a second object is to use a conventionally known tin stabilizer. The fine vinyl chloride fiber that can be produced safely and stably, improving the quality of vinyl chloride fibers, such as plastic touch, sparkling surface, crumpled finger feel, and heat shrinkability. It is in providing a fiber and its manufacturing method. The third object is to solve various problems in melt spinning from a nozzle hole having a very small nozzle cross-sectional area, to achieve a high balance between nozzle pressure and melt spinning productivity. An object of the present invention is to provide a method for producing a fine vinyl chloride fiber having a high balance between pyrolysis and long-run properties.
[0008]
[Means for solving the problems]
In order to solve the above-mentioned problems, the present inventors have conducted extensive research on the composition system of the composition, the nozzle hole cross-sectional area, the melt spinning conditions, and the like, and as a result, are composed of vinyl chloride resin and chlorinated vinyl chloride resin When ethylene-vinyl acetate resin, heat stabilizer, and lubricant are blended in a specific range in a vinyl chloride mixture, it is very similar to human hair without using Cd-Pb heat stabilizer, lubricant, etc. It has been found that a fine fiber having a semi-glossy surface, a tactile sensation, and the like, which has solved the above-mentioned quality problems, can be stably obtained without lowering the melt spinning productivity, and the present invention has been completed.
[0009]
That is, the present invention provides (a) 1 ethylene-vinyl acetate resin for 100 parts by weight of a vinyl chloride mixture comprising 100 to 60% by weight of vinyl chloride resin and 0 to 40% by weight of chlorinated vinyl chloride resin. ~ 35 parts by weight, (b) 0.2 to 5.0 parts by weight of heat stabilizer, and (c) 0.2 to 5.0 parts by weight of lubricant, and a vinyl chloride resin composition. It is a vinyl chloride fiber, and the heat stabilizer (b) is selected from the group consisting of a tin heat stabilizer, a Ca-Zn heat stabilizer, a hydrotalcite heat stabilizer, and a zeolite heat stabilizer. And the lubricant (c) is a metal soap lubricant containing no cadmium or lead, a polyethylene lubricant, a higher fatty acid lubricant, a pentaerythritol lubricant, a higher alcohol lubricant, and montan. Acid wax system At least one member selected from the group consisting of agents can be used.
[0010]
Further, 1 to 35 parts by weight of (a) ethylene-vinyl acetate resin is used with respect to 100 parts by weight of vinyl chloride mixture comprising 90 to 75% by weight of vinyl chloride resin and 10 to 25% by weight of chlorinated vinyl chloride resin. And (b) at least one heat stabilizer selected from the group consisting of a mercaptotin heat stabilizer, a maleate tin heat stabilizer, and a laurate tin heat stabilizer is 0.2 to 5.0. 0.2 to 5.0 weight by weight of at least one selected from the group consisting of parts by weight and (c) a metal soap-based lubricant containing no cadmium or lead, a polyethylene-based lubricant, and a pentaerythritol-based lubricant A vinyl chloride resin composition comprising 1 part by weight, and (a) 1 to 35 parts by weight of ethylene-vinyl acetate resin with respect to 100 parts by weight of vinyl chloride resin; b) Mel 0.2 to 5.0 parts by weight of at least one heat stabilizer selected from the group consisting of a captotin heat stabilizer, a maleate tin heat stabilizer, and a laurate tin heat stabilizer; c) Compounding 0.2 to 5.0 parts by weight of at least one lubricant selected from the group consisting of metal soap-based lubricants not containing cadmium or lead, polyethylene lubricants, and pentaerythritol lubricants. A vinyl chloride resin composition can be used.
The vinyl chloride resin according to the present invention is at least one resin selected from the group consisting of vinyl chloride homopolymer, ethylene-vinyl chloride copolymer resin, and vinyl acetate-vinyl chloride copolymer resin, and chlorine. As the vinyl chloride resin, it is preferable to use a raw material vinyl chloride resin having a polymerization degree of 350 to 1100 and a chlorine content of 60 to 70% by weight.
[0011]
On the other hand, the production method of the present invention comprises (a) ethylene-vinyl acetate with respect to 100 parts by weight of a vinyl chloride mixture comprising 100 to 60% by weight of vinyl chloride resin and 0 to 40% by weight of chlorinated vinyl chloride resin. A vinyl chloride resin comprising 1 to 35 parts by weight of a resin, (b) 0.2 to 5.0 parts by weight of a heat stabilizer, and (c) 0.2 to 5.0 parts by weight of a lubricant. The composition is melt-spun into a vinyl chloride fiber.
[0012]
As the heat stabilizer (b), at least one selected from the group consisting of a tin-based heat stabilizer, a Ca—Zn-based heat stabilizer, a hydrotalcite-based heat stabilizer, and a zeolite-based heat stabilizer is used. The lubricant (c) is composed of a metal soap lubricant containing no cadmium or lead, a polyethylene lubricant, a higher fatty acid lubricant, a pentaerythritol lubricant, a higher alcohol lubricant, and a montanic acid wax lubricant. At least one selected from the group can be used.
[0013]
Further, 1 to 35 parts by weight of (a) ethylene-vinyl acetate resin is used with respect to 100 parts by weight of vinyl chloride mixture comprising 90 to 75% by weight of vinyl chloride resin and 10 to 25% by weight of chlorinated vinyl chloride resin. And (b) 0.2 to 5.0 weights of at least one heat stabilizer selected from the group consisting of mercaptotin heat stabilizers, maleate tin heat stabilizers, and laurate tin heat stabilizers. 0.2 to 5.0 parts by weight of at least one lubricant selected from the group consisting of: (c) a metal soap-based lubricant containing no cadmium or lead, a polyethylene-based lubricant, and a pentaerythritol-based lubricant The vinyl chloride resin composition is blended and melt spun into a vinyl chloride fiber, and (a) ethylene-vinyl acetate resin is added to 100 parts by weight of the vinyl chloride resin. 1 -35 parts by weight, and (b) at least one heat stabilizer selected from the group consisting of mercaptotin heat stabilizers, maleate tin heat stabilizers, and laurate tin heat stabilizers is 0.2. -5.0 parts by weight and (c) at least one lubricant selected from the group consisting of metal soap-based lubricants containing no cadmium or lead, polyethylene-based lubricants, and pentaerythritol-based lubricants It is also possible to melt-spin a vinyl chloride resin composition formed by blending 5.0 parts by weight into a vinyl chloride fiber.
[0014]
In the production method of the present invention, when the vinyl chloride resin composition of the present invention is melt-spun, the sectional area of one nozzle hole is 0.5 mm. 2 It can be melted and discharged from the following nozzle holes.
In addition, when the melt spinning is performed, the sectional area of one nozzle hole is 0.5 mm. 2 It is also possible to melt and flow out from the following nozzle holes to produce an undrawn yarn of 300 denier or less, and then subject the undrawn yarn to drawing treatment and heat treatment to obtain a fiber of 100 denier or less.
[0015]
Further, the vinyl chloride resin composition of the present invention is applied with a nozzle pressure of 500 kg / cm. 2 Hereinafter, a method in which undrawn yarn is drawn at a resin temperature of 195 ° C. or lower at the same time as melting and flowing out from the nozzle hole and a spinning draft ratio of 25 or lower can be used. There are 50 to 300 nozzle holes in the nozzle to be used, and the nozzle holes are arranged in a circle, ellipse, rectangle, or square, and between the centers of adjacent nozzle holes (in a modified cross-sectional shape). In this case, it is also possible to use nozzles arranged so that the distance between the centers of gravity of the cross section is at least 0.8 mm or more.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The vinyl chloride resin used in the present invention is a homopolymer resin, which is a conventionally known homopolymer of vinyl chloride, or various conventionally known copolymer resins, and is not particularly limited. As the copolymer resin, conventionally known copolymer resins can be used, such as vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl propionate copolymer resins, and the like. Copolymer resins of vinyl chloride and acrylates such as vinyl-butyl acrylate copolymer resin, vinyl chloride-ethyl acrylate copolymer resin, vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene copolymer resin, etc. Typical examples thereof include copolymer resins of vinyl chloride and olefins, vinyl chloride-acrylonitrile copolymer resins, and the like. It is particularly preferable to use a vinyl chloride homopolymer, an ethylene-vinyl chloride copolymer resin, a vinyl acetate-vinyl chloride copolymer resin, or the like. In the copolymer resin, the content of the comonomer is not particularly limited, and can be determined according to required qualities such as moldability and yarn characteristics. Particularly preferably, the comonomer content is 2 to 30%.
[0017]
The viscosity average polymerization degree of the vinyl chloride resin used in the present invention is preferably 450 to 1800. If it is less than 450, the properties of the fiber, particularly the heat shrinkage rate, curl retention, glossiness and the like tend to be inferior. On the other hand, if it exceeds 1800, the melt viscosity becomes high, the nozzle pressure becomes high, and safe production becomes difficult.
From the balance between moldability and fiber properties, when using a vinyl chloride single resin, a region having a viscosity average polymerization degree of 650 to 1450 is particularly preferable. When using a copolymer resin, the content of comonomer is reduced. However, the viscosity average degree of polymerization is particularly preferably in the range of 1000 to 1700.
[0018]
In addition, the vinyl chloride resin used in the present invention can be prepared by emulsion polymerization, bulk polymerization or suspension polymerization. However, in consideration of the initial colorability of the fiber, the resin prepared by suspension polymerization is used. It is preferred to use.
The chlorinated vinyl chloride resin used in the present invention is made from a vinyl chloride resin as a raw material and subjected to addition reaction with chlorine to increase the chlorine content to 58 to 72% by weight, preferably 60 to 70% by weight. Although it is preferable to use a thing, as a main objective, it can be used in order to reduce the thermal contraction rate of a fiber. The chlorinated vinyl chloride resin preferably has a viscosity average polymerization degree (viscosity average polymerization degree of the raw vinyl chloride resin) of 300 to 1100. When the viscosity average degree of polymerization is less than 300, the effect of lowering the thermal shrinkage rate of the fiber becomes small, so that the fiber has a slightly high shrinkage rate. On the other hand, if the viscosity average polymerization degree exceeds 1100, the melt viscosity becomes high and the nozzle pressure at the time of spinning becomes high, which not only makes safe operation difficult, but also breaks the yarn at the time of melt spinning (yarn breakage). ) Is remarkably frequent and stable operation tends to be difficult. More preferably, the viscosity average degree of polymerization is preferably 350 to 1100, particularly 500 to 900. When the chlorine content is less than 58% by weight, the effect of lowering the thermal shrinkage of the fiber is reduced. Conversely, when the chlorine content exceeds 72% by weight, the melt viscosity becomes high and stable operation becomes difficult. There is a tendency and it is not preferable.
[0019]
The vinyl chloride resin used as a raw material for the chlorinated vinyl chloride resin is the same as the vinyl chloride resin described above, but a vinyl chloride single resin or an ethylene-vinyl chloride copolymer resin may be used as a raw material. Is particularly preferred.
In the present invention, the use ratio of the vinyl chloride resin and the chlorinated vinyl chloride resin is (vinyl chloride / chlorinated vinyl chloride) = (100 to 60 wt% / 0 to 40 wt%). A mixture is preferred. If the vinyl chloride is less than 60% by weight, the chlorinated vinyl chloride resin becomes excessive, so that the melt viscosity becomes high, the nozzle pressure at the time of melt spinning becomes high, and there is a tendency that safe operation becomes difficult. Absent. In addition, when the ratio of a vinyl chloride resin is high, there exists a tendency for it to become a fiber with a high heat shrinkage rate, and it can adjust and use a usage ratio suitably according to the objective.
[0020]
In the present invention, the main purpose is to increase the flexibility of the fiber, to make it a soft, supple and smooth fiber with 100 parts by weight of ethylene chloride with respect to 100 parts by weight of the vinyl chloride mixture. It is preferable to use 1 to 35 parts by weight of vinyl acetate resin (hereinafter abbreviated as EVA resin), and more preferably 3 to 35 parts by weight in terms of touch. In addition, the resin has the effect of adjusting the gelation / melting property of the composition, producing a uniform and appropriate molten state, and enabling an appropriate nozzle pressure.
[0021]
When the amount of the EVA-based resin used is less than 1 part by weight, not only the fiber flexibility improving effect becomes dilute, but also the gelling / melting property adjusting function is lowered and the nozzle pressure tends to increase. On the other hand, if it exceeds 35 parts by weight, the gelling / melting ability adjusting function of the composition is lowered, resulting in a non-uniform gelling / melting state. Alternatively, it is not preferable because the number of particles) that did not collapse due to shear stress increases and the frequency of yarn breakage during melt spinning or stretching / heat treatment tends to increase.
[0022]
The EVA resin referred to in the present invention is a conventionally known ethylene-vinyl acetate copolymer resin having a vinyl acetate content of 20 to 65% by weight, and further an ethylene-vinyl acetate copolymer obtained by introducing a carbonyl group as a polar group. It means EVA resin made of resin or EVA-vinyl chloride graft polymer resin obtained by graft polymerization of vinyl chloride on these EVA resins. The EVA-vinyl chloride graft polymer resin is easily obtained by adding an EVA resin to a polymerization system and proceeding with polymerization when suspension polymerization or emulsion polymerization of vinyl chloride in an aqueous medium. The resin is a mixture of an EVA resin component, a polyvinyl chloride resin component, and an EVA-vinyl chloride graft polymer component obtained by chemically bonding vinyl chloride to the EVA resin component by fractionation with a solvent.
[0023]
The vinyl acetate content of the EVA resin used in the present invention is preferably 20 to 65% by weight. If the vinyl acetate content is less than 20% by weight or more than 65% by weight, the compatibility with the composition system is lowered, and the gelling / melting property adjusting function of the composition is lowered, resulting in a non-uniform gelling / melting state. Thus, there is a tendency that the number of “bumps” in the undrawn yarn increases and the frequency of yarn breakage during melt spinning or during drawing and heat treatment tends to increase. On the other hand, if the vinyl acetate content is less than 20% by weight, the fiber flexibility improving effect becomes insufficient. Conversely, if the vinyl acetate content exceeds 65% by weight, EVA in the composition that has not been uniformly mixed is used. There is a problem in that it becomes difficult to obtain an undrawn yarn because the resin component is melted during melt spinning and melted down from the heating cylinder or nozzle tip.
[0024]
The melt index (MI: gr / 10 min), which is a measure of the molecular weight of the resin, is preferably in the range of about 1 to 260. When the melt index is less than 1, the melt viscosity of the EVA resin component increases, and the nozzle pressure during melt spinning tends to increase. On the other hand, if the melt index exceeds 260, the viscosity of the resin is lowered, the melting of the vinyl chloride mixture component becomes insufficient, the uniform melting becomes insufficient, and it remains in the “unstretched” yarn as a “buzz” shape. Therefore, the frequency of yarn breakage during spinning tends to increase, which is not preferable.
[0025]
The EVA-vinyl chloride graft polymer resin that can be used in the present invention preferably has an EVA component content in the range of 3 to 45% by weight. If the content is less than 3% by weight, the fiber flexibility improving effect becomes insufficient. Conversely, if the content exceeds 45% by weight, the gelling / melting property adjusting function of the composition is lowered, resulting in uneven gelation.・ Because it is in a molten state, the number of “strips” in the undrawn yarn tends to increase, and the frequency of yarn breakage during melt spinning or drawing / heat treatment tends to increase.
[0026]
As the heat stabilizer used in the present invention, conventionally known heat stabilizers can be used, among which a tin heat stabilizer, a Ca-Zn heat stabilizer, a hydrotalcite heat stabilizer, and a zeolite heat stabilizer are selected. It is preferable to use 0.2 to 5.0 parts by weight of one or more heat stabilizers. The heat stabilizer is used to improve thermal decomposition during molding, long run property, and color tone of the fiber, and particularly preferably a scale generated around the nozzle during spinning (hereinafter abbreviated as nozzle grease). .) A tin-based heat stabilizer with a relatively small amount of generation is preferable, and in particular, one or more of mercaptotin-based heat stabilizer, maleate-tin-based heat stabilizer, and laurate-tin-based heat stabilizer should be used. . For example, mercaptotin thermal stabilizers such as dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, maleate tin thermal stabilizers such as dimethyltin maleate, dibutyltin maleate, dioctyltin maleate, dioctyltin maleate polymer, dimethyl Examples include laurate tin-based heat stabilizers such as tin laurate, dibutyltin laurate, and dioctyltin laurate.
[0027]
In order to suppress the initial coloration of the fibers and increase the whiteness of the natural composition containing no pigment, the mercaptotin-based heat stabilizer is at least 0.1 to 1.4 with respect to 100 parts by weight of the vinyl chloride mixture. It is particularly preferable to use parts by weight and use in combination with other heat stabilizers so that the total is in the range of 0.2 to 5.0 parts by weight with respect to 100 parts by weight of the vinyl chloride mixture. The amount of the heat stabilizer used is 0.2 to 5.0 parts by weight, but if it is less than 0.2 parts by weight, the effect of preventing thermal decomposition during molding tends to be reduced. On the other hand, if the amount exceeds 5.0 parts by weight, the occurrence of nozzle grease increases during spinning, and the occurrence of outflow fluctuation during spinning tends to increase, which is not preferable.
[0028]
As the lubricant used in the present invention, a conventionally known lubricant containing no cadmium or lead can be used. Particularly, a metal soap lubricant, a polyethylene lubricant, a higher fatty acid lubricant, a pentaerythritol lubricant, a higher alcohol lubricant, It is preferable to use 0.2 to 5.0 parts by weight of one or more selected from montanic acid wax lubricants with respect to 100 parts by weight of the vinyl chloride mixture. The lubricant is used to control the melted state of the composition and the adhesive state between the composition and the metal surface. The surface state of the fiber, the touch, the frequency of thread breakage, the frequency of nozzle grease generation, the nozzle pressure, etc. Greatly affects.
[0029]
In order to obtain a relatively smooth feel, it is preferable to use a metal soap lubricant. In particular, from the viewpoint of hygiene, metal soaps other than cadmium and lead are preferable. For example, metal soaps such as stearates such as Na, Mg, Al, Ca and Ba, laurates, palmitates and oleates are exemplified. Further, in order to reduce the occurrence of nozzle grease and keep the nozzle pressure low, it is preferable to use a polyethylene-based lubricant, and a conventionally known polyethylene-based lubricant can be used, and an average molecular weight of 1500 to 1500 is particularly preferable. A non-oxidizing type or a very slightly polar type polyethylene lubricant having a density of 4000 to 0.97 is particularly preferred. The polyethylene-based lubricant is particularly preferably used in the range of 0.2 to 1.3 parts by weight.
[0030]
In the present invention, higher fatty acid lubricants, pentaerythritol lubricants, higher alcohol lubricants, and montanic acid wax lubricants are preferably used mainly for controlling the molten state of the composition. Examples of the higher fatty acid lubricant include saturated fatty acids such as stearic acid, palmitic acid, myristic acid, lauric acid and capric acid, unsaturated fatty acids such as oleic acid, and mixtures thereof. Examples of pentaerythritol lubricants include monoesters, diesters, triesters, tetraesters, and mixtures of pentaerythritol or dipentaerythritol and higher fatty acids. Examples of higher alcohol lubricants include stearyl alcohol, palmityl alcohol, myristyl alcohol, lauryl alcohol, oleyl alcohol, and the like. Furthermore, examples of the montanic acid wax-based lubricant include esters of montanic acid and higher alcohols such as stearyl alcohol, palmityl alcohol, myristyl alcohol, lauryl alcohol, and oleyl alcohol.
[0031]
A particularly preferred amount of use of the lubricant system is 0.5 to 3.0 parts by weight in the case of a metal soap-based lubricant containing no cadmium or lead with respect to 100 parts by weight of the vinyl chloride mixture, and a polyethylene lubricant. If present, 0.2 to 1.8 parts by weight, and in the case of a pentaerythritol lubricant, 0.2 to 1.0 parts by weight are particularly preferably used in combination.
The vinyl chloride resin composition according to the present invention comprises (a) 100 parts by weight of a vinyl chloride mixture comprising 100 to 60% by weight of vinyl chloride resin and 0 to 40% by weight of chlorinated vinyl chloride resin. In addition to 1 to 35 parts by weight of EVA resin, (b) 0.2 to 5.0 parts by weight of heat stabilizer, and (c) 0.2 to 5.0 parts by weight of lubricant, vinyl chloride (A) 1-35 parts by weight of EVA-based resin and (b) mercaptotin-based with respect to 100 parts by weight of vinyl chloride-based mixture comprising 90-75% by weight of resin and 10-25% by weight of chlorinated vinyl chloride-based resin 0.2 to 5.0 parts by weight of one or more heat stabilizers selected from heat stabilizers, maleate tin heat stabilizers, laurate tin heat stabilizers, and (c) cadmium and lead. Contains no metal soap lubricant, polyethylene lubricant, pentaerythritol May be used alone or two or more of a lubricant formed by blending 0.2 to 5.0 parts by weight vinyl chloride resin composition is selected from a lubricant.
[0032]
The resin composition is preferable in that the occurrence of yarn breakage is small, stable production can be achieved, and the quality can be balanced.
Also, from 100 parts by weight of vinyl chloride resin, (a) 1-35 parts by weight of EVA resin and (b) mercaptotin heat stabilizer, maleate tin heat stabilizer, laurate tin heat stabilizer One or more selected thermal stabilizers are selected from 0.2 to 5.0 parts by weight and (c) cadmium, lead-free metal soap-based lubricant, polyethylene-based lubricant, and pentaerythritol-based lubricant. A vinyl chloride resin composition comprising 0.2 to 5.0 parts by weight of one or more lubricants may also be used.
[0033]
The resin composition has a tendency that the thermal shrinkage rate of the fibers tends to be slightly high, but the production has an advantage of being more stable, and is preferable for applications that prefer a high shrinkage rate.
In the present invention, depending on the purpose, known compounding agents used for vinyl chloride compositions, such as processing aids, reinforcing agents, ultraviolet absorbers, antioxidants, plasticizers, antistatic agents, Fillers, flame retardants, pigments and the like can be used. In some cases, special compounding agents such as a foaming agent, a crosslinking agent, a tackifier, a hydrophilicity imparting agent, a conductivity imparting agent, and a fragrance can be appropriately used.
[0034]
Examples of the processing aid include an acrylic processing aid having methyl methacrylate as a main component or a polyester processing aid having thermoplastic polyester as a main component. The amount of the processing aid used is preferably about 0.2 to 12 parts by weight with respect to 100 parts by weight of the vinyl chloride mixture. In addition, these processing aids can be used alone or in combination of two or more.
[0035]
Examples of the filler used in the present invention include calcium carbonate, magnesium carbonate, magnesium oxide, aluminum oxide, magnesium hydroxide, aluminum hydroxide, talc, mica and clay. The amount of the filler used is preferably about 0.2 to 5.0 parts by weight with respect to 100 parts by weight of the vinyl chloride mixture. In addition, these fillers can be used alone or in combination of two or more.
[0036]
Examples of the plasticizer used in the present invention include phthalic acid plasticizers such as dibutyl phthalate, di-2-ethylhexyl phthalate, and diisononyl phthalate, trimellitic plasticizers such as octyl trimellitate, octyl pyromellitate, and the like. Pyromellitic acid plasticizers, polyester plasticizers, epoxy plasticizers and the like can be used. The amount of the plasticizer used is preferably about 0.2 to 5.0 parts by weight with respect to 100 parts by weight of the vinyl chloride mixture. Moreover, these plasticizers can be used alone or in combination of two or more.
[0037]
The vinyl chloride resin composition used in the present invention is a powder compound obtained by mixing using a conventionally known mixer such as a Henschel mixer, a super mixer, a ribbon blender, or a pellet compound obtained by melt-mixing the powder compound. Can be used as The powder compound can be produced under conventional conditions known in the art, and may be hot blend or cold blend. It is particularly preferable to use a hot blend in which the cut temperature during blending is increased to 105 to 155 ° C. in order to reduce the volatile content in the composition. The pellet compound can be produced in the same manner as ordinary vinyl chloride-based pellet compounds. For example, pellet compound using a kneader such as a single screw extruder, a different direction twin screw extruder, a conical twin screw extruder, a same direction twin screw extruder, a kneader, a planetary gear extruder, or a roll kneader. It can be. The conditions for producing the pellet compound are not particularly limited, but the resin temperature is preferably set to 185 ° C. or lower. In addition, in order to remove foreign matters such as metal pieces of cleaning tools that can be mixed into the pellet compound, a fine mesh stainless steel mesh can be installed in the kneading machine, or can be mixed during cold cutting. Although a method of removing the “and the like” or performing a hot cut can be freely used, it is particularly preferable to use a hot cut method in which “chip” is less mixed.
[0038]
When the vinyl chloride resin composition is made into a fibrous undrawn yarn, a conventionally known extruder can be used. For example, a single-screw extruder, a different-direction twin-screw extruder, a conical twin-screw extruder or the like can be used. Particularly preferably, the single-screw extruder has a diameter of about 35 to 85 mmφ or the conical extruder has a diameter of about 35 to 50 mmφ. Good to use. If the diameter is excessive, the amount of extrusion increases, the nozzle pressure becomes excessive, or the undrawn yarn outflow rate is too fast, and winding tends to be difficult.
[0039]
In the present invention, the sectional area of one nozzle hole is 0.5 mm. 2 It is preferable to perform melt spinning by attaching the following nozzle to the tip of the die. The cross-sectional area is 0.5 mm 2 When a nozzle exceeding 1 is used, the fineness of the undrawn yarn becomes large, and in order to obtain a fine fiber, it is necessary to increase the draw ratio during the drawing treatment. For this reason, the fine fibers (drawn yarns) after the drawing treatment are glossed, making it difficult to maintain a semi-gloss to seven-part gloss state. In addition, it is not preferable because the fiber has a rough feel, a glittery feeling, or a plastic sliding feel.
[0040]
The arrangement and positional relationship of the nozzle holes present in the nozzle are greatly related to the ease of winding. The number of arrangements is particularly preferably 1 to 5 rows, and if it exceeds this, the flow rate difference of the melt in the die increases, the outflow rate distribution widens, and the “swimming” of the undrawn yarn tends to increase. Absent. Further, it is desirable that the arrangement shape of the nozzle holes is a circle, an ellipse, or a polygon having four or more corners. A triangular shape is not preferable because the flow rate difference of the melt in the die increases, the outflow rate distribution widens, and the “swimming” of undrawn yarn tends to increase. Further, the number of nozzle holes present in one nozzle is preferably 50 to 300. If the number of nozzle holes is too small, the productivity is lowered, and conversely if too large, the probability of occurrence of troubles such as “thread breakage” increases, which is not preferable.
In the present invention, it is preferable that the distance between the centers of adjacent nozzle holes (in the case of irregularly shaped cross sections, the center of gravity of the cross section) is at least 0.8 mm. When the distance is less than 0.8 mm, when melt spinning, the contact frequency between the undrawn yarns is increased, which causes yarn breakage. On the other hand, if the distance is too long, the nozzle itself becomes large and heavy, or the number of holes arranged in the nozzle is reduced, resulting in a decrease in processing productivity. A particularly preferable range is a range of 0.8 to 3.8 mm.
[0041]
In the present invention, it is preferable that the undrawn yarn has a fineness of 300 denier or less. When the undrawn yarn has a fineness of more than 300 denier, it is necessary to increase the draw ratio during the drawing process in order to obtain a fine fiber. The (drawn yarn) becomes glossy, making it difficult to maintain a semi-gloss to seven-part gloss state. Moreover, it tends to be a plastic sliding feel. The nozzle pressure is 500 kg / cm during melt spinning. 2 It is preferred to spin below. Nozzle pressure is 500Kg / cm 2 Exceeding this is not preferable because the load applied to the thrust portion of the extruder becomes excessive, and problems are likely to occur in the extruder. It is preferable to control the nozzle pressure by changing the screw rotation speed or the feed amount and controlling the extrusion amount because the quality is not affected. However, since productivity decreases when the amount of extrusion is reduced, from this balance, 480-300 Kg / cm 2 The range of is particularly preferable. In order to reduce the nozzle pressure, it is possible to use a lubricant having a high sliding effect with the metal surface, or to use a large amount of a melt viscosity reducing agent such as a plasticizer or a polymer plasticizer. By such means, the nozzle pressure is set to 200 kg / cm. 2 When the composition is made below, the gelled / molten state of the composition becomes extremely non-uniform, the frequency of thread breakage increases, production becomes difficult, and there is a tendency that the quality of the glossy state, touch, etc. is insufficient. Therefore, pressure control by controlling the amount of extrusion as described above is preferable.
[0042]
At the time of melt spinning, the strand melted and discharged from the nozzle hole is drawn to an undrawn yarn of 300 denier or less, and the draft ratio at that time is particularly preferably 25 or less. If the draft ratio exceeds 25, the surface is excessively stretched at the time of the undrawn yarn, so that the glossiness of the fine fibers after the drawing treatment is given, and the semi-gloss to seven-part gloss state is obtained. Tend to be difficult to maintain. Moreover, it tends to be a plastic sliding feel. Further, it is preferable to spin at a resin temperature of 195 ° C. or lower. Spinning at a temperature exceeding 195 ° C. is not preferable because the fiber tends to be colored and tends to be a yellowish fiber. Therefore, it is particularly preferable that the cylinder temperature is about 150 to 185 ° C and the die temperature is about 160 to 190 ° C.
[0043]
As described above, in the present invention, the cross-sectional area of one nozzle hole is 0.5 mm during melt spinning. 2 It is preferable to produce an undrawn yarn of 300 denier or less using the following nozzles. In particular, the resin temperature is 195 ° C. or less, the draft ratio is 25 or less, and the nozzle pressure is 500 kg / cm. 2 In the following, the method is particularly excellent in that the number of nozzle holes is 50 to 300, the nozzle arrangement is circular, elliptical, or polygonal with four or more corners, and the number of nozzle arrangement is 1 to 5.
[0044]
The undrawn yarn obtained by the melt spinning can be drawn and heat-treated by a known method to obtain a fiber (drawn yarn) having a fineness of 100 denier or less. The fiber for hair decoration is particularly preferably in the range of 25 to 100 denier, and the fiber for doll hair is particularly preferably in the range of 10 to 65 denier.
As stretching conditions, it is particularly preferable that the stretching ratio is stretched by about 200 to 450% in an atmosphere at a stretching temperature of 70 to 150 ° C. If the drawing temperature is less than 70 ° C., the strength of the fiber is lowered and yarn breakage is liable to occur. Conversely, if the temperature exceeds 150 ° C., the tactile feel of the fiber becomes a plastic sliding feel. On the other hand, if the draw ratio is less than 200%, the fiber strength is not sufficiently developed, and if it exceeds 450%, yarn breakage is liable to occur during the drawing treatment.
[0045]
Furthermore, the heat shrinkage rate can be lowered by subjecting the fiber subjected to the stretching treatment to a heat treatment to relax the fiber at a relaxation rate of 2 to 75%. In addition, the relaxation treatment is also preferable in order to adjust the unevenness of the fiber surface so that it has a tactile sensation similar to human hair and a semi-gloss to seven-part gloss surface. If the relaxation rate is out of the range, the quality tends to decrease as a fiber for artificial hair or as a hair fiber for dolls. The heat treatment can be carried out in conjunction with the stretching treatment or can be carried out separately, but as a condition, it is particularly preferred to carry out at an ambient temperature of 80 to 150 ° C. In the present invention, conventionally known melt spinning techniques, for example, various nozzle cross-sectional techniques, heating cylinder techniques, drawing process techniques, heat treatment techniques, etc. can be freely combined. It is possible to use.
[0046]
【Example】
Next, although an example is given and the detailed mode of the present invention is clarified, the present invention is not limited only to these examples.
In addition, the composition display etc. in a table | surface are abbreviated as follows.
Vinyl chloride resin: “PVC”, chlorinated vinyl chloride resin: “CPVC”, vinyl acetate: “VAc”, viscosity average degree of polymerization: “M”, melt index: “MI”. Moreover, the numerical value of the compounding agent in a composition in Table 2, 4-6, 8-9 represents the weight part of each compounding agent with respect to the sum total of PVC and CPVC = 100 weight part.
[0047]
[Experiments 1-5 (PVC / CPVC blending ratio)]
Weigh so that 100 parts by weight of the vinyl chloride mixture is 4 kg, then weigh each of the compounding agents shown in Table 2 and put them into a 20 L Henschel mixer, and while stirring, the temperature of the contents reaches 115 ° C. Stir and mix until complete. Thereafter, stirring and mixing were continued while flowing cooling water through the jacket of the Henschel mixer, and the contents were cooled until the temperature reached 75 ° C. to obtain a vinyl chloride powder compound. The powder compound was subjected to melt spinning / drawing / heat treatment experiments under the conditions shown in Table 1 (spinning conditions 1).
[0048]
[Table 1]
In the melt spinning experiment, after reaching a steady state, the relationship between the screw rotation speed and the extrusion amount was obtained, and the screw rotation speed was determined so that the extrusion amount was 7.0 kg / hrs. The nozzle pressure and the resin temperature were measured by installing a die pressure gauge and a resin temperature sensor in the nozzle part.
In the vertical direction, the strand melted and discharged from the nozzle is introduced into the heated spinning cylinder, where the strand is heated and melted instantaneously, and the undrawn yarn is fixed by a take-up machine installed at a position of about 3 m directly under the nozzle. Winded up at speed. At this time, the take-up speed was adjusted so that the fineness of the undrawn yarn was about 165 to 185 denier. At the stage of producing this undrawn yarn, the occurrence of yarn breakage was visually observed and evaluated as follows.
[0050]
[Yarn breakage during melt spinning]
A: No thread breakage occurs.
○: Occurs within 3 times per hour.
Δ: Occurs 4 to 15 times per hour.
Further, the colored state of the undrawn yarn was evaluated by visual observation as follows.
[0051]
[Colored state of undrawn yarn]
A: Milky white and no yellowish taste.
○: Milky white but slightly yellowish.
(Triangle | delta): There exists quite strong yellowishness.
The undrawn yarn was introduced into a drawing / heat treatment machine and subjected to drawing treatment and then heat relaxation treatment to produce drawn yarn. At this time, the thermal relaxation treatment was fixed at 25% relaxation, and in the drawing treatment, the draw ratio was slightly adjusted so that the final drawn yarn had a fineness of 65 to 68 denier. The occurrence of yarn breakage that occurred during the drawing and heat treatment was visually observed and evaluated as follows.
[0052]
[Thread breakage during drawing and heat treatment]
A: No thread breakage occurs.
○: Occurs within 3 times per hour.
Δ: Occurs 4 to 15 times per hour.
Further, the surface gloss and gloss of the drawn yarn were visually observed and evaluated as follows.
[0053]
[Glossy state of drawn yarn]
A (semi-glossy state): The surface is smooth and slightly dull.
○ (Seven-part gloss state): The surface is smooth and has a dull luster.
● (Complete matte state): The surface is rough and not glossy.
Δ (8-minute glossy state): The surface is rough, gloss is locally, and there is a feeling of glitter.
X (Glossy state): The surface is smooth, glossy on the whole surface, and shine.
Further, the drawn yarn was touched by hand, and the touch feeling was evaluated as follows.
[0054]
[Feeling of drawn yarn]
(Double-circle): The surface is smooth and there is a smooth touch.
○: The surface is smooth and has a slightly moist touch, but it has a smooth feel.
Δ (Rough feel): The surface is rough and feels rough.
● (Plastic feel): The surface is smooth, there is a plastic touch, and there is a sliding touch.
Further, the drawn yarn was wound around the finger several times, and the repulsive force, tactile sensation, and flexibility at that time were evaluated as follows.
[0055]
[Flexibility of drawn yarn]
A: It is soft on the finger and can be wound up flexibly.
○: Although there is a slight rebound feeling, it can be wound up flexibly.
(Triangle | delta): There exists a quite strong repulsive feeling with the hard feeling as a whole.
The drawn yarn was subjected to a tensile test and a heat shrinkage test, and the strength and the heat shrinkage rate were obtained. In addition, the measurement of the heat shrinkage rate of the drawn yarn was carried out at an ambient temperature of 100 ° C. for 25 minutes, and the calculation was performed as follows.
(Drawn yarn length before heat treatment-drawn yarn length after heat treatment) / drawn yarn length before heat treatment × 100 = heat shrinkage (%)
These evaluation results are shown in Table 2.
[0056]
[Table 2]
As can be seen from the comparison of Experiments 1 to 5, when the blending ratio of the chlorinated vinyl chloride resin exceeds 40% by weight, the nozzle pressure is 500 kg / cm. 2 As a result, the design pressure of the extruder is exceeded, and safe production becomes difficult. Further, when the screw rotation speed is lowered, the extrusion amount is lowered and productivity tends to be lowered. In addition, when the blending ratio of the chlorinated vinyl chloride resin exceeds 40% by weight, yarn breakage frequently occurs during melt spinning, or the colored state of the undrawn yarn tends to be slightly yellowish, In addition, the gloss of the drawn yarn is excessively disappeared, the tactile feeling is also rough, and the suppleness of the fiber tends to be inferior. From these experiments, it can be seen that the mixing ratio of the vinyl chloride resin and the chlorinated vinyl chloride resin is optimal in the range of 100 to 60% by weight for the former and 0 to 40% by weight for the latter.
[0058]
[Experiments 6 to 11 (addition effect of EVA resin)]
As in Experiments 1 to 5, 100 parts by weight of the vinyl chloride mixture was weighed to 4 kg, then the addition amount of EVA resin was changed, and each of the compounding agents shown in Table 4 was weighed to give 20 L The mixture was put into a Henschel mixer and stirred and mixed until the temperature of the contents reached 135 ° C. while stirring. Thereafter, stirring and mixing were continued while flowing cooling water through the jacket of the Henschel mixer, and the contents were cooled until the temperature reached 70 ° C. to obtain a vinyl chloride powder compound. The powder compound was subjected to melt spinning / drawing / heat treatment experiments under the spinning conditions, drawing conditions, and thermal relaxation treatment conditions shown in Table 3 (spinning conditions 2).
[0059]
[Table 3]
In the melt spinning experiment, after reaching a steady state, the relationship between the feed amount and screw rotation speed and the extrusion amount was determined, and the feed amount and screw rotation speed were determined so that the extrusion amount became 7.0 kg / hrs. The nozzle pressure and the resin temperature were measured by installing a die pressure gauge and a resin temperature sensor in the nozzle part.
In the vertical direction, the strand melted and discharged from the nozzle is introduced into a heated spinning cylinder, where the strand is heated and melted instantaneously, and the unstretched yarn is removed by a take-up machine installed at a position of about 3 m directly under the nozzle. It was wound up at a constant speed. At this time, the take-up speed was adjusted so that the fineness of the undrawn yarn was about 154 to 176 denier. The other spinning conditions and the like were the same as the methods shown in Experiments 1 to 5, and the evaluation method and the like were exactly the same as the methods shown in Experiments 1 to 5. These evaluation results are shown in Table 4.
[0061]
[Table 4]
As can be seen from the comparison of Experiments 6 to 11, when the amount of the EVA-based resin added is less than 1 part by weight, the stretched yarn lacks flexibility, resulting in a tactile fiber. Also, the heat shrinkage rate tends to be slightly higher. On the other hand, when the amount of the EVA resin added exceeds 35 parts by weight, the composition becomes nonuniform (melting of the CPVC component becomes nonuniform), and yarn breakage frequently occurs during melt spinning or stretching. Furthermore, the nozzle pressure also tends to increase, and the tactile feel of the fibers becomes rough. From these experiments, the addition amount of the EVA resin is optimally in the range of 1 to 35 parts by weight with respect to 100 parts by weight of the vinyl chloride mixture, and further in the range of 3 to 35 parts by weight in terms of touch. It turns out that it is preferable.
[0063]
[Experiments 12 to 16 (addition effect of heat stabilizer and combined use)]
As in Experiments 1 to 5, 100 parts by weight of the vinyl chloride mixture was weighed to 4 kg, then the type and amount of heat stabilizer were changed, and the ingredients shown in Table 5 were weighed. The mixture was put into a 20 L Henschel mixer and stirred and mixed until the temperature of the contents reached 135 ° C. while stirring. Thereafter, stirring and mixing were continued while flowing cooling water through the jacket of the Henschel mixer, and the contents were cooled until the temperature reached 75 ° C. to obtain a vinyl chloride powder compound. The EVA resin used was an EVA-vinyl chloride graft resin in which vinyl chloride was graft-polymerized on an EVA resin having a vinyl acetate content of 25% by weight and a melt index of 5 and the EVA content was adjusted to 40%. The powder compound was subjected to melt spinning / drawing / heat treatment experiments under the same spinning conditions, drawing conditions, and thermal relaxation treatment conditions as shown in Experiments 6-11. Further, the undrawn yarn and the drawn yarn were evaluated in exactly the same manner by the test methods and evaluation methods shown in Experiments 6 to 11. These evaluation results are shown in Table 5.
[0064]
[Table 5]
As can be seen from the comparison of Experiments 12 to 16, the initial coloration of the undrawn yarn is good if the addition amount of the heat stabilizer is an appropriate amount, but if the butyltin maleate is used excessively, the heat shrinkage rate of the fiber is increased. Extremely high, resulting in poor quality fiber. In addition, when an inorganic powder-like heat stabilizer such as zeolite is used in excess, not only is the fiber with a tactile feel, but also yarn breakage becomes significant and the strength of the fiber also decreases. From these experiments, it can be seen that the amount of heat stabilizer added is optimally in the range of 0.2 to 5.0 parts by weight with respect to 100 parts by weight of the vinyl chloride mixture.
[0066]
[Experiments 17-21 (effect of nozzle cross-sectional area)]
As in Experiments 1 to 5, weighed 100 parts by weight of the vinyl chloride mixture to 4 kg, then weighed the ingredients shown in Table 6 and put them into a 20 L Henschel mixer. The mixture was stirred and mixed until the temperature of the product reached 125 ° C. Thereafter, stirring and mixing were continued while flowing cooling water through the jacket of the Henschel mixer, and the contents were cooled until the temperature reached 75 ° C. to obtain a vinyl chloride powder compound. The EVA-based resin used was an EVA-vinyl chloride graft resin in which vinyl chloride was graft-polymerized to an EVA resin having a vinyl acetate content of 65% by weight and a melt index of 15 to adjust the EVA content to 25%. The powder compound was subjected to melt spinning / stretching / heat treatment experiments under the same spinning conditions, stretching conditions, and thermal relaxation treatment conditions as shown in Experiments 1-5. At this time, the spinning experiment was performed by changing the nozzle hole cross-sectional area and the number of holes shown in Table 6. The extrusion amount was 7.8 kg / hrs, and the take-up speed and draw ratio were adjusted accordingly. Furthermore, the undrawn yarn and the drawn yarn were evaluated in exactly the same manner by the test methods and evaluation methods shown in Experiments 1 to 5. The evaluation results are shown in Table 6.
[0067]
[Table 6]
As can be seen from the comparison of Experiments 17 to 21, the sectional area of one nozzle hole is 0.5 mm. 2 If it is below, it will be in the state where the various performances at the time of spinning, the performance at the time of a extending | stretching process and heat processing, and the performance of a fiber were highly balanced. On the other hand, the cross-sectional area of one nozzle hole is 0.5mm 2 Beyond, the gloss of the drawn yarn will appear, giving it a glittering visual feeling, and the tactile sensation will also be a plastic sliding sensation, resulting in an insufficiently quality fiber. Further, when the cross-sectional area of one nozzle hole is increased, the draft ratio at the time of melt spinning is increased, the frequency of yarn breakage at the time of drawing is increased, and the thermal contraction rate of the fiber tends to be increased.
[0069]
[Experiments 22 to 26 (effect of fineness of undrawn yarn)]
As in Experiments 1 to 5, 100 parts by weight of the vinyl chloride mixture was weighed to 4 kg, then the ingredients shown in Table 8 were weighed, put into a 20 L Henschel mixer and stirred. The mixture was stirred and mixed until the temperature of the product reached 135 ° C. Thereafter, stirring and mixing were continued while flowing cooling water through the jacket of the Henschel mixer, and the contents were cooled until the temperature reached 75 ° C. to obtain a vinyl chloride powder compound. The EVA-based resin used was an EVA-VCL graft resin in which vinyl chloride was graft-polymerized to an EVA resin having a vinyl acetate content of 35% by weight and a melt index of 10 to adjust the EVA content to 35%. The powder compound was made into a pellet compound as shown in Table 7 (pelletizing conditions) and then subjected to a melt spinning experiment.
[0070]
[Table 7]
The pellet compound was subjected to melt spinning / drawing / heat treatment experiments under the same spinning conditions, drawing conditions, and thermal relaxation treatment conditions as shown in Experiments 1-5. At this time, the take-up speed was changed, and the fineness of the undrawn yarn was set as shown in Table 8. Further, the undrawn yarn and the drawn yarn were evaluated in exactly the same manner by the test methods and evaluation methods shown in Experiments 1 to 5. The evaluation results are shown in Table 8.
[0072]
[Table 8]
As can be seen from the comparison of Experiments 22 to 26, when the fineness of the undrawn yarn exceeds 300 denier, it is necessary to draw excessively in the drawing treatment in order to obtain a drawn yarn of 65 to 70 denier. For this reason, when the drawing treatment is performed, not only the frequency of yarn breakage is increased, but also the feel of the drawn yarn becomes a plastic sliding feel, and the gloss becomes glossy and the fiber is insufficient in quality. On the other hand, if the undrawn yarn has a fineness of 300 denier or less, these qualities are highly balanced, and excellent fibers for artificial hair that are very similar to human hair can be obtained.
[0074]
[Experiments 27 to 31 (effect of fineness of drawn yarn)]
Weigh so that 100 parts by weight of the vinyl chloride mixture is 4 kg, then weigh each of the compounding agents shown in Table 9 and put them into a 20 L Henschel mixer. Stir and mix until complete. Thereafter, stirring and mixing were continued while flowing cooling water through the jacket of the Henschel mixer, and the contents were cooled until the temperature reached 75 ° C. to obtain a vinyl chloride powder compound. The EVA-based resin used was an EVA-VCL graft resin in which vinyl chloride was graft-polymerized to an EVA resin having a vinyl acetate content of 35% by weight and a melt index of 10 to adjust the EVA content to 35%. The powder compound was subjected to melt spinning / drawing / heat treatment experiments under the same spinning conditions, drawing conditions, and thermal relaxation treatment conditions as shown in Experiments 1-5. At this time, the draw ratio was changed, and the fineness of the drawn yarn was set to Table 9. Further, the undrawn yarn and the drawn yarn were evaluated in exactly the same manner by the test methods and evaluation methods shown in Experiments 1 to 5. Table 9 shows the evaluation results.
[0075]
[Table 9]
As can be seen from the comparison of Experiments 27 to 31, when the fineness of the drawn yarn exceeds 100 denier, the feel of the drawn yarn becomes stiff and hard, and the suppleness is inferior. Insufficient fiber. On the other hand, if the fineness of the drawn yarn is 100 deniers or less, these qualities are highly balanced, and excellent fibers for artificial hair that are very similar to human hair can be obtained.
[0077]
【The invention's effect】
As described above, by using the vinyl chloride resin composition of the present invention, it is possible to obtain a vinyl chloride fiber excellent in quality and having a smooth touch with a 7-part to semi-glossy surface very similar to human hair, Moreover, if the manufacturing method of this invention is used, the target vinyl chloride type fiber can be manufactured safely, maintaining high spinning productivity. The vinyl chloride fiber of the present invention is useful as a fiber for artificial hair for hair decoration, or as a hair fiber for dolls such as doll hair.
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07761798A JP3791177B2 (en) | 1997-07-31 | 1998-03-25 | Vinyl chloride fiber and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-206414 | 1997-07-31 | ||
| JP20641497 | 1997-07-31 | ||
| JP07761798A JP3791177B2 (en) | 1997-07-31 | 1998-03-25 | Vinyl chloride fiber and method for producing the same |
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| Publication Number | Publication Date |
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| JPH11100714A JPH11100714A (en) | 1999-04-13 |
| JP3791177B2 true JP3791177B2 (en) | 2006-06-28 |
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| JP07761798A Expired - Lifetime JP3791177B2 (en) | 1997-07-31 | 1998-03-25 | Vinyl chloride fiber and method for producing the same |
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| KR20060065725A (en) * | 2003-10-03 | 2006-06-14 | 덴끼 가가꾸 고교 가부시키가이샤 | Vinyl Chloride Fiber and Manufacturing Method Thereof |
| US20070270532A1 (en) * | 2004-09-30 | 2007-11-22 | Kaneka Corporation | Polyvinyl Chloride Fiber and Process for Production Thereof |
| KR101228471B1 (en) * | 2010-03-16 | 2013-02-08 | (주)우노 앤 컴퍼니 | Polyvinyl Chloride Filaments for Artificial Hair and Method for Preparing Same |
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