JPH04253764A - Polyester-polyester block copolymer composition - Google Patents
Polyester-polyester block copolymer compositionInfo
- Publication number
- JPH04253764A JPH04253764A JP977791A JP977791A JPH04253764A JP H04253764 A JPH04253764 A JP H04253764A JP 977791 A JP977791 A JP 977791A JP 977791 A JP977791 A JP 977791A JP H04253764 A JPH04253764 A JP H04253764A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- block copolymer
- polyester block
- compound
- melt viscosity
- 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.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 88
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- -1 phosphorus compound Chemical class 0.000 abstract description 41
- 150000001875 compounds Chemical class 0.000 abstract description 25
- 239000004593 Epoxy Substances 0.000 abstract description 23
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- UPWGGXLAZRGSTI-UHFFFAOYSA-N CCCC[Zr](CCCC)(CCCC)CCCC Chemical compound CCCC[Zr](CCCC)(CCCC)CCCC UPWGGXLAZRGSTI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical class C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- MXTOFRMIIQQSOE-UHFFFAOYSA-N butane;titanium(4+) Chemical compound [Ti+4].CCC[CH2-].CCC[CH2-].CCC[CH2-].CCC[CH2-] MXTOFRMIIQQSOE-UHFFFAOYSA-N 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 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
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- WTLNIWWRURSHGY-UHFFFAOYSA-N oxiran-2-ylmethyl 4-(oxiran-2-ylmethoxy)benzoate Chemical compound C=1C=C(OCC2OC2)C=CC=1C(=O)OCC1CO1 WTLNIWWRURSHGY-UHFFFAOYSA-N 0.000 description 1
- ZYDGQQTXLBNSGJ-UHFFFAOYSA-N oxonan-2-one Chemical compound O=C1CCCCCCCO1 ZYDGQQTXLBNSGJ-UHFFFAOYSA-N 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は結晶性芳香族ポリエステ
ルをハードセグメントとし、脂肪族ポリエステルのポリ
ラクトンをソフトセグメントとするポリエステルポリエ
ステルブロック共重合体組成物に関するものである。さ
らに詳しくは、溶融粘度、および成形時の熱安定性の改
善された衝撃強度に優れたポリエステルポリエステルブ
ロック共重合体組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester-polyester block copolymer composition having a crystalline aromatic polyester as a hard segment and an aliphatic polyester polylactone as a soft segment. More specifically, the present invention relates to a polyester-polyester block copolymer composition that has excellent melt viscosity, improved thermal stability during molding, and excellent impact strength.
【０００２】0002
【従来の技術】ポリブチレンテレフタレートのような結
晶性芳香族ポリエステルがハードセグメントを構成し、
ポリラクトンがソフトセグメントを構成するポリエステ
ルポリエステルタイプのブロック共重合体は、引張強度
、衝撃強度、屈曲疲労性、耐熱劣化性、耐光性に優れた
熱可塑性エラストマである。[Prior Art] A crystalline aromatic polyester such as polybutylene terephthalate constitutes a hard segment,
A polyester-polyester type block copolymer in which polylactone constitutes a soft segment is a thermoplastic elastomer with excellent tensile strength, impact strength, bending fatigue resistance, heat deterioration resistance, and light resistance.
【０００３】このポリエステルポリエステルブロック共
重合体は、特公昭４８−４１１６号公報にある、結晶性
芳香族ポリエステルとラクトン化合物とを溶融混合して
反応させる方法、特公昭５２−４９０３７号公報にある
、結晶性芳香族ポリエステルの存在下にラクトンを前者
が固相の状態で重合する方法などによって得られること
が知られている。[0003] This polyester polyester block copolymer can be produced by the method described in Japanese Patent Publication No. 48-4116, in which a crystalline aromatic polyester and a lactone compound are melt-mixed and reacted, and the method described in Japanese Patent Publication No. 52-49037. It is known that it can be obtained by polymerizing lactone in the presence of a crystalline aromatic polyester while the former is in a solid phase.
【０００４】しかしながら、これらの方法で得られたポ
リマは溶融粘度が低く、衝撃強度に劣るという問題を有
している。このポリエステルポリエステルブロック共重
合体の溶融粘度の低さを改善する方法としては、特開昭
６０−４５１８号公報に、２官能以上のイソシアネート
化合物を配合することが提案されている。However, the polymers obtained by these methods have the problem of low melt viscosity and poor impact strength. As a method for improving the low melt viscosity of this polyester polyester block copolymer, it has been proposed in JP-A-60-4518 to blend a difunctional or higher functional isocyanate compound.
【０００５】また、エポキシ化合物を配合する方法とし
ては、特開昭５８−１６２６５４号公報に、１官能以上
のエポキシ化合物、および反応促進剤としてトリフェニ
ルホスフィン等の３価のリン化合物、アミン類、炭素数
１０以上のカルボン酸のＩ−ａあるいはＩＩ−ａ族の金
属塩などを配合することが提案されている。[0005] Furthermore, as a method of blending an epoxy compound, JP-A-58-162654 discloses a method of blending an epoxy compound with one or more functional groups, a trivalent phosphorus compound such as triphenylphosphine, amines, etc. as a reaction accelerator. It has been proposed to incorporate a group I-a or II-a metal salt of a carboxylic acid having 10 or more carbon atoms.
【０００６】また、溶融粘度の温度依存性を改善する方
法として有機亜リン酸エステルを配合する方法が、特開
昭５２−４７７８３号公報に提案されている。Furthermore, as a method of improving the temperature dependence of melt viscosity, a method of blending an organic phosphite is proposed in JP-A-52-47783.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、上記、
特開昭６０−４５１８号公報記載の組成物では、低溶融
粘度および衝撃強度に劣るという問題を有している。[Problem to be solved by the invention] However, the above,
The composition described in JP-A-60-4518 has the problems of low melt viscosity and poor impact strength.
【０００８】また、特開昭５８−１６２６５４号公報記
載の組成物は、成形時の熱安定性が不十分なため、衝撃
強度に劣るという問題を有している。[0008] Furthermore, the composition described in JP-A-58-162654 has a problem of poor impact strength due to insufficient thermal stability during molding.
【０００９】また、特開昭５２−４７７８３号公報によ
る有機亜リン酸エステルを配合する組成物は、添加量が
多いため有機亜リン酸エステルが成形材料の表面に析出
するため実用に供し得ない。[0009] Furthermore, the composition containing an organic phosphite according to JP-A-52-47783 cannot be put to practical use because the amount added is large and the organic phosphite precipitates on the surface of the molding material. .
【００１０】よって、本発明の目的は、溶融粘度が高く
、さらに溶融滞留中の溶融粘度の低下がなく、安定して
成形できる衝撃強度に優れたポリエステルポリエステル
ブロック共重合体組成物を提供するものである。Therefore, an object of the present invention is to provide a polyester-polyester block copolymer composition which has high melt viscosity, does not decrease in melt viscosity during melt retention, can be stably molded, and has excellent impact strength. It is.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、ポリエス
テルポリエステルブロック共重合体の溶融粘度と成形時
における熱安定性の問題点を解決すべく鋭意検討した結
果、１官能以上のエポキシ化合物と５価のリン化合物を
ポリエステルポリエステルブロック共重合体に配合する
ことによって、ポリエステルポリエステルブロック共重
合体の低溶融粘度および熱安定性が改善され、衝撃強度
に優れることを見いだし、本発明に到達した。[Means for Solving the Problems] As a result of intensive studies to solve the problems of melt viscosity and thermal stability during molding of polyester polyester block copolymers, the present inventors have found that monofunctional or more functional epoxy compounds and We have discovered that by blending a pentavalent phosphorus compound into a polyester polyester block copolymer, the polyester polyester block copolymer has improved low melt viscosity and thermal stability, and has excellent impact strength, and has arrived at the present invention.
【００１２】すなわち本発明は、結晶性芳香族ポリエス
テルおよび、ポリラクトンを主たる構成成分とするポリ
エステルポリエステルブロック共重合体１００重量部に
対し、（ａ）１官能以上のエポキシ化合物を０．０１〜
１０重量部、および（ｂ）５価のリン化合物を０．００
５〜１重量部含有してなるポリエステルポリエステルブ
ロック共重合体組成物を提供するものである。That is, in the present invention, (a) 0.01 to 100 parts by weight of a monofunctional or more functional epoxy compound is added to 100 parts by weight of a polyester polyester block copolymer containing a crystalline aromatic polyester and a polylactone as main components.
10 parts by weight, and (b) 0.00 pentavalent phosphorus compound
A polyester polyester block copolymer composition containing 5 to 1 parts by weight is provided.
【００１３】本発明においては、５価のリン化合物をエ
ポキシ化合物とともにポリエステルポリエステルブロッ
ク共重合体組成物に添加することが重要である。これに
より、溶融粘度が十分高く、熱安定性の改善された、衝
撃強度に優れたポリエステルポリエステルブロック共重
合体組成物が得られるのである。In the present invention, it is important to add a pentavalent phosphorus compound to the polyester-polyester block copolymer composition together with the epoxy compound. As a result, a polyester-polyester block copolymer composition having sufficiently high melt viscosity, improved thermal stability, and excellent impact strength can be obtained.
【００１４】本発明で使用するポリエステルポリエステ
ルブロック共重合体とは、結晶性芳香族ポリエステルを
ハードセグメントとし、ポリラクトンをソフトセグメン
トとするポリエステルポリエステルブロック共重合体で
あれば、その製造方法は特に限定されるものではない。
例えば、撹拌翼を備えたバッチ式反応槽に結晶性芳香族
ポリエステルとラクトン化合物を投入し重合反応をおこ
なっても良いし、あるいは、押出機を重合反応装置とし
て用い、結晶性芳香族ポリエステルとラクトン化合物を
連続的に供給し、ポリエステルポリエステルブロック共
重合体を連続的に得ることもできる。また、芳香族ジカ
ルボン酸と脂肪族ジオールを撹拌翼を備えた反応容器に
仕込み、エステル化反応後、ポリカプロラクトンを投入
し減圧下で重縮合させることによってポリエステルポリ
エステルブロック共重合体を得ることもできる。[0014] The polyester-polyester block copolymer used in the present invention is a polyester-polyester block copolymer having a crystalline aromatic polyester as a hard segment and a polylactone as a soft segment, and the manufacturing method thereof is not particularly limited. It's not something you can do. For example, a polymerization reaction may be carried out by charging the crystalline aromatic polyester and the lactone compound into a batch type reaction tank equipped with a stirring blade, or alternatively, the crystalline aromatic polyester and the lactone compound may be charged into a batch type reaction tank equipped with stirring blades, or an extruder may be used as a polymerization reaction apparatus, and the crystalline aromatic polyester and the lactone compound may be charged into a batch type reaction tank equipped with a stirring blade. A polyester-polyester block copolymer can also be obtained continuously by continuously supplying the compound. Alternatively, a polyester-polyester block copolymer can also be obtained by charging an aromatic dicarboxylic acid and an aliphatic diol into a reaction vessel equipped with a stirring blade, and after the esterification reaction, polycaprolactone is added and polycondensation is performed under reduced pressure. .
【００１５】本発明において、結晶性芳香族ポリエステ
ルとは、主たる繰り返し単位中に少なくとも１種の芳香
族基とエステル結合を有する重合体であり、ポリエチレ
ンテレフタレート、ポリブチレンテレフタレート、ポリ
１，４−シクロヘキシレンジメチレンテレフタレート、
ポリエチレン２，６−ナフタレート、ポリブチレン２，
６−ナフタレートなどが挙げられるが、これらのポリエ
ステルの混合物や、これらのポリエステルにさらにイソ
フタル酸単位、アジピン酸、セバシン酸、ドデカン二酸
などの脂肪族ジカルボン酸単位、ｐ−オキシ安息香酸単
位などが共重合された共重合ポリエステルも挙げること
ができる。なかでも、ポリブチレンテレフタレートは、
結晶性に優れており特に好ましい。[0015] In the present invention, the crystalline aromatic polyester is a polymer having at least one aromatic group and an ester bond in the main repeating unit, and includes polyethylene terephthalate, polybutylene terephthalate, poly 1,4-cyclohexyl silane dimethylene terephthalate,
polyethylene 2,6-naphthalate, polybutylene 2,
6-naphthalate, mixtures of these polyesters, isophthalic acid units, aliphatic dicarboxylic acid units such as adipic acid, sebacic acid, dodecanedioic acid, p-oxybenzoic acid units, etc. Mention may also be made of copolymerized polyesters. Among them, polybutylene terephthalate is
It has excellent crystallinity and is particularly preferred.
【００１６】本発明においてラクトン化合物としては、
ε−カプロラクトン、エナントラクトン、カプリロラク
トンなどが挙げられ、またこれらの混合物を用いること
もできる。なかでも、結晶性芳香族ポリエステルとの反
応性や得られるポリエステルポリエステルブロック共重
合体の弾性特性から、ε−カプロラクトンが好ましい。
本発明で使用されるポリエステルポリエステルブロ
ック共重合体における結晶性芳香族ポリエステルとラク
トン化合物の組成比は、得られるポリエステルポリエス
テルブロック共重合体の機械的性質から、結晶性芳香族
ポリエステル／ラクトン化合物の重量比で、９９／１〜
２０／８０が好ましく、特に好ましくは、９８／２〜３
０／７０である。[0016] In the present invention, the lactone compound includes:
Examples include ε-caprolactone, enantlactone, caprylolactone, and mixtures thereof can also be used. Among these, ε-caprolactone is preferred from the viewpoint of reactivity with the crystalline aromatic polyester and elastic properties of the resulting polyester-polyester block copolymer. The composition ratio of the crystalline aromatic polyester and the lactone compound in the polyester polyester block copolymer used in the present invention is determined based on the mechanical properties of the obtained polyester polyester block copolymer by the weight of the crystalline aromatic polyester/lactone compound. Ratio: 99/1~
20/80 is preferred, particularly preferably 98/2-3
It is 0/70.
【００１７】本発明で使用されるポリエステルポリエス
テルブロック共重合体を得るために結晶性芳香族ポリエ
ステルとラクトン化合物を反応させる際、触媒を添加し
ても良いし、無触媒で反応させても良い。触媒としては
、ラクトン化合物の開環重合触媒で公知の触媒がすべて
使用でき、具体的にはリチウム、カリウム、ナトリウム
、マグネシウム、カルシウム、バリウム、亜鉛、アルミ
ニウム、チタン、コバルト、ゲルマニウム、錫、アンチ
モン、カドミウム、マンガン、ジルコニウムなどの金属
、これらの有機金属化合物、有機酸塩、アルコラート、
アルコキシド等が挙げられる。特に好ましくは、ジアシ
ル第一錫、テトラアシル第二錫、モノブチル錫オキサイ
ド、モノブチルモノヒドロキシ錫オキサイド、ジブチル
錫オキサイド、ジブチル錫ジラウレート、錫テトラアセ
テートなどの錫化合物、トリイソブチルアルミニウム、
テトラブチルチタン、テトラブチルジルコニウム、二酸
化ゲルマニウム、三酸化アンチモン、酢酸コバルトなど
が使用でき、またこれらの触媒は２種以上併用しても良
い。When reacting the crystalline aromatic polyester and the lactone compound to obtain the polyester polyester block copolymer used in the present invention, a catalyst may be added or the reaction may be carried out without a catalyst. As the catalyst, all known catalysts for ring-opening polymerization of lactone compounds can be used, specifically lithium, potassium, sodium, magnesium, calcium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, antimony, Metals such as cadmium, manganese, zirconium, their organometallic compounds, organic acid salts, alcoholates,
Examples include alkoxides. Particularly preferred are tin compounds such as diacyl stannous, tetraacyl stannous, monobutyltin oxide, monobutyl monohydroxytin oxide, dibutyltin oxide, dibutyltin dilaurate, tin tetraacetate, triisobutylaluminum,
Tetrabutyl titanium, tetrabutyl zirconium, germanium dioxide, antimony trioxide, cobalt acetate, etc. can be used, and two or more of these catalysts may be used in combination.
【００１８】本発明に使用されるエポキシ化合物とは、
同一分子内に１個以上のエポキシ基を有するものであれ
ば、その構造は特に制限されない。具体的には、下記一
般式（Ｉ）〜（Ｖ）で示される化合物を例として挙げる
ことができる。The epoxy compound used in the present invention is:
The structure is not particularly limited as long as it has one or more epoxy groups in the same molecule. Specifically, compounds represented by the following general formulas (I) to (V) can be mentioned as examples.
【００１９】[0019]
【化１】[Chemical formula 1]
【００２０】（式中、Ｒ１ 、Ｒ２ は１価の、側鎖を
有するか有しないアルキル基、側鎖を有するか有しない
アルキレン基、芳香族または置換基を有するその誘導体
、脂環族基または置換基を有するその誘導体、Ｒ３〜Ｒ
５ は２価の、側鎖を有するか有しないアルキル基、側
鎖を有するか有しないアルキレン基、芳香族または置換
基を有するその誘導体、脂環族基または置換基を有する
その誘導体を表わす。）さらに具体的には、メチルグリ
シジルエーテル、フェニルグリシジルエーテル、ジエチ
レングリコールジグリシジルエーテル、水添イソフタル
酸ジグリシジルエステル、ビスフェノールＡジグリシジ
ルエーテル、ｐ−グリシジルオキシベンゾエートグリシ
ジルエステルなどがエポキシ化合物の例として挙げられ
る。本発明においては、２官能以上のエポキシ化合物の
使用が特に好ましい。これらのエポキシ化合物は、２種
以上を併用してもよい。(wherein R1 and R2 are monovalent alkyl groups with or without side chains, alkylene groups with or without side chains, aromatic groups or derivatives thereof with substituents, alicyclic groups, or Derivatives thereof with substituents, R3-R
5 represents a divalent alkyl group with or without a side chain, an alkylene group with or without a side chain, an aromatic group or a derivative thereof having a substituent, an alicyclic group or a derivative thereof having a substituent. ) More specifically, examples of epoxy compounds include methyl glycidyl ether, phenyl glycidyl ether, diethylene glycol diglycidyl ether, hydrogenated isophthalic acid diglycidyl ester, bisphenol A diglycidyl ether, p-glycidyloxybenzoate glycidyl ester, etc. . In the present invention, it is particularly preferable to use a difunctional or higher functional epoxy compound. Two or more of these epoxy compounds may be used in combination.
【００２１】本発明におけるエポキシ化合物の添加量は
、ポリエステルポリエステルブロック共重合体１００重
量部に対して０．０１重量部〜１０重量部であり、特に
好ましくは０．１重量部〜３重量部である。０．０１重
量部未満ではエポキシ化合物の効果が小さく、１０重量
部を越えるとエポキシ化合物によっては溶融滞留中に溶
融粘度が増加し、好ましくない。The amount of the epoxy compound added in the present invention is from 0.01 parts by weight to 10 parts by weight, particularly preferably from 0.1 parts by weight to 3 parts by weight, based on 100 parts by weight of the polyester polyester block copolymer. be. If it is less than 0.01 part by weight, the effect of the epoxy compound is small, and if it exceeds 10 parts by weight, the melt viscosity may increase during melt retention depending on the epoxy compound, which is not preferable.
【００２２】本発明に用いられる５価のリン化合物とは
リン酸、ホスホン酸、ホスフィン酸、リン酸エステル、
ホスホン酸エステル、ホスフィン酸エステル等のリン化
合物であり、具体的には、下記一般式（Ｉ）〜（ＩＩＩ
） で示される化合物を例に挙げることができる。The pentavalent phosphorus compounds used in the present invention include phosphoric acid, phosphonic acid, phosphinic acid, phosphoric ester,
These are phosphorus compounds such as phosphonic acid esters and phosphinic acid esters, and specifically, the following general formulas (I) to (III
) can be cited as an example.
【００２３】[0023]
【化２】[Case 2]
【００２４】（式中、Ｒ１ 、Ｒ２ 、Ｒ３ は水素原
子、または炭素数１〜２５の炭化水素基であってそれぞ
れ同一であっても異なっていてもよく、また炭化水素基
中に−ＣＯＯ−、−ＣＯＮＨ−結合のいずれかを有する
ことができる。）本発明における５価のリン化合物の添
加量は、ポリエステルポリエステルブロック共重合体１
００重量部に対して０．００５〜１重量部であり、好ま
しくは０．０１〜１重量部である。０．００５重量部未
満では本発明の効果が少なく、１重量部を越えると成形
品の表面にリン化合物が析出するため好ましくない。(In the formula, R1, R2, and R3 are hydrogen atoms or hydrocarbon groups having 1 to 25 carbon atoms, and may be the same or different, and -COO- , -CONH- bond.) The amount of the pentavalent phosphorus compound added in the present invention is as follows: polyester polyester block copolymer 1
The amount is 0.005 to 1 part by weight, preferably 0.01 to 1 part by weight. If it is less than 0.005 part by weight, the effect of the present invention will be small, and if it exceeds 1 part by weight, a phosphorus compound will precipitate on the surface of the molded product, which is not preferable.
【００２５】上記（ａ）エポキシ化合物、（ｂ）５価の
リン化合物の添加方法は特に限定されるものでなく、（
ａ）エポキシ化合物、（ｂ）５価のリン化合物を結晶性
芳香族ポリエステルとラクトン化合物の重合反応前に原
料である結晶性芳香族ポリエステルあるいはラクトン化
合物に、一緒にあるいは別々に添加する方法、結晶性芳
香族ポリエステルとラクトン化合物の反応で生成したポ
リエステルポリエステルブロック共重合体に反応直後の
溶融状態で混合する方法、生成したポリエステルポリエ
ステルブロック共重合体チップに添加し、加熱溶融混合
する方法などが挙げられる。生成したポリエステルポリ
エステルブロック共重合体に溶融添加する場合その温度
は、該ポリエステルポリエステルブロック共重合体の結
晶温度より５℃高い温度から２８０℃までが望ましい。
またその場合混合時間は、通常１５秒から１２０分で温
度や混合に使用する方法によって異なる。The method of adding the above (a) epoxy compound and (b) pentavalent phosphorus compound is not particularly limited;
A method in which a) an epoxy compound, and (b) a pentavalent phosphorus compound are added together or separately to a crystalline aromatic polyester or a lactone compound as a raw material before the polymerization reaction of the crystalline aromatic polyester and a lactone compound; Examples include a method of mixing the polyester polyester block copolymer produced by the reaction of an aromatic polyester and a lactone compound in a molten state immediately after the reaction, and a method of adding it to the produced polyester polyester block copolymer chips and heating and melt-mixing. It will be done. When melting and adding to the produced polyester-polyester block copolymer, the temperature is preferably from 5°C higher than the crystallization temperature of the polyester-polyester block copolymer to 280°C. In that case, the mixing time usually ranges from 15 seconds to 120 minutes and varies depending on the temperature and the method used for mixing.
【００２６】また本発明組成物は、本発明の目的を損な
わない範囲で、公知のヒンダードフェノール系、ホスフ
ァイト系、チオエーテル系、アミン系などの酸化防止剤
、ベンゾフェノン系、ヒンダードアミン系などの耐候剤
、含フッ素系ポリマ、シリコーンオイル、ステアリン酸
金属塩、モンタン酸金属塩、モンタン酸エステルワック
ス、ポリエチレンワックスなどの離型剤、染料や顔料な
どの着色剤、酸化チタン、カーボンブラックなどの紫外
線遮断剤、ガラス繊維やカーボンファイバー、チタン酸
カリファイバーなどの強化剤、シリカ、クレー、炭酸カ
ルシウム、硫酸カルシウム、ガラスビーズなどの充填剤
、タルクなどの核剤、難燃剤、可塑剤、接着剤、接着助
剤などを任意に含有せしめることができる。これらの添
加剤は、あらかじめポリエステルポリエステルブロック
共重合体に配合していても良いし、上記（ａ）エポキシ
化合物（ｂ）５価のリン化合物とともにポリエステルポ
リエステルブロック共重合体に配合しても良いし、また
上記（ａ）エポキシ化合物（ｂ）５価のリン化合物を添
加して得られる組成物に添加しても良い。The composition of the present invention may also contain weather-resistant antioxidants such as known hindered phenol-based, phosphite-based, thioether-based, and amine-based antioxidants, and benzophenone-based and hindered amine-based antioxidants, to the extent that the objects of the present invention are not impaired. Mold release agents such as agents, fluorine-containing polymers, silicone oils, metal stearates, metal salts of montanate, montanate ester wax, polyethylene wax, coloring agents such as dyes and pigments, and ultraviolet blocking agents such as titanium oxide and carbon black. reinforcing agents such as glass fiber, carbon fiber, and caulifiber titanate, fillers such as silica, clay, calcium carbonate, calcium sulfate, and glass beads, nucleating agents such as talc, flame retardants, plasticizers, adhesives, and adhesives. Auxiliary agents and the like can be optionally included. These additives may be blended in advance into the polyester polyester block copolymer, or may be blended into the polyester polyester block copolymer together with the above (a) epoxy compound (b) pentavalent phosphorus compound. It may also be added to a composition obtained by adding (a) the epoxy compound and (b) the pentavalent phosphorus compound.
【００２７】[0027]
【作用】本発明では、ポリエステルポリエステルブロッ
ク共重合体に（ａ）エポキシ化合物（ｂ）５価のリン化
合物を添加することによって、溶融粘度が高く、さらに
成形時の溶融滞留時における熱安定性が改善され、衝撃
強度に優れたポリエステルポリエステルブロック共重合
体組成物が得られる。[Function] In the present invention, by adding (a) an epoxy compound and (b) a pentavalent phosphorus compound to the polyester polyester block copolymer, the melt viscosity is high and the thermal stability during melt retention during molding is improved. A polyester-polyester block copolymer composition with improved impact strength is obtained.
【００２８】[0028]
【実施例】以下に実施例によって本発明の効果を説明す
る。なお、実施例中の％および部とは、ことわりのない
場合すべて重量基準である。実施例、比較例中に示され
る物性は次のように測定した。[Example] The effects of the present invention will be explained below with reference to Examples. Note that all percentages and parts in the examples are based on weight unless otherwise specified. The physical properties shown in Examples and Comparative Examples were measured as follows.
【００２９】成形機中のポリマの平均滞留時間が約２０
分の５オンスの射出成形能力を有する射出成形機と金型
を用いて、シリンダー温度２４０℃、金型温度６０℃で
１／２インチ厚さのアイゾット衝撃試験片を射出成形し
た。アイゾット衝撃強度の評価方法は、ＡＳＴＭ Ｄ
−２５６に従って測定した。The average residence time of the polymer in the molding machine is approximately 20
1/2 inch thick Izod impact test specimens were injection molded using an injection molding machine and mold having a 5/4 oz injection molding capacity at a cylinder temperature of 240°C and a mold temperature of 60°C. The evaluation method for Izod impact strength is ASTM D
-256.
【００３０】溶融粘度指数（ＭＩ値）はＡＳＴＭ Ｄ
−１２３８に従って、温度２４０℃、荷重２１６０ｇで
測定した。[0030] Melt viscosity index (MI value) is ASTM D
-1238, the temperature was 240°C and the load was 2160g.
【００３１】熱安定性は射出成形品のＭＩ値を測定して
、射出成形前のＭＩ値との差を比較した。Thermal stability was determined by measuring the MI value of the injection molded product and comparing the difference with the MI value before injection molding.
【００３２】製造例１
ポリブチレンテレフタレート７５部、ε−カプロラクト
ン２５部、および触媒としてモノブチルモノヒドロキシ
錫オキサイド０．０３部を撹拌翼および減圧装置を備え
た反応器にとり、窒素雰囲気下２３０℃で撹拌しながら
３０分間溶融反応させた。ついで減圧下で未反応ε−カ
プロラクトンを除去し、ポリエステルポリエステルブロ
ック共重合体Ａ−１を得た。得られたポリマの融点は２
０８℃であった。Production Example 1 75 parts of polybutylene terephthalate, 25 parts of ε-caprolactone, and 0.03 part of monobutyl monohydroxytin oxide as a catalyst were placed in a reactor equipped with a stirring blade and a pressure reduction device, and the mixture was heated at 230°C under a nitrogen atmosphere. The melt reaction was carried out for 30 minutes while stirring. Then, unreacted ε-caprolactone was removed under reduced pressure to obtain polyester polyester block copolymer A-1. The melting point of the obtained polymer is 2
The temperature was 08°C.
【００３３】製造例２
ポリブチレンテレフタレート５０部、ε−カプロラクト
ン５０部を製造例１と同様に反応させ、ポリエステルポ
リエステルブロック共重合体Ａ−２を得た。得られたポ
リマの融点は１９２℃であった。Production Example 2 50 parts of polybutylene terephthalate and 50 parts of ε-caprolactone were reacted in the same manner as in Production Example 1 to obtain polyester polyester block copolymer A-2. The melting point of the obtained polymer was 192°C.
【００３４】実施例１〜４、比較例３〜５ポリエステル
ポリエステルブロック共重合体Ａ−１およびＡ−２に表
１に示すエポキシ化合物、および５価または３価のリン
化合物を同表に示す配合量で、Ｖ−ブレンダーを用いて
混合し、４５ｍｍφのスクリューを有する２軸押出機を
用いて２４０℃で溶融混練し、ポリエステルポリエステ
ルブロック共重合体組成物を得た。Examples 1 to 4, Comparative Examples 3 to 5 Polyester polyester block copolymers A-1 and A-2 were mixed with the epoxy compounds shown in Table 1 and the pentavalent or trivalent phosphorus compounds shown in the same table. The mixture was mixed using a V-blender and melt-kneaded at 240°C using a twin-screw extruder having a screw of 45 mmφ to obtain a polyester-polyester block copolymer composition.
【００３５】[0035]
【表１】[Table 1]
【００３６】比較例１〜２
製造例１のポリエステルポリエステルブロック共重合体
Ａ−１を比較例１のポリマ、製造例２のＡ−２を比較例
２のポリマとする。Comparative Examples 1 to 2 The polyester polyester block copolymer A-1 of Production Example 1 was used as the polymer of Comparative Example 1, and A-2 of Production Example 2 was used as the polymer of Comparative Example 2.
【００３７】実施例１〜４および比較例１〜５のポリマ
の物性を表２に示す。Table 2 shows the physical properties of the polymers of Examples 1 to 4 and Comparative Examples 1 to 5.
【００３８】[0038]
【表２】[Table 2]
【００３９】比較例１と実施例１〜３の比較によりポリ
エステルポリエステルブロック共重合体にエポキシ化合
物と５価のリン化合物を配合することによって、溶融粘
度および衝撃強度が著しく改善される。さらに、比較例
２と実施例４の比較により共重合成分量が異なっていて
も同様に、上記の性能は著しく改善されることが判明し
た。また、比較例３に示すエポキシ化合物のみの配合、
比較例４に示すエポキシ化合物とトリフェニルフォスフ
ィンの３価のリン化合物を配合したポリマは、成形前の
溶融粘度は改善されるものの射出成形品の溶融粘度指数
（ＭＩ値）は成形前より大きくなっていることから熱安
定性に劣り、衝撃強度はほとんど改善されないことが明
白である。また、比較例５に示す５価のリン化合物のみ
を配合したポリマは熱安定性には優れるものの溶融粘度
の改善効果が認められなく衝撃強度も低いことが明白で
ある。A comparison between Comparative Example 1 and Examples 1 to 3 shows that melt viscosity and impact strength are significantly improved by blending an epoxy compound and a pentavalent phosphorus compound into a polyester-polyester block copolymer. Further, by comparing Comparative Example 2 and Example 4, it was found that the above-mentioned performance was similarly significantly improved even if the copolymerization content was different. In addition, the formulation of only the epoxy compound shown in Comparative Example 3,
Although the melt viscosity before molding of the polymer blended with the epoxy compound and the trivalent phosphorus compound of triphenylphosphine shown in Comparative Example 4 was improved, the melt viscosity index (MI value) of the injection molded product was larger than before molding. It is clear that the thermal stability is poor and the impact strength is hardly improved. Further, it is clear that the polymer shown in Comparative Example 5 containing only a pentavalent phosphorus compound has excellent thermal stability, but does not show any improvement in melt viscosity and has low impact strength.
【００４０】[0040]
【発明の効果】本発明は、（ａ）１官能以上のエポキシ
化合物および（ｂ）５価のリン化合物を配合することに
より、溶融粘度と成形時の溶融滞留時の熱安定性が改善
され、衝撃強度に優れ、安定して成形できるポリエステ
ルポリエステルブロック共重合体組成物を提供するもの
である。さらには、熱安定性に優れることからリサイク
ル性にも優れることが期待でき、安定して成形できる熱
可塑性エラストマとしてポリエステルポリエステルブロ
ック共重合体の用途が拡大されることが予想される。Effects of the Invention The present invention improves melt viscosity and thermal stability during melt retention during molding by blending (a) an epoxy compound with more than one functionality and (b) a pentavalent phosphorus compound. The present invention provides a polyester-polyester block copolymer composition that has excellent impact strength and can be stably molded. Furthermore, since it has excellent thermal stability, it is expected to have excellent recyclability, and it is expected that the use of the polyester-polyester block copolymer will be expanded as a thermoplastic elastomer that can be stably molded.
Claims (1)
ントとし、ポリラクトンをソフトセグメントとするポリ
エステルポリエステルブロック共重合体１００重量部に
対し、（ａ）１官能以上のエポキシ化合物を０．０１〜
１０重量部、および（ｂ）５価のリン化合物を０．００
５〜１重量部含有してなるポリエステルポリエステルブ
ロック共重合体組成物。Claim 1: (a) 0.01 to 100 parts by weight of a polyester-polyester block copolymer having a crystalline aromatic polyester as a hard segment and a polylactone as a soft segment;
10 parts by weight, and (b) 0.00 pentavalent phosphorus compound
A polyester polyester block copolymer composition containing 5 to 1 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP977791A JPH04253764A (en) | 1991-01-30 | 1991-01-30 | Polyester-polyester block copolymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP977791A JPH04253764A (en) | 1991-01-30 | 1991-01-30 | Polyester-polyester block copolymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04253764A true JPH04253764A (en) | 1992-09-09 |
Family
ID=11729676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP977791A Pending JPH04253764A (en) | 1991-01-30 | 1991-01-30 | Polyester-polyester block copolymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04253764A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5869582A (en) * | 1997-01-22 | 1999-02-09 | Alliedsignal Inc. | Diblock polyester copolymer and process for making |
| JP2002003605A (en) * | 2000-06-21 | 2002-01-09 | Daicel Chem Ind Ltd | Polyester block copolymer resin composition and method of manufacture |
| WO2002098946A1 (en) * | 2001-06-05 | 2002-12-12 | Cyclics Corporation | Copolyesters and polymerization of macrocyclic oligoesters |
| US6593434B1 (en) * | 1999-08-05 | 2003-07-15 | Daicel Chemical Industries, Ltd. | Preparing polyester block copolymer with excess unreacted lactones to be removed |
| US6613257B2 (en) | 1998-05-22 | 2003-09-02 | Alliedsignal Inc. | Process for making load limiting yarn |
| EP1378540A4 (en) * | 2001-04-03 | 2005-04-27 | Daicel Chem | Polyester block copolymer composition |
| JP2006016446A (en) * | 2004-06-30 | 2006-01-19 | Toray Ind Inc | Resin composition and molded article comprised of the same |
| WO2007111059A1 (en) * | 2006-03-24 | 2007-10-04 | Daicel Chemical Industries, Ltd. | Polyester resin composition and molded body |
| US7745561B2 (en) | 2006-01-31 | 2010-06-29 | Cyclics Corporation | Processes for making copolymers using macrocyclic oligoesters, and copolymers therefrom |
| US8283437B2 (en) | 2000-09-01 | 2012-10-09 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
| CN108138409A (en) * | 2015-10-16 | 2018-06-08 | 东洋纺株式会社 | The excellent reticular structure body of hydrolytic resistance and its manufacturing method |
-
1991
- 1991-01-30 JP JP977791A patent/JPH04253764A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5869582A (en) * | 1997-01-22 | 1999-02-09 | Alliedsignal Inc. | Diblock polyester copolymer and process for making |
| US6613257B2 (en) | 1998-05-22 | 2003-09-02 | Alliedsignal Inc. | Process for making load limiting yarn |
| US6593434B1 (en) * | 1999-08-05 | 2003-07-15 | Daicel Chemical Industries, Ltd. | Preparing polyester block copolymer with excess unreacted lactones to be removed |
| JP2002003605A (en) * | 2000-06-21 | 2002-01-09 | Daicel Chem Ind Ltd | Polyester block copolymer resin composition and method of manufacture |
| US8283437B2 (en) | 2000-09-01 | 2012-10-09 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
| US6914101B2 (en) | 2001-04-03 | 2005-07-05 | Daicel Chemical Industries, Ltd. | Polyester block copolymer composition |
| EP1378540A4 (en) * | 2001-04-03 | 2005-04-27 | Daicel Chem | Polyester block copolymer composition |
| WO2002098946A1 (en) * | 2001-06-05 | 2002-12-12 | Cyclics Corporation | Copolyesters and polymerization of macrocyclic oligoesters |
| JP2006016446A (en) * | 2004-06-30 | 2006-01-19 | Toray Ind Inc | Resin composition and molded article comprised of the same |
| US7745561B2 (en) | 2006-01-31 | 2010-06-29 | Cyclics Corporation | Processes for making copolymers using macrocyclic oligoesters, and copolymers therefrom |
| WO2007111059A1 (en) * | 2006-03-24 | 2007-10-04 | Daicel Chemical Industries, Ltd. | Polyester resin composition and molded body |
| JPWO2007111059A1 (en) * | 2006-03-24 | 2009-08-06 | ダイセル化学工業株式会社 | Polyester resin composition and molded body |
| CN108138409A (en) * | 2015-10-16 | 2018-06-08 | 东洋纺株式会社 | The excellent reticular structure body of hydrolytic resistance and its manufacturing method |
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