JPH04372646A - Copolymer composition - Google Patents
Copolymer compositionInfo
- Publication number
- JPH04372646A JPH04372646A JP15039091A JP15039091A JPH04372646A JP H04372646 A JPH04372646 A JP H04372646A JP 15039091 A JP15039091 A JP 15039091A JP 15039091 A JP15039091 A JP 15039091A JP H04372646 A JPH04372646 A JP H04372646A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- mol
- resin
- thermoplastic resin
- composition
- 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
- 239000000203 mixture Substances 0.000 title claims description 39
- 229920001577 copolymer Polymers 0.000 title 1
- 229920001634 Copolyester Polymers 0.000 claims abstract description 23
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 22
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 229920000728 polyester Polymers 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 abstract description 20
- 239000011347 resin Substances 0.000 abstract description 20
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 abstract description 5
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 14
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920000106 Liquid crystal polymer Polymers 0.000 description 5
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 4
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 1
- YIYBRXKMQFDHSM-UHFFFAOYSA-N 2,2'-Dihydroxybenzophenone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1O YIYBRXKMQFDHSM-UHFFFAOYSA-N 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical class CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- YXGOYRIWPLGGKN-UHFFFAOYSA-N 2,3-ditert-butylbenzene-1,4-diol Chemical class CC(C)(C)C1=C(O)C=CC(O)=C1C(C)(C)C YXGOYRIWPLGGKN-UHFFFAOYSA-N 0.000 description 1
- KRIDOPOPBBSDNT-UHFFFAOYSA-N 2,4,5-trimethylbenzene-1,3-diol Chemical class CC1=CC(O)=C(C)C(O)=C1C KRIDOPOPBBSDNT-UHFFFAOYSA-N 0.000 description 1
- UPQDHGRRFJDNOG-UHFFFAOYSA-N 2-(1,1-diphenylethyl)propanedioic acid Chemical class C=1C=CC=CC=1C(C(C(O)=O)C(O)=O)(C)C1=CC=CC=C1 UPQDHGRRFJDNOG-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical class OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical class C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- VSZJLXSVGVDPMJ-UHFFFAOYSA-N 2-phenylterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C=2C=CC=CC=2)=C1 VSZJLXSVGVDPMJ-UHFFFAOYSA-N 0.000 description 1
- QPGBFKDHRXJSIK-UHFFFAOYSA-N 2-tert-butylbenzene-1,3-dicarboxylic acid Chemical compound CC(C)(C)C1=C(C(O)=O)C=CC=C1C(O)=O QPGBFKDHRXJSIK-UHFFFAOYSA-N 0.000 description 1
- WUGKVYDVIGOPSI-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)-2-methylphenol Chemical group C1=C(O)C(C)=CC(C=2C=C(C)C(O)=CC=2)=C1 WUGKVYDVIGOPSI-UHFFFAOYSA-N 0.000 description 1
- OQBPCYUKFSJTDU-UHFFFAOYSA-N 4-Hydroxyphenyl-4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1OC(=O)C1=CC=C(O)C=C1 OQBPCYUKFSJTDU-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 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
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid 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
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ビス（ヒドロキシフェ
ニル）サルホンを一成分として有する共重合ポリエステ
ルと熱可塑性樹脂とを含む共重合ポリエステル組成物に
関するものであり、詳しくは、該熱可塑性樹脂より機械
強度が改良され、溶融加工性が優れた共重合ポリエステ
ル組成物に関するものである。[Field of Industrial Application] The present invention relates to a copolyester composition containing a thermoplastic resin and a copolyester having bis(hydroxyphenyl)sulfone as one component. The present invention relates to a copolyester composition with improved mechanical strength and excellent melt processability.
【０００２】0002
【従来の技術】近年、有機高分子材料の高性能化にたい
する産業界の要求が高まっており強度や弾性率などの力
学的性質及び耐熱性などの熱的性質の優れた射出成形品
、フィルム、繊維などの各種製品の出現が強く望まれて
いる。[Prior Art] In recent years, there has been an increasing demand in the industry for higher performance organic polymer materials, and injection molded products, films, etc. that have excellent mechanical properties such as strength and elastic modulus, and thermal properties such as heat resistance, The emergence of various products such as textiles is strongly desired.
【０００３】なかでもエンジニヤリングプラスチックに
分類される樹脂と光学的に異方性の溶融相を示すサーモ
トロピック液晶ポリマーとからなる組成物は、エンジニ
ヤリングプラスチックの強度や熱的性質などを改良した
新しい樹脂の創生を目的に広く研究されている。[0003] Among these, a composition consisting of a resin classified as an engineering plastic and a thermotropic liquid crystal polymer exhibiting an optically anisotropic melt phase is a new material that improves the strength and thermal properties of engineering plastics. It is widely studied for the purpose of creating resins.
【０００４】例えば、特開昭５６−１１５３５７号公報
、特開昭５７−２５３５４号公報、特開昭５７−４０５
５０号公報、特開昭５７−４０５５１号公報、特開昭５
７−４０５５５号公報、特開昭５７−５１７３９号公報
、特開昭５３−３４４６号公報、特開昭５９−４７２２
９号公報、特開昭６１−１２０８５１号公報などは、サ
−モトロピック液晶性共重合ポリエステルを応用した代
表的なものである。[0004] For example, JP-A-56-115357, JP-A-57-25354, and JP-A-57-405.
No. 50, JP-A-57-40551, JP-A-Sho 5
7-40555, JP 57-51739, JP 53-3446, JP 59-4722
No. 9, JP-A No. 61-120851, etc. are typical examples of applications of thermotropic liquid crystalline copolyester.
【０００５】しかしこれらに類するサ−モトロピック液
晶ポリマ−と熱可塑性樹脂とからなる組成物においては
、それら両者の混合や更には成形を行う際に、サ−モト
ロピック液晶ポリマ−を溶融する温度範囲で熱可塑性樹
脂が熱劣化や熱分解を起こしやすいことに起因する不都
合だけでなく、例え、その溶融温度範囲が適正であって
もこれらの混合が十分なされないために混合される樹脂
成分の分散性が不十分となり、熱可塑性樹脂の十分な効
果が得られなかった。また、サ−モトロピック液晶ポリ
マ−の分子量を小さくして混合しても、更に溶媒を存在
させて混合しても分散性が十分でなく、この為、成形品
の強度が不十分であったりした。このように通常の混合
方法（通称、ブレンド法）ではこれらの組成物の性能を
向上させるのは非常に困難であった。However, in compositions made of a thermotropic liquid crystal polymer and a thermoplastic resin similar to these, when mixing or even molding the two, the thermotropic liquid crystal polymer must be melted within the temperature range. Not only are there disadvantages due to the fact that thermoplastic resins are prone to thermal deterioration and thermal decomposition, but even if the melting temperature range is appropriate, the dispersibility of the resin components that are mixed is poor due to insufficient mixing of these components. was insufficient, and the sufficient effect of the thermoplastic resin could not be obtained. Furthermore, even if the thermotropic liquid crystal polymer is mixed with a lower molecular weight or in the presence of a solvent, the dispersibility is not sufficient, and as a result, the strength of the molded product may be insufficient. . As described above, it has been extremely difficult to improve the performance of these compositions using the usual mixing method (commonly known as the blending method).
【０００６】[0006]
【発明が解決しようとする課題】本発明は従来のサ−モ
トロピック液晶ポリマ−と熱可塑性樹脂とから力学的性
質や熱的性能、更には成形加工性など高分子材料として
優れた性質を有する組成物を提供することを目的とする
。[Problems to be Solved by the Invention] The present invention aims to create a composition that has excellent properties as a polymer material, such as mechanical properties, thermal performance, and moldability, by combining a conventional thermotropic liquid crystal polymer and a thermoplastic resin. The purpose is to provide something.
【０００７】[0007]
【課題を解決するための手段】本発明者はこのような現
状に鑑み、通常のブレンド法でみられるような分散性が
劣るため生じると考えられる力学的性能などの低下なし
に共重合ポリエステルと熱可塑性樹脂とを混合させるこ
とについて鋭意研究を行った結果、共重合ポリエステル
を構成する一成分にある特定の割合でビス（ヒドロキシ
フェニル）サルホン類を導入し、更に得られる共重合ポ
リエステルの軟化温度や結晶度を適正な値に調節した限
られた組成の共重合ポリエステルとすることにより、そ
れと熱可塑性樹脂とを通常のブレンド方法でブレンドし
て優れた力学的性能並びに熱的性質のバランスのとれた
組成物がえられることを見いだし、本発明に至ったもの
である。[Means for Solving the Problems] In view of the current situation, the present inventor has developed a copolymerized polyester without deterioration in mechanical performance, etc., which is thought to occur due to poor dispersibility as seen in ordinary blending methods. As a result of intensive research on mixing with thermoplastic resins, we introduced bis(hydroxyphenyl) sulfones in a certain proportion to one of the components constituting the copolyester, and the softening temperature of the resulting copolyester By creating a copolymerized polyester with a limited composition and adjusting crystallinity to an appropriate value, it can be blended with a thermoplastic resin using a conventional blending method to achieve excellent mechanical performance and a well-balanced thermal property. The inventors have discovered that it is possible to obtain a composition that can achieve the desired results, leading to the present invention.
【０００８】即ち、本発明は下記構造単位（Ａ）、（Ｂ
）、（Ｃ）及び（Ｄ）からなる共重合ポリエステルと熱
可塑性樹脂とからなる共重合ポリエステル組成物に関す
る。That is, the present invention provides the following structural units (A) and (B).
), (C) and (D) and a thermoplastic resin.
【０００９】[0009]
【化８】[Chemical formula 8]
【００１０】0010
【化９】[Chemical formula 9]
【００１１】[0011]
【化１０】[Chemical formula 10]
【００１２】0012
【化１１】[Chemical formula 11]
【００１３】（但し、Ｒ１〜Ｒ３は下式（Ｉ）、（ＩＩ
）、（ＩＩＩ）及びそれらの誘導体。(However, R1 to R3 are represented by the following formulas (I), (II)
), (III) and derivatives thereof.
【００１４】[0014]
【化１２】[Chemical formula 12]
【００１５】[0015]
【化１３】[Chemical formula 13]
【００１６】[0016]
【化１４】[Chemical formula 14]
【００１７】Ｘは−Ｏ−、−ＣＯ−、−ＣＯＯ−、アル
キレン。ｍ、ｎは０又は１。）さらに共重合ポリエステ
ルが軟化温度２００〜４００℃、結晶度５〜６０を有し
、上記構造単位（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）がそ
れぞれ３０〜８０モル％、５〜３５モル％、１０〜３５
モル％、０．１〜２５モル％であることを特徴とする共
重合ポリエステル組成物に関する。X is -O-, -CO-, -COO-, alkylene. m and n are 0 or 1. ) Furthermore, the copolymerized polyester has a softening temperature of 200 to 400°C and a crystallinity of 5 to 60, and the above structural units (A), (B), (C) and (D) are respectively 30 to 80 mol% and 5 to 60% by mole. 35 mol%, 10-35
The present invention relates to a copolyester composition characterized in that the amount is 0.1 to 25 mol%.
【００１８】本発明は上記の如き構造単位の特定の比率
よりなる組合せにより、特に（Ｄ）の特定含量域で望ま
しくは光学的に異方性の溶融相を示す共重合ポリエステ
ルを製造し、それを熱可塑性樹脂とブレンドして組成物
とし優れた力学的性能や熱的性質更には成形加工性も優
れた高分子材料を実現するものである。[0018] The present invention produces a copolyester which exhibits an optically anisotropic melt phase, preferably in a specific content range of (D), by combining the structural units as described above in a specific ratio. The composition is blended with a thermoplastic resin to create a polymeric material with excellent mechanical performance, thermal properties, and even moldability.
【００１９】本発明に係わる組成物に使用する共重合ポ
リエステルの構成単位である（Ａ）を与える具体的な原
料化合物は、芳香族オキシカルボン酸類であるり、例え
ば、４−ヒドロキシ安息香酸、３−ヒドロキシ安息香酸
、４−ヒドロキシ４’−カルボキシジフェニルエ−テル
、４−ヒドロキシ４’カルボキシジフェニル、ヒドロキ
シナフトエ酸類、及びこれらのハロゲン置換体、メチル
基やフェニル基などのアルキル及びアリ−ル置換体など
があげられるが、必ずしもこれらに限定されるものでは
ない。また、これらは２種以上を混合して使用してもよ
い。Specific raw material compounds that provide (A), which is a structural unit of the copolyester used in the composition of the present invention, are aromatic oxycarboxylic acids, such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, -Hydroxybenzoic acid, 4-hydroxy 4'-carboxydiphenyl ether, 4-hydroxy 4'carboxydiphenyl, hydroxynaphthoic acids, and halogen-substituted products, alkyl and aryl-substituted products such as methyl group and phenyl group These include, but are not necessarily limited to. Moreover, you may use these as a mixture of 2 or more types.
【００２０】構造単位である（Ｂ）を与える具体的な原
料化合物は、芳香族ジオキシ化合物類であり、例えば、
ハイドロキノン、レゾルシン、メチルハイドロキノン、
ｔ−ブチルハイドロキノン、ジｔ−ブチルハイドロキノ
ン類、トリメチルハイドロキノン類、トリメチルレゾル
シン類、ジヒドロキシナフタレン類、４，４’ジヒドロ
キシビフェニル、ジヒドロキシビフェニル類、３，３’
ジメチル４，４’ジヒドロキシビフェニル、メチルジヒ
ドロキシビフェニル類、ビスフェノ−ル類、ビス（ヒド
ロキシフェニル）ケトン類、ビス（ヒドロキシフェニル
）エ−テル類、（４−ヒドロキシフェニル）−４−ヒド
ロキシベンゾエ−ト、ジヒドロキシベンゾフェノン類な
どの例があげられるが必ずしもこれらに限定されるもの
ではない。また、これらは、２種以上を混合して使用し
てもよい。[0020] Specific raw material compounds that provide the structural unit (B) are aromatic dioxy compounds, for example,
Hydroquinone, resorcinol, methylhydroquinone,
t-Butylhydroquinone, di-t-butylhydroquinones, trimethylhydroquinones, trimethylresorcinols, dihydroxynaphthalenes, 4,4'dihydroxybiphenyl, dihydroxybiphenyls, 3,3'
Dimethyl 4,4'dihydroxybiphenyl, methyldihydroxybiphenyls, bisphenols, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)ethers, (4-hydroxyphenyl)-4-hydroxybenzoate , dihydroxybenzophenones, etc., but are not necessarily limited to these. Moreover, you may use these as a mixture of 2 or more types.
【００２１】構造単位である（Ｃ）を与える具体的な原
料化合物は、芳香族ジカルボン酸類であり、例えば、テ
レフタル酸、イソフタル酸、メチルイソフタル酸、５−
ｔ−ブチルイソフタル酸、フェニルテレフタル酸、ナフ
タレンジカルボン酸類、ジフェニルジカルボン酸類、ジ
フェニルエ−テルジカルボン酸類、ジフェニルケトンジ
カルボン酸、ジフェニルプロパンジカルボン酸類、など
のような例が上げられるが、必ずしもこれらに限定され
るものではない。また、これらは２種以上を混合して使
用してもよい。[0021] Specific raw material compounds providing the structural unit (C) are aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, methylisophthalic acid, 5-
Examples include t-butyl isophthalic acid, phenyl terephthalic acid, naphthalene dicarboxylic acids, diphenyl dicarboxylic acids, diphenyl ether dicarboxylic acids, diphenyl ketone dicarboxylic acid, diphenylpropane dicarboxylic acids, but are not necessarily limited to these. It's not something you can do. Moreover, you may use these as a mixture of 2 or more types.
【００２２】構造単位である（Ｄ）を与える具体的な原
料化合物は、ビス（ヒドロキシフェニル）サルホン類で
あり、特に４，４’−ジヒドロキシジフェニルサルホン
である。また、本発明の目的の範囲内で芳香族環にメチ
ル基などの置換基を有するものも併用できる。
なお、本発明の目的の範囲
内で芳香族アミノフェノ−ル類及び芳香族アミノカルボ
ン酸類、脂肪族ジカルボン酸類、脂肪族及び脂環式ジオ
−ル類も少量の範囲で共重合し同様に併用できる。[0022] Specific starting compounds for providing the structural unit (D) are bis(hydroxyphenyl)sulfones, particularly 4,4'-dihydroxydiphenylsulfone. Moreover, those having a substituent such as a methyl group on the aromatic ring can also be used in combination within the scope of the purpose of the present invention.
Incidentally, within the scope of the purpose of the present invention, aromatic aminophenols, aromatic aminocarboxylic acids, aliphatic dicarboxylic acids, aliphatic and alicyclic diols can also be copolymerized in small amounts and used in the same manner. .
【００２３】これらの共重合ポリエステルは種々の方法
によって製造されるが、通常は反応原料のヒドロキシル
基をアシル化剤によって低級アルキルエステルの形に変
形し、しかるのちに脱酢酸縮重合を行ういわゆるアシド
リシス法で溶融重合を行うのが得策である。また、溶融
重合の後固相重合を行ってもよい。アシル化剤としては
無水酢酸が好ましい。[0023] These copolymerized polyesters can be produced by various methods, but usually the so-called acidolysis is carried out in which the hydroxyl group of the reaction raw material is transformed into a lower alkyl ester form using an acylating agent, and then the acetic acid is removed by condensation polymerization. It is advisable to carry out melt polymerization by a method. Further, solid phase polymerization may be performed after melt polymerization. Acetic anhydride is preferred as the acylating agent.
【００２４】本発明に用いる共重合ポリエステルは前述
の如き溶融重合法に基づいて製造するのが重合後の後処
理が不要であるため工業的に有利であるが、他の重合法
、例えば、溶液重合法、界面重合法、などにより行うこ
ともできる。It is industrially advantageous to produce the copolymerized polyester used in the present invention based on the above-mentioned melt polymerization method because no post-treatment is required after polymerization, but other polymerization methods such as solution It can also be carried out by a polymerization method, an interfacial polymerization method, or the like.
【００２５】本発明で共重合ポリエステルと組み合わせ
て使用する熱可塑性樹脂としては、ポリサルフォンやポ
リエ−テルサルフォンなどのポリサルフォン系樹脂、ポ
リフェニレンサルファイド樹脂、ポリイミド樹脂、ポリ
エ−テルイミド樹脂、ポリアミドイミド樹脂、ポリエチ
レンテレフタレ−トやポリブチレンテレフタレ−ト、ポ
リアリレ−トなどのポリエステル系樹脂、ポリカ−ボネ
−ト樹脂、６−ナイロンや６，６ナイロンなどのポリア
ミド系樹脂、ポリフェニレンオキシド及びそれらのポリ
マ−アロイ樹脂、ポリエ−テルエ−テルケトンやポリエ
−テルケトンなどのポリエ−テルケトン系樹脂、ポリア
セタ−ル樹脂、フッ素樹脂、ポリエチレン、ポリプロピ
レン、エチレンプロピレンタ−ポリマ−などのポリオレ
フィン系樹脂、ポリスチレン、ＡＳ、ＡＢＳなどのポリ
スチレン系樹脂、ポリ塩化ビニル、アクリル系樹脂、シ
リコン樹脂、下記構造単位（Ａ）、（Ｂ）、（Ｃ）及び
（Ｅ）からなり軟化温度２００〜４００℃、結晶度５〜
６０を有する共重合ポリエステル樹脂及び共重合ポリエ
ステルアミド樹脂などである。The thermoplastic resins used in combination with the copolymerized polyester in the present invention include polysulfone resins such as polysulfone and polyethersulfone, polyphenylene sulfide resins, polyimide resins, polyetherimide resins, polyamideimide resins, and polyethylene terephthalate resins. Polyester resins such as talate, polybutylene terephthalate, and polyarylate, polycarbonate resins, polyamide resins such as 6-nylon and 6,6 nylon, polyphenylene oxide, and their polymer alloy resins. , polyetherketone resins such as polyetheretherketone and polyetherketone, polyacetal resins, fluororesins, polyolefin resins such as polyethylene, polypropylene, and ethylene propylene terpolymers, polystyrenes such as polystyrene, AS, and ABS. system resin, polyvinyl chloride, acrylic resin, silicone resin, consisting of the following structural units (A), (B), (C) and (E), softening temperature 200-400°C, crystallinity 5-
60, copolymerized polyester resin, copolymerized polyesteramide resin, etc.
【００２６】[0026]
【化１５】[Chemical formula 15]
【００２７】[0027]
【化１６】[Chemical formula 16]
【００２８】[0028]
【化１７】[Chemical formula 17]
【００２９】[0029]
【化１８】[Chemical formula 18]
【００３０】（但し、Ｒ１〜Ｒ３は下式（Ｉ）、（ＩＩ
）、（ＩＩＩ）及びそれらの誘導体。(However, R1 to R3 are represented by the following formulas (I), (II)
), (III) and derivatives thereof.
【００３１】[0031]
【化１９】[Chemical formula 19]
【００３２】[0032]
【化２０】[C20]
【００３３】[0033]
【化２１】[C21]
【００３４】Ｘは−Ｏ−、−ＣＯ−、−ＣＯＯ−、アル
キレン。ｍ、ｎは０又は１。）なお、本発明の目的の範
囲内でこれらの樹脂は併用して使用することができる。X is -O-, -CO-, -COO-, alkylene. m and n are 0 or 1. ) Note that these resins can be used in combination within the scope of the purpose of the present invention.
【００３５】本発明に係わる組成物において使用する共
重合ポリエステルの軟化温度は２００〜４００℃の範囲
であり、組み合わせる熱可塑性樹脂の性質により調節さ
れる。例えば、エンジニアリングプラスチック等の軟化
温度の高い熱可塑性樹脂を使用した場合には、２５０〜
４００℃の高い軟化温度の共重合ポリエステルが適切で
あり、軟化温度の低い熱可塑性樹脂の場合には、より低
い軟化温度の共重合ポリエステルが使用される。The softening temperature of the copolyester used in the composition of the present invention is in the range of 200 to 400°C, and is adjusted depending on the properties of the thermoplastic resin to be combined. For example, when using a thermoplastic resin with a high softening temperature such as engineering plastic,
Copolyesters with a high softening temperature of 400° C. are suitable; in the case of thermoplastics with a low softening temperature, copolyesters with a lower softening temperature are used.
【００３６】本発明に係わる組成物において使用する共
重合ポリエステルの結晶度は５〜６０の範囲であり、１
０〜４０の範囲が好ましい。５より低いと共重合ポリエ
ステルの効果が不足し、６０より高いと、それなりの効
果はあるが、熱可塑性樹脂への分散性が減少するため、
共重合ポリエステルの特徴は十分に発揮されない。The crystallinity of the copolyester used in the composition according to the present invention is in the range of 5 to 60, with a crystallinity of 1
A range of 0 to 40 is preferred. If it is lower than 5, the effect of the copolymerized polyester will be insufficient, and if it is higher than 60, it will have some effect, but the dispersibility in thermoplastic resin will decrease.
The characteristics of copolymerized polyester are not fully exhibited.
【００３７】本発明に係わる組成物において使用する共
重合ポリエステル中の構造単位（Ｄ）の含有量は０．１
〜２５モル％の範囲である。０．１モル％より低いと熱
可塑性樹脂との組成物において共重合ポリエステルの効
果が不足し、２５モル％より高いと共重合ポリエステル
の軟化温度や結晶度が不適切となり熱可塑性樹脂との組
成物の特徴が発揮されない。The content of the structural unit (D) in the copolyester used in the composition according to the present invention is 0.1
It is in the range of ~25 mol%. If it is lower than 0.1 mol%, the effect of the copolyester will be insufficient in the composition with the thermoplastic resin, and if it is higher than 25 mol%, the softening temperature and crystallinity of the copolyester will be inappropriate and the composition with the thermoplastic resin will be insufficient. The characteristics of things are not exhibited.
【００３８】本発明に係わる組成物において使用する共
重合ポリエステル中の構造単位（Ａ）の含有量は３０〜
８０モル％の範囲である。３０モル％より低すぎる場合
や８０モル％より高すぎると得られる共重合ポリエステ
ルの軟化温度や溶融粘度が高くなり、熱可塑性樹脂との
組成物を製造することが不可能となる。４０〜７０モル
％の範囲が最も適切である。[0038] The content of the structural unit (A) in the copolyester used in the composition according to the present invention is from 30 to
It is in the range of 80 mol%. If it is too low than 30 mol% or higher than 80 mol%, the softening temperature and melt viscosity of the copolymerized polyester obtained will become high, making it impossible to produce a composition with a thermoplastic resin. A range of 40 to 70 mol% is most suitable.
【００３９】本発明に係わる組成物において使用する共
重合ポリエステル中の構造単位（Ｃ）の含有量は実質的
に構造単位（Ｂ）と構造単位（Ｄ）の合計モル数に等し
くすることが望ましい。構造単位（Ａ）の使用量の最も
望ましい範囲が４０〜７０モル％であるので、その含有
量の最適範囲も必然的に決まるものである。It is desirable that the content of the structural unit (C) in the copolymerized polyester used in the composition according to the present invention is substantially equal to the total number of moles of the structural unit (B) and the structural unit (D). . Since the most desirable range for the amount of structural unit (A) to be used is 40 to 70 mol%, the optimal range for its content is also necessarily determined.
【００４０】本発明に係わる組成物において使用する共
重合ポリエステルの含有量は組成物重量に対して０．５
〜９９重量％である。これより低すぎると効果を示さな
いし、９９重量％以上で使用してもそれなりに効果はあ
るが、大抵の応用分野においては１〜８０重量％の範囲
で使用するのが好ましい。The content of the copolyester used in the composition according to the present invention is 0.5 based on the weight of the composition.
~99% by weight. If it is lower than this, it will not be effective, and if it is used at 99% by weight or more, it will still have some effect, but in most application fields it is preferable to use it in the range of 1 to 80% by weight.
【００４１】本発明に係わる組成物の特徴は、その衝撃
強度が上昇することであり特に熱可塑性樹脂単独と比較
して耐衝撃強性が向上する。更に他の特徴は成形性が向
上することである。A feature of the composition according to the present invention is that its impact strength is increased, and in particular, the impact strength is improved compared to a thermoplastic resin alone. Yet another feature is improved moldability.
【００４２】これらの共重合ポリエステルと熱可塑性樹
脂とをブレンドすることにより、力学的性能などが優れ
た組成物が得られる理由は確かではないが、構造単位（
Ｄ）を一成分とする共重合ポリエステルを使用すること
によって両者の樹脂成分の界面における相溶性が増大す
るためと推定される。前記した特許の公報の例は二つの
樹脂成分の相溶性が過度に小さいために得られた組成物
が十分な性能を示さなかったものと推定される。Although it is not clear why a composition with excellent mechanical performance can be obtained by blending these copolymerized polyesters and a thermoplastic resin, it is difficult to understand why the structural unit (
This is presumed to be because the use of a copolymerized polyester containing D) as one component increases the compatibility at the interface between the two resin components. It is presumed that in the example of the patent publication mentioned above, the resulting composition did not exhibit sufficient performance because the compatibility of the two resin components was too low.
【００４３】本発明の組成物は使用目的に応じて各種の
繊維状、粉末状、板状などの無機及び有機の充填剤を配
合することができる。繊維状充填剤としては、ガラス繊
維、アスベスト繊維、シリカ繊維、シリカアルミナ繊維
、アルミナ繊維、ジルコニア繊維、窒化ほう素繊維、窒
化珪素繊維、ほう素繊維、チタン酸カリ繊維、更にステ
ンレス、アルミニュウム、チタン、銅、しんちゅうなど
の金属の繊維や無機質繊維、及びポリアミド樹脂、フッ
ソ樹脂、ポリエステル樹脂、アクリル系樹脂などの高融
点有機質繊維などがあげられる。なかでもガラス繊維、
ポリアミド繊維などが代表的であり、それらの繊維のア
スペクト比などを選択して組成物の性能を調節すること
ができる。The composition of the present invention may contain various inorganic and organic fillers in the form of fibers, powders, plates, etc., depending on the purpose of use. Examples of fibrous fillers include glass fiber, asbestos fiber, silica fiber, silica alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, as well as stainless steel, aluminum, and titanium. Examples include metal fibers and inorganic fibers such as copper and brass, and high melting point organic fibers such as polyamide resin, fluorocarbon resin, polyester resin, and acrylic resin. Among them, glass fiber,
Polyamide fibers are typical, and the performance of the composition can be adjusted by selecting the aspect ratio of these fibers.
【００４４】粉末状充填剤としてはカ−ボンブラック、
亜鉛、シリカ、硫黄粉末、ガラスビ−ズ、ガラスバル−
ン、ガラス粉末、硫酸カルシュウム、珪酸アルミニュウ
ム、カオリン、タルク、クレ−、珪藻土、ウオストナイ
トのごとき珪酸塩、酸化鉄、酸化チタン、酸化亜鉛、酸
化アンチモン、アルミナのごとき金属酸化物、炭酸カル
シュウム、炭酸マグネシュウムのごとき金属の炭酸塩、
硫酸カルシュウム、硫酸バリュウムのごとき金属の硫酸
塩、その他、フェライト、炭化珪素、窒化ほお素、各種
金属粉末などがあげられる。[0044] As the powder filler, carbon black,
Zinc, silica, sulfur powder, glass beads, glass bulbs
silicates such as iron oxide, titanium oxide, zinc oxide, antimony oxide, alumina, calcium carbonate, magnesium carbonate. carbonates of metals, such as
Examples include metal sulfates such as calcium sulfate and barium sulfate, ferrite, silicon carbide, boron nitride, and various metal powders.
【００４５】板状充填剤としてはマイカ、ガラスフレ−
ク、各種金属箔などがあげられる。これらの充填剤は、
一種または二種以上併用することができる。例えば、繊
維状充填剤と粉末状または板状充填剤との併用は機械物
性と寸法安定性、電気特性などを兼備する上では好まし
いものである。これらの充填剤の量は１〜６０重量％で
使用される。又、必要に応じてこれらの充填剤は各種の
表面処理剤を併用するのが望ましい。[0045] As the plate-shaped filler, mica and glass flakes are used.
and various metal foils. These fillers are
They can be used alone or in combination. For example, the combined use of a fibrous filler and a powdery or plate-like filler is preferable in order to achieve both mechanical properties, dimensional stability, electrical properties, and the like. The amount of these fillers used is from 1 to 60% by weight. Moreover, it is desirable to use various surface treatment agents in combination with these fillers as necessary.
【００４６】本発明に係る組成物は、バンバリ−ミキサ
−、ロ−ル、ニ−ダ−などの各種の混合機や各種の押出
機などの混練機を用いて２００〜４００℃の温度で溶融
混練して製造される。例えば、各種の一軸型及び二軸型
押出機が特に望ましく、また各種の混合機と組み合わせ
て使用してもよい。The composition according to the present invention is melted at a temperature of 200 to 400°C using various mixers such as Banbury mixers, rolls, and kneaders, and kneaders such as various extruders. Manufactured by kneading. For example, various single-screw and twin-screw extruders are particularly desirable, and may also be used in combination with various mixers.
【００４７】かくして得られる樹脂組成物は通常の射出
成形機に供することができ三次元成形品などに射出成形
することができる。The resin composition thus obtained can be applied to a conventional injection molding machine and can be injection molded into a three-dimensional molded article.
【００４８】[0048]
【実施例】以下に実施例を挙げて本発明の効果を説明す
る。なお、実施例及び比較例中で示される各特性値は次
のように測定した。
■ 軟化温度：セイコ−電子工業（株）製ＤＳＣ−２１
０型示差走査熱量計を用いて、２０℃／分の昇温速度で
測定して得られた融点より３０℃高い温度で圧縮成形し
て厚さ２ｍｍの試験片を作るか、あるいは射出成形にて
厚さ２ｍｍの試験片を作り、それを同社のＴＭＡ／ＳＳ
１２０（針入法）を用いて５℃／分の昇温速度で測定し
た。
■結晶度：理学電気（株）製Ｘ線回折装置を使用して、
１ｍｍ以下に裁断した試料をガラス板に固定し、回折角
２°〜４０°まで回折強度を測定した後、ピ−ク分離法
により結晶部分を算出し％表示して結晶度とした。
■機械物性：射出成形で得られたＪＩＳに規定された試
験片を使用しＪＩＳ試験法により行った。
■成形性：射出成形で厚さ１．０ｍｍの成形品を成形し
たときの流動性や良品が得られる難易の程度を定性的に
Ａ（優）〜Ｅ（劣）段階に評価した。[Examples] The effects of the present invention will be explained below with reference to Examples. In addition, each characteristic value shown in an Example and a comparative example was measured as follows. ■ Softening temperature: DSC-21 manufactured by Seiko Electronics Industry Co., Ltd.
Test specimens with a thickness of 2 mm are made by compression molding at a temperature 30 °C higher than the melting point obtained by measuring at a heating rate of 20 °C/min using a Type 0 differential scanning calorimeter, or by injection molding. A test piece with a thickness of 2 mm was made using the company's TMA/SS.
120 (penetration method) at a heating rate of 5° C./min. ■Crystallinity: Using an X-ray diffraction device manufactured by Rigaku Denki Co., Ltd.
A sample cut to 1 mm or less was fixed on a glass plate, and the diffraction intensity was measured at a diffraction angle of 2° to 40°.The crystalline portion was calculated by the peak separation method and expressed as a percentage to indicate the degree of crystallinity. ■Mechanical properties: Tested according to the JIS test method using JIS-specified test pieces obtained by injection molding. (1) Moldability: The degree of fluidity and difficulty in obtaining a good product when molded by injection molding into a molded product with a thickness of 1.0 mm was qualitatively evaluated from A (excellent) to E (poor).
【００４９】
合成例１：共重合ポリエステル（１）の合成攪拌機、Ｎ
２ 導入口を備えた反応器に ２，６ナフタレン
ジカルボン酸 ０．３
モル テレフタル酸
０．７
モル ４，４’−ジヒドロキシビフェニル
０．７ モル ４，４’
−ジヒドロキシジフェニルサルフォン ０．３ モ
ル ４−ヒドロキシ安息香酸
３．０ モルを仕込み減
圧下に窒素置換した後、窒素シ−ルして無水酢酸５．５
モルを加えた。続いて攪拌下で１４５℃に加熱し、３時
間反応させた後、３時間かけて２９０℃に昇温させて反
応を続け、更に１ｍｍＨｇの減圧下で反応した。得られ
た粗ポリマ−を粉砕し、１ｍｍＨｇの減圧下で１０時間
かけて２９０℃に昇温し、固相重合を行った。得られた
ポリマ−の軟化温度は３００℃、結晶度は２２であった
。Synthesis Example 1: Synthesis of copolymerized polyester (1) Stirrer, N
2 Into a reactor equipped with an inlet, add 0.3 of 2,6 naphthalene dicarboxylic acid.
mole terephthalic acid
0.7
Mol 4,4'-dihydroxybiphenyl
0.7 mole 4,4'
-dihydroxydiphenylsulfone 0.3 mol 4-hydroxybenzoic acid
After charging 3.0 mol and purging with nitrogen under reduced pressure, sealing with nitrogen and adding 5.5 mol of acetic anhydride.
Added moles. Subsequently, the mixture was heated to 145° C. with stirring and reacted for 3 hours, and then the temperature was raised to 290° C. over 3 hours to continue the reaction, and the reaction was further carried out under reduced pressure of 1 mmHg. The obtained crude polymer was pulverized and heated to 290° C. over 10 hours under a reduced pressure of 1 mmHg to perform solid phase polymerization. The resulting polymer had a softening temperature of 300°C and a crystallinity of 22.
【００５０】
合成例２：共重合ポリエステル（２）の合成攪拌機、Ｎ
２ 導入口を備えた反応器に ２，６ナフタレン
ジカルボン酸 ０．２
モル テレフタル酸
０．８
モル ４，４’−ジヒドロキシビフェニル
０．５ モル ４，４’
−ジヒドロキシジフェニルサルフォン ０．５ モ
ル ４−ヒドロキシ安息香酸
２．０ モルを仕込み減
圧下に窒素置換した後、窒素シ−ルして無水酢酸４．５
モルを加え、以下合成例（１）と同様に行った。得られ
たポリマ−の軟化温度は３１０℃、結晶度は２０であっ
た。Synthesis Example 2: Synthesis of copolymerized polyester (2) Stirrer, N
2 Into a reactor equipped with an inlet, add 0.2 of 2,6 naphthalene dicarboxylic acid.
mole terephthalic acid
0.8
Mol 4,4'-dihydroxybiphenyl
0.5 mole 4,4'
-dihydroxydiphenylsulfone 0.5 mol 4-hydroxybenzoic acid
After charging 2.0 mol and purging with nitrogen under reduced pressure, sealing with nitrogen and adding 4.5 mol of acetic anhydride.
mol was added, and the following procedure was carried out in the same manner as in Synthesis Example (1). The resulting polymer had a softening temperature of 310°C and a crystallinity of 20.
【００５１】
合成例３：共重合ポリエステル（３）の合成攪拌機、Ｎ
２ 導入口を備えた反応器に イソフタル酸
０．４５ モル テレフタル酸
０．５５ モル ４，４’−ジヒド
ロキシビフェニル １．０
モル ４−ヒドロキシ安息香酸
３．０ モル
を仕込み以下Ａ同様に行った。得られたポリマ−の軟化
温度は３００℃、結晶度は２９であった。
実施例１〜６、比較例１〜２
小型ロ−タ−ミキサ−を使用して共重合ポリエステル（
１）、（２）及び（３）（比較例）と熱可塑性樹脂とを
表１のような使用量にて混練した。得られた重合体組成
物を射出成形機にてアイゾット衝撃試験片を成形し、Ｊ
ＩＳ Ｋ７１１０法に準じて衝撃強度（ノッチ付き）
を測定した。結果を表１に示した。Synthesis Example 3: Synthesis of copolymerized polyester (3) Stirrer, N
2. In a reactor equipped with an inlet, add isophthalic acid.
0.45 mol terephthalic acid
0.55 mol 4,4'-dihydroxybiphenyl 1.0
Mol 4-hydroxybenzoic acid
3.0 mol was prepared and the following steps were carried out in the same manner as in A. The resulting polymer had a softening temperature of 300°C and a crystallinity of 29. Examples 1 to 6, Comparative Examples 1 to 2 Copolymerized polyester (
1), (2), and (3) (comparative examples) and a thermoplastic resin were kneaded in the amounts used as shown in Table 1. The obtained polymer composition was molded into an Izod impact test piece using an injection molding machine, and J
Impact strength according to IS K7110 method (notched)
was measured. The results are shown in Table 1.
【００５２】[0052]
【表１】[Table 1]
【００５３】[0053]
【発明の効果】本発明の組成物は衝撃性に優れ、機械強
度も高く、優れた性能を発現することができ、通常の成
形機で成形できる成形性を有している。[Effects of the Invention] The composition of the present invention has excellent impact resistance, high mechanical strength, can exhibit excellent performance, and has moldability that allows it to be molded using an ordinary molding machine.
Claims (4)
Ｄ）からなる共重合ポリエステルと、熱可塑性樹脂とか
らなる共重合ポリエステル組成物。 【化１】 【化２】 【化３】 【化４】 （但し、Ｒ１〜Ｒ３は下式（Ｉ）、（ＩＩ）、（ＩＩＩ
）及びそれらの誘導体。 【化５】 【化６】 【化７】 Ｘは−Ｏ−、−ＣＯ−、−ＣＯＯ−、アルキレン。ｍ、
ｎは０又は１。）Claim 1: The following structural units (A), (B), (C), (
A copolymerized polyester composition comprising a copolymerized polyester consisting of D) and a thermoplastic resin. [Formula 1] [Formula 2] [Formula 3] [Formula 4] (However, R1 to R3 are represented by the following formulas (I), (II), (III)
) and their derivatives. [Formula 5] [Formula 6] [Formula 7] X is -O-, -CO-, -COO-, and alkylene. m,
n is 0 or 1. )
４００℃、結晶度５〜６０を有することを特徴とする請
求項１記載の共重合ポリエステル組成物。Claim 2: The copolymerized polyester has a softening temperature of 200 to
The copolyester composition according to claim 1, having a crystallinity of 5 to 60 at 400°C.
）がそれぞれ３０〜８０モル％、５〜３５モル％、１０
〜３５モル％、０．１〜２５モル％であることを特徴と
する請求項１又は２記載の共重合ポリエステル組成物。Claim 3: Structural units (A), (B), (C) and (D
) are 30 to 80 mol%, 5 to 35 mol%, and 10, respectively.
3. The copolyester composition according to claim 1 or 2, wherein the content is 0.1 to 25 mol%.
て１〜６０重量％の充填剤を配合してなる請求項１〜３
のいずれか１項記載の共重合ポリエステル組成物。4.Claims 1 to 3 in which a filler is blended in an amount of 1 to 60% by weight based on the total weight of the copolyester composition.
The copolyester composition according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15039091A JPH04372646A (en) | 1991-06-21 | 1991-06-21 | Copolymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15039091A JPH04372646A (en) | 1991-06-21 | 1991-06-21 | Copolymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04372646A true JPH04372646A (en) | 1992-12-25 |
Family
ID=15495948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15039091A Pending JPH04372646A (en) | 1991-06-21 | 1991-06-21 | Copolymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04372646A (en) |
-
1991
- 1991-06-21 JP JP15039091A patent/JPH04372646A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1359187B1 (en) | A flame retardant resin composition | |
| JP5369054B2 (en) | Liquid crystal polyester blend composition | |
| EP3183320B1 (en) | Composition containing a polyaryletherketone and low naphthenic liquid crystalline polymer | |
| EP0398624B1 (en) | Flame-retardant liquid crystalline polyester composition, process for preparation thereof and injection-molded article composed thereof | |
| JPH0395260A (en) | Liquid crystal polyester resin composition improved in flowability | |
| WO1994019407A1 (en) | Liquid-crystal polyester resin composition and process for producing the same | |
| EP0470557A2 (en) | Resin composition | |
| JPH06240114A (en) | Glass fiber-reinforced liquid crystalline resin composition | |
| JP3111471B2 (en) | Liquid crystalline polymer resin composition | |
| JP6703426B2 (en) | Polyethylene terephthalate resin composition | |
| JPH04372646A (en) | Copolymer composition | |
| JP4498810B2 (en) | Liquid crystal resin composition | |
| JPH0525370A (en) | Polyester copolymer composition | |
| JP3036450B2 (en) | Liquid crystal polyester resin composition | |
| JPH04213354A (en) | Liquid crystal polyester resin composition | |
| JPH02206644A (en) | Production of thermoplastic resin composition | |
| JP2000159999A (en) | Fiber-reinforced resin composition for case body and case body | |
| JPH05170903A (en) | Copolyester amide and its production | |
| JPH0288667A (en) | Liquid crystal polyester resin composition | |
| JPH0539410A (en) | Resin composition | |
| JPH0532870A (en) | Liquid crystalline polyester resin composition | |
| JP2505590B2 (en) | Flame-retardant liquid crystal polyester composition | |
| JP3385734B2 (en) | Liquid crystal polyester, composition thereof and molded article thereof | |
| JP3259108B2 (en) | Liquid crystal polyester resin composition | |
| JPH055054A (en) | Resin composition |