JP5759111B2 - Copolymer and molded body - Google Patents
Copolymer and molded body Download PDFInfo
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- JP5759111B2 JP5759111B2 JP2010108643A JP2010108643A JP5759111B2 JP 5759111 B2 JP5759111 B2 JP 5759111B2 JP 2010108643 A JP2010108643 A JP 2010108643A JP 2010108643 A JP2010108643 A JP 2010108643A JP 5759111 B2 JP5759111 B2 JP 5759111B2
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- 229920001577 copolymer Polymers 0.000 title claims description 59
- 125000003118 aryl group Chemical group 0.000 claims description 39
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 235000021384 green leafy vegetables Nutrition 0.000 claims 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 29
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 27
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 17
- -1 isopropyl ester Chemical group 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 229920000728 polyester Polymers 0.000 description 14
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 13
- 230000006378 damage Effects 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 8
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 5
- 239000011654 magnesium acetate Substances 0.000 description 5
- 229940069446 magnesium acetate Drugs 0.000 description 5
- 235000011285 magnesium acetate Nutrition 0.000 description 5
- 235000011056 potassium acetate Nutrition 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 150000004075 acetic anhydrides Chemical class 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 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
- 239000012298 atmosphere Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus 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
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 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 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 230000007423 decrease Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000004492 methyl ester group Chemical group 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 150000003151 propanoic acid esters Chemical class 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(*[N+](C)[O-])N*C(C)(C)[N+](C)[O-] Chemical compound CC(C)(*[N+](C)[O-])N*C(C)(C)[N+](C)[O-] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-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
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical group CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 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
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Polyamides (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、共重合体及びそれを含む樹脂組成物からなる成形体に関するものである。 The present invention relates to a molded body comprising a copolymer and a resin composition containing the copolymer.
全芳香族ポリエステルに代表される液晶ポリマーは、高い耐熱性と優れた電気特性を有し、主として電気・電子部品に使用されている。このような部品は、全芳香族ポリエステル樹脂組成物を射出成形や押出成形することにより作製され、エポキシ系、ウレタン系、アクリル系などの接着剤で他の部材に接合される。 Liquid crystal polymers typified by wholly aromatic polyesters have high heat resistance and excellent electrical properties, and are mainly used for electrical and electronic parts. Such parts are produced by injection molding or extrusion molding of a wholly aromatic polyester resin composition, and are joined to other members with an epoxy, urethane, acrylic, or other adhesive.
一般に、共重合体を含む樹脂組成物から成形体を作製する場合、用途に合った特性が得られるように共重合成分を変更することが行われる。全芳香族ポリエステルについても、種々の化合物を共重合成分として用いて特定の構造単位を組み入れることで全芳香族ポリエステルの特性を改善する試みがなされている(例えば、特許文献1及び2を参照)。 Generally, when producing a molded object from the resin composition containing a copolymer, changing a copolymerization component is performed so that the characteristic suitable for a use may be acquired. As for wholly aromatic polyesters, attempts have been made to improve the properties of wholly aromatic polyesters by incorporating specific structural units using various compounds as copolymerization components (see, for example, Patent Documents 1 and 2). .
ところで、全芳香族ポリエステルの成形体は、接着剤との親和性が低いため、同質あるいは異質の部材との接合が困難となる場合があった。接着剤の改良はなされているが、接着剤による接着強度の改善にも限界がある。 By the way, a molded product of wholly aromatic polyester has a low affinity with an adhesive, so that it may be difficult to join the same or different members. Although the adhesive has been improved, there is a limit to the improvement of the adhesive strength by the adhesive.
上記特許文献のように全芳香族ポリエステルの共重合成分を変更して接着性を改善することが考えられる。しかし、十分な改善効果を得るために変更する構造単位の割合が大きくなりすぎると、全芳香族ポリエステルが有している耐熱性、成形性などの利点を損なってしまう。 It is conceivable to improve the adhesiveness by changing the copolymerization component of the wholly aromatic polyester as in the above patent document. However, if the proportion of structural units to be changed in order to obtain a sufficient improvement effect becomes too large, advantages such as heat resistance and moldability of the wholly aromatic polyester are impaired.
本発明は、上記事情に鑑みてなされたものであり、全芳香族ポリエステルの優れた耐熱性及び成形性を十分維持しつつ、成形体の接着強度を向上させることができる共重合体及び成形体を提供することを目的とする。 The present invention has been made in view of the above circumstances, and a copolymer and a molded body capable of improving the adhesive strength of the molded body while sufficiently maintaining the excellent heat resistance and moldability of the wholly aromatic polyester. The purpose is to provide.
上記課題を解決するために本発明は、下記一般式(1)で表される繰り返し構造単位を40〜99モル%と、下記一般式(3)で表される繰り返し構造単位を1〜15モル%と、下記一般式(4)で表される繰り返し構造単位を0モル%超30モル%以下と、下記一般式(5)で表される繰り返し構造単位を1モル%超30モル%以下と、を含有してなり、下記一般式(1)及び(3)〜(5)の構造単位の合計が100モル%であり、且つ、下記一般式(3)及び(4)の構造単位の含有割合の合計と、下記一般式(5)の構造単位の含有割合とが等しい、共重合体を提供する。
In order to solve the above problems, the present invention provides 40 to 99 mol% of a repeating structural unit represented by the following general formula (1) and 1 to 15 mol of a repeating structural unit represented by the following general formula (3). %, A repeating structural unit represented by the following general formula (4) more than 0 mol% and 30 mol% or less, and a repeating structural unit represented by the following general formula (5) more than 1 mol% and 30 mol% or less , Ri Na contain a total of 100 mole% of structural units of the following general formula (1) and (3) to (5), and, the structural units of the following general formula (3) and (4) Provided is a copolymer in which the total content is equal to the content of the structural unit of the following general formula (5) .
式(1)中、Xは、下記式(A)又は(B)で表される2価の芳香族基を示す。
In formula (1), X represents a divalent aromatic group represented by the following formula (A) or (B) .
式(A)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。Two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.
式(3)中、L1は、−CH2−、−(CH3)2C−、−O−、又は−SO2−を示す。
In Formula (3), L 1 represents —CH 2 —, — (CH 3 ) 2 C—, —O—, or —SO 2 —.
式(4)中、Yは、下記式(4−1)で表される2価の基を示す。
式(4−1)中、Ar 1 は下記式(A)又は(B)で表される2価の芳香族基を示し、Y 1 は下記式(4−2)で表される2価の基を示し、tは、0又は1の整数を示す。
なお、式(A)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。
式(4−2)中、L 2 は−O−、−S−又は−SO−を示し、sは0又は1の整数を示す。なお、式(4−2)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。
In formula (4), Y represents a divalent group represented by the following formula (4-1).
In formula (4-1), Ar 1 represents a divalent aromatic group represented by the following formula (A) or (B), and Y 1 represents a divalent group represented by the following formula (4-2). Represents a group, and t represents an integer of 0 or 1.
Note that the two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.
In formula (4-2), L 2 represents —O—, —S— or —SO—, and s represents an integer of 0 or 1. In addition, the two bonds of the benzene ring represented by the formula (4-2) are in a meta position or a para position.
式(5)中、Zは、下記式(5−1)で表される2価の基を示す。
式(5−1)中、Ar 2 は下記式(A)又は(B)で表される2価の芳香族基を示し、Z 1 は下記式(5−2)で表される2価の基を示し、vは、0又は1の整数を示す。
なお、式(A)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。
式(5−2)中、L 3 は、2価の炭化水素基、−O−、−SO−、−SO 2 −、又は−CO−を示し、uは、0又は1の整数を示す。なお、式(5−2)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。
In the formula (5), Z represents a divalent group represented by the following formula (5-1) .
In formula (5-1), Ar 2 represents a divalent aromatic group represented by the following formula (A) or (B), and Z 1 represents a divalent group represented by the following formula (5-2). Represents a group, and v represents an integer of 0 or 1.
Note that the two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.
In formula (5-2), L 3 represents a divalent hydrocarbon group, —O—, —SO—, —SO 2 —, or —CO—, and u represents an integer of 0 or 1. Note that the two bonds of the benzene ring represented by the formula (5-2) are in a meta position or a para position.
本発明の共重合体によれば、上記特定の構造単位を上記特定の割合で含有するものであることにより、全芳香族ポリエステルの優れた耐熱性及び成形性を十分維持しつつ、成形体の接着強度を向上させることができる。 According to the copolymer of the present invention, by containing the specific structural unit in the specific ratio, while maintaining the excellent heat resistance and moldability of the wholly aromatic polyester, Adhesive strength can be improved.
本発明はまた、上記本発明の共重合体が含まれる樹脂組成物を成形してなる成形体を提供する。係る樹脂組成物からなる成形体は、耐熱性に優れ且つ接着性が向上したものになり得る。 The present invention also provides a molded article obtained by molding a resin composition containing the copolymer of the present invention. A molded body made of such a resin composition can be excellent in heat resistance and improved in adhesiveness.
本発明によれば、全芳香族ポリエステルの優れた耐熱性及び成形性を十分維持しつつ、成形体の接着強度を向上させることができる共重合体及び成形体を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the copolymer and molded object which can improve the adhesive strength of a molded object can be provided, fully maintaining the outstanding heat resistance and moldability of wholly aromatic polyester.
本発明の共重合体は、下記一般式(1)で表される繰り返し構造単位を40〜99モル%と、下記式(2)で表される繰り返し構造単位及び下記一般式(3)で表される繰り返し構造単位のうちの1種以上の繰り返し構造単位を合計で1〜15モル%と、式(2)で表される繰り返し構造単位以外の下記一般式(4)で表される繰り返し構造単位を0〜30モル%と、下記一般式(5)で表される繰り返し構造単位を0〜30モル%と、を含有してなるものである。 The copolymer of the present invention is represented by 40 to 99 mol% of a repeating structural unit represented by the following general formula (1), a repeating structural unit represented by the following formula (2), and the following general formula (3). 1 to 15 mol% in total of one or more kinds of repeating structural units among the repeating structural units to be expressed, and a repeating structure represented by the following general formula (4) other than the repeating structural unit represented by the formula (2) The unit contains 0 to 30 mol% and the repeating structural unit represented by the following general formula (5) contains 0 to 30 mol%.
式(1)中、Xは、芳香族基を含む2価の有機基を示す。
In formula (1), X represents a divalent organic group containing an aromatic group.
式(3)中、L1は、−CH2−、−(CH3)2C−、−O−、又は−SO2−を示す。
In Formula (3), L 1 represents —CH 2 —, — (CH 3 ) 2 C—, —O—, or —SO 2 —.
式(4)中、Yは、芳香族基を含む2価の有機基を示す。
In formula (4), Y represents a divalent organic group containing an aromatic group.
式(5)中、Zは、芳香族基を含む2価の有機基を示す。
In formula (5), Z represents a divalent organic group containing an aromatic group.
上記一般式(1)中のXとしては、耐熱性及び成形加工性の観点から、下記式(A)又は下記式(B)で表される2価の芳香族基であることが好ましい。なお、式(A)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。 X in the general formula (1) is preferably a divalent aromatic group represented by the following formula (A) or the following formula (B) from the viewpoint of heat resistance and molding processability. Note that the two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.
上記一般式(4)中のYとしては、例えば、下記一般式(4−1)で表される2価の基が挙げられる。 Examples of Y in the general formula (4) include a divalent group represented by the following general formula (4-1).
式(4−1)中、Ar1は2価の芳香族基を示し、Y1は芳香環を有する2価の基を示し、tは、0又は1の整数を示す。
In formula (4-1), Ar 1 represents a divalent aromatic group, Y 1 represents a divalent group having an aromatic ring, and t represents an integer of 0 or 1.
Ar1としては、耐熱性及び成形加工性の点で、下記式(A)又は(B)で表される2価の芳香族基が好ましい。なお、式(A)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。 Ar 1 is preferably a divalent aromatic group represented by the following formula (A) or (B) in terms of heat resistance and molding processability. Note that the two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.
Y1としては、下記式(4−2)で表される2価の基が挙げられる。 Examples of Y 1 include a divalent group represented by the following formula (4-2).
式(4−2)中、L2は、−O−、−S−、又は−SO−を示し、sは、0又は1の整数を示す。なお、式(4−2)中のベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。
In formula (4-2), L 2 represents —O—, —S—, or —SO—, and s represents an integer of 0 or 1. In addition, the two bonds of the benzene ring in formula (4-2) are in a meta-position or a para-position.
本発明の共重合体においては、特に射出成形時の流動性を向上させる観点から、上記一般式(4)中のYが、下記式(4−3)で表される2価の基であることが好ましい。 In the copolymer of the present invention, Y in the general formula (4) is a divalent group represented by the following formula (4-3) particularly from the viewpoint of improving fluidity during injection molding. It is preferable.
上記一般式(5)中のZとしては、例えば、下記一般式(5−1)で表される2価の基が挙げられる。 Examples of Z in the general formula (5) include a divalent group represented by the following general formula (5-1).
式(5−1)中、Ar2は2価の芳香族基を示し、Z1は芳香環を有する2価の基を示し、vは、0又は1の整数を示す。
In Formula (5-1), Ar 2 represents a divalent aromatic group, Z 1 represents a divalent group having an aromatic ring, and v represents an integer of 0 or 1.
Ar2としては、耐熱性及び成形加工性の点で、下記式(A)又は(B)で表される2価の芳香族基が好ましい。なお、式(A)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。 Ar 2 is preferably a divalent aromatic group represented by the following formula (A) or (B) in terms of heat resistance and molding processability. Note that the two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.
Z1としては、下記式(5−2)で表される2価の基が挙げられる。 Examples of Z 1 include a divalent group represented by the following formula (5-2).
式(5−2)中、L3は、2価の炭化水素基、−O−、−S−、−SO−、−SO2−、又は−CO−を示し、uは、0又は1の整数を示す。2価の炭化水素基としては、炭素数1〜3のアルカンジイル基が挙げられ、そのうち、−C(CH3)2−又は−CH(CH3)−が好ましい。なお、式(5−2)中のベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。
In Formula (5-2), L 3 represents a divalent hydrocarbon group, —O—, —S—, —SO—, —SO 2 —, or —CO—, and u is 0 or 1 Indicates an integer. Examples of the divalent hydrocarbon group include alkanediyl groups having 1 to 3 carbon atoms, and among them, —C (CH 3 ) 2 — or —CH (CH 3 ) — is preferable. In addition, the two bonds of the benzene ring in formula (5-2) are in a meta-position or a para-position.
本発明の共重合体においては、上記一般式(5)中のZが、下記式(5−3)又は下記式(5−4)で表される2価の基であることが好ましい。特に、テレフタル酸などを用いて式(5−3)で表わされる2価の基を組み入れた場合には、耐熱性を向上させることができる。イソフタル酸などを用いて式(5−4)で表わされる2価の基を組み入れた場合には、耐熱性が低下する傾向にあるが、上記2種類の化合物を併用して式(5−3)及び式(5−4)で表される2価の基を組み入れることにより融点を微調整することができる。 In the copolymer of the present invention, Z in the general formula (5) is preferably a divalent group represented by the following formula (5-3) or the following formula (5-4). In particular, when a divalent group represented by the formula (5-3) is incorporated using terephthalic acid or the like, the heat resistance can be improved. When the divalent group represented by the formula (5-4) is incorporated using isophthalic acid or the like, the heat resistance tends to be lowered, but the above two types of compounds are used in combination to formula (5-3). ) And a divalent group represented by the formula (5-4) can be finely adjusted.
本発明の共重合体は従来のポリエステルの重縮合法に準じて製造することができる。 The copolymer of the present invention can be produced according to a conventional polyester polycondensation method.
上記一般式(1)で表される繰り返し構造単位は、例えば、パラヒドロキシ安息香酸、メタヒドロキシ安息香酸、サリチル酸、これらのフェノール部位をプロピオン酸エステル、酢酸エステル又はギ酸エステルで変性したもの及びこれらのカルボン酸部位をメチルエステル、エチルエステル、イソプロピルエステル又はフェニルエステルなどで変性したもの、並びに、2−ヒドロキシ−6−ナフトエ酸、その位置異性体、これらのフェノール部位をプロピオン酸エステル、酢酸エステル又はギ酸エステルで変性したもの及びこれらのカルボン酸部位をメチルエステル、エチルエステル、イソプロピルエステル又はフェニルエステルなどで変性したもののうちの1種以上の化合物を共重合成分として用いることにより共重合体に組み入れることができる。 The repeating structural unit represented by the general formula (1) includes, for example, parahydroxybenzoic acid, metahydroxybenzoic acid, salicylic acid, those obtained by modifying these phenol sites with propionate, acetate or formate, and these Carboxylic acid moiety modified with methyl ester, ethyl ester, isopropyl ester or phenyl ester, etc., as well as 2-hydroxy-6-naphthoic acid, its positional isomer, and these phenol moieties as propionic acid ester, acetate ester or formic acid Incorporation into the copolymer by using one or more compounds of those modified with esters and those modified with methyl ester, ethyl ester, isopropyl ester or phenyl ester as the copolymer component. It can be.
これらの化合物は、上記一般式(1)で表される繰り返し構造単位が共重合体中40〜99モル%となる割合で配合される。 These compounds are blended in such a proportion that the repeating structural unit represented by the general formula (1) is 40 to 99 mol% in the copolymer.
射出成形向けの共重合体を製造する場合には、ポリマー分子の絡み合いが少なくなるパラヒドロキシ安息香酸及び/又はその誘導体を使用することが好ましい。押出成形向けの共重合体を製造する場合には、ポリマー分子の絡み合いが多くなる2−ヒドロキシ−6−ナフトエ酸及び/又はその誘導体を試用することが好ましい。 In the case of producing a copolymer for injection molding, it is preferable to use parahydroxybenzoic acid and / or a derivative thereof that reduces entanglement of polymer molecules. When producing a copolymer for extrusion molding, it is preferable to try 2-hydroxy-6-naphthoic acid and / or a derivative thereof that increases the entanglement of polymer molecules.
パラヒドロキシ安息香酸及びその誘導体、並びに、2−ヒドロキシ−6−ナフトエ酸及びその誘導体は1種を単独で或いは2種以上を組み合わせて使用することができる。本実施形態においては、例えば、(a)パラヒドロキシ安息香酸及び/又はその誘導体と、(b)2−ヒドロキシ−6−ナフトエ酸及び/又はその誘導体とを併用することができる。この場合の使用割合としては、モル比(a)/(b)が0.1〜10となる範囲が好ましく、0.3〜8となる範囲がより好ましく、0.4〜5となる範囲が更により好ましい。(a)の割合が多くなると、ポリマー分子の絡み合いが少なくなり、縦裂き性など押出成形、特にフィルム成形に好ましくない性質が発現する傾向にある。 Parahydroxybenzoic acid and derivatives thereof, and 2-hydroxy-6-naphthoic acid and derivatives thereof can be used singly or in combination of two or more. In this embodiment, for example, (a) parahydroxybenzoic acid and / or a derivative thereof and (b) 2-hydroxy-6-naphthoic acid and / or a derivative thereof can be used in combination. As a use ratio in this case, the range in which the molar ratio (a) / (b) is 0.1 to 10 is preferable, the range in which 0.3 to 8 is more preferable, and the range in which 0.4 to 5 is set. Even more preferred. When the proportion of (a) increases, the entanglement of polymer molecules decreases, and properties unfavorable for extrusion molding, particularly film molding, such as longitudinal tearability tend to be exhibited.
上記一般式(2)で表される繰り返し構造単位は、例えば、下記式(2−A)で表される化合物、このフェノール部位をプロピオン酸エステル、酢酸エステル又はギ酸エステルで変性したもののうちの1種以上の化合物を共重合成分として用いることにより共重合体に組み入れることができる。 The repeating structural unit represented by the general formula (2) is, for example, a compound represented by the following formula (2-A), one of those obtained by modifying this phenol moiety with a propionic acid ester, acetate ester or formate ester. More than one type of compound can be incorporated into the copolymer by using it as a copolymerization component.
また、上記一般式(3)で表される繰り返し構造単位は、例えば、4,4’−ジアミノジフェニルメタン、4,4’−ジアミノ−2,2−ジフェニルプロパン、4,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルスルフォン、及び、これらのアミン部位をプロピオン酸アミド、酢酸アミド又はギ酸アミドで変性したもののうちの1種以上の化合物を共重合成分として用いることにより共重合体に組み入れることができる。 The repeating structural unit represented by the general formula (3) includes, for example, 4,4′-diaminodiphenylmethane, 4,4′-diamino-2,2-diphenylpropane, 4,4′-diaminodiphenyl ether, 4 , 4'-diaminodiphenylsulfone and one or more of these amine moieties modified with propionic acid amide, acetic acid amide or formic acid amide can be incorporated into the copolymer as a copolymerization component. it can.
上記の化合物は、上記式(2)で表される繰り返し構造単位及び上記記一般式(3)で表される繰り返し構造単位が合計で共重合体中1〜15モル%となる割合で配合され、好ましくは1〜14モル%、より好ましくは1〜13モル%となる割合で配合される。上記の化合物を上記構造単位が15モル%を超える量で用いると、重合時に過剰に粘度が上昇したり極端な場合には炭化を起こしたりする。また、上記構造単位が1%未満となる量では、接着性の向上効果が十分に得られなくなる。 Said compound is mix | blended in the ratio from which the repeating structural unit represented by said Formula (2) and the repeating structural unit represented by the said General formula (3) become 1-15 mol% in a copolymer in total. , Preferably 1 to 14 mol%, more preferably 1 to 13 mol%. When the above compound is used in an amount exceeding 15 mol%, the viscosity excessively increases during polymerization or, in the extreme case, carbonization occurs. Further, when the amount of the structural unit is less than 1%, the effect of improving adhesiveness cannot be obtained sufficiently.
上記一般式(4)で表される繰り返し構造単位は、例えば、4,4’−ビフェノール、ハイドロキノン、2,6−ナフタレンジオール、及びこれらのフェノール部位をプロピオン酸エステル、酢酸エステル、ギ酸エステル、フェニルエステルで変性したもののうちの1種以上の化合物を共重合成分として用いることにより共重合体に組み入れることができる。これらの中でも、機械的強度の観点から、4,4’−ビフェノールが好ましく使用される。 The repeating structural unit represented by the general formula (4) includes, for example, 4,4′-biphenol, hydroquinone, 2,6-naphthalenediol, and these phenol moieties as propionate, acetate, formate, phenyl. One or more of the compounds modified with an ester can be incorporated into the copolymer by using it as a copolymerization component. Among these, 4,4'-biphenol is preferably used from the viewpoint of mechanical strength.
これらの化合物は、上記一般式(4)で表される繰り返し構造単位が共重合体中0〜30モル%となる割合で配合され、低コスト化の点で好ましくは27モル%以下、よりこのましくは25モル%以下となる割合で配合される。 These compounds are blended in such a proportion that the repeating structural unit represented by the above general formula (4) is 0 to 30 mol% in the copolymer, and preferably 27 mol% or less from the viewpoint of cost reduction. Preferably, it is blended at a ratio of 25 mol% or less.
上記一般式(5)で表される繰り返し構造単位は、例えば、テレフタル酸、イソフタル酸、これらのカルボン酸部位をメチルエステル、エチルエステル、イソプロピルエステル又はフェニルエステルで変性したもののうちの1種以上の化合物を共重合成分として用いることにより共重合体に組み入れることができる。 The repeating structural unit represented by the general formula (5) is, for example, one or more of terephthalic acid, isophthalic acid, and those obtained by modifying these carboxylic acid sites with methyl ester, ethyl ester, isopropyl ester or phenyl ester The compound can be incorporated into the copolymer by using it as a copolymerization component.
これらの化合物は、上記一般式(5)で表される繰り返し構造単位が共重合体中0〜30モル%となる割合で配合され、好ましくは27モル%以下、よりこのましくは25モル%以下となる割合で配合される。上記の化合物を、上記一般式(5)で表される繰り返し構造単位が30モル%を超えるようになる量で使用すると、重合中に高粘度となるため好ましくない。 These compounds are blended in such a proportion that the repeating structural unit represented by the general formula (5) is 0 to 30 mol% in the copolymer, preferably 27 mol% or less, more preferably 25 mol%. It mix | blends in the ratio used as follows. If the above compound is used in such an amount that the repeating structural unit represented by the general formula (5) exceeds 30 mol%, it is not preferable because the viscosity becomes high during the polymerization.
上述した各共重合成分については、上記式(1)〜(5)におけるカルボン酸残基の合計モル数とヒドロキシ残基及びアミノ残基の合計モル数とが等しくなるように、組成を選択することが肝要である。本発明の共重合体において、上記一般式(4)で表される構造単位や上記一般式(5)で表される構造単位は含まれていなくてもよいが、式(4)の構造単位及び(5)の構造単位が含まれる場合、式(1)〜(5)の構造単位の合計が100モル%となり、式(2)〜(4)の構造単位の含有割合の合計と、(5)の構造単位の含有割合とが等しくなるように設定することができる。また、式(4)の構造単位が含まれず、(5)の構造単位が含まれる場合、式(1)〜(3)及び(5)の構造単位の合計が100モル%となり、式(2)〜(3)の構造単位の含有割合の合計と、(5)の構造単位の含有割合とが等しくなるように設定することができる。 About each copolymer component mentioned above, a composition is selected so that the total mole number of a carboxylic acid residue in said formula (1)-(5) and the total mole number of a hydroxy residue and an amino residue may become equal. It is important. In the copolymer of the present invention, the structural unit represented by the general formula (4) and the structural unit represented by the general formula (5) may not be included. When the structural units of (5) and (5) are included, the sum of the structural units of the formulas (1) to (5) is 100 mol%, and the total content of the structural units of the formulas (2) to (4) It can be set so that the content ratio of the structural unit in 5) is equal. When the structural unit of formula (4) is not included and the structural unit of (5) is included, the total of the structural units of formulas (1) to (3) and (5) is 100 mol%, and the formula (2 ) To (3) can be set so that the total content of the structural units is equal to the content of the structural units (5).
本発明の共重合体は、共重合体を板状、シート状又はフィルム状に成形したときの表面エネルギーが35mJ/m2以上であることが好ましい。この場合、極性基を有する接着剤や金属との親和性が高くなり、他の部材と強固に密着させることが可能となる。例えば、上記の式(2)で表される繰り返し構造単位及び/又は式(3)で表される繰り返し構造単位の含有割合を多くすることによって、共重合体の表面エネルギーを大きくすることができる。 The copolymer of the present invention preferably has a surface energy of 35 mJ / m 2 or more when the copolymer is molded into a plate, sheet or film. In this case, the affinity with an adhesive or metal having a polar group is increased, and it is possible to firmly adhere to another member. For example, the surface energy of the copolymer can be increased by increasing the content of the repeating structural unit represented by the above formula (2) and / or the repeating structural unit represented by the formula (3). .
また、本発明の共重合体は、示差走査熱量計(DSC)において測定される融点が300〜400℃の範囲にあることが望ましい。融点が300℃未満では、耐熱性が不十分となる傾向にあり、一方、融点が400℃を超えると、成形時に多大なエネルギーを必要とし、また成形性が著しく低下するため好ましくない。 The copolymer of the present invention preferably has a melting point measured by a differential scanning calorimeter (DSC) in the range of 300 to 400 ° C. If the melting point is less than 300 ° C, the heat resistance tends to be insufficient. On the other hand, if the melting point exceeds 400 ° C, a large amount of energy is required at the time of molding, and the moldability is remarkably lowered.
本発明の共重合体は、従来のポリエステルの重縮合法に準じて製造することができる。製造方法について何ら限定はないが、例えば、下記の方法が挙げられる。
A:芳香族ジヒドロキシ化合物、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸、場合により芳香族ジアミンを配合したものに無水酢酸を添加し、脱酢酸重縮合反応によって製造する方法。
B:芳香族ジヒドロキシ化合物のジアシル化物、芳香族ヒドロキシカルボン酸のアシル化物、芳香族ジカルボン酸、場合により芳香族ジアミンのジアミド化合物を配合したものからら脱酢酸重縮合によって製造する方法。
C:芳香族ジヒドロキシ化合物、芳香族ヒドロキシカルボン酸のフェニルエステル、芳香族ジカルボン酸のジフェニルエステル、場合により芳香族ジアミンを配合したものから脱フェノール重縮合によって製造する方法。
D:芳香族ヒドロキシカルボン酸及び芳香族ジカルボン酸を所定量のジフェニルカーボネートと反応させ、カルボキシル基をフェニルエステル化した後、芳香族ジヒドロキシ化合物、場合により芳香族ジアミンを加え、脱フェノール重縮合によって製造する方法。
The copolymer of the present invention can be produced according to a conventional polyester polycondensation method. Although there is no limitation about a manufacturing method, the following method is mentioned, for example.
A: A method in which acetic anhydride is added to a mixture of an aromatic dihydroxy compound, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, and optionally an aromatic diamine, followed by a deacetic acid polycondensation reaction.
B: A method of producing by deacetic acid polycondensation from a diacylated product of an aromatic dihydroxy compound, an acylated product of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and optionally a diamide compound of an aromatic diamine.
C: A method of producing by dephenol polycondensation from an aromatic dihydroxy compound, a phenyl ester of an aromatic hydroxycarboxylic acid, a diphenyl ester of an aromatic dicarboxylic acid, and optionally an aromatic diamine.
D: produced by dephenol polycondensation after reacting aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid with a predetermined amount of diphenyl carbonate to convert the carboxyl group to phenyl ester, adding aromatic dihydroxy compound, and optionally aromatic diamine how to.
代表的な例を挙げると、パラヒドロキシ安息香酸、テレフタル酸、イソフタル酸、4,4’−ビフェノール、4,4’−ジアミノジフェニルメタンを反応器に投入し、無水酢酸を加えて無水酢酸還流下でアセトキシ化を行う。その後、昇温して250〜350℃の温度範囲で酢酸を留出しながら脱酢酸重縮合を行うことにより、ポリエステル又はポリエステルアミドを製造することができる。重合時間は1〜100時間の範囲で選択することができる。 As a typical example, parahydroxybenzoic acid, terephthalic acid, isophthalic acid, 4,4′-biphenol, and 4,4′-diaminodiphenylmethane are put into a reactor, acetic anhydride is added and acetic anhydride is refluxed. Acetoxylation is performed. Thereafter, the polyester or polyester amide can be produced by performing deacetic acid polycondensation while raising the temperature and distilling acetic acid in the temperature range of 250 to 350 ° C. The polymerization time can be selected in the range of 1 to 100 hours.
また、上記のような重縮合反応を行う際、触媒を用いることができる。具体的には、酢酸マグネシウム、酢酸第一錫、酢酸鉛、酢酸ナトリウム、酢酸カリウム、三酸化アンチモン、テトラメトキシチタン、テトラエトキシチタン、テトライソプロポキシチタン、テトラプロポキシチタン、テトラブトキシチタン、N−メチルイミダゾールなどが挙げられる。 Moreover, a catalyst can be used when performing the above polycondensation reaction. Specifically, magnesium acetate, stannous acetate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, N-methyl Examples include imidazole.
本発明の共重合体は、上記の重合反応のそれぞれについて、溶融重合と固相重合を併用して製造することができる。固相重合とは、溶融重合により重縮合を終えたプレポリマーをさらに高度に重合する方法である。固相重合は、例えば、溶融重合により得られたプレポリマーを窒素などの不活性ガス雰囲気下、あるいは減圧下において、200〜350℃の温度範囲で1〜30時間熱処理することにより行うことができる。実験室レベルではクーゲルロール装置が使用できる。工業的には円筒型回転式リアクターが好適に使用される。 The copolymer of the present invention can be produced by using both melt polymerization and solid phase polymerization for each of the above polymerization reactions. Solid-phase polymerization is a method for further polymerizing a prepolymer that has been subjected to polycondensation by melt polymerization. Solid-phase polymerization can be performed, for example, by heat-treating a prepolymer obtained by melt polymerization in an atmosphere of an inert gas such as nitrogen or under reduced pressure at a temperature range of 200 to 350 ° C. for 1 to 30 hours. . At the laboratory level, a Kugelrohr device can be used. Industrially, a cylindrical rotary reactor is preferably used.
溶融重合における重合器は特に限定されるものではないが、一般の高粘度反応に用いられる攪拌設備、例えば、錨型、多段型、螺旋帯、螺旋軸などの形状の攪拌機を有する攪拌槽型重合機、より具体的にはワーナー式ミキサー、バンバリーミキサー、ポニーミキサー、ミュラーミキサー、ロールミル、連続走査可能なコニーダー、パグミル、ギアーコンパウンダーなどを使用することができる。 The polymerization vessel in the melt polymerization is not particularly limited, but a stirring tank type polymerization having a stirrer having a shape such as a vertical type, a multistage type, a spiral band, and a helical axis, which is used for a general high viscosity reaction. More specifically, a Warner mixer, a Banbury mixer, a pony mixer, a Mueller mixer, a roll mill, a continuous scan capable kneader, a pug mill, a gear compounder, or the like can be used.
本発明の共重合体は、単独で又は他の樹脂と混合し、必要に応じて添加剤が配合された樹脂組成物として使用することができる。 The copolymer of the present invention can be used alone or mixed with other resins and used as a resin composition in which additives are blended as necessary.
本発明に係る樹脂組成物には、主として機械的強度の向上を目的として、繊維状、分粒状、板状などの無機又は有機充てん剤を配合することができる。 In the resin composition according to the present invention, for the purpose of mainly improving the mechanical strength, inorganic or organic fillers such as a fibrous shape, a granular shape, and a plate shape can be blended.
繊維状の充てん剤としては、例えば、ガラス繊維、シリカ繊維、シリカアルミナ繊維、チタン酸カリウム繊維、炭素繊維、アルミニウム、チタン及び銅などの金属の繊維が挙げられる。 Examples of the fibrous filler include glass fiber, silica fiber, silica alumina fiber, potassium titanate fiber, carbon fiber, metal fiber such as aluminum, titanium and copper.
粒状の充てん剤としては、例えば、カーボンブラック、黒鉛、シリカ、石英粉末、ガラスビーズ、ミルドガラスファイバー、ガラスバルーン、ガラス粉、ケイ酸カルシウム、ケイ酸アルミニウム、タルク、クレー、珪藻土、ウォラストナイトなどのケイ酸塩、酸化鉄、酸化チタン、酸化亜鉛、三酸化アンチモン、アルミナ、硫酸カルシウム、その他各種金属粉末が挙げられる。 Examples of granular fillers include carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium silicate, aluminum silicate, talc, clay, diatomaceous earth, and wollastonite. Silicate, iron oxide, titanium oxide, zinc oxide, antimony trioxide, alumina, calcium sulfate, and other various metal powders.
板状充てん剤としては、例えば、マイカ、ガラスフレーク、各種金属箔などが挙げられる。 Examples of the plate-like filler include mica, glass flakes and various metal foils.
有機充てん剤としては、例えば、ポリエステル、ポリイミド、ポリアミドからなる繊維などが挙げられる。 Examples of the organic filler include fibers made of polyester, polyimide, and polyamide.
無機充てん剤を配合する場合、その配合量は組成物全体に対して10〜90質量%であることが好ましく、10〜80質量%であることがより好ましい。配合量が90質量%を超える場合、機械的強度が低下する傾向にあり、一方、配合量が10質量%未満の場合、配合効果が現れにくくなる。 When mix | blending an inorganic filler, it is preferable that the compounding quantity is 10-90 mass% with respect to the whole composition, and it is more preferable that it is 10-80 mass%. If the blending amount exceeds 90% by mass, the mechanical strength tends to decrease. On the other hand, if the blending amount is less than 10% by mass, the blending effect hardly appears.
本発明に係る樹脂組成物には、上記以外に従来公知の酸化防止剤、熱安定化剤、補強剤、顔料、難燃化剤などの添加剤を適宜添加することができる。これらの添加剤は、単独で又は2種類以上を適宜組み合わせて使用することができる。 In addition to the above, additives such as conventionally known antioxidants, heat stabilizers, reinforcing agents, pigments, flame retardants and the like can be appropriately added to the resin composition according to the present invention. These additives can be used individually or in combination of 2 or more types as appropriate.
本発明の共重合体を含む樹脂組成物は、従来公知の成形方法、射出成形、フィルム成形、シート成形、ブロー成形、圧縮成形などの溶融成形加工することができる。そのような加工法を通じ、繊維、フィルム、シート、容器、ホース、三次元成形品などに加工して、成形品を得ることができる。なお、このようにして得られた成形品は、適当な条件による熱処理によって高強度化・高弾性率化することができる。この熱処理は、例えば、成形品を不活性雰囲気中、酸素含有雰囲気中、あるいは減圧下において、組成物の融点以下の温度で加熱することにより行うことができる。 The resin composition containing the copolymer of the present invention can be subjected to a melt molding process such as a conventionally known molding method, injection molding, film molding, sheet molding, blow molding, and compression molding. Through such a processing method, a molded product can be obtained by processing into a fiber, a film, a sheet, a container, a hose, a three-dimensional molded product, or the like. The molded product thus obtained can be increased in strength and elastic modulus by a heat treatment under appropriate conditions. This heat treatment can be performed, for example, by heating the molded article in an inert atmosphere, an oxygen-containing atmosphere, or under reduced pressure at a temperature below the melting point of the composition.
本発明の共重合体を含む樹脂組成物を成形してなる成形体の具体的な用途としては、携帯電話、デジタルカメラなどのカメラモジュール部品、LED部品、銅張積層板などの基板、その他電気・電子部品に好適に使用することができる。 Specific uses of the molded product formed by molding the resin composition containing the copolymer of the present invention include camera module parts such as mobile phones and digital cameras, LED parts, substrates such as copper-clad laminates, and other electrical devices. -It can be used suitably for electronic components.
以下、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.
(実施例1)
機械式攪拌機を備え付けた200mLの三口フラスコに、パラヒドロキシ安息香酸(PHBA)33g(0.24モル)、4,4’−ビフェノール(BP)11g(0.06モル)、テレフタル酸(TPA)10g(0.06モル)、イソフタル酸(IPA)3g(0.02モル)、4,4’−ジアミノジフェニルスルフォン5g(0.02モル)を導入した。更にこれに、無水酢酸を40mLと、酢酸マグネシウム10mg及び酢酸カリウム10mgを加えた。この無水酢酸スラリーを、マントルヒーターを使用して140℃に制御して2時間加熱還流した。
Example 1
In a 200 mL three-necked flask equipped with a mechanical stirrer, 33 g (0.24 mol) of parahydroxybenzoic acid (PHBA), 11 g (0.06 mol) of 4,4′-biphenol (BP), and 10 g of terephthalic acid (TPA) (0.06 mol), 3 g (0.02 mol) of isophthalic acid (IPA), and 5 g (0.02 mol) of 4,4′-diaminodiphenylsulfone were introduced. Furthermore, 40 mL of acetic anhydride, 10 mg of magnesium acetate and 10 mg of potassium acetate were added thereto. This acetic anhydride slurry was heated to reflux for 2 hours under control of 140 ° C. using a mantle heater.
次に、還流装置を留出装置に変え、さらにマントルヒーターを溶融塩バスに変えた。酢酸を留去しながら、180℃から300℃まで5℃/10分の速度で昇温した。300℃で10分間保持した後、内容物をステンレスバットに流し入れ、得られた重合物を放冷した。次いで、冷却された重合物を粉砕機にて粉砕して粉末状のプレポリマーを得た。 Next, the reflux device was changed to a distillation device, and the mantle heater was changed to a molten salt bath. While acetic acid was distilled off, the temperature was increased from 180 ° C. to 300 ° C. at a rate of 5 ° C./10 minutes. After maintaining at 300 ° C. for 10 minutes, the content was poured into a stainless steel vat, and the resulting polymer was allowed to cool. Next, the cooled polymer was pulverized with a pulverizer to obtain a powdery prepolymer.
次に、上記で得られたプレポリマーをクーゲルロール装置に入れ、減圧にして290℃に加熱することで、低分子量成分を留去しながら固相重合した。こうして共重合体を得た。 Next, the prepolymer obtained above was put into a Kugelrohr apparatus and heated to 290 ° C. under reduced pressure, whereby solid phase polymerization was performed while distilling off low molecular weight components. A copolymer was thus obtained.
上記で得られた共重合体について、以下の方法にしたがって表面エネルギー、融点、ピール強度、及び見かけ粘度の測定を行った。結果を表2に示す。なお、ピール強度の測定後のサンプルの破壊形態は樹脂の破壊であった。 The copolymer obtained above was measured for surface energy, melting point, peel strength, and apparent viscosity according to the following method. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.
[表面エネルギーの測定]
共重合体を350℃でプレス成形して板状サンプル(3cm×6cm×1.5mm)を作成した。自動接触角計(協和界面化学(株)製、DM−501)を用いて、純水及びジヨードメタンの液滴(1.0μL)をシリンジの針先から板状サンプル上にたらし、その接触角を読み取り、Owens式を用いて表面エネルギーを求めた。
[Measurement of surface energy]
The copolymer was press-molded at 350 ° C. to prepare a plate-like sample (3 cm × 6 cm × 1.5 mm). Using an automatic contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd., DM-501), a drop of pure water and diiodomethane (1.0 μL) was dropped from the tip of a syringe onto a plate sample, and the contact angle The surface energy was determined using the Owens equation.
[融点の測定]
示差走査熱量計(セイコー電子工業(株)製)を用いて、リファレンスとしてα-アルミナを使用した。測定条件は、室温から20℃/分で420℃まで昇温し、共重合体を溶融させた後、10℃/分で150℃まで降温し、さらに20℃/分で430℃まで昇温したときに得られた吸熱ピークの頂点を融点とした。
[Measurement of melting point]
Using a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd.), α-alumina was used as a reference. The measurement conditions were that the temperature was raised from room temperature to 420 ° C. at 20 ° C./min, the copolymer was melted, then the temperature was lowered to 150 ° C. at 10 ° C./min, and further raised to 430 ° C. at 20 ° C./min. The peak of the endothermic peak that was sometimes obtained was taken as the melting point.
[ピール強度の測定]
共重合体からプレス成形機を用いて3cm×6cm×1.5mmの試験片を作製した。作製条件は、330℃、5MPaであり、時間は2分間とした。その際、あらかじめアセトンで脱脂した銅箔(3cm×10cm×0.02mm)を片面に接着させた。このサンプルについて、引張試験機を用いて、引張角度90度、引張速度5cm/分の条件でピール強度を測定した。
[Measurement of peel strength]
A test piece of 3 cm × 6 cm × 1.5 mm was produced from the copolymer using a press molding machine. The production conditions were 330 ° C. and 5 MPa, and the time was 2 minutes. At that time, a copper foil (3 cm × 10 cm × 0.02 mm) previously degreased with acetone was adhered to one side. The peel strength of this sample was measured using a tensile tester under the conditions of a tensile angle of 90 degrees and a tensile speed of 5 cm / min.
[見かけ粘度]
(株)インテスコ製キャピラリーレオメーター(2010型)にて、キャピラリー径1.0mm、長さ40mm、流入角90°の物を用い、せん断速度100sec−1で融点−30℃から融点+20℃まで、+4℃/分の昇温速度で等速加熱する等速昇温法における320℃での粘度を読み取った。
[Apparent viscosity]
Using a capillary rheometer (2010 type) manufactured by Intesco with a capillary diameter of 1.0 mm, a length of 40 mm, and an inflow angle of 90 °, a melting rate of −30 ° C. to a melting point of + 20 ° C. at a shear rate of 100 sec −1 The viscosity at 320 ° C. was read in a constant temperature heating method in which heating was carried out at a constant rate of + 4 ° C./min.
(実施例2)
4,4’−ジアミノジフェニルスルフォンに代えて4,4’−ジアミノジフェニルエーテルを4g(0.02モル)用いたこと以外は、実施例1と同様にして共重合体を得た。得られた共重合体について実施例1と同様の評価を行った。結果を表2に示す。なお、ピール強度の測定後のサンプルの破壊形態は樹脂の破壊であった。
(Example 2)
A copolymer was obtained in the same manner as in Example 1 except that 4 g (0.02 mol) of 4,4′-diaminodiphenyl ether was used in place of 4,4′-diaminodiphenyl sulfone. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.
(実施例3)
4,4’−ジアミノジフェニルスルフォンに代えて4,4’−ジアミノジフェニルメタンを8g(0.04モル)用い、4,4’−ビフェノールを7.4g(0.04モル)用いたこと以外は、実施例1と同様にして共重合体を得た。得られた共重合体について実施例1と同様の評価を行った。結果を表2に示す。なお、ピール強度の測定後のサンプルの破壊形態は樹脂の破壊であった。
(Example 3)
Except for using 4 g (0.04 mol) of 4,4′-diaminodiphenylmethane instead of 4,4′-diaminodiphenylsulfone and using 7.4 g (0.04 mol) of 4,4′-biphenol, A copolymer was obtained in the same manner as in Example 1. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.
(実施例4)
4,4’−ジアミノジフェニルスルフォンに代えて4,4’−ジアミノ−2,2−ジフェニルプロパンを4g(0.02モル)用いたこと以外は、実施例1と同様にして共重合体を得た。得られた共重合体について実施例1と同様の評価を行った。結果を表2に示す。なお、ピール強度の測定後のサンプルの破壊形態は樹脂の破壊であった。
Example 4
A copolymer was obtained in the same manner as in Example 1 except that 4 g (0.02 mol) of 4,4′-diamino-2,2-diphenylpropane was used in place of 4,4′-diaminodiphenylsulfone. It was. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.
(参考例5)
4,4’−ジアミノジフェニルスルフォンに代えて下記式(2−A)で表されるリン系化合物Aを6.5g(0.02モル)用いたこと以外は、実施例1と同様にして共重合体を得た。得られた共重合体について実施例1と同様の評価を行った。結果を表2に示す。なお、ピール強度の測定後のサンプルの破壊形態は樹脂の破壊であった。
( Reference Example 5)
In the same manner as in Example 1, except that 6.5 g (0.02 mol) of phosphorus compound A represented by the following formula (2-A) was used instead of 4,4′-diaminodiphenylsulfone. A polymer was obtained. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.
(参考例6)
機械式攪拌機を備え付けた200mLの三口フラスコに、パラヒドロキシ安息香酸(PHBA)32g(0.23モル)、2−ヒドロキシ−6−ナフトエ酸(HNA)11g(0.06モル)、上記式(2−A)で表されるリン系化合物A11g(0.03モル)、イソフタル酸(IPA)6g(0.04モル)を導入した。更にこれに、無水酢酸を40mLと、酢酸マグネシウム10mg及び酢酸カリウム10mgを加えた。この無水酢酸スラリーを、マントルヒーターを使用して140℃に制御して2時間加熱還流した。
( Reference Example 6)
In a 200 mL three-necked flask equipped with a mechanical stirrer, 32 g (0.23 mol) of parahydroxybenzoic acid (PHBA), 11 g (0.06 mol) of 2-hydroxy-6-naphthoic acid (HNA), the above formula (2 Phosphorus compound A11 g (0.03 mol) represented by -A) and 6 g (0.04 mol) of isophthalic acid (IPA) were introduced. Furthermore, 40 mL of acetic anhydride, 10 mg of magnesium acetate and 10 mg of potassium acetate were added thereto. This acetic anhydride slurry was heated to reflux for 2 hours under control of 140 ° C. using a mantle heater.
次に、還流装置を留出装置に変え、さらにマントルヒーターを溶融塩バスに変えた。酢酸を留去しながら、180℃から270℃まで5℃/10分の速度で昇温した。その後、内容物をステンレスバットに流し入れ、得られた重合物を放冷した。次いで、冷却された重合物を粉砕機にて粉砕して粉末状のプレポリマーを得た。 Next, the reflux device was changed to a distillation device, and the mantle heater was changed to a molten salt bath. While acetic acid was distilled off, the temperature was raised from 180 ° C. to 270 ° C. at a rate of 5 ° C./10 minutes. Thereafter, the content was poured into a stainless steel vat, and the resulting polymer was allowed to cool. Next, the cooled polymer was pulverized with a pulverizer to obtain a powdery prepolymer.
次に、上記で得られたプレポリマーをクーゲルロール装置に入れ、減圧にして290℃に加熱することで、低分子量成分を留去しながら固相重合した。こうして共重合体を得た。得られた共重合体について実施例1と同様の評価を行った。結果を表2に示す。なお、ピール強度の測定後のサンプルの破壊形態は樹脂の破壊であった。 Next, the prepolymer obtained above was put into a Kugelrohr apparatus and heated to 290 ° C. under reduced pressure, whereby solid phase polymerization was performed while distilling off low molecular weight components. A copolymer was thus obtained. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. In addition, the destruction mode of the sample after the measurement of peel strength was resin destruction.
(比較例1)
4,4’−ジアミノジフェニルスルフォンを配合しなかったこと、及び4,4’−ビフェノールを15g(0.08モル)用いたこと以外は、実施例1と同様にして共重合体を得た。得られた共重合体について実施例1と同様の評価を行った。結果を表2に示す。なお、ピール強度の測定後のサンプルの破壊形態は銅と樹脂との界面の剥がれ(界面破壊)であった。
(Comparative Example 1)
A copolymer was obtained in the same manner as in Example 1 except that 4,4′-diaminodiphenylsulfone was not blended and 15 g (0.08 mol) of 4,4′-biphenol was used. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. Note that the fracture mode of the sample after the peel strength measurement was peeling of the interface between copper and resin (interfacial fracture).
(比較例2)
機械式攪拌機を備え付けた200mLの三口フラスコに、パラヒドロキシ安息香酸(PHBA)11g(0.08モル)、2−ヒドロキシ−6−ナフトエ酸(HNA)8g(0.04モル)、4,4’−ビフェノール(BP)22g(0.12モル)、テレフタル酸20g(TPA)(0.12モル)、イソフタル酸(IPA)3g(0.02モル)、4,4’−ジアミノジフェニルスルフォン5g(0.04モル)を導入した。更にこれに、無水酢酸を40mLと、酢酸マグネシウム10mg及び酢酸カリウム10mgを加えた。この無水酢酸スラリーを、マントルヒーターを使用して140℃に制御して2時間加熱還流した。
(Comparative Example 2)
In a 200 mL three-necked flask equipped with a mechanical stirrer, 11 g (0.08 mol) of parahydroxybenzoic acid (PHBA), 8 g (0.04 mol) of 2-hydroxy-6-naphthoic acid (HNA), 4,4 ′ -22 g (0.12 mol) of biphenol (BP), 20 g (TPA) (0.12 mol) of terephthalic acid, 3 g (0.02 mol) of isophthalic acid (IPA), 5 g of 4,4′-diaminodiphenylsulfone (0 .04 mol) was introduced. Furthermore, 40 mL of acetic anhydride, 10 mg of magnesium acetate and 10 mg of potassium acetate were added thereto. This acetic anhydride slurry was heated to reflux for 2 hours under control of 140 ° C. using a mantle heater.
次に、還流装置を留出装置に変え、さらにマントルヒーターを溶融塩バスに変えた。酢酸を留去しながら、180℃から5℃/10分の速度で昇温した。250℃付近で重合物の流動性が失われ、270℃付近から著しい焦げ付きが見られた。 Next, the reflux device was changed to a distillation device, and the mantle heater was changed to a molten salt bath. While acetic acid was distilled off, the temperature was increased from 180 ° C. at a rate of 5 ° C./10 minutes. The fluidity of the polymer was lost at around 250 ° C., and marked scorching was observed from around 270 ° C.
(比較例3)
リン系化合物Aを配合しなかったこと、及び4,4’−ビフェノールを6.5g(0.03モル)用いたこと以外は、参考例6と同様にして共重合体を得た。得られた共重合体について実施例1と同様の評価を行った。結果を表2に示す。なお、ピール強度の測定後のサンプルの破壊形態は銅と樹脂との界面の剥がれ(界面破壊)であった。
(Comparative Example 3)
A copolymer was obtained in the same manner as in Reference Example 6 except that the phosphorus compound A was not blended and 6.5 g (0.03 mol) of 4,4′-biphenol was used. Evaluation similar to Example 1 was performed about the obtained copolymer. The results are shown in Table 2. Note that the fracture mode of the sample after the peel strength measurement was peeling of the interface between copper and resin (interfacial fracture).
(比較例4)
機械式攪拌機を備え付けた200mLの三口フラスコに、パラヒドロキシ安息香酸(PHBA)9.5g(0.07モル)、テレフタル酸10g(TPA)(0.06モル)、イソフタル酸(IPA)3g(0.02モル)、4,4’−ジアミノジフェニルエーテル16g(0.08モル)を導入した。更にこれに、無水酢酸を40mLと、酢酸マグネシウム10mg及び酢酸カリウム10mgを加えた。この無水酢酸スラリーを、マントルヒーターを使用して140℃に制御して2時間加熱還流した。
(Comparative Example 4)
In a 200 mL three-necked flask equipped with a mechanical stirrer, 9.5 g (0.07 mol) of parahydroxybenzoic acid (PHBA), 10 g of terephthalic acid (TPA) (0.06 mol), 3 g of isophthalic acid (IPA) (0 0.02 mol), 16 g (0.08 mol) of 4,4′-diaminodiphenyl ether were introduced. Furthermore, 40 mL of acetic anhydride, 10 mg of magnesium acetate and 10 mg of potassium acetate were added thereto. This acetic anhydride slurry was heated to reflux for 2 hours under control of 140 ° C. using a mantle heater.
次に、還流装置を留出装置に変え、さらにマントルヒーターを溶融塩バスに変えた。酢酸を留去しながら、180℃から5℃/10分の速度で昇温した。230℃付近で重合物の流動性が失われ、260℃付近から著しい焦げ付きが見られた。 Next, the reflux device was changed to a distillation device, and the mantle heater was changed to a molten salt bath. While acetic acid was distilled off, the temperature was increased from 180 ° C. at a rate of 5 ° C./10 minutes. The fluidity of the polymer was lost around 230 ° C., and significant scorching was seen from around 260 ° C.
本発明によれば、全芳香族ポリエステルの優れた耐熱性及び成形性を十分維持しつつ、成形体の接着強度を向上させることができる共重合体を提供することができる。また、本発明の共重合体を含む樹脂組成物からなる成形体は、エポキシ系、ウレタン系、アクリル系といった接着剤との親和性に優れ、優れた接着性を発現することができる。また、本発明に係る成形体によれば、金属との親和性が高いことから、金属との複合体、例えば銅張積層板などを、金属と本発明に係る成形体とを熱圧着するだけで成形することが可能になる。
ADVANTAGE OF THE INVENTION According to this invention, the copolymer which can improve the adhesive strength of a molded object can be provided, fully maintaining the outstanding heat resistance and moldability of wholly aromatic polyester. Moreover, the molded object which consists of a resin composition containing the copolymer of this invention is excellent in affinity with adhesives, such as an epoxy type, a urethane type, and an acryl type, and can express the outstanding adhesiveness. Further, according to the molded body according to the present invention, since the affinity with the metal is high, a composite with the metal, for example, a copper-clad laminate, is simply thermocompression bonded between the metal and the molded body according to the present invention. It becomes possible to mold with.
Claims (6)
下記一般式(3)で表される繰り返し構造単位を1〜15モル%と、
下記一般式(4)で表される繰り返し構造単位を0モル%超30モル%以下と、
下記一般式(5)で表される繰り返し構造単位を1モル%超30モル%以下と、を含有してなり、
前記一般式(1)及び(3)〜(5)の構造単位の合計が100モル%であり、且つ、前記一般式(3)及び(4)の構造単位の含有割合の合計と、前記一般式(5)の構造単位の含有割合とが等しい、共重合体。
[式(1)中、Xは、下記式(A)又は(B)で表される2価の芳香族基を示す。
(式(A)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。)]
[式(3)中、L1は、−CH2−、−(CH3)2C−、−O−、又は−SO2−を示す。]
[式(4)中、Yは、下記式(4−1)で表される2価の基を示す。
{式(4−1)中、Ar1は下記式(A)又は(B)で表される2価の芳香族基を示し、Y1は下記式(4−2)で表される2価の基を示し、tは、0又は1の整数を示す。
(式(A)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。)
(式(4−2)中、L2は−O−、−S−又は−SO−を示し、sは0又は1の整数を示す。なお、式(4−2)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。)}]
[式(5)中、Zは、下記式(5−1)で表される2価の基を示す。
{式(5−1)中、Ar2は下記式(A)又は(B)で表される2価の芳香族基を示し、Z1は下記式(5−2)で表される2価の基を示し、vは、0又は1の整数を示す。
(式(A)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。)
(式(5−2)中、L3は、2価の炭化水素基、−O−、−SO−、−SO2−、又は−CO−を示し、uは、0又は1の整数を示す。なお、式(5−2)で表されるベンゼン環の2つの結合手はメタ位又はパラ位の関係にある。)}] 40-99 mol% of repeating structural units represented by the following general formula (1),
1 to 15 mol% of repeating structural units represented by the following general formula (3),
The repeating structural unit represented by the following general formula (4) is more than 0 mol% and 30 mol% or less,
And 1 mol percent to 30 mol percent of the repeating structural unit represented by the following general formula (5), Ri greens contain,
The sum of the structural units of the general formulas (1) and (3) to (5) is 100 mol%, and the total content of the structural units of the general formulas (3) and (4) A copolymer having the same content ratio of the structural unit of the formula (5) .
[In Formula (1), X shows the bivalent aromatic group represented by a following formula (A) or (B).
(Two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.)]
[In the formula (3), L 1 represents —CH 2 —, — (CH 3 ) 2 C—, —O—, or —SO 2 —. ]
[In formula (4), Y represents a divalent group represented by the following formula (4-1).
{In Formula (4-1), Ar 1 represents a divalent aromatic group represented by the following Formula (A) or (B), and Y 1 represents a divalent group represented by the following Formula (4-2). T represents an integer of 0 or 1.
(Two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.)
(In the formula (4-2), L 2 represents —O—, —S— or —SO—, and s represents an integer of 0 or 1. The benzene ring represented by the formula (4-2) The two bonds in are in the meta or para position.)}]
[In the formula (5), Z represents a divalent group represented by the following formula (5-1).
{In Formula (5-1), Ar 2 represents a divalent aromatic group represented by the following Formula (A) or (B), and Z 1 is a divalent represented by the following Formula (5-2). V represents an integer of 0 or 1.
(Two bonds of the benzene ring represented by the formula (A) are in a meta position or a para position.)
(In Formula (5-2), L 3 represents a divalent hydrocarbon group, —O—, —SO—, —SO 2 —, or —CO—, and u represents an integer of 0 or 1. Note that the two bonds of the benzene ring represented by the formula (5-2) are in a meta-position or a para-position)}]
前記一般式(5)で表される繰り返し構造単位が、下記式(5−3)又は下記式(5−4)で表される2価の基である、請求項1に記載の共重合体。
The copolymer according to claim 1, wherein the repeating structural unit represented by the general formula (5) is a divalent group represented by the following formula (5-3) or the following formula (5-4). .
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