JP3733722B2 - Liquid crystalline resins and molded products - Google Patents
Liquid crystalline resins and molded products Download PDFInfo
- Publication number
- JP3733722B2 JP3733722B2 JP35087297A JP35087297A JP3733722B2 JP 3733722 B2 JP3733722 B2 JP 3733722B2 JP 35087297 A JP35087297 A JP 35087297A JP 35087297 A JP35087297 A JP 35087297A JP 3733722 B2 JP3733722 B2 JP 3733722B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystalline
- acid
- resin composition
- crystalline resin
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000007788 liquid Substances 0.000 title claims description 107
- 229920006038 crystalline resin Polymers 0.000 title claims description 64
- 239000011342 resin composition Substances 0.000 claims description 35
- 229920000728 polyester Polymers 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 24
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000002835 absorbance Methods 0.000 claims description 16
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000003287 optical effect Effects 0.000 claims description 15
- 239000004973 liquid crystal related substance Substances 0.000 claims description 13
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 12
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011256 inorganic filler Substances 0.000 claims description 5
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- 125000000524 functional group Chemical group 0.000 claims description 4
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 3
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- 125000003277 amino group Chemical group 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Chemical group 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 28
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- 239000003365 glass fiber Substances 0.000 description 5
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- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 238000005917 acylation reaction Methods 0.000 description 3
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 2
- JCJUKCIXTRWAQY-UHFFFAOYSA-N 6-hydroxynaphthalene-1-carboxylic acid Chemical compound OC1=CC=C2C(C(=O)O)=CC=CC2=C1 JCJUKCIXTRWAQY-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
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- 101100288569 Drosophila melanogaster Lcp65Ag1 gene Proteins 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001378 barium hypophosphite Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- FAARTQSZKSBAOS-UHFFFAOYSA-N barium(2+);diphosphite Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])[O-].[O-]P([O-])[O-] FAARTQSZKSBAOS-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000019827 calcium polyphosphate Nutrition 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-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
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 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
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 description 1
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 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 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
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000004065 semiconductor Substances 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- VMFOHNMEJNFJAE-UHFFFAOYSA-N trimagnesium;diphosphite Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])[O-].[O-]P([O-])[O-] VMFOHNMEJNFJAE-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- Liquid Crystal Substances (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、液晶性樹脂の改質に関するものであり、さらに詳しくは色調、耐加水分解性、耐熱性が向上し、さらには熱滞留時の酢酸発生量を低減させた液晶性樹脂および成形品に関するものである。
【0002】
【従来の技術】
近年プラスチックの高性能化に対する要求がますます高まり、種々の新規性能を有するポリマーが数多く開発され、市場に供されているが、中でも分子鎖の平行な配列を特徴とする光学異方性の液晶性ポリマーが優れた流動性と機械的性質を有する点で注目され、特に高い剛性を有することから電気・電子分野や事務機器分野などで小型成形品としての需要が大きくなってきている。
【0003】
また、p−ヒドロキシ安息香酸とポリエチレンテレフタレートを共重合した液晶性ポリマー(特公昭56−18016号公報)やp−ヒドロキシ安息香酸とポリエチレンテレフタレートにさらに4,4’−ジヒドロキシビフェニルなどの芳香族ジオールおよび芳香族ジカルボン酸などの共重合成分を追加し、流動性、耐熱性を向上させた液晶性ポリマー(特開昭63−30523号公報)、p−ヒドロキシ安息香酸に4、4’−ジヒドロキシビフェニルとt−ブチルハイドロキノンとテレフタル酸を共重合した液晶性ポリマー(特開昭62−164719号公報)、p−ヒドロキシ安息香酸に4、4’−ジヒドロキシビフェニルとイソフタル酸とテレフタル酸を共重合した液晶性ポリマー(特公昭57−24407号公報、特開昭60−25046号公報)、p−ヒドロキシ安息香酸に6−ヒドロキシ−2−ナフトエ酸を共重合した液晶性ポリマー(特開昭54−77691号公報)、などが知られている。
【0004】
しかしながら、これらはポリエチレンテレフタレートやポリブチレンテレフタレートのような一般のポリエステルに比較して高い融点を有するため、重合時および成形時に着色したり、熱劣化して機械的特性が低下する問題があった。その対策として特公平2−51524号公報では、重合時に有機リン化合物、ヒンダードフェノールなどの耐熱安定剤を添加して長期の耐熱性を向上させる方法が提案されている。また、特開平8−53605号公報には液晶ポリエステル及び/または液晶ポリエステルアミドに対して亜リン酸、次亜リン酸およびそれらの金属塩などを含有せしめること、特開平6−32880号公報には反応系内溶融状態にある間にリン酸系化合物を添加せしめること、特開平7−179743号公報には非液晶性ポリエステルと液晶性ポリエステルからなる樹脂にリン化合物を配合せしめることが記載されている。
【0005】
【発明が解決しようとする課題】
ところが特公平2−51524号公報に記載されている耐熱剤は滞留時の熱安定性や熱劣化による着色に対する効果が必ずしも十分でないことがわかった。また、特開昭63−30523号公報記載の液晶性ポリマーは重合時にヒドロキシ末端に対して1.1モル倍量と過剰にアセチル化剤を添加するためその残存アセチル化剤により若干の着色があり、また、特開平8−53605号公報記載の方法においてもなお、特開昭63−30523号公報記載の液晶ポリマーと同様に重合時に過剰にアセチル化剤を添加するため、特に色調が要求される用途において十分とはいえない場合がある。さらに特開平6−32880号公報には、過剰のアセチル化剤を添加する上、有機リン化合物を添加、特開平7−179743号公報においても樹脂成分に有機リン系化合物を添加するために色調に対する改良効果が十分ではないことがわかった。
【0006】
よって本発明は、上述の問題を解消し、色調に優れ、成形時の滞留安定性や乾熱劣化特性などの熱特性に優れ、かつ耐加水分解性、また、押出機および成形機等などのスクリュウの腐食の原因となる酢酸発生量低減などの新たな特性をも付与した樹脂組成物およびおよび成形品の取得を課題とする。
【0007】
【課題を解決するための手段】
本発明者らは上記課題を解決すべく鋭意検討した結果、本発明に到達した。
【0008】
すなわち、本発明は、(1)異方性溶融相を形成する液晶性ポリエステルおよび液晶性ポリエステルアミドから選ばれた1種以上の液晶性ポリマーに、亜リン酸、次亜リン酸及びそれらの金属塩から選ばれた少なくとも1種以上の化合物を添加せしめてなる液晶性樹脂組成物であって、ペンタフルオロフェノールとクロロホルムの重量比が1である混合溶媒に液晶性樹脂組成物の濃度が0.5重量%になるように溶解した溶液において10mm光路長で測定した380nmの吸光度が0.5以下である液晶性樹脂組成物、
(2)液晶性ポリマーが下記(I)、(II)および(IV)の構造単位からなる液晶性ポリエステル、または、(I)、(II)、(III) および(IV)の構造単位からなる液晶性ポリエステルである(1)記載の液晶性樹脂組成物、
【化4】
(ただし式中のR1 は、
【化5】
から選ばれた一種以上の基を示し、R2 は、
【化6】
から選ばれた一種以上の基を示す。また、式中Xは水素原子または塩素原子を示す。)
(3)液晶性ポリマー100重量部に対して、亜リン酸、次亜リン酸およびそれらの金属塩から選ばれた少なくとも1種以上の化合物を0.001〜5重量部添加せしめてなる(1)または(2)記載の液晶性樹脂組成物、
(4)亜リン酸、次亜リン酸およびそれらの金属塩から選ばれた少なくとも1種以上の化合物が亜リン酸および/または次亜リン酸のナトリウム金属塩である(1)から(3)のいずれか記載の液晶性樹脂組成物、
(5)(1)〜(4)のいずれか記載の液晶性樹脂組成物100重量部に無機充填材を5〜300重量部含有せしめてなる液晶性樹脂組成物、
(6)ヒドロキシカルボン酸、ジヒドロキシ化合物、ジカルボン酸から選ばれた1種以上を含む、液晶性ポリエステルおよび/または液晶性ポリエステルアミド形成性原料をアシル化剤の存在下に反応せしめて液晶性ポリエステルおよび/または液晶性ポリエステルアミドを重合する際に、亜リン酸、次亜リン酸およびそれらの金属塩の少なくとも1種以上の化合物を重合時に添加し、かつアシル化剤のモル当量(原料モノマー中のヒドロキシ基量(モル)に対するアシル化剤のヒドロキシ基をアシル化可能な官能基の量(モル)の比)が1.1未満となるようにアシル化剤を存在させることを特徴とする液晶性樹脂組成物の製造方法、
(7)液晶性ポリエステルおよび/または液晶性ポリエステルアミド形成性原料がさらにポリアルキレンテレフタレート、アミノ基含有単量体から選ばれた1種以上を含むものである(6)記載の液晶性樹脂組成物の製造方法、
(8)(1)〜(5)いずれか記載の液晶性樹脂組成物を成形してなる成形品である。
【0009】
【発明の実施の形態】
本発明に用いる液晶性ポリマーは異方性溶融相を形成する液晶性ポリエステルおよび液晶性ポリエステルアミドから選ばれた1種以上であり、液晶性ポリエステルとしては、芳香族オキシカルボニル単位などのオキシカルボニル単位、芳香族ジオキシ単位、エチレンジオキシ単位などのアルキレンジオキシ単位などのジオキシ単位、芳香族ジカルボニル単位などのジカルボニル単位などから選ばれた1種以上の構造単位からなる異方性溶融相を形成する液晶性ポリエステルが挙げられ、また、液晶性ポリエステルアミドとしては、上記単位の1種以上から選択される構造単位と芳香族イミノカルボニル単位、芳香族ジイミノ単位、芳香族イミノオキシ単位などから選ばれた1種以上の構造単位からなる異方性溶融相を形成する液晶性ポリエステルアミドが挙げられる。
【0010】
異方性溶融相を形成する液晶性ポリエステルの例としては、下記(I)、(II)、(III) および(IV)の構造単位からなる液晶ポリエステル、または、(I)、(III) および(IV)の構造単位からなる異方性溶融相を形成する液晶性ポリエステルなどが挙げられる。
【0011】
【化7】
(ただし式中のR1 は、
【化8】
から選ばれた一種以上の基を示し、R2 は、
【化9】
から選ばれた一種以上の基を示す。また、式中Xは水素原子または塩素原子を示す。)
なお、上記構造単位(II)および(III) の合計と構造単位(IV)は実質的に等モルであることが好ましい。
【0012】
上記構造単位(I)はp−ヒドロキシ安息香酸から生成した構造単位であり、構造単位(II)は4,4’−ジヒドロキシビフェニル、3,3’,5,5’−テトラメチル−4,4’−ジヒドロキシビフェニル、ハイドロキノン、t−ブチルハイドロキノン、フェニルハイドロキノン、2,6−ジヒドロキシナフタレン、2,7−ジヒドロキシナフタレン、2,2−ビス(4−ヒドロキシフェニル)プロパンおよび4,4’−ジヒドロキシジフェニルエーテルから選ばれた芳香族ジヒドロキシ化合物から生成した構造単位を、構造単位(III )はエチレングリコールから生成した構造単位を、構造単位(IV)はテレフタル酸、イソフタル酸、4,4’−ジフェニルジカルボン酸、2,6−ナフタレンジカルボン酸、1,2−ビス(フェノキシ)エタン−4,4’−ジカルボン酸、1,2−ビス(2−クロルフェノキシ)エタン−4,4’−ジカルボン酸および4,4’ジフェニルエーテルジカルボン酸から選ばれた芳香族ジカルボン酸から生成した構造単位を各々示す。
【0013】
また、液晶性ポリエステルアミドの例としては、2、6−ヒドロキシナフトエ酸、p−アミノフェノールとテレフタル酸から生成した液晶性ポリエステルアミド、p−ヒドロキシ安息香酸、4,4’−ジヒドロキシビフェニルとテレフタル酸、p−アミノ安息香酸およびポリエチレンテレフタレートから生成した液晶性ポリエステルアミド(特開昭64−33123号公報参照)などが挙げられる。
【0014】
本発明においてさらに好ましく使用できる液晶性ポリエステルは、上記構造単位(I)、(II)および(IV)からなる共重合体、または、(I)、(II)、(III) および(IV)からなる共重合体であり、上記構造単位(I)、(II)、(III) および(IV)の共重合量は任意である。しかし、流動性の点から次の共重合量であることが好ましい。
【0015】
すなわち、上記構造単位(III) を含む場合は、耐熱性、難燃性および機械的特性の点から上記構造単位(I)および(II)の合計は構造単位(I)、(II)および(III) の合計に対して35〜95モル%が好ましく、40〜93モル%がより好ましい。また、構造単位(III) は構造単位(I)、(II)および(III) の合計に対して65〜5モル%が好ましく、60〜7モル%がより好ましい。また、構造単位(I)と(II)のモル比[(I)/(II)]は耐熱性と流動性のバランスの点から好ましくは70/30〜95/5であり、より好ましくは75/25〜93/7である。また、構造単位(IV)は構造単位(II)および(III) の合計と実質的に等モルであることが好ましい。
【0016】
一方、上記構造単位(III) を含まない場合は流動性の点から上記構造単位(I)は構造単位(I)および(II)の合計に対して40〜90モル%であることが好ましく、60〜88モル%であることが特に好ましく、構造単位(IV)は構造単位(II)と実質的に等モルであることが好ましい。
【0017】
なお、本発明で好ましく使用できる上記液晶性ポリマーを重縮合する際には上記構造単位(I)〜(IV)を構成する成分以外に3,3’−ジフェニルジカルボン酸、2,2’−ジフェニルジカルボン酸などの芳香族ジカルボン酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジオン酸などの脂肪族ジカルボン酸、ヘキサヒドロテレフタル酸などの脂環式ジカルボン酸、クロルハイドロキノン、メチルハイドロキノン、4,4’−ジヒドロキシジフェニルスルホン、4,4’−ジヒドロキシジフェニルスルフィド、4,4’−ジヒドロキシベンゾフェノン等の芳香族ジオール、1,4−ブタンジオール、1,6−ヘキサンジオール、ネオペンチルグリコール、1,4−シクロヘキサンジオール、1,4−シクロヘキサンジメタノール等の脂肪族、脂環式ジオールおよびm−ヒドロキシ安息香酸、2,6−ヒドロキシナフトエ酸などの芳香族ヒドロキシカルボン酸およびp−アミノフェノール、p−アミノ安息香酸およびそれらの誘導体などを液晶性を損なわない程度の少割合の範囲でさらに共重合せしめることができる。
【0018】
本発明の液晶性樹脂組成物は、上記したような液晶性ポリマーを含有するものであり、ペンタフルオロフェノールとクロロホルムの重量比が1の混合溶媒に液晶性樹脂組成物の濃度が0.5重量%となるように溶解した溶液について10mm光路長で測定した380nmの吸光度が0.5以下、好ましくは0.4以下、特に好ましくは0.3以下のものである。吸光度が0.5を越えるものは酸化劣化による着色を意味し、色調が改良されておらず、
【0019】
上記液晶性樹脂組成物の吸光度は、通常、液晶性樹脂をペンタフルオロフェノールに50℃でまず液晶性樹脂組成物の濃度が1重量%となるように4時間かけて溶解し、さらにクロロホルムで液晶性樹脂組成物の濃度0.5重量%になるように混合し得た溶液を10mmの光路長の石英ガラス製セルに入れ、混合溶媒をブランクとして分光光度計(島津製作所製、UV−240)を用いて、380nmの光で測定した次式より求めることができる。
【0020】
吸光度=−Log(透過光強度/入射光強度)
かかる液晶性樹脂組成物を得るためには、亜リン酸、次亜リン酸およびそれらの金属塩から選ばれた少なくとも1種以上の化合物を含有していることが必須である。
【0021】
本発明の液晶性樹脂組成物は亜リン酸、次亜リン酸およびそれらの金属塩から選ばれた少なくとも1種以上を添加することによって得ることができる。かかる亜リン酸、次亜リン酸の金属塩の具体例としては下記のものが挙げられる。すなわち亜リン酸金属塩、次亜リン酸金属塩の金属種についてはリチウム、ナトリウム、カリウムなどのアルカリ金属、マグネシウム、カルシウム、バリウムなどのアルカリ土類金属が好ましく、より好ましくはアルカリ金属である。さらに具体的には、次亜リン酸カルシウム、次亜リン酸マグネシウム、次亜リン酸バリウム、次亜リン酸ナトリウム、次亜リン酸カリウム、亜リン酸カリウム、亜リン酸マグネシウム、亜リン酸バリウム、亜リン酸ナトリウムなどが挙げられる。最も好ましいものは次亜リン酸ナトリウム、亜リン酸ナトリウムなどのナトリウム金属塩である。
【0022】
また、亜リン酸、次亜リン酸およびそれらの金属塩の添加量は、得られる液晶性樹脂組成物の色調、耐熱性、機械特性の点から、通常、液晶性ポリマー100重量部当り0.001〜5重量部、好ましくは0.01〜3重量部である。
【0023】
なお、亜リン酸、次亜リン酸およびそれらの金属塩の添加時期は得られる液晶性樹脂組成物の色調の点から重合完結前に添加することが好ましい。
【0024】
また、亜リン酸、次亜リン酸およびそれらの金属塩は固体としてまたは亜リン酸、次亜リン酸およびそれらの金属塩の融点以上の温度で液体として加えることができる。配合を低い温度で行う場合、亜リン酸、次亜リン酸およびそれらの金属塩を溶液として加えることも可能である。
【0025】
本発明においてはさらに滞留安定性を向上させるために亜リン酸および次亜リン酸以外の金属塩を加えることができる。亜リン酸および次亜リン酸以外の金属塩としては有機または無機のものを用いることができるが、硫酸、ハロゲン化水素、硝酸、ホウ酸、リン酸、ピロリン酸、酢酸、シュウ酸、安息香酸などのアルカリ金属塩、アルカリ土類金属塩を用いることが好ましい。更に具体的には硫酸カリウム、酢酸ナトリウム、酢酸バリウム、酢酸マグネシウム、安息香酸ナトリウム、リン酸水素ナトリウムなどの金属塩を用いることができる。
【0026】
また、亜リン酸および次亜リン酸以外の金属塩の添加量は、通常、液晶ポリマー100重量部当り0.001〜5重量部、好ましくは0.01〜3重量部である。
【0027】
また、亜リン酸および次亜リン酸以外の金属塩は固体としてまたはその融点以上の温度で液体として加えることができる。配合を低い温度で行う場合は溶液として加えることも可能である。
【0028】
本発明で用いる液晶性樹脂組成物の製造方法は、上記吸光度の範囲を満足する液晶性樹脂が得られる限り、制限はないが、色調、耐熱性、耐加水分解性の点から、次の方法で製造することが好ましい。すなわち、上記液晶性ポリマーを構成するのに必要な原料、例えば、ヒドロキシカルボン酸、ジヒドロキシ化合物、ジカルボン酸から選ばれた1種以上を含み、また、必要に応じてさらにポリアルキレンテレフタレート、アミノ基含有単量体から選ばれた1種以上を含む液晶性ポリエステルおよび/または液晶性ポリエステルアミド形成性原料をアシル化剤の存在下に反応せしめて液晶性ポリエステルおよび/または液晶性ポリエステルアミドを重合する際に、かつアシル化剤のモル当量(原料モノマー中のヒドロキシ基量(モル)に対するアシル化剤のヒドロキシ基をアシル化可能な官能基の量(モル)の比)が比較的小さくなるようにアシル化剤を存在させる方法である。
【0029】
アシル化剤としては、無水酢酸、無水プロピオン酸、無水酪酸、無水安息香酸などが挙げられるが、なかでも無水酢酸が反応性の点で好ましく用いられる。
【0030】
熱滞留時の酢酸発生量を低減するためにアシル化剤のモル当量(原料モノマー中のヒドロキシ基量(モル)に対するアシル化剤のヒドロキシ基をアシル化可能な官能基の量(モル)の比)を比較的小さくすること、例えば1.1未満であることが好ましく、より好ましくは1.090以下、特に1.080以下とすることが好ましい。下限としては特に制限はないが、得られる液晶性ポリマーの重合度の点から1.0以上であることが好ましく、1.02以上であることがより好ましく、1.05以上であることがさらに好ましい。
【0031】
上記のように、アシル化剤の使用量を小さくすると、通常、ポリマーの重合度が上がりにくくなる傾向にあるが、亜リン酸、次亜リン酸およびそれらの金属塩の少なくとも1種以上の化合物を重合時に添加することにより、アシル化剤の使用量を低減しても十分な重合度であって、かつ、熱滞留時の酢酸発生量が少なく、色調にすぐれた液晶性樹脂組成物が得られる。
【0032】
アシル化剤を添加する場合は、重縮合に先立ち、アシル化反応を行なうことが好ましい。アシル化反応は窒素気流下、80〜300℃、好ましくは100〜250℃で行なう。
【0033】
その他は特に制限がなく、公知のポリエステルの重縮合法に準じて製造できる。
【0034】
例えば、上記好ましく用いられる液晶ポリエステルの製造において、次の製造方法が好ましく挙げられる。
【0035】
(1)p−ヒドロキシ安息香酸、4,4´−ジヒドロキシビフェニル、ハイドロキノンなどの芳香族ジヒドロキシ化合物、無水酢酸、テレフタル酸などの芳香族ジカルボン酸、ポリエチレンテレフタレートなどのポリエステルのポリマ、オリゴマまたはビス(β−ヒドロキシエチル)テレフタレートなど芳香族ジカルボン酸のビス(β−ヒドロキシエチル)エステルなどを添加し、100〜300℃でエステル化および/またはエステル交換反応を行なう。その後、必要とあれば触媒を添加して100〜250℃でアシル化反応を行なう。その後250〜350℃で真空下または減圧下で脱酢酸重縮合反応によって製造する方法。
【0036】
重縮合反応に使用する触媒としては、液晶ポリエステルや液晶ポリエステルアミドの重合触媒として公知のものを使用することができる。
【0037】
本発明で用いる液晶性樹脂組成物は、ペンタフルオロフェノール中で対数粘度を測定することが可能なものもあり、その際には0.1g/dlの濃度で60℃で測定した値で0.03以上が好ましく、0.05〜10.0dl/gが特に好ましい。
【0038】
また、本発明における液晶性樹脂組成物の溶融粘度は1〜2,000Pa・sが好ましく、特に2〜1,000Pa・sがより好ましい。
【0039】
なお、この溶融粘度は融点(Tm)+10℃の条件で、ずり速度1,000(1/秒)の条件下で高化式フローテスターによって測定した値である。
【0040】
ここで、融点(Tm)とは示差熱量測定において、重合を完了したポリマを室温から20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm1 )の観測後、Tm1 +20℃の温度で5分間保持した後、20℃/分の降温条件で室温まで一旦冷却した後、再度20℃/分の昇温条件で測定した際に観測される吸熱ピーク温度(Tm2 )を指す。
【0041】
本発明の液晶性樹脂組成物には必要に応じて無機充填材を含有せしめることにより液晶性樹脂組成物とすることができる。無機充填剤としては、特に限定されるものではないが、繊維状、板状、粉末状、粒状などの充填剤を使用することができる。具体的には例えば、ガラス繊維、PAN系やピッチ系の炭素繊維、ステンレス繊維、アルミニウム繊維や黄銅繊維などの金属繊維、芳香族ポリアミド繊維などの有機繊維、石膏繊維、セラミック繊維、アスベスト繊維、ジルコニア繊維、アルミナ繊維、シリカ繊維、酸化チタン繊維、炭化ケイ素繊維、ロックウール、チタン酸カリウムウィスカー、チタン酸バリウムウィスカー、ほう酸アルミウィスカー、窒化ケイ素ウィスカーなどの繊維状、ウィスカー状充填剤、マイカ、タルク、カオリン、シリカ、炭酸カルシウム、ガラスビーズ、ガラスフレーク、ガラスマイクロバルーン、クレー、二硫化モリブデン、ワラステナイト、酸化チタン、酸化亜鉛、ポリリン酸カルシウム、グラファイトなどの粉状、粒状あるいは板状の充填剤が挙げられる。上記充填剤中、ガラス繊維が好ましく使用される。ガラス繊維の種類は、一般に樹脂の強化用に用いるものなら特に限定はなく、例えば長繊維タイプや短繊維タイプのチョップドストランド、ミルドファイバーなどから選択して用いることができる。また、上記の充填剤は2種以上を併用して使用することもできる。なお、本発明に使用する上記の充填剤はその表面を公知のカップリング剤(例えば、シラン系カップリング剤、チタネート系カップリング剤など)、その他の表面処理剤で処理して用いることもできる。
【0042】
また、ガラス繊維はエチレン/酢酸ビニル共重合体などの熱可塑性樹脂、エポキシ樹脂などの熱硬化性樹脂で被覆あるいは集束されていてもよい。
【0043】
上記の充填剤の添加量は液晶性樹脂組成物100重量部に対し通常、300重量部以下であり、好ましくは5〜300重量部、特に好ましくは10〜250重量部、より好ましくは20〜150重量部である。
【0044】
本発明の液晶性樹脂組成物には、酸化防止剤および熱安定剤(たとえばヒンダードフェノール、ヒドロキノン、ホスファイト類およびこれらの置換体など)、紫外線吸収剤(たとえばレゾルシノール、サリシレート、ベンゾトリアゾール、ベンゾフェノンなど)、滑剤および離型剤(モンタン酸およびその塩、そのエステル、そのハーフエステル、ステアリルアルコール、ステアラミドおよびポリエチレンワックスなど)、染料(たとえばニグロシンなど)および顔料(たとえば硫化カドミウム、フタロシアニンなど)を含む着色剤、結晶核剤、可塑剤、難燃剤、難燃助剤、帯電防止剤などの通常の添加剤を添加して、所定の特性をさらに付与することができる。
【0045】
これらを添加する方法は溶融混練することが好ましく、溶融混練には公知の方法を用いることができる。たとえば、バンバリーミキサー、ゴムロール機、ニーダー、単軸もしくは二軸押出機などを用い、180〜370℃の温度で溶融混練して組成物とすることができる。
【0046】
本発明において、上述の如き液晶性樹脂組成物を用いて液晶性樹脂の吸光度を測定する場合、あらかじめGC−MS、LC−MSその他の分析機器を用いて液晶性樹脂組成物の成分を分析し、液晶性樹脂以外の添加剤および充填材をはじめに分離し、しかる後、前述の方法により、測定できる。液晶性樹脂とそれ以外の添加剤および充填材との分離は以下のようにして行うことができる。すなわち、液晶性樹脂組成物がペンタフルオロフェノールに不溶な添加剤、充填材を含む場合、液晶性樹脂組成物からペンタフルオロフェノール不溶分を0.45μmのフィルターでろ取し、ろ液(液晶性樹脂のペンタフルオロフェノール溶液)から、メタノールなどの貧溶媒を用いて液晶性樹脂を分離する。また、液晶性樹脂組成物がペンタフルオロフェノールに溶解する添加剤を含む場合は、液晶性樹脂組成物を細かく粉砕し、トルエン、アセトン、ベンゼン、メタノール、DMF、MNPから選択された溶媒で添加剤を抽出分離する。ペンタフルオロフェノールに可溶・不溶の両方の添加剤が添加されている場合は上記の分離方法を併用して行う。そして、上記の如く液晶性樹脂組成物から添加剤あるいは充填剤を分離したものを液晶性樹脂として、前述のとおり、ペンタフルオロフェノールとクロロホルムの重量比が1である混合溶媒に液晶性樹脂濃度が0.5重量%になるように溶解し、10mm光路長で、380nmの吸光度を求めることができる。
【0047】
かくして得られる液晶性樹脂組成物は射出成形、押出成形、圧縮成形など通常の成形に供することができ、各種成形品として電気・電子部品、精密部品、自動車部品などに極めて有用である。また、色調、滞留安定性に優れるため、着色剤を配合することにより、優れた着色成形品とすることができる
【0048】
本発明の液晶性樹脂組成物からなる成形品は優れた耐熱性、優れた耐加水分解性、色調に優れていることから三次元成形品、シート、容器パイプなどに加工することが可能であり、例えば、各種ギヤー、各種ケース、センサー、LEPランプ、コネクター、ソケット、抵抗器、リレーケーススイッチコイルボビン、コンデンサー、バリコンケース、光ピックアップ、発振子、各種端子板、変成器、プラグ、プリント配線板、チューナー、スピーカー、マイクロフォン、ヘッドフォン、小型モーター、磁気ヘッドベース、パワーモジュール、ハウジング、半導体、液晶、FDDキャリッジ、FDDシャーシ、モーターブラッシュホルダー、パラボラアンテナ、コンピューター関連部品などに代表される電気・電子部品;VTR部品、テレビ部品、アイロン、ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、オーディオ・レーザーディスク・コンパクトディスクなどの音声機器部品、照明部品、冷蔵庫部品、エアコン部品、タイプライター部品、ワードプロセッサー部品などに代表される家庭、事務電気製品部品、オフィスコンピューター関連部品、電話機関連部品、ファクシミリ関連部品複写機関連部品、洗浄用治具、オイルレス軸受、船尾軸受、水中軸受、などの各種軸受、モーター部品、ライター、タイプライターなどに代表される機械関連部品、顕微鏡、双眼鏡、カメラ、時計などに代表される光学機器、精密機械関連部品;オルタネーターターミナル、オルタネーターコネクター、ICレギュレーター、ライトディヤー用ポテンショメーターベース、排気ガスバルブなどの各種バルブ、燃料関係・排気系・吸気系各種パイプ、エアーインテークノズルスノーケル、インテークマニホールド、燃料ポンプ、エンジン冷却水ジョイント、キャブレターメインボディー、キャブレタースペーサー、排気ガスセンサー、冷却水センサー、油温センサー、ブレーキパットウェアーセンサー、スロットルポジションセンサー、クランクシャフトポジションセンサー、エアーフローメーター、ブレーキバット磨耗センサー、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダー、ウォーターポンプインペラー、タービンべイン、ワイパーモーター関係部品、デュストリビュター、スタータースィッチ、スターターリレー、トランスミッション用ワイヤーハーネス、ウィンドウオッシャーノズル、エアコンパネルスィッチ基板、燃料関係電磁気弁用コイル、ヒューズ用コネクター、ホーンターミナル、電装部品絶縁板、ステップモーターローター、ランプソケット、ランプリフレクター、ランプハウジング、ブレーキピストン、ソレノイドボビン、エンジンオイルフィルター、点火装置ケースなどの自動車・車両関連部品、その他各種用途に有用である。
【0049】
なかでも、優れた色調、耐熱性、耐加水分解性など、本発明の液晶性樹脂組成物の優れた特徴をいかして小型成形部品、例えば樹脂の容積が5cc以下の小型部品に使用される小型の成形品として極めて実用的に使用できる。特にSIMMソケットなどのコネクター、CDピックアップレンズホルダー、各種小型ギアなどの小型の組み込み部品となる成形品に極めて実用的である。
【0050】
【実施例】
以下に実施例を挙げて本発明をさらに詳述するが、本発明はその要旨を越えない限り以下の実施例に限定されるものではない。
【0051】
比較例1
LCP1: p−ヒドロキシ安息香酸11.05kg、4、4’−ジヒドロキシビフェニル1.40kg、テレフタル酸1.25kg、固有粘度が約0.6dl/gのポリエチレンテレフタレート2.40kgおよび無水酢酸10.67kgを圧力容器に仕込み、窒素ガス雰囲気下に100〜250℃で1.5時間反応させた後、315℃、1時間で66Paに減圧し、さらに1.25時間反応させ、重縮合を完結させたところ、ほぼ理論量の酢酸が留出し、ペレットを得た。液晶性樹脂(LCP1)の10mm光路長で測定した380nmの吸光度は1.1であった。
【0052】
比較例2
LCP2: p−ヒドロキシ安息香酸11.05kg、4、4’−ジヒドロキシビフェニル1.40kg、テレフタル酸1.25kg、固有粘度が約0.6dl/gのポリエチレンテレフタレート2.40kgおよび無水酢酸10.38kg圧力容器に仕込み、LCP1と同様の条件で重合を行なったところ重合度が上がらず、良好なペレットが得られなかった。
【0053】
実施例1
LCP3: p−ヒドロキシ安息香酸11.05kg、4、4’−ジヒドロキシビフェニル1.40kg、テレフタル酸1.25kg、固有粘度が約0.6dl/gのポリエチレンテレフタレート2.40kgおよび無水酢酸10.38kg、次亜リン酸ナトリウム28.6gを圧力容器に仕込み、LCP1と同様に重合を行い、ペレットを得た。液晶性樹脂(LCP3)の10mm光路長で測定した380nmの吸光度は0.1であった。
【0054】
実施例2
LCP4: p−ヒドロキシ安息香酸11.05kg、4、4’−ジヒドロキシビフェニル1.40kg、テレフタル酸1.25kg、固有粘度が約0.6dl/gのポリエチレンテレフタレート2.40kgおよび無水酢酸10.38kg、亜リン酸ナトリウム28.6gを圧力容器に仕込み、LCP1と同様に重合を行い、ペレットを得た。液晶性樹脂(LCP4)の10mm光路長で測定した380nmの吸光度は0.2であった。
【0055】
実施例3
LCP5: p−ヒドロキシ安息香酸11.05kg、4、4’−ジヒドロキシビフェニル1.40kg、テレフタル酸1.25kg、固有粘度が約0.6dl/gのポリエチレンテレフタレート2.40kgおよび無水酢酸10.38kg、次亜リン酸ナトリウム57.2gを圧力容器に仕込み、LCP1と同様に重合を行い、ペレットを得た。液晶性樹脂(LCP5)の10mm光路長で測定した380nmの吸光度は0.1であった。
【0056】
比較例3
LCP6: p−ヒドロキシ安息香酸11.05kg、4、4’−ジヒドロキシビフェニル1.40kg、テレフタル酸1.25kg、固有粘度が約0.6dl/gのポリエチレンテレフタレート2.40kgおよび無水酢酸10.67kg、アデカ・アーガス化学社製MARK PEP−36(ビス(4−メチル−2,6−t−ブチル)ペンタエリスチトールジホスファイト)) 28.6gを圧力容器に仕込み、LCP1と同様に重合を行い、ペレットを得た。液晶性樹脂(LCP6)の10mm光路長で測定した380nmの吸光度は0.9であった。
【0057】
比較例4
LCP7: p−ヒドロキシ安息香酸11.05kg、4、4’−ジヒドロキシビフェニル1.40kg、テレフタル酸1.25kg、固有粘度が約0.6dl/gのポリエチレンテレフタレート2.40kgおよび無水酢酸10.67kg、アデカ・アーガス化学社製MARK HP−10(2,2−メチレンビス(4,6−ジ−t−ブチルフェニル)オクチルホスファイト) 28.6gを圧力容器に仕込み、LCP1と同様に重合を行い、ペレットを得た。液晶性樹脂(LCP7)の10mm光路長で測定した380nmの吸光度は0.8であった。
【0058】
比較例5
LCP8: p−ヒドロキシ安息香酸11.05kg、4、4’−ジヒドロキシビフェニル1.40kg、テレフタル酸1.25kg、固有粘度が約0.6dl/gのポリエチレンテレフタレート2.40kgおよび無水酢酸10.67kg、次亜リン酸カルシウム 28.6gを圧力容器に仕込み、LCP1と同様に重合を行い、ペレットを得た。液晶性樹脂(LCP8)の10mm光路長で測定した380nmの吸光度は0.55であった。
【0059】
各評価については、次に述べる方法にしたがって測定した。
【0060】
(1)吸光度
ペンタフルオロフェノールとクロロホルムの混合溶液(重量比1:1)で液晶性樹脂の濃度が0.5重量%になるように混合して得た溶液を10mmの光路長の石英ガラス製セルに入れ、混合溶媒をブランクとして分光光度計(島津製作所製、UV−240)を用いて、380nmの光で測定した次式より求めた。
【0061】
吸光度=−Log(透過光強度/入射光強度)
(2)白色度(W値)、黄色度(YI値)
127mm×12.7mm×3.12mmの曲げ試験片を住友重機プロマット25/40でシリンダー温度325℃、金型温度90℃で成形し、この試験片をスガ試験機(株)製SMカラーコンピューター装置を用いて白色度(W値)を測定した。
【0062】
(3)滞留安定性
成形滞留時間を4分間と20分間に変えた2条件で127mm×12.7mm×3.12mmの曲げ試験片を住友重機プロマット25/40でシリンダー温度330℃、金型温度90℃で成形し、ASTM D790に基づき曲げ強度を測定して、成形滞留時間20分間の時の曲げ強度/成形滞留時間4分間の時の曲げ強度×100を曲げ強度保持率として求めた。
【0063】
(4)耐熱エージング試験
ASTM1号引張試験片を東芝IS−55EPNでシリンダー温度325℃、金型温度90℃で成形し、得られた試験片を熱風オーブン中で240℃で30日間処理した後、ASTM D638に基づいて引張強度を測定して、240℃で30日間処理後の引張強度/初期の引張強度×100を引張強度保持率として求めた。
【0064】
(5)加水分解試験
ASTM1号引張試験片を東芝IS−55EPNでシリンダー温度325℃、金型温度90℃で成形し、得られた試験片をオートクレーブに水とともに仕込み120℃で3日間処理した後、ASTM D638に基づいて引張強度を測定し、120℃で3日間処理した時の引張強度/初期の引張強度×100を引張強度保持率とした。
【0065】
(6)酢酸発生量
50mmφの試験管に樹脂を0.3gはかりとり、10Torrまで減圧し、密封系で330℃で30分間放置し、その後窒素で常圧に戻し酢酸用の検知管(ガステック社製、No.81)を用い試験管内の酢酸濃度を測定した。
【0066】
実施例4〜6、比較例6〜9
実施例1〜3、比較例1、3〜5に示したLCP1、3〜8 100重量部に対して、表1に示した割合で無機充填材(9μm径、3mm長のガラス繊維)をドライブレンドした後、30mmφ2軸押出機で溶融混練してペレットを得た。ついでこのペレットを各評価項目ごとの方法で試験片を得た。なお、吸光度および酢酸発生量については混練前の液晶性樹脂を測定している。
【0067】
評価結果を表1に示す。
【0068】
【表1】
表1の結果から本発明の液晶性樹脂組成物は色調が大巾に改良され、滞留時の熱安定性や耐熱エージング特性などの耐熱性、さらに耐加水分解特性も改良された材料を得ることができる。
【0069】
【発明の効果】
本発明の液晶性樹脂組成物および成形品は、色調が大巾に改良され、優れた耐熱性、耐加水分解特性を有するので電気・電子関連機器、精密機械関連機器、事務用機器、自動車・車両関連部品など、その他各種用途に好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a modification of a liquid crystalline resin. More specifically, the present invention relates to a liquid crystalline resin having improved color tone, hydrolysis resistance, and heat resistance, and further reducing the amount of acetic acid generated during heat retention, and a molded product. It is about.
[0002]
[Prior art]
In recent years, there has been an increasing demand for higher performance of plastics, and many new polymers with various new performances have been developed and put on the market. Among them, optically anisotropic liquid crystals characterized by parallel arrangement of molecular chains In view of the excellent fluidity and mechanical properties of the water-soluble polymer, it has been attracting attention, and since it has particularly high rigidity, the demand for small molded products is increasing in the electric / electronic field and the office equipment field.
[0003]
In addition, a liquid crystalline polymer obtained by copolymerization of p-hydroxybenzoic acid and polyethylene terephthalate (Japanese Patent Publication No. 56-18016), p-hydroxybenzoic acid and polyethylene terephthalate, and an aromatic diol such as 4,4′-dihydroxybiphenyl; Addition of copolymerization component such as aromatic dicarboxylic acid to improve liquidity and heat resistance (Japanese Patent Laid-Open No. 63-30523), p-hydroxybenzoic acid with 4,4′-dihydroxybiphenyl and Liquid crystalline polymer obtained by copolymerization of t-butylhydroquinone and terephthalic acid (Japanese Patent Laid-Open No. 62-164719), liquid crystallinity obtained by copolymerization of p-hydroxybenzoic acid with 4,4′-dihydroxybiphenyl, isophthalic acid and terephthalic acid Polymer (Japanese Patent Publication No. 57-24407, JP-A-60-25) 46 JP), p-hydroxybenzoic acid 6-hydroxy-2-naphthoic acid copolymerized with liquid polymer (JP-54-77691 JP), and the like are known.
[0004]
However, since these have a higher melting point than general polyesters such as polyethylene terephthalate and polybutylene terephthalate, there are problems in that they are colored at the time of polymerization and molding, and are deteriorated due to thermal deterioration. Japanese Patent Publication No. 2-51524 proposes a method for improving long-term heat resistance by adding a heat-resistant stabilizer such as an organic phosphorus compound or a hindered phenol during polymerization. JP-A-8-53605 discloses that liquid crystal polyester and / or liquid crystal polyesteramide contain phosphorous acid, hypophosphorous acid, and metal salts thereof, and JP-A-6-32880 discloses. JP-A-7-179743 describes adding a phosphoric acid compound to a resin composed of a non-liquid crystalline polyester and a liquid crystalline polyester while adding a phosphoric acid compound while the reaction system is in a molten state. .
[0005]
[Problems to be solved by the invention]
However, it has been found that the heat-resistant agent described in Japanese Patent Publication No. 2-51524 is not necessarily sufficiently effective for coloring due to thermal stability during thermal residence or thermal degradation. In addition, the liquid crystalline polymer described in JP-A-63-30523 is slightly colored due to the residual acetylating agent because an excess amount of the acetylating agent is added in an amount of 1.1 mol times the hydroxy terminal during polymerization. Further, in the method described in JP-A-8-53605, too, an acetylating agent is added excessively at the time of polymerization similarly to the liquid crystal polymer described in JP-A-63-30523. It may not be sufficient in the application. Furthermore, in JP-A-6-32880, an excess acetylating agent is added, and an organophosphorus compound is added. In JP-A-7-179743, an organophosphorus compound is added to the resin component. It turned out that the improvement effect is not enough.
[0006]
Therefore, the present invention solves the above-mentioned problems, has excellent color tone, excellent thermal properties such as retention stability during molding and dry heat deterioration characteristics, and is resistant to hydrolysis, as well as an extruder and a molding machine. It is an object of the present invention to obtain a resin composition and a molded product imparted with new characteristics such as reduction in the amount of acetic acid that causes corrosion of a screw.
[0007]
[Means for Solving the Problems]
As a result of intensive studies aimed at solving the above problems, the present inventors have reached the present invention.
[0008]
That is, the present invention provides (1) one or more liquid crystalline polymers selected from liquid crystalline polyester and liquid crystalline polyester amide forming an anisotropic melt phase.A liquid crystalline resin composition comprising at least one compound selected from phosphorous acid, hypophosphorous acid and metal salts thereofA liquid crystalline resin in a mixed solvent having a weight ratio of pentafluorophenol and chloroform of 1Of compositionLiquid crystalline resin having an absorbance at 380 nm of 0.5 or less measured with a 10 mm optical path length in a solution dissolved so as to have a concentration of 0.5% by weight.Composition,
(2) The liquid crystalline polymer is composed of a liquid crystalline polyester composed of the following structural units (I), (II) and (IV), or structural units (I), (II), (III) and (IV). The liquid crystalline resin composition according to (1), which is a liquid crystalline polyester,
[Formula 4]
(However, R in the formula1 Is
[Chemical formula 5]
One or more groups selected from R and R2 Is
[Chemical 6]
One or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. )
(3) 0.001 to 5 parts by weight of at least one compound selected from phosphorous acid, hypophosphorous acid and metal salts thereof is added to 100 parts by weight of the liquid crystalline polymer (1 ) Or (2) liquid crystalline resin composition,
(4) At least one compound selected from phosphorous acid, hypophosphorous acid and metal salts thereof is phosphorous acid and / or sodium metal salt of hypophosphorous acid (1)To any of (3)The liquid crystalline resin composition according to the description,
(5) (1)Any one of (4)A liquid crystalline resin composition comprising 5 to 300 parts by weight of an inorganic filler in 100 parts by weight of the liquid crystalline resin composition,
(6) A liquid crystalline polyester and / or a liquid crystalline polyester amide-forming raw material containing at least one selected from a hydroxycarboxylic acid, a dihydroxy compound and a dicarboxylic acid are reacted in the presence of an acylating agent, and When polymerizing the liquid crystalline polyesteramide, at least one compound of phosphorous acid, hypophosphorous acid and their metal salts is added during the polymerization, and the molar equivalent of the acylating agent (in the raw material monomer) Liquid crystallinity characterized in that the acylating agent is present so that the ratio of the amount (mole) of the functional group capable of acylating the hydroxy group of the acylating agent to the amount of hydroxy group (mole) is less than 1.1. Production method of resin composition,
(7) Production of liquid crystalline resin composition according to (6), wherein the liquid crystalline polyester and / or liquid crystalline polyester amide-forming raw material further contains at least one selected from polyalkylene terephthalate and amino group-containing monomers. Method,
(8) (1)~ (5)It is a molded product formed by molding any of the liquid crystalline resin compositions.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The liquid crystalline polymer used in the present invention is at least one selected from a liquid crystalline polyester and a liquid crystalline polyester amide that form an anisotropic melt phase. The liquid crystalline polyester includes an oxycarbonyl unit such as an aromatic oxycarbonyl unit. An anisotropic molten phase comprising one or more structural units selected from dioxy units such as aromatic dioxy units, alkylene dioxy units such as ethylene dioxy units, and dicarbonyl units such as aromatic dicarbonyl units. Examples of the liquid crystalline polyester to be formed include a structural unit selected from one or more of the above units, an aromatic iminocarbonyl unit, an aromatic diimino unit, and an aromatic iminooxy unit. Liquid crystalline polyester forming an anisotropic molten phase composed of one or more structural units Ruamido and the like.
[0010]
Examples of the liquid crystalline polyester that forms the anisotropic molten phase include liquid crystalline polyesters composed of structural units of the following (I), (II), (III) and (IV), or (I), (III) and Examples thereof include liquid crystalline polyester that forms an anisotropic molten phase composed of the structural unit (IV).
[0011]
[Chemical 7]
(However, R in the formula1 Is
[Chemical 8]
One or more groups selected from R and R2 Is
[Chemical 9]
One or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. )
The total of the structural units (II) and (III) and the structural unit (IV) are preferably substantially equimolar.
[0012]
The structural unit (I) is a structural unit generated from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4. From '-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether A structural unit generated from the selected aromatic dihydroxy compound, a structural unit (III) is a structural unit generated from ethylene glycol, a structural unit (IV) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ester -4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and a structure formed from an aromatic dicarboxylic acid selected from 4,4'diphenyl ether dicarboxylic acid Each unit is indicated.
[0013]
Examples of liquid crystalline polyester amides include 2,6-hydroxynaphthoic acid, liquid crystalline polyester amides formed from p-aminophenol and terephthalic acid, p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl and terephthalic acid. , Liquid crystalline polyesteramides formed from p-aminobenzoic acid and polyethylene terephthalate (see JP-A No. 64-33123).
[0014]
The liquid crystalline polyester that can be more preferably used in the present invention is a copolymer comprising the structural units (I), (II), and (IV), or (I), (II), (III), and (IV). The amount of copolymerization of the structural units (I), (II), (III) and (IV) is arbitrary. However, the following copolymerization amount is preferable from the viewpoint of fluidity.
[0015]
That is, when the structural unit (III) is contained, the total of the structural units (I) and (II) is the structural units (I), (II) and (II) in terms of heat resistance, flame retardancy and mechanical properties. It is preferably 35 to 95 mol%, more preferably 40 to 93 mol%, based on the total of III). The structural unit (III) is preferably 65 to 5 mol%, more preferably 60 to 7 mol%, based on the total of the structural units (I), (II) and (III). The molar ratio [(I) / (II)] of the structural units (I) and (II) is preferably 70/30 to 95/5, more preferably 75 from the viewpoint of the balance between heat resistance and fluidity. / 25 to 93/7. The structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (III).
[0016]
On the other hand, when the structural unit (III) is not included, the structural unit (I) is preferably 40 to 90 mol% based on the total of the structural units (I) and (II) from the viewpoint of fluidity. It is particularly preferably 60 to 88 mol%, and the structural unit (IV) is preferably substantially equimolar to the structural unit (II).
[0017]
In the polycondensation of the liquid crystalline polymer that can be preferably used in the present invention, 3,3′-diphenyldicarboxylic acid and 2,2′-diphenyl are added in addition to the components constituting the structural units (I) to (IV). Aromatic dicarboxylic acids such as dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, 4,4 ' -Aromatic diols such as dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexane Diol, 1,4-cyclohexanedimethanol, etc. Does not impair liquid crystal properties of aliphatic, cycloaliphatic diols and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid and p-aminophenol, p-aminobenzoic acid and their derivatives. Further copolymerization can be carried out in a small proportion.
[0018]
Liquid crystalline resin of the present inventionCompositionContains a liquid crystalline polymer as described above, and the liquid crystalline resin is mixed in a mixed solvent having a weight ratio of pentafluorophenol to chloroform of 1.CompositionThe absorbance at 380 nm, measured with a 10 mm optical path length, of the solution dissolved so that the concentration of the solution is 0.5% by weight is 0.5 or less, preferably 0.4 or less, particularly preferably 0.3 or less. Those whose absorbance exceeds 0.5 means coloring due to oxidative degradation, and the color tone is not improved,
[0019]
Liquid crystalline resinCompositionFirst, the liquid crystal resin is first converted into pentafluorophenol at 50 ° C.Of compositionDissolve over 4 hours so that the concentration is 1% by weight, and then use liquid crystalline resin with chloroform.Of compositionA solution obtained by mixing so as to have a concentration of 0.5% by weight is put in a quartz glass cell having an optical path length of 10 mm, and a mixed solvent is used as a blank, using a spectrophotometer (manufactured by Shimadzu Corporation, UV-240) at 380 nm. It can obtain | require from the following formula measured with light.
[0020]
Absorbance = −Log (transmitted light intensity / incident light intensity)
TakeLiquid crystalline resin compositionTo getAt least one compound selected from phosphorous acid, hypophosphorous acid and metal salts thereofMay containIt is essential.
[0021]
Liquid crystalline resin composition of the present inventionCan be obtained by adding at least one selected from phosphorous acid, hypophosphorous acid and metal salts thereof. Specific examples of such metal salts of phosphorous acid and hypophosphorous acid include the following. That is, the metal species of the metal phosphite and the metal hypophosphite are preferably alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as magnesium, calcium and barium, more preferably alkali metals. More specifically, calcium hypophosphite, magnesium hypophosphite, barium hypophosphite, sodium hypophosphite, potassium hypophosphite, potassium phosphite, magnesium phosphite, barium phosphite, Examples thereof include sodium phosphate. Most preferred are sodium metal salts such as sodium hypophosphite and sodium phosphite.
[0022]
In addition, the amount of phosphorous acid, hypophosphorous acid and their metal salts added is the liquid crystalline resin obtainedCompositionIn general, from the viewpoint of color tone, heat resistance, and mechanical propertiespolymer0.001 to 5 parts by weight per 100 parts by weight, preferably 0.01 to 3 parts by weight.
[0023]
The addition timing of phosphorous acid, hypophosphorous acid and their metal salts is the liquid crystalline resin obtainedCompositionFrom the viewpoint of the color tone, it is preferably added before the completion of polymerization.
[0024]
Also, phosphorous acid, hypophosphorous acid and their metal salts can be added as solids or as liquids at temperatures above the melting point of phosphorous acid, hypophosphorous acid and their metal salts. It is also possible to add phosphorous acid, hypophosphorous acid and their metal salts as a solution when compounding is carried out at low temperatures.
[0025]
In the present invention, a metal salt other than phosphorous acid and hypophosphorous acid can be added to further improve the retention stability. Organic or inorganic metal salts other than phosphorous acid and hypophosphorous acid can be used, but sulfuric acid, hydrogen halide, nitric acid, boric acid, phosphoric acid, pyrophosphoric acid, acetic acid, oxalic acid, benzoic acid It is preferable to use alkali metal salts such as alkaline earth metal salts. More specifically, metal salts such as potassium sulfate, sodium acetate, barium acetate, magnesium acetate, sodium benzoate and sodium hydrogen phosphate can be used.
[0026]
Moreover, the addition amount of metal salts other than phosphorous acid and hypophosphorous acid is usuallyLiquid crystal polymer0.001 to 5 parts by weight per 100 parts by weight, preferably 0.01 to 3 parts by weight.
[0027]
Moreover, metal salts other than phosphorous acid and hypophosphorous acid can be added as a solid or as a liquid at a temperature higher than its melting point. When blending is performed at a low temperature, it can be added as a solution.
[0028]
Liquid crystalline resin used in the present inventionCompositionThe production method is not limited as long as a liquid crystalline resin satisfying the above absorbance range is obtained, but is preferably produced by the following method from the viewpoint of color tone, heat resistance, and hydrolysis resistance. That is, it contains one or more materials selected from the raw materials necessary for constituting the liquid crystalline polymer, for example, hydroxycarboxylic acid, dihydroxy compound, dicarboxylic acid, and further contains polyalkylene terephthalate and amino group as necessary. When polymerizing liquid crystalline polyester and / or liquid crystalline polyester amide by reacting a liquid crystalline polyester and / or liquid crystalline polyester amide-forming raw material containing at least one selected from monomers in the presence of an acylating agent And the acyl equivalent of the acylating agent (ratio of the amount of the functional group capable of acylating the hydroxy group of the acylating agent (mole) to the amount of the hydroxyl group (mole) of the raw material monomer) is relatively small. It is a method in which an agent is present.
[0029]
Examples of the acylating agent include acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, etc. Among them, acetic anhydride is preferably used in terms of reactivity.
[0030]
In order to reduce the amount of acetic acid generated during thermal residence, the molar equivalent of the acylating agent (ratio of the amount of the functional group capable of acylating the hydroxy group of the acylating agent (mole) to the amount of hydroxy group in the raw material monomer (mole)) ) Is relatively small, for example, less than 1.1, more preferably 1.090 or less, and particularly preferably 1.080 or less. Although there is no restriction | limiting in particular as a minimum, It is preferable that it is 1.0 or more from the point of the polymerization degree of the liquid crystalline polymer obtained, It is more preferable that it is 1.02 or more, It is further that it is 1.05 or more preferable.
[0031]
As described above, when the amount of the acylating agent used is small, usually the degree of polymerization of the polymer tends to be difficult to increase, but at least one compound of phosphorous acid, hypophosphorous acid and their metal salts Is a liquid crystalline resin that has a sufficient degree of polymerization even when the amount of the acylating agent used is reduced, and has a small amount of acetic acid generated during heat retention and has a good color tone.CompositionIs obtained.
[0032]
When an acylating agent is added, it is preferable to perform an acylation reaction prior to polycondensation. The acylation reaction is carried out at 80 to 300 ° C, preferably 100 to 250 ° C under a nitrogen stream.
[0033]
Others are not particularly limited and can be produced according to a known polyester polycondensation method.
[0034]
For example, in the production of the above preferably used liquid crystal polyester, the following production method is preferably exemplified.
[0035]
(1) Aromatic dihydroxy compounds such as p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl and hydroquinone, aromatic dicarboxylic acids such as acetic anhydride and terephthalic acid, polyester polymers such as polyethylene terephthalate, oligomers or bis (β A bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as -hydroxyethyl) terephthalate is added, and esterification and / or transesterification is performed at 100 to 300 ° C. Thereafter, if necessary, a catalyst is added and an acylation reaction is carried out at 100 to 250 ° C. Thereafter, a method for producing by a deacetic acid polycondensation reaction at 250 to 350 ° C. under vacuum or under reduced pressure.
[0036]
As the catalyst used for the polycondensation reaction, those known as polymerization catalysts for liquid crystal polyesters and liquid crystal polyester amides can be used.
[0037]
Liquid crystalline resin used in the present inventionCompositionHas a capability of measuring logarithmic viscosity in pentafluorophenol, and in that case, 0.03 or more is preferable as a value measured at 60 ° C. at a concentration of 0.1 g / dl, 10.0 dl / g is particularly preferred.
[0038]
The liquid crystalline resin in the present inventionCompositionThe melt viscosity of is preferably 1 to 2,000 Pa · s, more preferably 2 to 1,000 Pa · s.
[0039]
The melt viscosity is a value measured by a Koka flow tester under the condition of melting point (Tm) + 10 ° C. and shear rate of 1,000 (1 / second).
[0040]
Here, the melting point (Tm) is the Tm1 +20 after the observation of the endothermic peak temperature (Tm1) observed when the polymer having been polymerized is measured from room temperature under a temperature rising condition of 20 ° C./min in differential calorimetry. This is the endothermic peak temperature (Tm2) observed when the temperature is kept at a temperature of 5 ° C. for 5 minutes, then cooled to room temperature under a temperature drop condition of 20 ° C./minute, and then measured again under a temperature rise condition of 20 ° C./minute. .
[0041]
Liquid crystalline resin of the present inventionCompositionCan be made into a liquid crystalline resin composition by containing an inorganic filler as required. Although it does not specifically limit as an inorganic filler, Fillers, such as a fibrous form, plate shape, powder form, a granular form, can be used. Specifically, for example, glass fibers, PAN and pitch carbon fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia Fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, borate aluminum whisker, silicon nitride whisker, etc., whisker-like filler, mica, talc, Examples include powdery, granular or plate-like fillers such as kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate, and graphite. Is . Among the fillers, glass fibers are preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. Moreover, said filler can also be used in combination of 2 or more types. The surface of the filler used in the present invention can be used by treating the surface with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. .
[0042]
The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, or a thermosetting resin such as an epoxy resin.
[0043]
Addition amount of the above filler is liquid crystalline resinCompositionThe amount is usually 300 parts by weight or less with respect to 100 parts by weight, preferably 5 to 300 parts by weight, particularly preferably 10 to 250 parts by weight, and more preferably 20 to 150 parts by weight.
[0044]
Liquid crystalline resin of the present inventionCompositionAntioxidants and heat stabilizers (such as hindered phenols, hydroquinones, phosphites and their substitutes), UV absorbers (such as resorcinol, salicylate, benzotriazole, benzophenone), lubricants and mold release agents (Montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide, polyethylene wax, etc.), dyes (eg, nigrosine) and pigments (eg, cadmium sulfide, phthalocyanine, etc.), crystal nucleating agents, plastics A predetermined characteristic can be further imparted by adding a usual additive such as an agent, a flame retardant, a flame retardant aid, and an antistatic agent.
[0045]
The method of adding these is preferably melt kneading, and a known method can be used for melt kneading. For example, using a Banbury mixer, rubber roll machine, kneader, single-screw or twin-screw extruder, the composition can be melt-kneaded at a temperature of 180 to 370 ° C. to obtain a composition.
[0046]
In the present invention, when measuring the absorbance of the liquid crystalline resin using the liquid crystalline resin composition as described above, the components of the liquid crystalline resin composition are analyzed in advance using an analytical instrument such as GC-MS, LC-MS or the like. The additives and fillers other than the liquid crystalline resin are first separated and then measured by the method described above. Separation of the liquid crystalline resin from other additives and fillers can be performed as follows. That is, when the liquid crystalline resin composition contains an additive or filler insoluble in pentafluorophenol, the pentafluorophenol insoluble matter is filtered from the liquid crystalline resin composition with a 0.45 μm filter, and the filtrate (liquid crystalline resin The liquid crystalline resin is separated from the pentafluorophenol solution using a poor solvent such as methanol. In addition, when the liquid crystalline resin composition contains an additive that dissolves in pentafluorophenol, the liquid crystalline resin composition is finely pulverized, and the additive is used in a solvent selected from toluene, acetone, benzene, methanol, DMF, and MNP. Extract and separate. When both soluble and insoluble additives are added to pentafluorophenol, the above separation method is used in combination. A liquid crystal resin is obtained by separating the additive or filler from the liquid crystal resin composition as described above. As described above, the liquid crystal resin concentration in the mixed solvent having a weight ratio of pentafluorophenol to chloroform of 1 is as follows. It melt | dissolves so that it may become 0.5 weight%, and the light absorbency of 380 nm can be calculated | required by 10 mm optical path length.
[0047]
Liquid crystalline resin thus obtainedCompositionCan be used for normal molding such as injection molding, extrusion molding, compression molding, etc., and is extremely useful as various molded products for electric / electronic parts, precision parts, automobile parts and the like. Moreover, since it is excellent in color tone and retention stability, it can be made into an excellent colored molded product by blending a colorant.
[0048]
Liquid crystalline resin of the present inventionCompositionThe molded product made of can be processed into three-dimensional molded products, sheets, container pipes, etc. because of its excellent heat resistance, excellent hydrolysis resistance, and color tone. For example, various gears, various cases , Sensor, LEP lamp, connector, socket, resistor, relay case switch coil bobbin, condenser, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, Small motor, magnetic head base, power module, housing, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, electric and electronic parts represented by computer related parts; VTR parts, TV parts, irons, Hair dry -Home appliances such as rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, office electricity Product parts, office computer-related parts, telephone-related parts, facsimile-related parts, copying machine-related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings, and other various bearings, motor parts, lighters, typewriters, etc. Machine-related parts, optical instruments such as microscopes, binoculars, cameras, watches, precision machine-related parts; alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, various valves such as exhaust gas valves, fuel Relations ・ Exhaust system ・ Intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, Throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dus Tributer, starter switch, starter relay, wire harness for transmission, window sash Nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition It is useful for automobile / vehicle-related parts such as device cases and other various applications.
[0049]
Among them, the liquid crystalline resin of the present invention such as excellent color tone, heat resistance, hydrolysis resistance, etc.CompositionIt can be used practically as a small molded part used for a small molded part, for example, a small part having a resin volume of 5 cc or less. In particular, it is extremely practical for molded products that are small embedded parts such as connectors such as SIMM sockets, CD pickup lens holders, and various small gears.
[0050]
【Example】
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
[0051]
Comparative Example 1
LCP1: 11.05 kg of p-hydroxybenzoic acid, 1.40 kg of 4,4′-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 10.67 kg of acetic anhydride When charged in a pressure vessel and reacted at 100 to 250 ° C. for 1.5 hours in a nitrogen gas atmosphere, the pressure was reduced to 66 Pa at 315 ° C. for 1 hour, and further reacted for 1.25 hours to complete the polycondensation. Almost the theoretical amount of acetic acid was distilled off to obtain pellets. The absorbance at 380 nm measured with a 10 mm optical path length of the liquid crystalline resin (LCP1) was 1.1.
[0052]
Comparative Example 2
LCP2: 11.05 kg of p-hydroxybenzoic acid, 1.40 kg of 4,4′-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and pressure of 10.38 kg of acetic anhydride When charged in a container and polymerized under the same conditions as LCP1, the degree of polymerization did not increase, and good pellets could not be obtained.
[0053]
Example 1
LCP3: 11.05 kg of p-hydroxybenzoic acid, 1.40 kg of 4,4′-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, and 10.38 kg of acetic anhydride, Sodium hypophosphite (28.6 g) was charged into a pressure vessel and polymerized in the same manner as LCP1 to obtain pellets. The absorbance at 380 nm measured with a 10 mm optical path length of the liquid crystalline resin (LCP3) was 0.1.
[0054]
Example 2
LCP4: 11.05 kg of p-hydroxybenzoic acid, 1.40 kg of 4,4′-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 10.38 kg of acetic anhydride, Sodium phosphite (28.6 g) was charged into a pressure vessel and polymerized in the same manner as LCP1 to obtain pellets. The absorbance at 380 nm measured with a 10 mm optical path length of the liquid crystalline resin (LCP4) was 0.2.
[0055]
Example 3
LCP5: 11.05 kg of p-hydroxybenzoic acid, 1.40 kg of 4,4′-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 10.38 kg of acetic anhydride, Sodium hypophosphite (57.2 g) was charged into a pressure vessel and polymerized in the same manner as LCP1 to obtain pellets. The absorbance at 380 nm measured with a 10 mm optical path length of the liquid crystalline resin (LCP5) was 0.1.
[0056]
Comparative Example 3
LCP6: 11.05 kg of p-hydroxybenzoic acid, 1.40 kg of 4,4′-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 10.67 kg of acetic anhydride, MARK PEP-36 (bis (4-methyl-2,6-t-butyl) pentaerythritol diphosphite) manufactured by Adeka Argus Chemical Co., Ltd. was charged in a pressure vessel and polymerized in the same manner as LCP1. Pellets were obtained. The absorbance at 380 nm measured with a 10 mm optical path length of the liquid crystalline resin (LCP6) was 0.9.
[0057]
Comparative Example 4
LCP7: 11.05 kg of p-hydroxybenzoic acid, 1.40 kg of 4,4′-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 10.67 kg of acetic anhydride, MARK HP-10 (2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite) manufactured by Adeka Argus Chemical Co. was charged in a pressure vessel, polymerized in the same manner as LCP1, and pelletized Got. The absorbance at 380 nm measured with a 10 mm optical path length of the liquid crystalline resin (LCP7) was 0.8.
[0058]
Comparative Example 5
LCP8: 11.05 kg of p-hydroxybenzoic acid, 1.40 kg of 4,4′-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 10.67 kg of acetic anhydride, 28.6 g of calcium hypophosphite was charged into a pressure vessel and polymerized in the same manner as LCP1 to obtain pellets. The absorbance at 380 nm measured with a 10 mm optical path length of the liquid crystalline resin (LCP8) was 0.55.
[0059]
Each evaluation was measured according to the following method.
[0060]
(1) Absorbance
The solution obtained by mixing the liquid crystalline resin with a mixed solution of pentafluorophenol and chloroform (weight ratio 1: 1) so that the concentration is 0.5% by weight is put in a quartz glass cell having an optical path length of 10 mm. It calculated | required from the following formula measured with the light of 380 nm using the spectrophotometer (the Shimadzu make, UV-240) by making a mixed solvent into a blank.
[0061]
Absorbance = −Log (transmitted light intensity / incident light intensity)
(2) Whiteness (W value), Yellowness (YI value)
A 127 mm × 12.7 mm × 3.12 mm bending test piece was molded with Sumitomo Heavy Industries Promat 25/40 at a cylinder temperature of 325 ° C. and a mold temperature of 90 ° C., and this test piece was SM color computer manufactured by Suga Test Instruments Co., Ltd. Whiteness (W value) was measured using an apparatus.
[0062]
(3) Residence stability
A bending test piece of 127 mm x 12.7 mm x 3.12 mm was molded with Sumitomo Heavy Industries Promat 25/40 at a cylinder temperature of 330 ° C and a mold temperature of 90 ° C under two conditions where the molding residence time was changed to 4 minutes and 20 minutes. The bending strength was measured based on ASTM D790, and the bending strength at a molding residence time of 20 minutes / bending strength at a molding residence time of 4 minutes × 100 was determined as a bending strength retention rate.
[0063]
(4) Heat aging test
ASTM No. 1 tensile test piece was molded with Toshiba IS-55EPN at a cylinder temperature of 325 ° C. and a mold temperature of 90 ° C., and the obtained test piece was treated in a hot air oven at 240 ° C. for 30 days, and then tensioned according to ASTM D638. The strength was measured, and the tensile strength after treatment for 30 days at 240 ° C./initial tensile strength × 100 was determined as the tensile strength retention rate.
[0064]
(5) Hydrolysis test
An ASTM No. 1 tensile test piece was molded with Toshiba IS-55EPN at a cylinder temperature of 325 ° C. and a mold temperature of 90 ° C., and the obtained test piece was placed in an autoclave with water and treated at 120 ° C. for 3 days. Then, based on ASTM D638 The tensile strength was measured, and the tensile strength retention rate was defined as tensile strength when treated at 120 ° C. for 3 days / initial tensile strength × 100.
[0065]
(6) Acetic acid generation amount
Weigh 0.3 g of resin in a 50 mmφ test tube, reduce the pressure to 10 Torr, leave it in a sealed system at 330 ° C. for 30 minutes, and then return to normal pressure with nitrogen. Detector tube for acetic acid (No. 81, manufactured by Gastec) ) Was used to measure the acetic acid concentration in the test tube.
[0066]
Examples 4-6, Comparative Examples 6-9
Inorganic fillers (9 μm diameter, 3 mm long glass fiber) were dried at the ratios shown in Table 1 with respect to LCP1, 3-8 100 parts by weight shown in Examples 1-3 and Comparative Examples 1, 3-5. After blending, the mixture was melt-kneaded with a 30 mmφ twin-screw extruder to obtain pellets. Then, a test piece was obtained from this pellet by the method for each evaluation item. In addition, about the light absorbency and the acetic acid generation amount, the liquid crystalline resin before kneading | mixing is measured.
[0067]
The evaluation results are shown in Table 1.
[0068]
[Table 1]
From the results shown in Table 1, the liquid crystalline resin composition of the present invention has a greatly improved color tone, and obtains a material having improved heat resistance such as thermal stability during residence and heat aging characteristics, and further improved hydrolysis resistance. Can do.
[0069]
【The invention's effect】
The liquid crystalline resin composition and molded product of the present invention have greatly improved color tone and excellent heat resistance and hydrolysis resistance, so that they are electrical / electronic related equipment, precision machinery related equipment, office equipment, automobile / It is suitable for various other uses such as vehicle-related parts.
Claims (8)
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JPH10237286A (en) | 1998-09-08 |
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