JP2010106078A - Flame-retardant thermoplastic polyester resin composition - Google Patents
Flame-retardant thermoplastic polyester resin composition Download PDFInfo
- Publication number
- JP2010106078A JP2010106078A JP2008277459A JP2008277459A JP2010106078A JP 2010106078 A JP2010106078 A JP 2010106078A JP 2008277459 A JP2008277459 A JP 2008277459A JP 2008277459 A JP2008277459 A JP 2008277459A JP 2010106078 A JP2010106078 A JP 2010106078A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyester resin
- weight
- resin composition
- thermoplastic polyester
- 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.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 43
- 229920006230 thermoplastic polyester resin Polymers 0.000 title claims abstract description 40
- 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 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- -1 organosiloxane compound Chemical class 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 125000000962 organic group Chemical group 0.000 claims abstract description 14
- 150000001642 boronic acid derivatives Chemical class 0.000 claims abstract description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 5
- 230000002787 reinforcement Effects 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 18
- 239000012779 reinforcing material Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 238000000465 moulding Methods 0.000 abstract description 10
- 150000001450 anions Chemical class 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 238000011109 contamination Methods 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- ZJKCITHLCNCAHA-UHFFFAOYSA-K aluminum dioxidophosphanium Chemical compound [Al+3].[O-][PH2]=O.[O-][PH2]=O.[O-][PH2]=O ZJKCITHLCNCAHA-UHFFFAOYSA-K 0.000 abstract 1
- 229910001382 calcium hypophosphite Inorganic materials 0.000 abstract 1
- LITFOGPYONJRNO-UHFFFAOYSA-L calcium phosphinate Chemical compound [Ca+2].[O-]P=O.[O-]P=O LITFOGPYONJRNO-UHFFFAOYSA-L 0.000 abstract 1
- 238000009413 insulation Methods 0.000 abstract 1
- 239000011342 resin composition Substances 0.000 description 42
- 238000012360 testing method Methods 0.000 description 23
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 17
- 235000010338 boric acid Nutrition 0.000 description 17
- 229920001296 polysiloxane Polymers 0.000 description 17
- 229960002645 boric acid Drugs 0.000 description 16
- 239000004327 boric acid Substances 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 229920002050 silicone resin Polymers 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000005452 bending Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 7
- 229920001225 polyester resin Polymers 0.000 description 7
- 239000004645 polyester resin Substances 0.000 description 7
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 description 2
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002013 dioxins Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDLGYWMNSPNNIV-UHFFFAOYSA-N manganese(3+);borate Chemical compound [Mn+3].[O-]B([O-])[O-] BDLGYWMNSPNNIV-UHFFFAOYSA-N 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- ZUHPIMDQNAGSOV-UHFFFAOYSA-N 2-benzyl-2-phenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)(C(O)=O)CC1=CC=CC=C1 ZUHPIMDQNAGSOV-UHFFFAOYSA-N 0.000 description 1
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GABQNAFEZZDSCM-RMKNXTFCSA-N Cinnamyl anthranilate Chemical compound NC1=CC=CC=C1C(=O)OC\C=C\C1=CC=CC=C1 GABQNAFEZZDSCM-RMKNXTFCSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- JVZQHCPKAARJDJ-UHFFFAOYSA-N [Ca].CP(O)=O Chemical compound [Ca].CP(O)=O JVZQHCPKAARJDJ-UHFFFAOYSA-N 0.000 description 1
- WMEFLUAXDSCMBO-UHFFFAOYSA-N [Ni+4].[O-]B([O-])OB([O-])[O-] Chemical compound [Ni+4].[O-]B([O-])OB([O-])[O-] WMEFLUAXDSCMBO-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PZTKTQUZLZVLLK-UHFFFAOYSA-K aluminum bis(2-methylpropyl)phosphinate Chemical compound [Al+3].CC(C)CP([O-])(=O)CC(C)C.CC(C)CP([O-])(=O)CC(C)C.CC(C)CP([O-])(=O)CC(C)C PZTKTQUZLZVLLK-UHFFFAOYSA-K 0.000 description 1
- AZBWLPLVVUOKPE-UHFFFAOYSA-K aluminum methyl(phenyl)phosphinate Chemical compound [Al+3].CP([O-])(=O)c1ccccc1.CP([O-])(=O)c1ccccc1.CP([O-])(=O)c1ccccc1 AZBWLPLVVUOKPE-UHFFFAOYSA-K 0.000 description 1
- QVKQNISQFCPYGN-UHFFFAOYSA-K aluminum;dimethylphosphinate Chemical compound [Al+3].CP(C)([O-])=O.CP(C)([O-])=O.CP(C)([O-])=O QVKQNISQFCPYGN-UHFFFAOYSA-K 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IKRMZAOEXULJQX-UHFFFAOYSA-N calcium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Ca+2].O1B([O-])OB2OB([O-])OB1O2 IKRMZAOEXULJQX-UHFFFAOYSA-N 0.000 description 1
- ZUUPOTBVNWNPNO-UHFFFAOYSA-N calcium;[hydroxy(methyl)phosphoryl]methyl-methylphosphinic acid Chemical compound [Ca].CP(O)(=O)CP(C)(O)=O ZUUPOTBVNWNPNO-UHFFFAOYSA-N 0.000 description 1
- DRYHXHUXMMIMPH-UHFFFAOYSA-L calcium;diethylphosphinate Chemical compound [Ca+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DRYHXHUXMMIMPH-UHFFFAOYSA-L 0.000 description 1
- DONULGYRZAGJQH-UHFFFAOYSA-L calcium;dimethylphosphinate Chemical compound [Ca+2].CP(C)([O-])=O.CP(C)([O-])=O DONULGYRZAGJQH-UHFFFAOYSA-L 0.000 description 1
- BFKPORWCVZVLTQ-UHFFFAOYSA-L calcium;ethyl(methyl)phosphinate Chemical compound [Ca+2].CCP(C)([O-])=O.CCP(C)([O-])=O BFKPORWCVZVLTQ-UHFFFAOYSA-L 0.000 description 1
- UUAUGMXREUNBAY-UHFFFAOYSA-L calcium;methyl(phenyl)phosphinate Chemical compound [Ca+2].CP([O-])(=O)C1=CC=CC=C1.CP([O-])(=O)C1=CC=CC=C1 UUAUGMXREUNBAY-UHFFFAOYSA-L 0.000 description 1
- VBUWHUGIXLGHTR-UHFFFAOYSA-L calcium;methyl(propyl)phosphinate Chemical compound [Ca+2].CCCP(C)([O-])=O.CCCP(C)([O-])=O VBUWHUGIXLGHTR-UHFFFAOYSA-L 0.000 description 1
- ILOKQJWLMPPMQU-UHFFFAOYSA-N calcium;oxido(oxo)borane Chemical compound [Ca+2].[O-]B=O.[O-]B=O ILOKQJWLMPPMQU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 150000002009 diols Chemical class 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
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- NDNPFWOOAFWTAI-UHFFFAOYSA-N hexazinc;tetraborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] NDNPFWOOAFWTAI-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- AAWVBZMCMMRKSG-UHFFFAOYSA-N manganese(2+);tetraborate Chemical compound [Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] AAWVBZMCMMRKSG-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000013500 performance material Substances 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UKUWOJWHPCYQDY-UHFFFAOYSA-N trimagnesium boric acid diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].OB(O)O.OB(O)O.[O-]B([O-])[O-].[O-]B([O-])[O-] UKUWOJWHPCYQDY-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GTOWTBKGCUDSNY-UHFFFAOYSA-K tris[[ethyl(methyl)phosphoryl]oxy]alumane Chemical compound [Al+3].CCP(C)([O-])=O.CCP(C)([O-])=O.CCP(C)([O-])=O GTOWTBKGCUDSNY-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- PZRXQXJGIQEYOG-UHFFFAOYSA-N zinc;oxido(oxo)borane Chemical compound [Zn+2].[O-]B=O.[O-]B=O PZRXQXJGIQEYOG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ハロゲン系難燃剤を含有しなくても優れた難燃性を有し、同時に優れた機械的物性を有する難燃性熱可塑性ポリエステル樹脂組成物及びそれを用いた成形品に関する。 The present invention relates to a flame-retardant thermoplastic polyester resin composition having excellent flame retardancy without containing a halogen-based flame retardant and simultaneously having excellent mechanical properties, and a molded article using the same.
熱可塑性ポリエステル樹脂は、その優れた特性から電気及び電子機器部品、並びに自動車部品などに広く用いられている。従来からこの樹脂に関しては、要求特性を満足させるべく様々な処方が開発され、それにより高機能化と高性能化を実現してきた。 Thermoplastic polyester resins are widely used in electrical and electronic equipment parts, automobile parts and the like because of their excellent characteristics. Conventionally, various formulations have been developed for this resin in order to satisfy the required characteristics, thereby realizing higher functionality and higher performance.
しかし近年、要求物性は益々高度化してきており、従来の処方では対応が困難になってきている。例えば、最近はコネクターなどの電子部品の軽量小型化が進み、成形品の肉厚が薄くなってきている。従って成形に用いる樹脂組成物にも、これに対応すべく、従来以上に機械的特性と難燃性に優れていることが要求されている。 However, in recent years, the required physical properties have become more and more sophisticated, and it has become difficult to cope with conventional prescriptions. For example, recently, electronic parts such as connectors have been reduced in weight and size, and the thickness of molded products has been reduced. Accordingly, the resin composition used for molding is also required to have better mechanical properties and flame retardance than before in order to cope with this.
従来、樹脂の難燃剤としては主にハロゲン系難燃剤が用いられていた。しかしハロゲン系難燃剤を含有する樹脂は、使用済み成形品を焼却処分する際にダイオキシンを発生する場合があり、非ハロゲン系難燃剤を用いることが求められている。この要求に応える方法の一つとして、リン系の化合物、中でもアニオン部分が下記式（１）又は（２）で表されるホスフィン酸のカルシウム塩又はアルミニウム塩を難燃剤として用いることが検討されている。 Conventionally, halogen-based flame retardants have been mainly used as resin flame retardants. However, a resin containing a halogen-based flame retardant may generate dioxins when used products are incinerated, and a non-halogen-based flame retardant is required to be used. As one method for meeting this requirement, it has been studied to use a phosphorus compound, particularly a calcium salt or an aluminum salt of phosphinic acid whose anion portion is represented by the following formula (1) or (2) as a flame retardant. Yes.
（式中、Ｒ１及びＲ２は各々独立して、炭素数１〜６のアルキル基又は置換されていてもよいアリール基を表し、Ｒ１同士は同一であることも異なっていることもある。Ｒ３は炭素数１〜１０のアルキレン基、置換されていてもよいアリーレン基、又はこれらの混合基を表す。ｎは０〜４の整数を表す。） (In the formula, R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R 1 may be the same or different. R 3 represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a mixed group thereof, and n represents an integer of 0 to 4.)
特許文献１には、難燃剤として、このホスフィン酸のカルシウム又はアルミニウム塩を用いることが記載されている。しかしこの方法では、良好な難燃性を得る為にこれらの塩が多量に必要となり、得られる樹脂組成物の成形性及び機械的特性が低下するという問題があった。 Patent Document 1 describes using a calcium or aluminum salt of this phosphinic acid as a flame retardant. However, this method has a problem that a large amount of these salts are required to obtain good flame retardancy, and the moldability and mechanical properties of the resulting resin composition are lowered.
特許文献２には、難燃剤としてホスフィン酸のカルシウムまたはアルミニウム塩にメラミンシアヌレートなどの有機窒素化合物を併用することが記載されている。この方法によれば難燃性はかなり改善されるが、成形時のガス発生が著しく多い為に金型汚染が酷く、更に成形品のウエルド強度が低く、靭性に乏しいという問題があった。 Patent Document 2 describes that an organic nitrogen compound such as melamine cyanurate is used in combination with a calcium or aluminum salt of phosphinic acid as a flame retardant. Although flame retardancy is considerably improved by this method, there is a problem that the mold contamination is severe due to remarkably large gas generation during molding, and further, the weld strength of the molded product is low and the toughness is poor.
尚、樹脂組成物に靭性を付与する方法としては、例えば特許文献３に記載されている様にエラストマー等の低弾性率の重合体を配合することが一般的である。しかしエラストマーの配合は樹脂組成物の難燃性を低下させるので、この方法では靭性と難燃性を両立させることは困難である。 As a method for imparting toughness to the resin composition, for example, a low elastic modulus polymer such as an elastomer is blended as described in Patent Document 3, for example. However, since the blending of the elastomer reduces the flame retardancy of the resin composition, it is difficult to achieve both toughness and flame retardancy with this method.
特許文献４には、難燃剤として特殊な有機リン化合物を用い、これに難燃助剤を配合することが記載されている。難燃助剤としては多種類のものが挙げられており、そのなかにはそれ自体で難燃剤として知られているものも含まれている。この文献に記載されている難燃助剤は、有機物から無機物まで広範囲にわたっているので、その全てが同じような効果を奏するか否かは疑問である。 Patent Document 4 describes that a special organic phosphorus compound is used as a flame retardant, and a flame retardant aid is added thereto. There are many types of flame retardant aids, including those known per se as flame retardants. Since the flame retardant aid described in this document covers a wide range from organic matter to inorganic matter, it is doubtful whether all of them have the same effect.
また成形品の剛性を高めるため、樹脂組成物にガラス繊維などの繊維状強化材を配合することが行われているが、繊維状強化材を配合した樹脂組成物で成形した製品は、燃焼時に繊維状強化材が蝋燭の芯のように作用するので、燃焼し易いという問題があった。 In addition, in order to increase the rigidity of the molded product, a fiber reinforcing material such as glass fiber is blended in the resin composition, but a product molded with the resin composition blended with the fibrous reinforcing material is Since the fibrous reinforcing material acts like a candle core, there is a problem that it easily burns.
従って繊維状強化材を配合した樹脂組成物を、ホスフィン酸のカルシウム又はアルミニウム塩で難燃化するには、格別の工夫が必要である。 Therefore, in order to make a resin composition containing a fibrous reinforcing material flame-retardant with a calcium or aluminum salt of phosphinic acid, special measures are required.
本発明は熱可塑性ポリエステル樹脂に繊維状強化材とホスフィン酸のカルシウム又はアルミニウム塩を配合してなり、且つ優れた機械的特性及び難燃性を有する難燃性熱可塑性樹脂組成物を提供しようとするものである。 An object of the present invention is to provide a flame retardant thermoplastic resin composition comprising a thermoplastic polyester resin blended with a fibrous reinforcing material and a calcium or aluminum salt of phosphinic acid and having excellent mechanical properties and flame retardancy. To do.
本発明者は、繊維状強化材及び難燃剤としてホスフィン酸のカルシウム又はアルミニウム塩を配合した熱可塑性ポリエステル樹脂に、アリール基を含有するオルガノシロキサン化合物及び更にはホウ酸金属塩を配合することにより、難燃性及び機械的特性に優れた、物性バランスの良い樹脂組成物となることを見出し、本発明を完成させた。 The inventor of the present invention, by blending an organosiloxane compound containing an aryl group and further a boric acid metal salt into a thermoplastic polyester resin blended with a fibrous reinforcing material and a calcium or aluminum salt of phosphinic acid as a flame retardant, The present invention was completed by finding a resin composition excellent in flame retardancy and mechanical properties and having a good balance of physical properties.
即ち本発明の要旨は、（Ａ）熱可塑性ポリエステル樹脂１００重量部に対し、（Ｂ）アニオン部分が式（１）又は（２）で表されるホスフィン酸のカルシウム又はアルミニウム塩であるホスフィン酸塩５〜４０重量部、（Ｃ）珪素原子に直接又は酸素原子を介して結合している有機基の４０モル％以上がアリール基であるオルガノシロキサン化合物１．５〜１０重量部、（Ｄ）繊維状強化材５〜８０重量部、及びホウ酸金属塩０〜２０重量部を配合したことを特徴とする難燃性熱可塑性ポリエステル樹脂組成物に存する。また本発明の他の要旨は、この樹脂組成物を射出成形して成る成形品に存する。 That is, the gist of the present invention is (A) a phosphinic acid salt in which (B) an anionic part is a calcium or aluminum salt of phosphinic acid represented by the formula (1) or (2) with respect to 100 parts by weight of a thermoplastic polyester resin. 5 to 40 parts by weight, (C) 1.5 to 10 parts by weight of an organosiloxane compound in which 40 mol% or more of the organic groups bonded directly or through oxygen atoms to silicon atoms are aryl groups, (D) fibers It exists in the flame-retardant thermoplastic polyester resin composition characterized by mix | blending 5-80 weight part of a shape reinforcement, and 0-20 weight part of boric-acid metal salts. Another gist of the present invention resides in a molded article formed by injection molding the resin composition.
（式中、Ｒ１及びＲ２は各々独立して、炭素数１〜６のアルキル基又は置換されていてもよいアリール基を表し、Ｒ１同士は同一でも異なっていてもよく、Ｒ３は炭素数１〜１０のアルキレン基、置換されていてもよいアリーレン基、又はこれらの混合基を表す．ｎは０〜４の整数を表す。） (In the formula, R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, R 1 may be the same or different, and R 3 represents carbon. Represents an alkylene group of formula 1 to 10, an arylene group which may be substituted, or a mixed group thereof, n represents an integer of 0 to 4)
本発明の難燃性熱可塑性ポリエステル樹脂組成物は、次のような特徴を有する。
（１）厚さ１ｍｍ以下の成形品とした場合でも優れた難燃性と機械的特性を有する。
（２）ハロゲン系難燃剤不含故、焼却時にダイオキシンを発生せず、環境汚染が少ない。
（３）離型性に優れているので、成形に際し変形などの恐れが少ない。
（４）モールドデポジットが極めて少ないので成形に際しての生産性がよい。
（５）射出成形品のウエルド部の強度が大きい。
（６）耐トラッキング性に優れ、広範囲の電気電子分野の用途に利用が可能である。
The flame-retardant thermoplastic polyester resin composition of the present invention has the following characteristics.
(1) Even when it is a molded product having a thickness of 1 mm or less, it has excellent flame retardancy and mechanical properties.
(2) Because it does not contain halogen flame retardants, dioxins are not generated during incineration, and environmental pollution is low.
(3) Since it has excellent releasability, there is little risk of deformation during molding.
(4) Since there is very little mold deposit, productivity at the time of shaping | molding is good.
(5) The strength of the weld part of the injection molded product is large.
(6) It has excellent tracking resistance and can be used in a wide range of applications in the electrical and electronic fields.
以下、本発明について詳しく説明する。
（Ａ）熱可塑性ポリエステル樹脂：
本発明の難燃性熱可塑性樹脂組成物の主成分である熱可塑性ポリエステル樹脂とは、ジカルボン酸化合物とジヒドロキシ化合物の重縮合、オキシカルボン酸化合物の重縮合、又はこれらの化合物の混合物の重縮合などによって得られるポリエステルであり、ホモポリエステル、コポリエステルのいずれであってもよい。熱可塑性ポリエステル樹脂を構成するジカルボン酸化合物としては、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジフェニルエーテルジカルボン酸、ジフェニルエタンジカルボン酸などの芳香族ジカルボン酸、シクロヘキサンジカルボン酸などの脂環式ジカルボン酸、アジピン酸、セバシン酸などの脂肪族ジカルボン酸が挙げられる。
The present invention will be described in detail below.
(A) Thermoplastic polyester resin:
The thermoplastic polyester resin that is the main component of the flame-retardant thermoplastic resin composition of the present invention is a polycondensation of a dicarboxylic acid compound and a dihydroxy compound, a polycondensation of an oxycarboxylic acid compound, or a polycondensation of a mixture of these compounds. Etc., and may be either a homopolyester or a copolyester. Examples of the dicarboxylic acid compound constituting the thermoplastic polyester resin include alicyclic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, and cyclohexanedicarboxylic acid. Aliphatic dicarboxylic acids such as dicarboxylic acid, adipic acid and sebacic acid can be mentioned.
これらは周知のように、遊離酸以外にジメチルエステルなどのエステル形成性誘導体として重縮合反応に用いることができる。オキシカルボン酸としてはパラオキシ安息香酸、オキシナフトエ酸、ジフェニレンオキシカルボン酸などが挙げられる。これらは単独で重縮合させることもできるが、ジカルボン酸化合物に少量併用することが多い。 As is well known, these can be used in polycondensation reactions as ester-forming derivatives such as dimethyl esters in addition to free acids. Examples of the oxycarboxylic acid include paraoxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid. These can be polycondensed alone, but are often used in a small amount together with a dicarboxylic acid compound.
ジヒドロキシ化合物としては、エチレングリコール、プロピレングリコール、ブタンジオール、ネオペンチルグリコール、ポリオキシアルキレングリコールなどの脂肪族ジオールが主として用いられるが、ハイドロキノン、レゾルシン、ナフタレンジオール、ジヒドロキシジフェニルエーテル、２，２−ビス（４−ヒドロキシフェニル）プロパンなどの芳香族ジオールやシクロヘキサンジオールなどの脂環式ジオールも用いることができる。 As the dihydroxy compound, aliphatic diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and polyoxyalkylene glycol are mainly used. Hydroquinone, resorcin, naphthalenediol, dihydroxydiphenyl ether, 2,2-bis (4 Aromatic diols such as -hydroxyphenyl) propane and cycloaliphatic diols such as cyclohexanediol can also be used.
またこのようなニ官能性化合物以外に、分岐構造を導入するためトリメリット酸、トリメシン酸、ピロメリット酸、ペンタエリスリトール、トリメチロールプロパンなどの三官能以上の多官能化合物や、分子量調節のための脂肪酸などの単官能化合物を少量併用することもできる。 In addition to these bifunctional compounds, trifunctional or higher polyfunctional compounds such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane are introduced to introduce a branched structure. A small amount of a monofunctional compound such as a fatty acid can also be used.
本発明では、熱可塑性ポリエステル樹脂としては、通常は主としてジカルボン酸化合物とジヒドロキシ化合物とから成る重縮合物、即ち計算上、ジカルボン酸化合物とジヒドロキシ化合物のエステルである構造単位が、樹脂全体の７０重量％以上、好ましくは９０重量％以上を占めるものを用いる。ジカルボン酸化合物としては芳香族ジカルボン酸が好ましく、ジヒドロキシ化合物としては脂肪族ジオールが好ましい。 In the present invention, the thermoplastic polyester resin is usually a polycondensate mainly composed of a dicarboxylic acid compound and a dihydroxy compound, that is, a structural unit which is an ester of a dicarboxylic acid compound and a dihydroxy compound in calculation, which is 70 wt. % Or more, preferably 90% by weight or more. The dicarboxylic acid compound is preferably an aromatic dicarboxylic acid, and the dihydroxy compound is preferably an aliphatic diol.
なかでも好ましいのは、酸性分の９５モル％以上がテレフタル酸であり、アルコール成分の９５モル％以上が脂肪族ジオールであるポリアルキレンテレフタレートである。その代表的なものはポリブチレンテレフタレート及びポリエチレンテレフタレートである。これらはホモエステルに近いもの、即ち樹脂全体の９５重量％以上がテレフタル酸成分及び１，４−ブタンジオール又はエチレングリコール成分から成るものであるのが好ましい。 Of these, polyalkylene terephthalate in which 95 mol% or more of the acidic component is terephthalic acid and 95 mol% or more of the alcohol component is an aliphatic diol is preferable. Typical examples are polybutylene terephthalate and polyethylene terephthalate. These are preferably close to homoesters, that is, 95% by weight or more of the total resin is composed of a terephthalic acid component and a 1,4-butanediol or ethylene glycol component.
熱可塑性ポリエステル樹脂の固有粘度は適宜選択して決定すればよいが、通常０．５〜２ｄｌ／ｇであることが好ましく、中でも樹脂組成物の成形性及び機械的特性の観点から０．６〜１．５ｄｌ／ｇであることが好ましい。固有粘度が０．５ｄｌ／ｇ未満のものを用いると、樹脂組成物から得られる成形品の機械的強度が低くなる傾向にあり、逆に２ｄｌ／ｇより大きいと樹脂組成物の流動性が低下し、成形性が低下する場合がある。 The intrinsic viscosity of the thermoplastic polyester resin may be appropriately selected and determined. However, it is usually preferably 0.5 to 2 dl / g, and in particular, from the viewpoint of moldability and mechanical properties of the resin composition, 0.6 to It is preferably 1.5 dl / g. If a material having an intrinsic viscosity of less than 0.5 dl / g is used, the mechanical strength of the molded product obtained from the resin composition tends to be low, and conversely if it is greater than 2 dl / g, the fluidity of the resin composition decreases. However, moldability may be reduced.
尚、本明細書においてポリエステル樹脂の固有粘度は、テトラクロロエタンとフェノールとの１：１（重量比）の混合溶媒中、３０℃で測定した値である。 In the present specification, the intrinsic viscosity of the polyester resin is a value measured at 30 ° C. in a 1: 1 (weight ratio) mixed solvent of tetrachloroethane and phenol.
（Ｂ）ホスフィン酸塩：
本発明で用いるホスフィン酸塩は、アニオン部分が下記式（１）又は（２）で表され、カチオン部分がカルシウム又はアルミニウムであるものである。
(B) Phosphinate:
The phosphinic acid salt used in the present invention is one in which the anion moiety is represented by the following formula (1) or (2) and the cation moiety is calcium or aluminum.
（式中、Ｒ１及びＲ２は、それぞれ独立して、炭素数１〜６のアルキル基又は置換されていてもよいアリール基を表し、Ｒ１同士は同一でも異なっていてもよく、Ｒ３は炭素数１〜１０のアルキレン基、置換されていてもよいアリーレン基、又はこれらの混合基を表す。ｎは０〜４の整数を表す。） (In the formula, R 1 and R 2 each independently represents an alkyl group or an optionally substituted aryl group having 1 to 6 carbon atoms, R 1 each other may be the same or different, R 3 Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a mixed group thereof, and n represents an integer of 0 to 4.)
Ｒ１及びＲ２が表すアルキル基としては、メチル基、エチル基、プロピル基、イソブチル基、ペンチル基などが挙げられるが、炭素数１〜４のアルキル基、特にメチル基又はエチル基が好ましい。アリール基としては、フェニル基やナフチル基が挙げられ、これらに結合する置換基としてはメチル基、エチル基、メトキシ基、エトキシ基などの炭素数１〜４のアルキル基やアルコキシ基が挙げられる。 Examples of the alkyl group represented by R 1 and R 2 include a methyl group, an ethyl group, a propyl group, an isobutyl group, and a pentyl group, and an alkyl group having 1 to 4 carbon atoms, particularly a methyl group or an ethyl group is preferable. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the substituent bonded thereto include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a methoxy group, and an ethoxy group, and an alkoxy group.
置換基の結合数は通常１〜２個である。アリール基はフェニル基又はこれに炭素数１〜２のアルキル基が１〜２個結合したものであるのが好ましい。 The number of bonds of the substituent is usually 1 to 2. The aryl group is preferably a phenyl group or a group in which 1 or 2 alkyl groups having 1 to 2 carbon atoms are bonded thereto.
Ｒ３が表すアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基など直鎖状のもの、及び２−エチルヘキシレン基など分岐鎖状のものなどが挙げられる。これらのなかでも好ましいのは炭素数１〜４のアルキレン基、とくにメチレン基又はエチレン基である。 Examples of the alkylene group represented by R 3 include a linear group such as a methylene group, an ethylene group, a propylene group, and a butylene group, and a branched chain group such as a 2-ethylhexylene group. Among these, an alkylene group having 1 to 4 carbon atoms, particularly a methylene group or an ethylene group is preferable.
アリーレン基としてはフェニレン基、ナフチレン基などが挙げられ、これに結合する置換基としては、上述のものと同様のものが挙げられる。置換基の結合数は通常は一個である。アリーレン基としてはフェニレン基又はこれに炭素数１〜２のアルキル基が結合したものが好ましい。混合基としてはメチレン基とフェニレン基が結合したもの、メチレン基に２個のフェニレン基が結合したもの、フェニレン基に２個のメチレン基が結合したものなどが挙げられる。 Examples of the arylene group include a phenylene group and a naphthylene group, and examples of the substituent bonded thereto include the same groups as those described above. The number of bonds of the substituent is usually one. The arylene group is preferably a phenylene group or a group in which an alkyl group having 1 to 2 carbon atoms is bonded thereto. Examples of the mixed group include a group in which a methylene group and a phenylene group are bonded, a group in which two phenylene groups are bonded to a methylene group, and a group in which two methylene groups are bonded to a phenylene group.
中でも本発明においては、上述したホスフィン酸塩として、アニオン部分が以下の式（１’）又は（２’）で表されるホスフィン酸のカルシウム又はアルミニウム塩を用いることが好ましい。 In particular, in the present invention, it is preferable to use a calcium or aluminum salt of phosphinic acid having an anion moiety represented by the following formula (1 ') or (2') as the phosphinate described above.
ホスフィン酸塩は、（Ａ）熱可塑性ポリエステル樹脂１００重量部に対し、５〜４０重量部配合する。配合量が５重量部未満では樹脂組成物の難燃性を十分に高くすることが困難であり、逆に４０重量部を超えると樹脂組成物の機械的特性が低下する。難燃性と機械的特性を両立させる点からして、配合量は１０〜３５重量部、特に２０〜３５重量部が好ましい The phosphinic acid salt is blended in an amount of 5 to 40 parts by weight per 100 parts by weight of the (A) thermoplastic polyester resin. If the blending amount is less than 5 parts by weight, it is difficult to make the flame retardance of the resin composition sufficiently high. Conversely, if it exceeds 40 parts by weight, the mechanical properties of the resin composition are lowered. From the viewpoint of achieving both flame retardancy and mechanical properties, the blending amount is preferably 10 to 35 parts by weight, particularly preferably 20 to 35 parts by weight.
本発明で用いるのに好ましいホスフィン酸塩としては、アニオン部分が式（１’）で表されるものとして、ジメチルホスフィン酸カルシウム、ジメチルホスフィン酸アルミニウム、エチルメチルホスフィン酸カルシウム、エチルメチルホスフィン酸アルミニウム、ジエチルホスフィン酸カルシウム、ジエチルホスフィン酸アルミニウム、メチル−ｎ―プロピルホスフィン酸カルシウム、メチル−ｎ―プロピルホスフィン酸アルミニウム、メチルフェニルホスフィン酸カルシウム、メチルフェニルホスフィン酸アルミニウム、ジイソブチルホスフィン酸アルミニウムなどが挙げられる。 Preferred phosphinates for use in the present invention include those having an anion moiety represented by the formula (1 ′): calcium dimethylphosphinate, aluminum dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, Examples thereof include calcium diethylphosphinate, aluminum diethylphosphinate, calcium methyl-n-propylphosphinate, aluminum methylmethyl-n-propylphosphinate, calcium methylphenylphosphinate, aluminum methylphenylphosphinate, aluminum diisobutylphosphinate and the like.
また、アニオン部分が式（２’）で表されるものとして、メチレンビス（メチルホスフィン酸）カルシウム、メチレンビス（メチルホスフィン酸）アルミニウム、フェニレン−１、４−ビス（メチルホスフィン酸）カルシウム、フェニレン−１，４―ビス（メチルホスフィン酸）アルミニウム等の、式（２’）においてｎ＝０のものが好ましい。 As the anion moiety represented by the formula (2 ′), methylene bis (methylphosphinic acid) calcium, methylenebis (methylphosphinic acid) aluminum, phenylene-1,4-bis (methylphosphinic acid) calcium, phenylene-1 In the formula (2 ′), n = 0 is preferable, such as, 4-bis (methylphosphinic acid) aluminum.
本発明に用いるホスフィン酸塩は、単独で、又は2種以上を任意の割合で併用してもよい。具体的には例えば、難燃性及び電気特性の観点から、上述したなかでもジエチルホスフィン酸のアルミニウム塩や、カルシウム塩が好ましい。また本発明の樹脂組成物から得られる成形品の機械的強度や外観の観点から、本発明に用いるホスフィン酸塩は、その９０重量％以上が粒径１００μｍ以下、特に５０μｍ以下である粉末を用いるのが好ましい。中でも９０重量％以上が粒径０．５〜２０μｍの粉末を用いることで、高い難燃性を発現し、且つ成形品の靭性が著しく高くなるので特に好ましい。尚、ここでの粒径とは、レーザー回折法により得られる値である。 The phosphinic acid salts used in the present invention may be used alone or in combination of two or more in any ratio. Specifically, for example, from the viewpoints of flame retardancy and electrical characteristics, among the above-mentioned, an aluminum salt of diethylphosphinic acid and a calcium salt are preferable. In addition, from the viewpoint of mechanical strength and appearance of a molded product obtained from the resin composition of the present invention, the phosphinic acid salt used in the present invention uses a powder whose 90% by weight or more has a particle size of 100 μm or less, particularly 50 μm or less. Is preferred. Among them, the use of a powder having a particle size of 0.5 to 20 μm of 90% by weight or more is particularly preferable because it exhibits high flame retardancy and remarkably increases the toughness of the molded product. Here, the particle size is a value obtained by a laser diffraction method.
（Ｃ）オルガノシロキサン化合物：
本発明の難燃性熱可塑性ポリエステル樹脂組成物は、アリール基を有するオルガノシロキサン化合物を含有することが必要である。このオルガノシロキサン化合物は、前述したホスフィン酸塩と組み合わせて用いることにより、熱可塑性ポリエステル樹脂組成物に高度な難燃性を付与する難燃剤として作用する。
(C) Organosiloxane compound:
The flame-retardant thermoplastic polyester resin composition of the present invention needs to contain an organosiloxane compound having an aryl group. This organosiloxane compound acts as a flame retardant that imparts a high degree of flame retardancy to the thermoplastic polyester resin composition when used in combination with the phosphinic acid salt described above.
その作用機序の一つは、樹脂組成物の燃焼に際し、オルガノシロキサン化合物が気化して樹脂組成物中に微小な気泡が多数生じ、この気泡の断熱作用により樹脂組成物がそれ以上燃焼するのが阻害されるものと推察される。 One of the mechanism of action is that when the resin composition is burned, the organosiloxane compound is vaporized and a large number of fine bubbles are generated in the resin composition. Is presumed to be inhibited.
本発明で用いるオルガノシロキサン化合物は、有機シラノールないしはその重合体であって、珪素原子に直接または酸素原子を介して結合している有機基、即ちＳｉ―Ｃ又はＳｉ―Ｏ―Ｃ結合を形成している有機基の４０モル％以上、好ましくは５０モル％以上がアリール基であるものである。アリール基としてはフェニル基やナフチル基が挙げられ、これらの基にはメチル基、エチル基、メトキシ基、エトキシ基など炭素数１〜４のアルキル基やアルコキシ基が１〜２個置換していてもよい。このアリール基としては、中でもフェニル基が好ましい。 The organosiloxane compound used in the present invention is an organic silanol or a polymer thereof, and forms an organic group bonded to a silicon atom directly or through an oxygen atom, that is, a Si—C or Si—O—C bond. 40 mol% or more, preferably 50 mol% or more of the organic group is an aryl group. Examples of the aryl group include a phenyl group and a naphthyl group, and these groups are substituted with 1 to 2 alkyl groups or alkoxy groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a methoxy group, and an ethoxy group. Also good. Among these aryl groups, a phenyl group is preferable.
オルガノシロキサン化合物を含有するポリエステル樹脂組成物は、一般に燃焼時に滴下を起こし易いが、有機基の４０モル％以上がアリール基であるオルガノシロキサン化合物を含有する樹脂組成物は燃焼時に滴下し難く、かつ燃焼が大幅に抑制される。オルガノシロキサン化合物のこれらの作用は、一般に有機基に占めるアリール基の割合が高いほど大きい。従ってオルガノシロキサン化合物としては有機基の８０モル％以上、さらには全て（１００％）がアリール基、特にフェニル基であるものを用いるのが、特に好ましい。 A polyester resin composition containing an organosiloxane compound generally tends to drop during combustion, but a resin composition containing an organosiloxane compound in which 40 mol% or more of the organic groups are aryl groups is difficult to drop during combustion, and Combustion is greatly suppressed. These actions of the organosiloxane compound are generally greater as the proportion of the aryl group in the organic group is higher. Accordingly, it is particularly preferable to use an organosiloxane compound in which 80 mol% or more, and all (100%) of the organic group is an aryl group, particularly a phenyl group.
オルガノシロキサン化合物としては、トリフェニルシラノールの様なモノマー、その環状４量体であるオクタフェニルテトラシクロシロキサンの様なオリゴマー、さらにはポリジフェニルシロキサンの様なポリマーの、いずれをも用いることができる。またこれらのフェニル基の一部は、メチル基やその他のアルキル基、メトキシ基やその他のアルコキシ基、フェノキシ基やその他のアリールオキシ基等に置換されていてもよい。 As the organosiloxane compound, any of a monomer such as triphenylsilanol, an oligomer such as octaphenyltetracyclosiloxane which is a cyclic tetramer thereof, and a polymer such as polydiphenylsiloxane can be used. Some of these phenyl groups may be substituted with a methyl group, other alkyl groups, a methoxy group, other alkoxy groups, a phenoxy group, other aryloxy groups, or the like.
更にフェニル基としては、その一部が水酸基に置換されていてもよいが、オルガノシロキサン化合物における水酸基の含有量が多過ぎると、高温多湿下において加水分解し易いので、水酸基の含有量は１〜１０重量％であることが好ましい。 Furthermore, as the phenyl group, a part thereof may be substituted with a hydroxyl group, but if the content of the hydroxyl group in the organosiloxane compound is too much, it is easily hydrolyzed under high temperature and high humidity. It is preferably 10% by weight.
尚、上述した様にオルガノシロキサン化合物としてはモノマーやオリゴマーも用いうるが、低分子量のものはモールドデポジットを起こし易いので、重量平均分子量が８００以上、特に１０００以上のポリマーを用いるのが好ましい。逆に分子量が大きすぎてもポリエステル樹脂との相溶性が低下するので、均一な樹脂組成物の調製が困難となる場合がある。よってオルガンシロキサン化合物の重量平均分子量としては１００００以下、中でも５０００以下が好ましい。ここで重量平均分子量とは、ゲル・パーメーション・クロマトグラフィー法（ＧＰＣ）で測定したポリスチレン換算値である。 As described above, monomers and oligomers may be used as the organosiloxane compound, but those having a low molecular weight are liable to cause mold deposits, so it is preferable to use a polymer having a weight average molecular weight of 800 or more, particularly 1000 or more. On the other hand, even if the molecular weight is too large, compatibility with the polyester resin is lowered, so that it may be difficult to prepare a uniform resin composition. Therefore, the weight average molecular weight of the organsiloxane compound is 10,000 or less, preferably 5000 or less. Here, the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC).
オルガノシロキサン化合物の中でも、特に好ましいのは、所謂シリコーンレジンである。シリコーンレジンは通常は下記のＤ単位、Ｔ単位、Ｑ単位などからなる重合体であり、末端はＭ単位で封止されていることもある。 Of the organosiloxane compounds, a so-called silicone resin is particularly preferable. The silicone resin is usually a polymer composed of the following D units, T units, Q units, and the like, and the ends may be sealed with M units.
本発明に用いるシリコーンレジンとしては、中でもＲＳｉＯ１．５で示されるＴ単位を含有するものが好ましく、特にＴ単位を多く含有するもの、具体的には５０モル％以上、中でも８０モル％以上含有するものが好ましく、特に末端封止基を除き全てがＴ単位から成るものが好ましい。 As the silicone resin used in the present invention, those containing T units represented by RSiO 1.5 are particularly preferred, especially those containing a large amount of T units, specifically 50 mol% or more, especially 80 mol% or more. In particular, those consisting of all T units except for the end-capping group are preferred.
一般的に、Ｔ単位の含有量が少ないシリコーンレジンは、それ自体の耐熱性が低く、かつ樹脂組成物中での分散性も低い。ここでＴ単位の含有率は、２９Ｓｉ−ＮＭＲで測定した値、即ちこの測定でＴ単位に帰属するピーク面積比からその含有率を算出した値である。 In general, a silicone resin having a low T unit content has low heat resistance and low dispersibility in the resin composition. Here, the content of the T unit is a value measured by 29 Si-NMR, that is, a value obtained by calculating the content from the peak area ratio attributed to the T unit in this measurement.
式（３）〜（６）において、Ｒは、炭素数１〜１２の一価の炭化水素基を表す。なお、各Ｒは同じでも異なっていてもよく、通常は、炭素数が１〜１２のアルキル基、炭素数が２〜１２のアルケニル基又は、炭素数が６〜１２のアリール基のいずれかである。 In formulas (3) to (6), R represents a monovalent hydrocarbon group having 1 to 12 carbon atoms. Each R may be the same or different, and is usually either an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. is there.
アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ブチル基、ヘキシル基、オクチル基、ドデシル基等が挙げられ、中でもメチル基が好ましい。アルケニル基としては、ビニル基、ブテニル基、アリール基等が挙げられる。アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基等が挙げられ、中でもフェニル基が好ましい。尚、アリール基にはメチル基、エチル基、メトキシ基、エトキシ基などの炭素数１〜４のアルキル基やアルコキシ基が１〜２個結合していてもよい。 Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, and among them, a methyl group is preferable. Examples of the alkenyl group include a vinyl group, a butenyl group, and an aryl group. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, and a tolyl group, and among them, a phenyl group is preferable. In addition, 1 to 2 alkyl groups or alkoxy groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a methoxy group, and an ethoxy group may be bonded to the aryl group.
また上記式において、Ｓｉ−Ｏ―の酸素原子は、水素原子や炭化水素基と結合して水酸基や炭化水素オキシ基を形成するか、または２個のＳｉ−Ｏ―が結合してＳｉ−Ｏ―Ｓｉ結合を形成している。酸素原子に結合する炭化水素基としては、上記式にＲとして示したものと同様のものが挙げられる。 In the above formula, the oxygen atom of Si—O— is bonded to a hydrogen atom or a hydrocarbon group to form a hydroxyl group or a hydrocarbon oxy group, or two Si—O— are bonded to form Si—O—. -A Si bond is formed. Examples of the hydrocarbon group bonded to the oxygen atom are the same as those shown as R in the above formula.
本発明では上述したシリコーンレジンのうち、珪素原子に直接または酸素原子を介して結合している有機基、即ちＳｉ―Ｃ又はＳｉ−Ｏ−Ｃ結合を形成している有機基のうち４０モル％以上、好ましくは５０モル％以上が、置換されていてもよいアリール基、好ましくはフェニル基であるものを用いる。 In the present invention, among the above-described silicone resins, 40 mol% of organic groups bonded to silicon atoms directly or through oxygen atoms, that is, organic groups forming Si—C or Si—O—C bonds. As described above, those in which 50 mol% or more is an optionally substituted aryl group, preferably a phenyl group, are used.
アリール基の含有量が４０モル％に満たなシリコーンレジンは、熱可塑性ポリエステル樹脂への相溶性が低く、得られる樹脂組成物が所望の高い難燃性を示さない場合がある。よってアリール基の含有量は該有機基の８０モル％以上、中でも１００％であることが好ましい。尚、アリール基の含有率も２９Ｓｉ−ＮＭＲによって測定可能であり、アリール−Ｓｉ及びＳｉ―Ｏ―アリールに帰属するピーク面積比から含有率を算出できる。 Silicone resins having an aryl group content of less than 40 mol% have low compatibility with thermoplastic polyester resins, and the resulting resin composition may not exhibit the desired high flame retardancy. Therefore, the aryl group content is preferably 80 mol% or more, more preferably 100% of the organic group. The content of the aryl group can also be measured by 29 Si-NMR, and the content can be calculated from the peak area ratio attributed to aryl-Si and Si—O—aryl.
またシリコーンレジンは、水酸基を少量含有することで難燃性が向上する場合がある。水酸基の含有量はシリコーンレジンの１〜１０重量％、中でも２〜８重量％であることが好ましい。尚、シリコーンレジンは単独で、又は２種以上を任意の割合で併用してもよい。 In addition, the silicone resin may improve flame retardancy by containing a small amount of hydroxyl groups. The content of the hydroxyl group is preferably 1 to 10% by weight, particularly 2 to 8% by weight of the silicone resin. In addition, you may use a silicone resin individually or in combination of 2 or more types in arbitrary ratios.
オルガノシロキサン化合物は、熱可塑性ポリエステル樹脂１００重量部に対して、１．５〜１０重量部、好ましくは２〜７重量部配合する。配合量が少ないと所望の難燃性を示さない。逆に配合量が多すぎても難燃性が低下する。これは樹脂組成物中のオルガノシロキサン化合物の量が多くなると、樹脂組成物の燃焼に際し気化したオルガノシロキサン化合物自体が燃焼し、かえって難燃性を低下させるためと考えられる。 The organosiloxane compound is blended in an amount of 1.5 to 10 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin. When the blending amount is small, the desired flame retardancy is not exhibited. Conversely, if the amount is too large, the flame retardancy is reduced. This is presumably because when the amount of the organosiloxane compound in the resin composition increases, the organosiloxane compound itself that is vaporized during the combustion of the resin composition burns, thereby reducing the flame retardancy.
（Ｄ）繊維状強化材：
繊維状強化材としては、熱可塑性樹脂に配合して剛性その他の機械的物性改良に用いられているガラス繊維、炭素繊維の他、玄武岩繊維、チタン酸カリウム繊維等の従来公知の任意のウイスカーを用いることができる。中でもガラス繊維又は炭素繊維が好ましい。
(D) Fibrous reinforcement:
As the fibrous reinforcement, any conventionally known whisker such as basalt fiber, potassium titanate fiber, etc. is used in addition to glass fiber and carbon fiber, which are mixed with thermoplastic resin and used for improvement of rigidity and other mechanical properties. Can be used. Of these, glass fiber or carbon fiber is preferred.
繊維状強化材は、その直径が太過ぎると柔軟性が低下し、また１μｍ未満の様に細すぎるものは大量入手が難しく、化学産業レベルでの使用は困難である。よってその直径は１〜１００μｍ、中でも２〜５０μｍであることが好ましい。入手が容易で且つ強化材としての効果も大きい点で、平均直径が３〜３０μｍ、特に５〜２０μｍのものが、特に好ましい。尚、繊維状強化材は通常は円形断面であるが、まゆ型や扁平形状などの異型断面形状のものであってもよい。 When the diameter of the fibrous reinforcing material is too large, the flexibility is lowered, and when the fibrous reinforcing material is too thin, such as less than 1 μm, it is difficult to obtain a large amount and it is difficult to use at the chemical industry level. Therefore, the diameter is preferably 1 to 100 μm, more preferably 2 to 50 μm. An average diameter of 3 to 30 [mu] m, particularly 5 to 20 [mu] m is particularly preferable because it is easily available and has a great effect as a reinforcing material. The fibrous reinforcing material usually has a circular cross section, but may have a different cross sectional shape such as an eyebrow shape or a flat shape.
繊維状強化材の長さは、補強効果の観点から０．１ｍｍ以上であることが好ましい。一般に長い方が補強効果が大きい反面、長い繊維状強化材は溶融混練により樹脂組成物を調製する際、折損して短くなる。よって２０ｍｍ以上の長さのものを用いても、その効果は一般的に低いので、通常は平均長さ０．３〜５ｍｍのものを用いればよい。繊維状強化材は、通常はこれらの繊維を多数本集束したものを、所定の長さに切断したチョップドストランドとして樹脂組成物の調製に供する。なお炭素繊維の配合は樹脂組成物に導電性を付与するので、高電気抵抗の樹脂組成物を所望の場合にはガラス繊維を用いる。 The length of the fibrous reinforcing material is preferably 0.1 mm or more from the viewpoint of the reinforcing effect. In general, the longer the reinforcing effect, the longer the fibrous reinforcing material, but when the resin composition is prepared by melt-kneading, it breaks and becomes shorter. Therefore, even when a length of 20 mm or more is used, the effect is generally low, and therefore, a mean length of 0.3 to 5 mm is usually used. The fibrous reinforcing material is usually used to prepare a resin composition as a chopped strand obtained by cutting a number of these fibers into a predetermined length. In addition, since mixing | blending of carbon fiber provides electroconductivity to a resin composition, glass fiber is used when the resin composition of high electrical resistance is desired.
繊維状強化材は、ポリエステル樹脂１００重量部に対して５〜８０重量部配合する。配合量が５重量部未満では補強効果が小さく、逆に８０重量部を超えると樹脂組成物の耐衝撃性などの機械的物性が低下するようになる。繊維状強化材の好ましい配合量は２０〜７０重量部である。 The fibrous reinforcing material is blended in an amount of 5 to 80 parts by weight with respect to 100 parts by weight of the polyester resin. If the blending amount is less than 5 parts by weight, the reinforcing effect is small. Conversely, if it exceeds 80 parts by weight, mechanical properties such as impact resistance of the resin composition are lowered. A preferable blending amount of the fibrous reinforcing material is 20 to 70 parts by weight.
（Ｅ）ホウ酸金属塩：
本発明においては、上述した（Ａ）〜（Ｄ）に加えて更に、ホウ酸金属塩を用いてもよい。ホウ酸金属塩を形成するホウ酸としては、オルトホウ酸、メタホウ酸等の非縮合ホウ酸、ピロホウ酸、四ホウ酸、五ホウ酸及び八ホウ酸等の縮合ホウ酸、並びに塩基性ホウ酸等が好ましい。これらと塩を形成する金属はアルカリ金属でもよいが、中でもアルカリ土類金属、遷移金属、周期律表２Ｂ族金属等の多価金属が好ましい。またホウ酸金属塩は水和物であってもよい。
(E) Metal borate:
In the present invention, in addition to the above-described (A) to (D), a metal borate may be further used. Examples of boric acid forming a boric acid metal salt include non-condensed boric acid such as orthoboric acid and metaboric acid, condensed boric acid such as pyroboric acid, tetraboric acid, pentaboric acid and octaboric acid, and basic boric acid. Is preferred. The metal that forms a salt with these may be an alkali metal, but among them, polyvalent metals such as alkaline earth metals, transition metals, and Group 2B metals of the periodic table are preferred. The metal borate may be a hydrate.
ホウ酸金属塩としては、非縮合ホウ酸金属塩と、縮合ホウ酸金属塩とがある。非縮合ホウ酸金属塩としては、オルトホウ酸カルシウム、メタホウ酸カルシウム等のアルカリ土類金属ホウ酸塩；オルトホウ酸マンガン、メタホウ酸銅等の遷移金属ホウ酸塩；メタホウ酸亜鉛、メタホウ酸カドミウム等の周期律表２Ｂ族金属のホウ酸塩などが挙げられる。これらのなかではメタホウ酸塩が好ましい。 Examples of the boric acid metal salt include a non-condensed boric acid metal salt and a condensed boric acid metal salt. Non-condensed borate metal salts include alkaline earth metal borates such as calcium orthoborate and calcium metaborate; transition metal borates such as manganese orthoborate and copper metaborate; zinc metaborate and cadmium metaborate Examples thereof include borate salts of Group 2B metals of the periodic table. Of these, metaborate is preferred.
縮合ホウ酸塩としては、四ホウ酸三マグネシウム、ピロホウ酸カルシウム等のアルカリ土類金属ホウ酸塩；四ホウ酸マンガン、二ホウ酸ニッケル等の遷移金属ホウ酸塩；四ホウ酸亜鉛、四ホウ酸カドミウム等の周期律表２Ｂ族金属のホウ酸塩等が挙げられる。塩基性ホウ酸塩としては塩基性ホウ酸亜鉛、塩基性ホウ酸カドミウム等の周期律表２Ｂ族金属の塩基性ホウ酸塩等が挙げられる。またこれらのホウ酸塩に対応するホウ酸水素塩（例えばオルトホウ酸水素マンガン等）も使用できる。 Condensed borates include alkaline earth metal borates such as trimagnesium tetraborate and calcium pyroborate; transition metal borates such as manganese tetraborate and nickel diborate; zinc tetraborate and tetraborate Examples thereof include borate salts of group 2B metals of the periodic table such as cadmium acid. Examples of the basic borate include basic borates of Group 2B metals of the periodic table such as basic zinc borate and basic cadmium borate. In addition, hydrogen borates corresponding to these borates (such as manganese orthoborate) can also be used.
本発明に用いるホウ酸金属塩としては、アルカリ土類金属又は周期律表２Ｂ族金属塩、例えばホウ酸亜鉛類やホウ酸カルシウム類を用いるのが好ましい。ホウ酸亜鉛類には、ホウ酸亜鉛（２ＺｎＯ・３Ｂ２Ｏ３）やホウ酸亜鉛・３．５水和物（２ＺｎＯ・３Ｂ２Ｏ３・３．５Ｈ２Ｏ）等が含まれ、ホウ酸カルシウム類にはホウ酸カルシウム（２ＣａＯ・３Ｂ２Ｏ３）やホウ酸カルシウム・５水和物（２ＣａＯ・３Ｂ２Ｏ３・５Ｈ２Ｏ）等が含まれる。これらホウ酸亜鉛類やホウ酸カルシウム類の中でも特に水和物が好ましい。 As the boric acid metal salt used in the present invention, it is preferable to use an alkaline earth metal or a Group 2B metal salt of the periodic table such as zinc borate or calcium borate. The zinc borate compounds, include such as zinc borate (2ZnO · 3B 2 O 3) and zinc borate · 3.5 hydrate (2ZnO · 3B 2 O 3 · 3.5H 2 O) is boric acid The calcium includes calcium borate (2CaO · 3B 2 O 3 ), calcium borate · pentahydrate (2CaO · 3B 2 O 3 · 5H 2 O) and the like. Among these zinc borates and calcium borates, hydrates are particularly preferable.
ホウ酸金属塩の配合により、樹脂組成物の燃焼阻止作用が向上する。現象的には、燃焼に際し発泡して未燃焼部分を炎から遮断する。ホウ酸金属塩の配合量は、熱可塑性ポリエステル樹脂１００重量部に対して０〜２０重量部であるが、配合効果を発現させるためには１重量部以上配合することが好ましいが、過剰に配合しても添加量増加に見合う効果の向上は頭打ちとなるので、ホウ酸金属塩の配合量は熱可塑性ポリエステル樹脂１００重量部に対して１〜１０重量部、中でも１〜５重量部であることが好ましい。 By adding the boric acid metal salt, the combustion inhibiting action of the resin composition is improved. Phenomenologically, it foams during combustion and blocks the unburned part from the flame. The compounding amount of the boric acid metal salt is 0 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin, but it is preferable to add 1 part by weight or more in order to express the compounding effect, but the compounding is excessive. However, since the improvement in the effect commensurate with the increase in the amount of addition becomes a peak, the compounding amount of the boric acid metal salt is 1 to 10 parts by weight, especially 1 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin. Is preferred.
更に本発明の樹脂組成物には、本発明の目的を損なわない範囲で、熱可塑性樹脂組成物に常用されている種々の添加剤を添加することができる。このような添加剤としては、酸化防止剤、紫外線吸収剤、光安定剤等の安定剤、耐加水分解抑制剤（エポキシ化合物、カルボジイミド化合物など）、帯電防止剤、滑剤、離型剤、染料や顔料等の着色剤、可塑剤などが挙げられる。特に酸化防止剤及び離型剤の添加は効果的である。 Furthermore, various additives commonly used in thermoplastic resin compositions can be added to the resin composition of the present invention within a range that does not impair the object of the present invention. Examples of such additives include stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, hydrolysis inhibitors (epoxy compounds, carbodiimide compounds, etc.), antistatic agents, lubricants, mold release agents, dyes, Colorants such as pigments, plasticizers and the like can be mentioned. In particular, the addition of an antioxidant and a release agent is effective.
また、乳化重合法で得られたポリテトラフルオロエチレンやヒュームドコロイダルシリカなどを添加して、燃焼時の滴下防止をより確実にすることもできる。 Moreover, polytetrafluoroethylene obtained by an emulsion polymerization method, fumed colloidal silica, or the like can be added to further prevent dripping during combustion.
本発明の難燃性ポリエステル樹脂組成物は、更に他の熱可塑性樹脂を補助的に用いてもよく、高温において安定な樹脂であれば使用可能であり、具体的には例えばポリカーボネート、ポリアミド、ポリフェニレンオキサイド、ポリスチレン系樹脂、ポリフェニレンサルファイドエチレン、ポリサルホン、ポリエーテルサルホン、ポリエーテルイミド、ポリエーテルケトン、フッ素樹脂等が挙げられる。 The flame retardant polyester resin composition of the present invention may be supplemented with other thermoplastic resins, and can be used as long as the resin is stable at high temperatures. Specifically, for example, polycarbonate, polyamide, polyphenylene Examples thereof include oxides, polystyrene resins, polyphenylene sulfide ethylene, polysulfone, polyether sulfone, polyether imide, polyether ketone, and fluororesin.
本発明の樹脂組成物の調製は、樹脂組成物調製の常法に従って行うことができる。通常は（Ａ）〜（Ｅ）の各成分及び所望により添加される種々の添加剤を一緒にしてよく混合し、次いで一軸又は二軸押出機で溶融混練する。また各成分を予め混合することなく、ないしはその一部のみを予め混合し、フイーダーを用いて押出機に供給して溶融混練し、本発明の樹脂組成物を調製することもできる。さらには、ポリエステル樹脂の一部に他の成分の一部を配合したものを溶融混練してマスターバッチを調製し、次いでこれに残りのポリエステル樹脂や他の成分を配合して溶融混練してもよい。 Preparation of the resin composition of this invention can be performed in accordance with the conventional method of resin composition preparation. Usually, the components (A) to (E) and various additives added as desired are mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Also, the resin composition of the present invention can be prepared by mixing each component in advance or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them. Further, a master batch is prepared by melting and kneading a part of a polyester resin and a part of other components, and then the remaining polyester resin and other ingredients are blended and melt kneaded. Good.
そして本発明の樹脂組成物を用いた樹脂成形品は、従来公知の任意の熱可塑性樹脂の成形方法に、上述してきた本発明の難燃性熱可塑性ポリエステル樹脂を適用して、得ることが出来る。 A resin molded article using the resin composition of the present invention can be obtained by applying the above-described flame-retardant thermoplastic polyester resin of the present invention to any conventionally known thermoplastic resin molding method. .
以下、実施例により本発明を更に具体的に説明するが、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。尚、樹脂組成物の評価は、以下の方法により行った。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The resin composition was evaluated by the following method.
曲げ強度：
厚さ１．６ｍｍのＵＬ９４（アンダーライターズラボラトリーズのサブジェクト９４）燃焼試験片を射出成形し、これを用いてスパン間４０ｍｍ、試験速度２ｍｍ／ｍｉｎの条件にて曲げ試験を実施した。
Bending strength:
A UL94 (Subject 94 of Underwriters Laboratories) combustion test piece having a thickness of 1.6 mm was injection-molded, and a bending test was performed using this with a span interval of 40 mm and a test speed of 2 mm / min.
ウエルド曲げ強度：
上述の曲げ強度試験で用いたのと同じ金型に、試験片の両側長手方向からの２点ゲートで樹脂を射出して、試験片中央部にウエルドラインが形成された厚さ１．６ｍｍのＵＬ９４燃焼試験片を射出成形し、これを用いて上述の曲げ強度試験の際と同じ条件にてウエルド曲げ試験を実施した。
ウエルド保持率は、（ウエルド有りの試験片の曲げ強度／ウエルド無しの試験片の曲げ強度）ｘ１００％で算出した。
Weld bending strength:
Resin was injected into the same mold used in the above bending strength test with a two-point gate from the longitudinal direction on both sides of the test piece, and a weld line was formed at the center of the test piece with a thickness of 1.6 mm A UL94 combustion test piece was injection-molded, and a weld bend test was performed under the same conditions as in the bending strength test described above.
The weld retention was calculated by (bending strength of test piece with weld / bending strength of test piece without weld) × 100%.
難燃性テスト：
ＵＬ９４の方法に準じ、５本の試験片（厚さ０．８ｍｍ）を用いて難燃性テストを行い、ＵＬ９４記載の評価方法に従い、Ｖ−０、Ｖ−１、Ｖ−２、ＨＢに分類した（Ｖ−０が最も難燃性が高いことを示す）。Ｔｏｔａｌ燃焼時間は、５本の合計燃焼時間（第一接炎時、第二接炎時の燃焼時間を含む）である。
Flame retardant test:
According to the method of UL94, a flame retardancy test is performed using five test pieces (thickness 0.8 mm), and classified into V-0, V-1, V-2, and HB according to the evaluation method described in UL94. (V-0 indicates the highest flame retardancy). The total combustion time is a total of five combustion times (including the combustion time at the time of first flame contact and the time of second flame contact).
比較トラッキング指数試験（略称：ＣＴＩ試験）：
試験片（厚さ３ｍｍの平板）について、国際規格ＩＥＣ６０１１２に定める試験法によりＣＴＩを決定した。ＣＴＩは固体電気絶縁材料の表面に電界が加わった状態で湿潤汚染されたとき、１００Ｖから６００Ｖの間の２５Ｖ刻みの電圧におけるトラッキングに対する対抗性を示すものであり、数値が高いほど良好であることを意味する。ＣＴＩは５００Ｖ以上であるのが好ましい。
Comparative tracking index test (abbreviation: CTI test):
For the test piece (a flat plate having a thickness of 3 mm), the CTI was determined by the test method defined in International Standard IEC60112. CTI indicates the resistance to tracking at a voltage in increments of 25 V between 100 V and 600 V when wet-contaminated with an electric field applied to the surface of a solid electrical insulating material. The higher the value, the better. Means. The CTI is preferably 500 V or higher.
モールドデポジット：
射出成形機として住友重機械（株）製ＳＥ５０を用い、射出圧力５０ＭＰａ射出速度８０ｍｍ／ｓｅｃ、シリンダー温度２６０℃、射出時間３ｓｅｃ、冷却８ｓｅｃ、金型温度８０℃、ザックバック３ｍｍの条件で、長さ３５ｍｍ、幅１４ｍｍ、厚さ２ｍｍの樹脂成形品をピンゲート金型を用いて製造した。
Mold deposit:
Using SE50 manufactured by Sumitomo Heavy Industries, Ltd. as an injection molding machine, injection pressure 50 MPa, injection speed 80 mm / sec, cylinder temperature 260 ° C., injection time 3 sec, cooling 8 sec, mold temperature 80 ° C., zack back 3 mm A resin molded product having a thickness of 35 mm, a width of 14 mm, and a thickness of 2 mm was produced using a pin gate mold.
この条件で連続的に射出成形し、１０００ショット実施後、金型に付着しているモールドデポジットの状態（金型汚染性）を肉眼で観察し、次の判定基準に従って評価した。
◎；モールドデポジットがほとんど認められない。
○；モールドデポジットがうっすらと認められる。
△；モールドデポジットがはっきりと認められる。
×；モールドデポジットが金型全面に厚く付着している。
Continuous injection molding was performed under these conditions, and after 1000 shots, the state of the mold deposit (mold contamination) adhered to the mold was observed with the naked eye and evaluated according to the following criteria.
A: Mold deposit is hardly recognized.
○: Mold deposit is slightly recognized.
Δ: Mold deposit is clearly recognized.
X: The mold deposit is thickly attached to the entire mold surface.
離型性：
樹脂温度２７０℃、金型温度８０℃、サイクル２５秒の条件で、ファナック製射出成形機（α−１００ｉＡ）を用いて、浅いコップ形状（肉厚３ｍｍ、外径１００ｍｍ、深さ２０ｍｍ）の成形品を連続射出成形し、突き出しピンの痕の有無を目視観察することにより離型性を測定した。ピンの痕がはっきりと認められるものを×、かすかに認められるものを○、認められないものを◎とした。
Release properties:
Molding in shallow cup shape (wall thickness 3mm, outer diameter 100mm, depth 20mm) using FANUC injection molding machine (α-100iA) under conditions of resin temperature 270 ° C, mold temperature 80 ° C, cycle 25 seconds The product was continuously injection-molded, and the releasability was measured by visually observing the presence or absence of protrusion pins. The pin mark was clearly recognized as x, the faintly recognized mark as ◯, and the pin mark as unacceptable as ◎.
実施例で使用した原料は、以下の通りである。 The raw materials used in the examples are as follows.
（Ａ）熱可塑性ポリエステル樹脂：
（Ａ―１）ＰＢＴ：５０２０三菱エンジニアリングプラスチックス社製 ノバデュラン（登録商標）５０２０、固有粘度１．２０ｄｌ／ｇのポリブチレンテレフタレート樹脂
(A) Thermoplastic polyester resin:
(A-1) PBT: 5020 Polybutylene terephthalate resin made by Mitsubishi Engineering Plastics Co., Ltd. Novaduran (registered trademark) 5020, intrinsic viscosity 1.20 dl / g
（Ａ―２）ＰＢＴ：５００８三菱エンジニアリングプラスチックス社製 ノバデュラン（登録商標）５００８、固有粘度０．８５ｄｌ／ｇのポリブチレンテレフタレート樹脂 (A-2) PBT: 5008 Polybutylene terephthalate resin made by Mitsubishi Engineering Plastics Co., Ltd. Novaduran (registered trademark) 5008, inherent viscosity 0.85 dl / g
（Ｂ）ホスフィン酸塩：
ジエチルホスフィン酸アルミニウム：クラリアント社製 ＯＰ１２４０（商品名）
(B) Phosphinate:
Aluminum diethylphosphinate: OP1240 (trade name) manufactured by Clariant
（Ｃ）オルガノシロキサン化合物：
（Ｃ−１）シリコーン化合物−１：東レ・ダウコーニング・シリコーン社製 ２１７Ｆｌａｋｅ（商品名）、重量平均分子量（Ｍｗ）：２０００、水酸基含有量：７重量（ｗｔ）％フェニル基含有量：１００モル％、平均分子式：（ＰｈＳｉＯ３／２）１．０（ＨＯ１／２）０．５７
(C) Organosiloxane compound:
(C-1) Silicone compound-1: 217 Flake (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., weight average molecular weight (Mw): 2000, hydroxyl group content: 7 wt (wt)% phenyl group content: 100 mol %, Average molecular formula: (PhSiO 3/2 ) 1.0 (HO 1/2 ) 0.57
（Ｃ−２）シリコーン化合物−２：東レ・ダウコーニング・シリコーン社製 ＴＭＳ２１７（商品名）、Ｍｗ：２０００、水酸基含有量：２ｗｔ％フェニル基含有量：１００モル％、Ｃ−１のシリコーン化合物にトリメチルシリル基で末端封止処理を施したシリコーンレジン (C-2) Silicone compound-2: TMS217 (trade name) manufactured by Toray Dow Corning Silicone Co., Mw: 2000, hydroxyl group content: 2 wt% phenyl group content: 100 mol%, C-1 silicone compound Silicone resin end-capped with trimethylsilyl groups
（Ｃ−３）シリコーン化合物−３：小西化学工業製 ＳＲ−２１（商品名）、Ｍｗ：３８００、水酸基含有量：６ｗｔ％フェニル基含有量：１００モル％、平均分子式：（ＰｈＳｉＯ３／２）１．０（ＨＯ１／２）０．４８ (C-3) Silicone compound-3: SR-21 (trade name) manufactured by Konishi Chemical Industry, Mw: 3800, hydroxyl group content: 6 wt% phenyl group content: 100 mol%, average molecular formula: (PhSiO3 / 2 ) 1.0 (HO 1/2 ) 0.48
（Ｃ−４）シリコーン化合物−４：小西化学工業製 ＳＲ−２０（商品名）、Ｍｗ：６７００、水酸基含有量：３ｗｔ％フェニル基含有量：１００モル％、平均分子式：（ＰｈＳｉＯ３／２）１．０（ＨＯ１／２）０．２４ (C-4) Silicone compound-4: SR-20 (trade name) manufactured by Konishi Chemical Industry, Mw: 6700, hydroxyl group content: 3 wt% phenyl group content: 100 mol%, average molecular formula: (PhSiO3 / 2 ) 1.0 (HO 1/2 ) 0.24
（Ｃ−５）シリコーン化合物−５：東レ・ダウコーニング・シリコーン社製 ＳＨ６０１８（商品名）、Ｍｗ：２０００、水酸基含有量：６ｗｔ％フェニル基含有量：７０モル％、プロピル基３０モル％、平均分子式：（ＰｈＳｉＯ３／２）０．７（ＰｒｏＳｉＯ３／２）０．３（ＨＯ１／２）０．４８ (C-5) Silicone compound-5: SH6018 (trade name) manufactured by Toray Dow Corning Silicone Co., Mw: 2000, hydroxyl group content: 6 wt% phenyl group content: 70 mol%, propyl group 30 mol%, average Molecular formula: (PhSiO 3/2 ) 0.7 (ProSiO 3/2 ) 0.3 (HO 1/2 ) 0.48
（Ｃ−６）シリコーン化合物−６：信越化学工業社製 Ｘ４０−９８０５（商品名）、メチルフェニル系オルガノシロキサン（フェニル基含有量５０モル％前後） (C-6) Silicone compound-6: X40-9805 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., methylphenyl organosiloxane (phenyl group content around 50 mol%)
（Ｃ−７）シリコーン化合物−７：東レ・ダウコーニング・シリコーン社製 Ｚ６８００（商品名）、トリフェニルシラノール（フェニル基含有量１００モル％） (C-7) Silicone compound-7: Z6800 (trade name) manufactured by Toray Dow Corning Silicone Co., triphenylsilanol (phenyl group content 100 mol%)
（Ｃ−８）シリコーン化合物−８：信越化学工業社製、オクタフェニルテトラシクロシロキサン（フェニル基含有量１００モル％） (C-8) Silicone compound-8: manufactured by Shin-Etsu Chemical Co., Ltd., octaphenyltetracyclosiloxane (phenyl group content: 100 mol%)
（Ｃ−９）シリコーン化合物−９：信越化学工業社製 ＫＲ−５１１（商品名）、メチルフェニル系シリコーンオリゴマー（フェニル基含有量５０モル％前後） (C-9) Silicone compound-9: KR-511 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., methylphenyl silicone oligomer (phenyl group content around 50 mol%)
（Ｃ−１０）シリコーン化合物−１０：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製 ＴＳＲ１６５（商品名）、ポリメチルフェニルメトキシシロキサン（フェニル基含有量５０モル％前後） (C-10) Silicone compound-10: TSR165 (trade name) manufactured by Momentive Performance Materials Japan, polymethylphenylmethoxysiloxane (phenyl group content around 50 mol%)
（Ｃ−１１）シリコーン化合物−１１：東レ・ダウコーニング・シリコーン社製 ＳＨ２００（商品名）、ポリジメチルシロキサン（水酸基含有量０ｗｔ％、フェニル基含有量０モル％、粘度６００００センチストークス） (C-11) Silicone compound-11: SH200 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., polydimethylsiloxane (hydroxyl group content 0 wt%, phenyl group content 0 mol%, viscosity 60000 centistokes)
（Ｄ）ガラス繊維：オーエンス・コーニング社製 ０３ＪＡ−ＦＴ５９２（商品名）、直径１０．５μｍ (D) Glass fiber: 03JA-FT592 (trade name) manufactured by Owens Corning, diameter 10.5 μm
（Ｅ）ホウ酸亜鉛：ＢＯＲＡＸ社製 Ｆｉｒｅｂｒａｋｅ５００（商品名）、Ｂ２Ｏ３５６．２ｗｔ％、ＺｎＯ４３．８ｗｔ％、粒径１０μｍ (E) Zinc borate: Firebrake 500 (trade name), B 2 O 3 56.2 wt%, ZnO 43.8 wt%, particle size 10 μm, manufactured by BORX
（Ｆ）その他の添加剤
（Ｆ−１）シアヌル酸メラミン：日本合成化学社製 ＭＸ４４（商品名）
(F) Other additives (F-1) Melamine cyanurate: Nippon Synthetic Chemical Co., Ltd. MX44 (trade name)
（Ｆ−２）フッ素系樹脂：住友３Ｍ社製 ＴＦ１７５０（商品名） (F-2) Fluororesin: Sumitomo 3M TF1750 (trade name)
（Ｆ−３）酸化防止剤：チバ・スペシャリティーケミカルズ社製 フェノール系酸化防止剤 イルガノックス１０１０（商品名） (F-3) Antioxidant: Phenol type antioxidant Irganox 1010 (trade name) manufactured by Ciba Specialty Chemicals
（Ｆ−４）リン系安定剤：旭電化社製 アデカスタブＰＥＰ３６（商品名） (F-4) Phosphorous stabilizer: ADK STAB PEP36 (trade name) manufactured by Asahi Denka Co., Ltd.
（Ｆ−５）離型剤：日本精鑞社製 パラフィンワックス ＦＴ１００（商品名） (F-5) Release agent: Paraffin wax FT100 (trade name) manufactured by Nippon Seiki Co., Ltd.
［実施例１〜１６及び比較例１〜９］
表１に示す重量比で、ガラス繊維以外の成分を一括してスーパーミキサー（新栄機械社製ＳＫ−３５０型）で混合し、混合物をＬ／Ｄ＝４２の２軸押出機（日本製鋼所社製、ＴＥＸ３０ＨＳＳＴ）のホッパーに投入し、ガラス繊維をサイドフィードして、吐出量２０ｋｇ／ｈ、スクリュー回転数２５０ｒｐｍ、バレル温度２６０℃の条件下で押出して、ポリブチレンテレフタレート樹脂組成物のペレットを得た。
[Examples 1 to 16 and Comparative Examples 1 to 9]
In the weight ratio shown in Table 1, components other than glass fiber are mixed together with a super mixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.), and the mixture is L / D = 42 twin screw extruder (Nippon Steel Works, Ltd.). Made of TEX30HSST), side feed the glass fiber, and extrude under the conditions of discharge rate 20kg / h, screw rotation speed 250rpm, barrel temperature 260 ° C to obtain pellets of polybutylene terephthalate resin composition It was.
この樹脂組成物ペレットから、射出成形機（住友重機械工業社製 型式ＳＥ５０）を用い、樹脂温度２６０℃、金型温度８０℃で、厚さ１．６ｍｍのＵＬ９４規格の燃焼試験片とウエルドラインを有する燃焼試験片（曲げ試験片として使用）、厚さ０．８ｍｍのＵＬ９４規格の燃焼試験片、及び比較トラッキング指数用試験片（縦横それぞれ１０ｃｍ、厚さ３ｍｍの平板試験片）を製造し、同時にこの成形条件でのモールドデポジット評価及び離型性評価を実施した。評価結果を表１に示す。 From this resin composition pellet, using an injection molding machine (model SE50 manufactured by Sumitomo Heavy Industries, Ltd.), a resin temperature of 260 ° C., a mold temperature of 80 ° C., and a thickness of 1.6 mm UL94 standard combustion test piece and weld line A combustion test piece having a thickness (used as a bending test piece), a UL94 standard combustion test piece with a thickness of 0.8 mm, and a comparative tracking index test piece (10 cm in length and width, a flat plate test piece with a thickness of 3 mm), At the same time, mold deposit evaluation and releasability evaluation were performed under these molding conditions. The evaluation results are shown in Table 1.
表１より以下のことが明白となる。即ち、比較例の樹脂組成物は、難燃性、ウエルド保持率、ＣＴＩそしてモールドデポジット、離型性の何れかが劣っており、物性バランスがよくない。これに対し本発明の難燃性熱可塑性ポリエステル樹脂組成物は、何れの物性も良好である。 From Table 1, the following becomes clear. That is, the resin composition of the comparative example is inferior in any of flame retardancy, weld retention, CTI, mold deposit and releasability, and the physical property balance is not good. On the other hand, the flame-retardant thermoplastic polyester resin composition of the present invention has good physical properties.
本発明の難燃性熱可塑性ポリエステル樹脂組成物を成形して得られる樹脂成形体は、優れた難燃性、ウエルド強度保持率、ＣＴＩ、離型性を有している。モールドデポジットの発生も殆ど無く、生産性に優れている。したがって本発明の樹脂組成物は、電気電子部品、例えばコネクター、ターミナルなどの広範囲の部品に特に好適に適用できる。また自動車部品や建材部品などにも好適に適用できる。 The resin molding obtained by molding the flame retardant thermoplastic polyester resin composition of the present invention has excellent flame retardancy, weld strength retention, CTI, and mold release properties. There is almost no mold deposit and the productivity is excellent. Therefore, the resin composition of the present invention can be particularly suitably applied to a wide range of parts such as electric and electronic parts such as connectors and terminals. It can also be suitably applied to automobile parts and building material parts.
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| JP2008277459A JP5357505B2 (en) | 2008-10-28 | 2008-10-28 | Flame retardant thermoplastic polyester resin composition |
| US13/055,407 US8796367B2 (en) | 2008-07-23 | 2009-07-22 | Thermoplastic polyester resin composition |
| CN200980128698.2A CN102105532B (en) | 2008-07-23 | 2009-07-22 | Thermoplastic polyester resin composition |
| EP09800207A EP2314643B1 (en) | 2008-07-23 | 2009-07-22 | Thermoplastic polyester resin composition |
| EP09800206A EP2308927B1 (en) | 2008-07-23 | 2009-07-22 | Thermoplastic polyester resin composition |
| PCT/JP2009/003420 WO2010010690A1 (en) | 2008-07-23 | 2009-07-22 | Thermoplastic polyester resin composition |
| CN2009801286963A CN102105531B (en) | 2008-07-23 | 2009-07-22 | Thermoplastic polyester resin composition |
| PCT/JP2009/003421 WO2010010691A1 (en) | 2008-07-23 | 2009-07-22 | Thermoplastic polyester resin composition |
| US13/055,420 US8338511B2 (en) | 2008-07-23 | 2009-07-22 | Thermoplastic polyester resin composition |
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| JP2001342357A (en) * | 2000-06-02 | 2001-12-14 | Polyplastics Co | Flame-retardant resin composition |
| JP2002161211A (en) * | 2000-11-24 | 2002-06-04 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
| JP2004537630A (en) * | 2001-08-07 | 2004-12-16 | ビーエーエスエフ アクチェンゲゼルシャフト | Halogen free flame retardant polyester |
| JP2005082723A (en) * | 2003-09-09 | 2005-03-31 | Mitsubishi Engineering Plastics Corp | Flame-retardant polycarbonate resin composition |
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| JP2000327886A (en) * | 1999-05-19 | 2000-11-28 | Polyplastics Co | Flame-retardant resin composition |
| JP2001342357A (en) * | 2000-06-02 | 2001-12-14 | Polyplastics Co | Flame-retardant resin composition |
| JP2002161211A (en) * | 2000-11-24 | 2002-06-04 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
| JP2004537630A (en) * | 2001-08-07 | 2004-12-16 | ビーエーエスエフ アクチェンゲゼルシャフト | Halogen free flame retardant polyester |
| JP2005082723A (en) * | 2003-09-09 | 2005-03-31 | Mitsubishi Engineering Plastics Corp | Flame-retardant polycarbonate resin composition |
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| KR101555808B1 (en) * | 2010-12-28 | 2015-09-24 | 데이진 듀폰 필름 가부시키가이샤 | Flame-retardant biaxially-oriented polyester film |
| KR101555770B1 (en) * | 2010-12-28 | 2015-09-25 | 데이진 듀폰 필름 가부시키가이샤 | Flame-retardant biaxially-oriented polyester film |
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