JP2022070452A - Polybutylene terephthalate resin composition, molded article made from polybutylene terephthalate resin composition, viscosity rise inhibitor of polybutylene terephthalate resin composition, and hydrolysis inhibitor of molded article made from polybutylene terephthalate resin composition - Google Patents
Polybutylene terephthalate resin composition, molded article made from polybutylene terephthalate resin composition, viscosity rise inhibitor of polybutylene terephthalate resin composition, and hydrolysis inhibitor of molded article made from polybutylene terephthalate resin composition Download PDFInfo
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- JP2022070452A JP2022070452A JP2020179523A JP2020179523A JP2022070452A JP 2022070452 A JP2022070452 A JP 2022070452A JP 2020179523 A JP2020179523 A JP 2020179523A JP 2020179523 A JP2020179523 A JP 2020179523A JP 2022070452 A JP2022070452 A JP 2022070452A
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- JP
- Japan
- Prior art keywords
- polybutylene terephthalate
- terephthalate resin
- quaternary ammonium
- resin composition
- dimensional accuracy
- 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.)
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- -1 Polybutylene terephthalate Polymers 0.000 title claims abstract description 151
- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 129
- 239000011342 resin composition Substances 0.000 title claims abstract description 76
- 239000003112 inhibitor Substances 0.000 title claims abstract description 40
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 35
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 110
- 239000011347 resin Substances 0.000 claims abstract description 110
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 60
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 229910045601 alloy Inorganic materials 0.000 claims description 26
- 239000000956 alloy Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 7
- 229940006460 bromide ion Drugs 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 238000000465 moulding Methods 0.000 description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000012765 fibrous filler Substances 0.000 description 7
- 208000029497 Elastoma Diseases 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 150000001718 carbodiimides Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000001053 orange pigment Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229920006127 amorphous resin Polymers 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 2
- 229910000568 zirconium hydride Inorganic materials 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- DCTMXCOHGKSXIZ-UHFFFAOYSA-N (R)-1,3-Octanediol Chemical class CCCCCC(O)CCO DCTMXCOHGKSXIZ-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- HRMCXDSWURAYFR-UHFFFAOYSA-N 3-phenoxyphthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=CC=CC=2)=C1C(O)=O HRMCXDSWURAYFR-UHFFFAOYSA-N 0.000 description 1
- JTGCXYYDAVPSFD-UHFFFAOYSA-N 4-(4-hydroxyphenyl)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=C(O)C=C1 JTGCXYYDAVPSFD-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- KTFUTPSBLYIILV-UHFFFAOYSA-N 6,6-dichlorohexan-1-amine Chemical compound NCCCCCC(Cl)Cl KTFUTPSBLYIILV-UHFFFAOYSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DUFKCOQISQKSAV-UHFFFAOYSA-N Polypropylene glycol (m w 1,200-3,000) Chemical class CC(O)COC(C)CO DUFKCOQISQKSAV-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 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
- 229930188620 butyrolactone Natural products 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- KKFPIBHAPSRIPB-UHFFFAOYSA-N cerium(3+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Ce+3].[Ce+3] KKFPIBHAPSRIPB-UHFFFAOYSA-N 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 229940115457 cetyldimethylethylammonium bromide Drugs 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 150000001793 charged compounds Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 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
- 239000003273 ketjen black Substances 0.000 description 1
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- 239000006233 lamp black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 description 1
- SYZCZDCAEVUSPM-UHFFFAOYSA-M tetrahexylazanium;bromide Chemical compound [Br-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC SYZCZDCAEVUSPM-UHFFFAOYSA-M 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- SPALIFXDWQTXKS-UHFFFAOYSA-M tetrapentylazanium;bromide Chemical compound [Br-].CCCCC[N+](CCCCC)(CCCCC)CCCCC SPALIFXDWQTXKS-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 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 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical class OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- 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 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ポリブチレンテレフタレート樹脂組成物、ポリブチレンテレフタレート樹脂組成物からなる成形品、ポリブチレンテレフタレート樹脂組成物の粘度上昇抑制剤、ポリブチレンテレフタレート樹脂組成物からなる成形品の加水分解抑制剤に関する。 The present invention relates to a polybutylene terephthalate resin composition, a molded product made of a polybutylene terephthalate resin composition, a viscosity increase inhibitor of the polybutylene terephthalate resin composition, and a hydrolysis inhibitor of a molded product made of a polybutylene terephthalate resin composition. ..
ポリブチレンテレフタレート（以下、「ＰＢＴ」とも呼ぶ）樹脂は、耐熱性、耐薬品性、電気特性、機械的特性、及び成形加工性などの種々の特性に優れるため、多くの用途に利用されている。 Polybutylene terephthalate (hereinafter, also referred to as "PBT") resin is used in many applications because it has excellent various properties such as heat resistance, chemical resistance, electrical properties, mechanical properties, and molding processability. ..
しかし、ポリブチレンテレフタレート樹脂は、結晶性樹脂であることから射出成形時の配向による収縮の異方性に起因する成形品の反り変形など、寸法精度の低下が生じうる。特に、ポリブチレンテレフタレート樹脂が繊維状充填剤を含む場合、ポリブチレンテレフタレート樹脂の分子配向だけでなく、繊維状充填剤の配向による収縮の異方性も発生しやすくなる。そこで、ポリブチレンテレフタレート樹脂に非晶性の樹脂やアスペクト比の小さい充填剤を添加することで、異方性を低減し、寸法精度を向上させることが検討されてきていた。 However, since the polybutylene terephthalate resin is a crystalline resin, dimensional accuracy may be reduced, such as warpage deformation of the molded product due to anisotropy of shrinkage due to orientation during injection molding. In particular, when the polybutylene terephthalate resin contains a fibrous filler, not only the molecular orientation of the polybutylene terephthalate resin but also the anisotropy of shrinkage due to the orientation of the fibrous filler is likely to occur. Therefore, it has been studied to reduce anisotropy and improve dimensional accuracy by adding an amorphous resin or a filler having a small aspect ratio to the polybutylene terephthalate resin.
また、ポリブチレンテレフタレート樹脂はポリエステル樹脂であることから、耐加水分解性の改善は耐久性向上に不可欠である。そのため、エポキシ系樹脂やカルボジイミドの添加等、添加剤による改良も従来からなされている。たとえば特許文献１には、非晶性樹脂とカルボジイミドを添加した、低反り性と耐加水分解性に優れるポリブチレンテレフタレート樹脂組成物が開示されている。 Further, since the polybutylene terephthalate resin is a polyester resin, improvement of hydrolysis resistance is indispensable for improvement of durability. Therefore, improvements with additives such as addition of epoxy resin and carbodiimide have been conventionally made. For example, Patent Document 1 discloses a polybutylene terephthalate resin composition having low warpage and excellent hydrolysis resistance, to which an amorphous resin and carbodiimide are added.
カルボジイミドは耐加水分解性の改善効果が非常に良好ではあるが、有毒なイソシアネートが発生する問題がある。また、エポキシ系樹脂の場合、耐加水分解性の改善効果が十分でなかったり、ＰＢＴのカルボン酸末端とエポキシ基が反応し粘度が上昇する場合があった。 Carbodiimide has a very good effect of improving hydrolysis resistance, but has a problem of generating toxic isocyanate. Further, in the case of an epoxy resin, the effect of improving hydrolysis resistance may not be sufficient, or the carboxylic acid terminal of PBT may react with an epoxy group to increase the viscosity.
なお、エポキシ系樹脂と開環触媒を組み合わせることは従来からよく知られている（特許文献２）。しかしながら、この文献において実際に開環触媒としての効果が示されているのはステアリン酸カルシウムのみである。 It has been well known to combine an epoxy resin and a ring-opening catalyst (Patent Document 2). However, only calcium stearate has actually been shown to be effective as a ring-opening catalyst in this document.
また、特許文献３には開環触媒が多数例示されている。４級アンモニウム塩としてはテトラブチルアンモニウムブロミドなどの記載はあるものの、特にステアリン酸ナトリウムが好ましいとの記載があり、４級アンモニウム塩の実際の評価はされてはいない。 Further, Patent Document 3 exemplifies a large number of ring-opening catalysts. Although there is a description such as tetrabutylammonium bromide as the quaternary ammonium salt, there is a description that sodium stearate is particularly preferable, and the actual evaluation of the quaternary ammonium salt has not been performed.
本発明は、寸法精度と耐加水分解性の改善効果に優れたポリブチレンテレフタレート樹脂組成物、成形品、ポリブチレンテレフタレート樹脂組成物の粘度上昇抑制剤、ポリブチレンテレフタレート樹脂組成物からなる成形品の加水分解抑制剤を提供することを課題とする。 INDUSTRIAL APPLICABILITY The present invention comprises a polybutylene terephthalate resin composition, a molded product, a polybutylene terephthalate resin composition viscosity increase inhibitor, and a polybutylene terephthalate resin composition, which are excellent in improving dimensional accuracy and hydrolysis resistance. An object of the present invention is to provide a hydrolysis inhibitor.
本発明者は、カルボン酸末端基が３５ｍｅｑ／ｋｇ以下のポリブチレンテレフタレート樹脂（Ａ）１００質量部に対し、エポキシ系樹脂（Ｂ）０．５質量部以上１０質量部以下と、第４級アンモニウム塩（Ｃ）と、寸法精度向上剤（Ｄ）を含有する、ポリブチレンテレフタレート樹脂組成物、上記のポリブチレンテレフタレート樹脂組成物からなる成形品、第４級アンモニウム塩を含有するポリブチレンテレフタレート樹脂組成物の粘度上昇抑制剤、第４級アンモニウム塩を含有するポリブチレンテレフタレート樹脂組成物からなる成形品の加水分解抑制剤により、上記の課題を解決できることを見出し、本発明を完成させるに至った。 The present inventor has 100 parts by mass of polybutylene terephthalate resin (A) having a carboxylic acid terminal group of 35 meq / kg or less, 0.5 parts by mass or more and 10 parts by mass or less of an epoxy resin (B), and quaternary ammonium. A polybutylene terephthalate resin composition containing a salt (C) and a dimensional accuracy improving agent (D), a molded product comprising the above-mentioned polybutylene terephthalate resin composition, and a polybutylene terephthalate resin composition containing a quaternary ammonium salt. It has been found that the above-mentioned problems can be solved by a polybutylene terephthalate resin composition containing a polybutylene terephthalate resin composition containing an agent for suppressing an increase in the viscosity of a product and an agent for suppressing the hydrolysis of a molded product, and the present invention has been completed.
すなわち、本発明は以下の（１）～（２０）に関する。
（１）カルボン酸末端基が３５ｍｅｑ／ｋｇ以下のポリブチレンテレフタレート樹脂（Ａ）１００質量部に対し、エポキシ系樹脂（Ｂ）０．５質量部以上１０質量部以下と、第４級アンモニウム塩（Ｃ）と、寸法精度向上剤（Ｄ）とを含有する、ポリブチレンテレフタレート樹脂組成物であり、第４級アンモニウム塩（Ｃ）を構成する第４級アンモニウムカチオンＮＲ４
＋の４つのＲは、それぞれ炭素原子数１～１５の、アルキル基、アリール基、アラルキル基のいずれか又はそれらの組み合わせであり、寸法精度向上剤（Ｄ）が寸法精度向上用アロイ樹脂（Ｄ－１）及び／又は寸法精度向上用充填剤（Ｄ－２）からなり、寸法精度向上剤（Ｄ）の含有量が、ポリブチレンテレフタレート樹脂（Ａ）１００質量部に対し、寸法精度向上用アロイ樹脂（Ｄ－１）０～１００質量部及び／又は寸法精度向上用充填剤（Ｄ－２）０～１００質量部、且つ寸法精度向上用アロイ樹脂（Ｄ－１）と寸法精度向上用充填剤（Ｄ－２）の合計で１０～２００質量部である、ポリブチレンテレフタレート樹脂組成物。
（２）前記第４級アンモニウム塩（Ｃ）を構成する前記４つのＲの炭素原子数が、いずれも１～１０である、（１）に記載のポリブチレンテレフタレート樹脂組成物。
（３）前記第４級アンモニウム塩（Ｃ）を構成する前記４つのＲの炭素原子数の合計が３０以下である、（１）または（２）に記載のポリブチレンテレフタレート樹脂組成物。
（４）前記第４級アンモニウム塩（Ｃ）を構成する前記４つのＲの炭素原子数の合計が２６以下である、（３）に記載のポリブチレンテレフタレート樹脂組成物。
（５）前記第４級アンモニウム塩（Ｃ）を構成する前記４つのＲの炭素原子数の合計が２２以下である、（４）に記載のポリブチレンテレフタレート樹脂組成物。
（６）前記第４級アンモニウム塩（Ｃ）を構成する前記４つのＲの炭素原子数の合計が１８以下である、（５）に記載のポリブチレンテレフタレート樹脂組成物。
（７）前記第４級アンモニウム塩（Ｃ）を構成するアニオンが臭化物イオンである、（１）から（６）のいずれかに記載のポリブチレンテレフタレート樹脂組成物。
（８）前記第４級アンモニウム塩（Ｃ）がテトラブチルアンモニウムブロミド及び／又はベンジルトリメチルアンモニウムブロミドである、（１）から（７）のいずれかに記載のポリブチレンテレフタレート樹脂組成物。
（９）前記第４級アンモニウム塩（Ｃ）の含有量が、前記ポリブチレンテレフタレート樹脂（Ａ）１００質量部に対し０.１質量部以上３.０質量部以下である、（１）から（８）のいずれかに記載のポリブチレンテレフタレート樹脂組成物。
（１０）（１）から（９）のいずれかに記載のポリブチレンテレフタレート樹脂組成物からなる成形品。
（１１）第４級アンモニウム塩（Ｃ）を含有する、ポリブチレンテレフタレート樹脂（Ａ）とエポキシ系樹脂（Ｂ）と寸法精度向上剤（Ｄ）とを含有するポリブチレンテレフタレート樹脂組成物の粘度上昇抑制剤であり、前記第４級アンモニウム塩（Ｃ）を構成する第４級アンモニウムカチオンＮＲ４
＋の４つのＲのうち、３つがメチル基であり、他１つがアルキル基、アリール基、アラルキル基から選択される炭素原子数６以上の官能基であり、寸法精度向上剤（Ｄ）が寸法精度向上用アロイ樹脂（Ｄ－１）及び／又は寸法精度向上用充填剤（Ｄ－２）からなり、寸法精度向上剤（Ｄ）の含有量が、ポリブチレンテレフタレート樹脂（Ａ）１００質量部に対し、寸法精度向上用アロイ樹脂（Ｄ－１）０～１００質量部及び／又は寸法精度向上用充填剤（Ｄ－２）０～１００質量部、且つ寸法精度向上用アロイ樹脂（Ｄ－１）と寸法精度向上用充填剤（Ｄ－２）の合計で１０～２００質量部である、粘度上昇抑制剤。
（１２）前記第４級アンモニウム塩がベンジルトリメチルアンモニウムブロミド又はドデシルトリメチルアンモニウムブロミドである、（１１）に記載の粘度上昇抑制剤。
（１３）第４級アンモニウム塩（Ｃ）を含有する、ポリブチレンテレフタレート樹脂（Ａ）とエポキシ系樹脂（Ｂ）と寸法精度向上剤（Ｄ）とを含有するポリブチレンテレフタレート樹脂組成物からなる成形品の加水分解抑制剤であり、前記第４級アンモニウム塩（Ｃ）を構成する第４級アンモニウムカチオンＮＲ４
＋の４つのＲは、それぞれ炭素原子数１～１５の、アルキル基、アリール基、アラルキル基のいずれか又はそれらの組み合わせであり、寸法精度向上剤（Ｄ）が寸法精度向上用アロイ樹脂（Ｄ－１）及び／又は寸法精度向上用充填剤（Ｄ－２）からなり、寸法精度向上剤（Ｄ）の含有量が、ポリブチレンテレフタレート樹脂（Ａ）１００質量部に対し、寸法精度向上用アロイ樹脂（Ｄ－１）０～１００質量部及び／又は寸法精度向上用充填剤（Ｄ－２）０～１００質量部、且つ寸法精度向上用アロイ樹脂（Ｄ－１）と寸法精度向上用充填剤（Ｄ－２）の合計で１０～２００質量部である、加水分解抑制剤。
（１４）前記第４級アンモニウム塩を構成する前記４つのＲの炭素原子数が、いずれも１～１０である、（１３）に記載の加水分解抑制剤。
（１５）前記第４級アンモニウム塩を構成する前記４つのＲの炭素原子数の合計が３０以下である、（１３）または（１４）に記載の加水分解抑制剤。
（１６）前記第４級アンモニウム塩を構成する前記４つのＲの炭素原子数の合計が２６以下である、（１５）に記載の加水分解抑制剤。
（１７）前記第４級アンモニウム塩を構成する前記４つのＲの炭素原子数の合計が２２以下である、（１６）に記載の加水分解抑制剤。
（１８）前記第４級アンモニウム塩を構成する前記４つのＲの炭素原子数の合計が１８以下である、（１７）に記載の加水分解抑制剤。
（１９）前記第４級アンモニウム塩を構成するアニオンが臭化物イオンである、（１３）から（１８）のいずれかに記載の加水分解抑制剤。
（２０）前記第４級アンモニウム塩がテトラブチルアンモニウムブロミド及び／又はベンジルトリメチルアンモニウムブロミドである、（１３）から（１９）のいずれかに記載の加水分解抑制剤。
That is, the present invention relates to the following (1) to (20).
(1) With respect to 100 parts by mass of the polybutylene terephthalate resin (A) having a carboxylic acid terminal group of 35 meq / kg or less, 0.5 parts by mass or more and 10 parts by mass or less of the epoxy resin (B) and a quaternary ammonium salt (1). The four Rs of the quaternary ammonium cation NR 4+ constituting the quaternary ammonium salt (C), which is a polybutylene terephthalate resin composition containing C) and the dimensional accuracy improving agent (D ) , are Any one or a combination of an alkyl group, an aryl group, and an aralkyl group having 1 to 15 carbon atoms, respectively, and the dimensional accuracy improving agent (D) is an alloy resin (D-1) for improving dimensional accuracy and / or dimensions. It is composed of an accuracy improving filler (D-2), and the content of the dimensional accuracy improving agent (D) is 100 parts by mass of the polybutylene terephthalate resin (A), and the dimensional accuracy improving alloy resin (D-1) 0. ~ 100 parts by mass and / or dimensional accuracy improving filler (D-2) 0 to 100 parts by mass, and total of dimensional accuracy improving alloy resin (D-1) and dimensional accuracy improving filler (D-2) A polybutylene terephthalate resin composition having an amount of 10 to 200 parts by mass.
(2) The polybutylene terephthalate resin composition according to (1), wherein the number of carbon atoms of the four Rs constituting the quaternary ammonium salt (C) is 1 to 10.
(3) The polybutylene terephthalate resin composition according to (1) or (2), wherein the total number of carbon atoms of the four Rs constituting the quaternary ammonium salt (C) is 30 or less.
(4) The polybutylene terephthalate resin composition according to (3), wherein the total number of carbon atoms of the four Rs constituting the quaternary ammonium salt (C) is 26 or less.
(5) The polybutylene terephthalate resin composition according to (4), wherein the total number of carbon atoms of the four Rs constituting the quaternary ammonium salt (C) is 22 or less.
(6) The polybutylene terephthalate resin composition according to (5), wherein the total number of carbon atoms of the four Rs constituting the quaternary ammonium salt (C) is 18 or less.
(7) The polybutylene terephthalate resin composition according to any one of (1) to (6), wherein the anion constituting the quaternary ammonium salt (C) is a bromide ion.
(8) The polybutylene terephthalate resin composition according to any one of (1) to (7), wherein the quaternary ammonium salt (C) is tetrabutylammonium bromide and / or benzyltrimethylammonium bromide.
(9) From (1), the content of the quaternary ammonium salt (C) is 0.1 part by mass or more and 3.0 part by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin (A). The polybutylene terephthalate resin composition according to any one of 8).
(10) A molded product comprising the polybutylene terephthalate resin composition according to any one of (1) to (9).
(11) Increase in viscosity of polybutylene terephthalate resin composition containing quaternary ammonium salt (C), polybutylene terephthalate resin (A), epoxy resin (B), and dimensional accuracy improving agent (D). Of the four Rs of the quaternary ammonium cation NR 4+ , which is an inhibitor and constitutes the quaternary ammonium salt (C ) , three are methyl groups and the other one is an alkyl group, an aryl group, and an aralkyl group. It is a functional group having 6 or more carbon atoms selected from, and the dimensional accuracy improving agent (D) is composed of an alloy resin (D-1) for improving dimensional accuracy and / or a filler (D-2) for improving dimensional accuracy. , The content of the dimensional accuracy improving agent (D) is 0 to 100 parts by mass of the dimensional accuracy improving alloy resin (D-1) with respect to 100 parts by mass of the polybutylene terephthalate resin (A) and / or the filling for improving the dimensional accuracy. The viscosity increase is suppressed by 0 to 100 parts by mass of the agent (D-2) and 10 to 200 parts by mass in total of the alloy resin (D-1) for improving dimensional accuracy and the filler (D-2) for improving dimensional accuracy. Agent.
(12) The viscosity increase inhibitor according to (11), wherein the quaternary ammonium salt is benzyltrimethylammonium bromide or dodecyltrimethylammonium bromide.
(13) Molding of a polybutylene terephthalate resin composition containing a quaternary ammonium salt (C), a polybutylene terephthalate resin (A), an epoxy resin (B), and a dimensional accuracy improving agent (D). The four Rs of the quaternary ammonium cation NR 4+ , which is a hydrolysis inhibitor of the product and constitutes the quaternary ammonium salt (C), are an alkyl group and an aryl group having 1 to 15 carbon atoms, respectively . One or a combination of aralkyl groups, the dimensional accuracy improving agent (D) is composed of an alloy resin (D-1) for improving dimensional accuracy and / or a filler (D-2) for improving dimensional accuracy. The content of the improver (D) is 0 to 100 parts by mass of the alloy resin (D-1) for improving dimensional accuracy and / or the filler (D) for improving dimensional accuracy with respect to 100 parts by mass of the polybutylene terephthalate resin (A). -2) A hydrolysis inhibitor having 0 to 100 parts by mass and a total of 10 to 200 parts by mass of the alloy resin (D-1) for improving dimensional accuracy and the filler (D-2) for improving dimensional accuracy.
(14) The hydrolysis inhibitor according to (13), wherein each of the four Rs constituting the quaternary ammonium salt has 1 to 10 carbon atoms.
(15) The hydrolysis inhibitor according to (13) or (14), wherein the total number of carbon atoms of the four Rs constituting the quaternary ammonium salt is 30 or less.
(16) The hydrolysis inhibitor according to (15), wherein the total number of carbon atoms of the four Rs constituting the quaternary ammonium salt is 26 or less.
(17) The hydrolysis inhibitor according to (16), wherein the total number of carbon atoms of the four Rs constituting the quaternary ammonium salt is 22 or less.
(18) The hydrolysis inhibitor according to (17), wherein the total number of carbon atoms of the four Rs constituting the quaternary ammonium salt is 18 or less.
(19) The hydrolysis inhibitor according to any one of (13) to (18), wherein the anion constituting the quaternary ammonium salt is a bromide ion.
(20) The hydrolysis inhibitor according to any one of (13) to (19), wherein the quaternary ammonium salt is tetrabutylammonium bromide and / or benzyltrimethylammonium bromide.
本発明によれば、寸法精度と耐加水分解性の改善効果に優れたポリブチレンテレフタレート樹脂組成物、成形品、ポリブチレンテレフタレート樹脂組成物の粘度上昇抑制剤、ポリブチレンテレフタレート樹脂組成物からなる成形品の加水分解抑制剤を提供することができる。 According to the present invention, molding comprising a polybutylene terephthalate resin composition, a molded product, a polybutylene terephthalate resin composition viscosity increase inhibitor, and a polybutylene terephthalate resin composition, which are excellent in improving dimensional accuracy and hydrolysis resistance. A hydrolysis inhibitor of an article can be provided.
以下、本発明の一実施形態について詳細に説明する。本発明は、以下の実施形態に限定されるものではなく、本発明の効果を阻害しない範囲で適宜変更を加えて実施することができる。また、本明細書において「Ｘ～Ｙ」との表現は、「Ｘ以上Ｙ以下」であることを意味している。 Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired. Further, in the present specification, the expression "XY" means "X or more and Y or less".
［ポリブチレンテレフタレート樹脂組成物］
（ポリブチレンテレフタレート樹脂）
ポリブチレンテレフタレート樹脂（ＰＢＴ樹脂）は、少なくともテレフタル酸又はそのエステル形成性誘導体（Ｃ１－６のアルキルエステルや酸ハロゲン化物等）を含むジカルボン酸成分と、少なくとも炭素原子数４のアルキレングリコール（１，４－ブタンジオール）又はそのエステル形成性誘導体（アセチル化物等）を含むグリコール成分とを重縮合して得られるポリブチレンテレフタレート樹脂である。本実施形態において、ポリブチレンテレフタレート樹脂はホモポリブチレンテレフタレート樹脂に限らず、ブチレンテレフタレート単位を６０モル％以上含有する共重合体であってもよい。
[Polybutylene terephthalate resin composition]
(Polybutylene terephthalate resin)
The polybutylene terephthalate resin (PBT resin) contains a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (such as an alkyl ester of C 1-6 or an acid halide) and an alkylene glycol having at least 4 carbon atoms (1). , 4-Butandiol) or a polybutylene terephthalate resin obtained by polycondensing with a glycol component containing an ester-forming derivative (acetylated product, etc.). In the present embodiment, the polybutylene terephthalate resin is not limited to the homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more of the butylene terephthalate unit.
ポリブチレンテレフタレート樹脂の末端カルボキシル基量は３５ｍｅｑ／ｋｇ以下であるが、本発明の目的を阻害しない限り特に限定されず、３０ｍｅｑ／ｋｇ以下が好ましく、２５ｍｅｑ／ｋｇ以下がより好ましい。 The amount of the terminal carboxyl group of the polybutylene terephthalate resin is 35 meq / kg or less, but is not particularly limited as long as the object of the present invention is not impaired, and is preferably 30 meq / kg or less, more preferably 25 meq / kg or less.
ポリブチレンテレフタレート樹脂の固有粘度（ＩＶ）は本発明の目的を阻害しない範囲で特に制限されないが、０．６０ｄＬ／ｇ以上１．２ｄＬ／ｇ以下であるのが好ましく、０．６５ｄＬ／ｇ以上０．９ｄＬ／ｇ以下であるのがより好ましい。このような範囲の固有粘度のポリブチレンテレフタレート樹脂を用いる場合には、得られるポリブチレンテレフタレート樹脂組成物が特に成形性に優れたものとなる。また、異なる固有粘度を有するポリブチレンテレフタレート樹脂をブレンドして、固有粘度を調整することもできる。例えば、固有粘度１．０ｄＬ／ｇのポリブチレンテレフタレート樹脂と固有粘度０．７ｄＬ／ｇのポリブチレンテレフタレート樹脂とをブレンドすることにより、固有粘度０．９ｄＬ／ｇのポリブチレンテレフタレート樹脂を調製することができる。ポリブチレンテレフタレート樹脂の固有粘度は、例えば、ｏ－クロロフェノール中で温度３５℃の条件で測定することができる。 The intrinsic viscosity (IV) of the polybutylene terephthalate resin is not particularly limited as long as it does not impair the object of the present invention, but is preferably 0.60 dL / g or more and 1.2 dL / g or less, and 0.65 dL / g or more and 0. It is more preferably 9.9 dL / g or less. When a polybutylene terephthalate resin having an intrinsic viscosity in such a range is used, the obtained polybutylene terephthalate resin composition is particularly excellent in moldability. It is also possible to adjust the intrinsic viscosity by blending polybutylene terephthalate resins having different intrinsic viscosities. For example, a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g can be prepared by blending a polybutylene terephthalate resin having an intrinsic viscosity of 1.0 dL / g and a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 dL / g. Can be done. The intrinsic viscosity of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol under the condition of a temperature of 35 ° C.
ポリブチレンテレフタレート樹脂の調製において、コモノマー成分としてテレフタル酸以外の芳香族ジカルボン酸又はそのエステル形成性誘導体を用いる場合、例えば、イソフタル酸、フタル酸、２，６－ナフタレンジカルボン酸、４，４’－ジカルボキシジフェニルエーテル等のＣ８－１４の芳香族ジカルボン酸；コハク酸、アジピン酸、アゼライン酸、セバシン酸等のＣ４－１６のアルカンジカルボン酸；シクロヘキサンジカルボン酸等のＣ５－１０のシクロアルカンジカルボン酸；これらのジカルボン酸成分のエステル形成性誘導体（Ｃ１－６のアルキルエステル誘導体や酸ハロゲン化物等）を用いることができる。これらのジカルボン酸成分は、単独で又は２種以上を組み合わせて使用できる。 When an aromatic dicarboxylic acid other than terephthalic acid or an ester-forming derivative thereof is used as a comonomer component in the preparation of a polybutylene terephthalate resin, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'- C 8-14 aromatic dicarboxylic acid such as dicarboxydiphenyl ether; C 4-16 alcandicarboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid; C 5-10 cycloalcandicarboxylic acid such as cyclohexanedicarboxylic acid. Acids; Ester-forming derivatives of these dicarboxylic acid components (C 1-6 alkyl ester derivatives, acid halides, etc.) can be used. These dicarboxylic acid components can be used alone or in combination of two or more.
これらのジカルボン酸成分の中では、イソフタル酸等のＣ８－１２の芳香族ジカルボン酸、及び、アジピン酸、アゼライン酸、セバシン酸等のＣ６－１２のアルカンジカルボン酸がより好ましい。 Among these dicarboxylic acid components, C 8-12 aromatic dicarboxylic acids such as isophthalic acid and C 6-12 alcandicarboxylic acids such as adipic acid, azelaic acid and sebacic acid are more preferable.
ポリブチレンテレフタレート樹脂の調製において、コモノマー成分として１，４－ブタンジオール以外のグリコール成分を用いる場合、例えば、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，３－ブチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、１，３－オクタンジオール等のＣ２－１０のアルキレングリコール；ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール等のポリオキシアルキレングリコール；シクロヘキサンジメタノール、水素化ビスフェノールＡ等の脂環式ジオール；ビスフェノールＡ、４，４’－ジヒドロキシビフェニル等の芳香族ジオール；ビスフェノールＡのエチレンオキサイド２モル付加体、ビスフェノールＡのプロピレンオキサイド３モル付加体等の、ビスフェノールＡのＣ２－４のアルキレンオキサイド付加体；又はこれらのグリコールのエステル形成性誘導体（アセチル化物等）を用いることができる。これらのグリコール成分は、単独で又は２種以上を組み合わせて使用できる。 When a glycol component other than 1,4-butanediol is used as the comonomer component in the preparation of the polybutylene terephthalate resin, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl C 2-10 alkylene glycols such as glycols and 1,3-octanediols; polyoxyalkylene glycols such as diethylene glycols, triethylene glycols and dipropylene glycols; alicyclic diols such as cyclohexanedimethanol and hydride bisphenol A; bisphenols Aromatic diols such as A, 4,4'-dihydroxybiphenyl; C 2-4 alkylene oxide adduct of bisphenol A such as ethylene oxide 2 mol adduct of bisphenol A and propylene oxide 3 mol adduct of bisphenol A; Alternatively, ester-forming derivatives of these glycols (acetylated products, etc.) can be used. These glycol components can be used alone or in combination of two or more.
これらのグリコール成分の中では、エチレングリコール、トリメチレングリコール等のＣ２－６のアルキレングリコール、ジエチレングリコール等のポリオキシアルキレングリコール、又は、シクロヘキサンジメタノール等の脂環式ジオール等がより好ましい。 Among these glycol components, C 2-6 alkylene glycols such as ethylene glycol and trimethylene glycol, polyoxyalkylene glycols such as diethylene glycol, and alicyclic diols such as cyclohexanedimethanol are more preferable.
ジカルボン酸成分及びグリコール成分の他に使用できるコモノマー成分としては、例えば、４－ヒドロキシ安息香酸、３－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、４－カルボキシ－４’－ヒドロキシビフェニル等の芳香族ヒドロキシカルボン酸；グリコール酸、ヒドロキシカプロン酸等の脂肪族ヒドロキシカルボン酸；プロピオラクトン、ブチロラクトン、バレロラクトン、カプロラクトン（ε－カプロラクトン等）等のＣ３－１２ラクトン；これらのコモノマー成分のエステル形成性誘導体（Ｃ１－６のアルキルエステル誘導体、酸ハロゲン化物、アセチル化物等）が挙げられる。 Examples of the comonomer component that can be used in addition to the dicarboxylic acid component and the glycol component include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-carboxy-4'-hydroxybiphenyl and the like. Aromatic hydroxycarboxylic acids; aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; C 3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (ε-caprolactone etc.); esters of these comonomer components Examples thereof include formable derivatives (C 1-6 alkyl ester derivatives, acid halides, acetylates, etc.).
ポリブチレンテレフタレート樹脂の含有量は、樹脂組成物の全質量の２０～９０質量％であることが好ましく、３０～８０質量％であることがより好ましく、４０～７０質量％であることがさらに好ましい。 The content of the polybutylene terephthalate resin is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, still more preferably 40 to 70% by mass, based on the total mass of the resin composition. ..
（エポキシ系樹脂）
本発明におけるエポキシ系樹脂を構成するエポキシ系化合物としては、例えば、ビフェニル型エポキシ化合物、ビスフェノールＡ型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物等の芳香族エポキシ化合物を挙げることができる。エポキシ化合物は、２種以上の化合物を任意に組み合わせて使用してもよい。エポキシ当量は、１５０～１５００ｇ／当量（ｇ／ｅｑ）であることが好ましい。
(Epoxy resin)
Examples of the epoxy compound constituting the epoxy resin in the present invention include aromatic epoxy compounds such as biphenyl type epoxy compound, bisphenol A type epoxy compound, phenol novolac type epoxy compound, and cresol novolac type epoxy compound. .. The epoxy compound may be used in any combination of two or more kinds of compounds. The epoxy equivalent is preferably 150 to 1500 g / equivalent (g / eq).
本発明のポリブチレンテレフタレート樹脂組成物におけるエポキシ系樹脂の含有量は、ポリブチレンテレフタレート樹脂１００質量部に対し、０．５質量部以上１０質量部以下であるが、０．５質量部以上８質量部以下であることが好ましく、０．５質量部以上６質量部以下であることがより好ましく、０．５質量部以上５質量部以下であることがさらに好ましく、０．５質量部以上４質量部以下であることが特に好ましい。 The content of the epoxy resin in the polybutylene terephthalate resin composition of the present invention is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin, but 0.5 parts by mass or more and 8 parts by mass. It is preferably 0.5 parts by mass or more, more preferably 6 parts by mass or less, further preferably 0.5 parts by mass or more and 5 parts by mass or less, and 0.5 parts by mass or more and 4 parts by mass. It is particularly preferable that the content is less than or equal to a portion.
（第４級アンモニウム塩）
本発明のポリブチレンテレフタレート樹脂組成物に含有される第４級アンモニウム塩を構成する第４級アンモニウムカチオンは、分子式ＮＲ４
＋で表される正電荷を持った多原子イオンである。４つのＲはそれぞれ炭素原子数１～１５の、アルキル基、アリール基、アラルキル基のいずれか又はそれらの組み合わせである。
(Quaternary ammonium salt)
The quaternary ammonium cation constituting the quaternary ammonium salt contained in the polybutylene terephthalate resin composition of the present invention is a polyatomic ion having a positive charge represented by the molecular formula NR 4+ . Each of the four Rs has an alkyl group, an aryl group, or an aralkyl group having 1 to 15 carbon atoms, or a combination thereof.
４つのＲの炭素原子数はいずれも１～１０であることが好ましく、１～８であることがより好ましく、１～７であることがさらに好ましく、２～４であることが特に好ましく、４（ブチル基）であることが最も好ましい。なお、４つのＲの炭素原子数は互いに異なっていてもよい。また、４つのＲの炭素原子数の合計は３０以下であることが好ましく、２６以下であることがより好ましく、２２以下であることがさらに好ましく、１８以下であることが特に好ましく、１６以下であることが最も好ましい。 The number of carbon atoms of each of the four Rs is preferably 1 to 10, more preferably 1 to 8, further preferably 1 to 7, and particularly preferably 2 to 4. It is most preferably (butyl group). The number of carbon atoms of the four Rs may be different from each other. Further, the total number of carbon atoms of the four Rs is preferably 30 or less, more preferably 26 or less, further preferably 22 or less, particularly preferably 18 or less, and 16 or less. Most preferably.
本発明のポリブチレンテレフタレート樹脂組成物に含有される第４級アンモニウム塩を構成するアニオンは、１価の負電荷を有している。そのアニオンは、ハロゲン化物イオンであることが好ましく、塩化物イオン、臭化物イオン、ヨウ化物イオンからなる群から選択されるイオンであることがより好ましく、塩化物イオン、臭化物イオンからなる群から選択されるイオンであることがさらに好ましく、臭化物イオンであることが特に好ましい。 The anion constituting the quaternary ammonium salt contained in the polybutylene terephthalate resin composition of the present invention has a monovalent negative charge. The anion is preferably a halide ion, more preferably an ion selected from the group consisting of chloride ion, bromide ion, and iodide ion, and more preferably selected from the group consisting of chloride ion and bromide ion. It is more preferably an ion, and particularly preferably a bromide ion.
本発明のポリブチレンテレフタレート樹脂組成物に含有される特に好ましい第４級アンモニウム塩として、テトラブチルアンモニウムブロミド、ベンジルトリメチルアンモニウムブロミドが挙げられる。 Particularly preferable quaternary ammonium salts contained in the polybutylene terephthalate resin composition of the present invention include tetrabutylammonium bromide and benzyltrimethylammonium bromide.
本発明のポリブチレンテレフタレート樹脂組成物に含有される第４級アンモニウム塩の含有量は、ポリブチレンテレフタレート樹脂（Ａ）１００質量部に対し０.１質量部以上３.０質量部以下であることが好ましく、０．１５質量部以上２．０質量部以下であることがより好ましく、０．２質量部以上１．０質量部以下であることがさらに好ましい。 The content of the quaternary ammonium salt contained in the polybutylene terephthalate resin composition of the present invention shall be 0.1 part by mass or more and 3.0 part by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin (A). Is more preferable, and it is more preferably 0.15 parts by mass or more and 2.0 parts by mass or less, and further preferably 0.2 parts by mass or more and 1.0 part by mass or less.
（ポリブチレンテレフタレート樹脂組成物の粘度上昇抑制剤）
また、第４級アンモニウム塩として、ＮＲ４
＋で表される第４級アンモニウムカチオンの４つのＲのうち、３つがメチル基であり、他１つがアルキル基、アリール基、アラルキル基から選択される炭素原子数６以上の官能基であるものを用いることにより、ポリブチレンテレフタレート樹脂とエポキシ系樹脂を含有するポリブチレンテレフタレート樹脂組成物の粘度上昇抑制剤とすることが可能である。本発明の粘度上昇抑制剤として好ましい第４級アンモニウム塩としては、ベンジルトリメチルアンモニウムブロミド、ドデシルトリメチルアンモニウムブロミドが挙げられる。
(Viscosity increase inhibitor of polybutylene terephthalate resin composition)
Further, as the quaternary ammonium salt, three of the four Rs of the quaternary ammonium cation represented by NR 4+ are methyl groups, and the other one is selected from an alkyl group, an aryl group and an aralkyl group . By using a functional group having 6 or more carbon atoms, it is possible to obtain a polybutylene terephthalate resin composition containing a polybutylene terephthalate resin and an epoxy resin as a viscosity increase inhibitor. Preferred quaternary ammonium salts as the viscosity increase inhibitor of the present invention include benzyltrimethylammonium bromide and dodecyltrimethylammonium bromide.
（ポリブチレンテレフタレート樹脂組成物からなる成形品の加水分解抑制剤）
さらに、第４級アンモニウム塩として、ＮＲ４
＋で表される第４級アンモニウムカチオンの４つのＲが、それぞれ炭素原子数１～１５の、アルキル基、アリール基、アラルキル基のいずれか又はそれらの組み合わせであるものを用いることにより、ポリブチレンテレフタレート樹脂とエポキシ系樹脂を含有するポリブチレンテレフタレート樹脂組成物からなる成形品の加水分解抑制剤とすることが可能である。
(A hydrolysis inhibitor for a molded product made of a polybutylene terephthalate resin composition)
Further, as the quaternary ammonium salt, each of the four Rs of the quaternary ammonium cation represented by NR 4+ has 1 to 15 carbon atoms, and either an alkyl group, an aryl group, or an aralkyl group, or any of them. By using a combination thereof, it is possible to obtain a hydrolysis inhibitor of a molded product made of a polybutylene terephthalate resin composition containing a polybutylene terephthalate resin and an epoxy resin.
（寸法精度向上剤）
本発明におけるポリブチレンテレフタレート樹脂組成物には、当該樹脂組成物からなる成形品の反り変形を抑制するために、寸法精度向上用アロイ樹脂（Ｄ－１）及び／又は寸法精度向上用充填剤（Ｄ－２）からなる寸法精度向上剤（Ｄ）が添加される。
(Dimensional accuracy improver)
The polybutylene terephthalate resin composition in the present invention includes an alloy resin (D-1) for improving dimensional accuracy and / or a filler for improving dimensional accuracy (D-1) in order to suppress warpage deformation of a molded product made of the resin composition. A dimensional accuracy improver (D) made of D-2) is added.
寸法精度向上用アロイ樹脂（Ｄ－１）としては、成形時や熱処理時の収縮率及び／又は線膨張係数が小さいのみならず、ポリブチレンテレフタレート樹脂（Ａ）との加工温度が近く、相溶性の良い樹脂を好ましく用いることができる。このような寸法精度向上用アロイ樹脂（Ｄ－１）としては、ポリアミド樹脂、ビニル系樹脂、アクリル系樹脂、ポリウレタン樹脂、ポリケトン樹脂、ポリフェニレンスルフィド樹脂、ポリエーテルエーテルケトン樹脂、ポリカーボネート樹脂、スチレン系樹脂（ポリスチレン樹脂、アクリロニトリル－スチレン共重合体、アクリロニトリル－ブタジエン－スチレン共重合体、スチレン－ブタジエン共重合体、スチレン－ブタジエン－スチレン共重合体、スチレン－イソプレン－スチレン共重合体、スチレン－エチレン－ブタジエン－スチレン共重合体等）、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、フェノキシ樹脂、ポリフェニレンエーテル樹脂、ポリエーテルイミド樹脂、ポリアミドイミド樹脂、ポリアセタール樹脂、不飽和ポリエステル樹脂、尿素樹脂、ポリブチレンテレフタレート以外のポリエステル樹脂（ポリエチレンテレフタレート樹脂、ポリプロピレンテレフタレート樹脂、ポリブチレンナフタレート樹脂、ポリエチレンナフタレート樹脂、ポリ乳酸樹脂等）、ポリオレフィン樹脂、オレフィン系エラストマ、コアシェル系エラストマ、ジエン系エラストマ、ポリエステル系エラストマ、ウレタン系エラストマ、シリコーン系エラストマ及びこれらの組み合わせを挙げることができる。中でも、ポリエチレンテレフタレート樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、およびスチレン系樹脂といった非晶性の熱可塑性樹脂は、成形品の収縮率やその異方性が小さいため低反り化の効果が得やすく、またポリブチレンテレフタレート樹脂組成物中に液状の添加剤が含有される場合に、そのブリードアウトを抑制する効果も得られるため特に好ましい。また、ポリオレフィン樹脂やオレフィン系エラストマ（エチレンエチルアクリレート共重合体など）は、ポリブチレンテレフタレート樹脂組成物に添加した際に、耐トラッキング性の低下が小さいことから、特に耐トラッキング性が要求される用途においては、これらを添加することも好ましい。なお、これらの樹脂とポリブチレンテレフタレート樹脂の親和性を向上させるために、公知の相溶化剤を併用しても良い。 As the alloy resin (D-1) for improving dimensional accuracy, not only the shrinkage rate and / or the coefficient of linear expansion during molding and heat treatment is small, but also the processing temperature is close to that of the polybutylene terephthalate resin (A), and the compatibility is compatible. A good resin can be preferably used. Examples of the alloy resin (D-1) for improving dimensional accuracy include polyamide resin, vinyl resin, acrylic resin, polyurethane resin, polyketone resin, polyphenylene sulfide resin, polyether ether ketone resin, polycarbonate resin, and styrene resin. (Polystyrene resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-ethylene-butadiene -Styrene copolymer, etc.), polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene ether resin, polyetherimide resin, polyamideimide resin, polyacetal resin, unsaturated polyester resin, urea resin, polybutylene terephthalate. Polyester resins other than (polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene naphthalate resin, polyethylene naphthalate resin, polylactic acid resin, etc.), polyolefin resin, olefin elastoma, core shell elastoma, diene elastoma, polyester elastoma, urethane Examples thereof include a based elastoma, a silicone-based elastoma, and a combination thereof. Among them, amorphous thermoplastic resins such as polyethylene terephthalate resin, polycarbonate resin, polyphenylene ether resin, and styrene resin have a small shrinkage rate and their anisotropy of the molded product, so that the effect of low warpage can be easily obtained. When the polybutylene terephthalate resin composition contains a liquid additive, it is particularly preferable because it also has an effect of suppressing bleed-out. Further, polyolefin resins and olefin-based elastomers (ethylene ethyl acrylate copolymers, etc.) have a small decrease in tracking resistance when added to a polybutylene terephthalate resin composition, and therefore, applications in which tracking resistance is particularly required. In, it is also preferable to add these. In addition, in order to improve the affinity between these resins and the polybutylene terephthalate resin, a known compatibilizer may be used in combination.
寸法精度向上用アロイ樹脂（Ｄ－１）の添加量は、ポリブチレンテレフタレート樹脂（Ａ）１００質量部に対し、０～１００質量部であり、５～９０質量部または１０～８０質量部であっても良い。ただし、ポリブチレンテレフタレート樹脂（Ａ）との相溶性によっては、多量に添加することで良好な分散状態が得られず、凝集塊や相間剥離により、組成物としての機械的特性を悪化させるおそれがあるため、寸法精度向上用アロイ樹脂（Ｄ－１）の含有量は、本発明におけるポリブチレンテレフタレート樹脂組成物全体に対し、４０質量％以下であることが好ましく、３５質量％以下であることがより好ましく、３０質量％以下であることがさらに好ましく、２５質量％以下であることが特に好ましい。 The amount of the alloy resin (D-1) for improving dimensional accuracy is 0 to 100 parts by mass, 5 to 90 parts by mass, or 10 to 80 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). May be. However, depending on the compatibility with the polybutylene terephthalate resin (A), a good dispersed state cannot be obtained by adding a large amount of the resin, and agglomerates and interphase peeling may deteriorate the mechanical properties of the composition. Therefore, the content of the alloy resin (D-1) for improving dimensional accuracy is preferably 40% by mass or less, and preferably 35% by mass or less, based on the entire polybutylene terephthalate resin composition in the present invention. It is more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
寸法精度向上用充填剤（Ｄ－２）としては、有機系充填剤、無機系充填剤、金属系充填剤及びこれらの組み合わせのいずれも用いることができるが、樹脂成形品の加工温度範囲や使用温度範囲における収縮率や線膨張係数の小さい、無機系充填剤、金属系充填剤が好ましい。また、金属部材と組み合わせる絶縁部材として用いる成形品においては、絶縁性を確保する意味で無機系充填剤を用いることが特に好ましい。 As the filler for improving dimensional accuracy (D-2), any of an organic filler, an inorganic filler, a metal filler and a combination thereof can be used, but the processing temperature range and use of the resin molded product can be used. Inorganic fillers and metal fillers having a small shrinkage rate and linear expansion coefficient in the temperature range are preferable. Further, in the molded product used as an insulating member to be combined with the metal member, it is particularly preferable to use an inorganic filler in order to secure the insulating property.
寸法精度向上用充填剤（Ｄ－２）の形状としては、繊維状充填剤、板状充填剤、球状充填剤、粉状充填剤、曲面状充填剤、不定形充填剤及びこれらの組み合わせのいずれも用いることができるが、反り変形を低減するには、異方性の小さい充填剤を用いることが好ましい。板状充填剤、球状充填剤、粉状充填剤等、特にアスペクト比が１に近い充填剤を用いることがより好ましい。一方、ガラス繊維等の繊維状充填剤を用いる場合、引張強度等の機械的特性の向上効果は大きいが、繊維状充填剤の配向に起因して、反りの原因となる収縮率の異方性が大きくなる傾向にあるため、本発明において寸法精度向上用充填剤（Ｄ－２）として用いる繊維状充填剤は、ミルドファイバやウィスカ等の繊維長÷繊維径の比が１００以下（好ましくは２～３０）の短繊維か、断面が繭型や長円形・楕円形といった扁平形状（断面の長径÷短径の比が１．３～１０、好ましくは１．５～５）の非円形断面繊維といった、アスペクト比が小さいものである。なお、これら繊維長や繊維径（断面の長径、短径含む）の比は、繊維状充填剤の製造元各社が開示するカタログや仕様書の値を用いて算出すればよい。 The shape of the filler (D-2) for improving dimensional accuracy includes a fibrous filler, a plate-shaped filler, a spherical filler, a powder-like filler, a curved-shaped filler, an amorphous filler, or a combination thereof. However, in order to reduce warpage deformation, it is preferable to use a filler having a small anisotropy. It is more preferable to use a filler having an aspect ratio close to 1, such as a plate-shaped filler, a spherical filler, and a powder-like filler. On the other hand, when a fibrous filler such as glass fiber is used, the effect of improving mechanical properties such as tensile strength is great, but the anisotropy of the shrinkage rate that causes warpage due to the orientation of the fibrous filler. In the fibrous filler used as the filler for improving dimensional accuracy (D-2) in the present invention, the ratio of fiber length ÷ fiber diameter of milled fiber, whiskers, etc. is 100 or less (preferably 2). ~ 30) short fibers or non-circular cross-section fibers with flat cross-sections such as cocoon-shaped or oval / elliptical (the ratio of major axis / minor axis of cross section is 1.3-10, preferably 1.5-5). The aspect ratio is small. The ratio of these fiber lengths and fiber diameters (including the major axis and the minor axis of the cross section) may be calculated using the values in the catalogs and specifications disclosed by the manufacturers of the fibrous fillers.
板状充填剤の具体例としては、板状タルク、マイカ、ガラスフレーク、金属片及びこれらの組み合わせ等を挙げることができ、球状充填剤の具体例としては、ガラスビーズ、ガラスバルーン、球状シリカ及びこれらの組み合わせ等を挙げることができ、粉状充填剤としてはガラス粉、タルク粉、石英粉末、石英粉末、カオリン、クレー、珪藻土、ウォラストナイト、炭化珪素、窒化珪素、金属粉、無機酸金属塩（炭酸カルシウム、ホウ酸亜鉛、ホウ酸カルシウム、スズ酸亜鉛、硫酸カルシウム、硫酸バリウム等）の粉末、金属酸化物（酸化マグネシウム、酸化鉄、酸化チタン、酸化亜鉛、アルミナ等）の粉末、金属水酸化物（水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、アルミナ水和物（ベーマイト）等）の粉末、金属硫化物（硫化亜鉛、硫化モリブデン、硫化タングステン等）の粉末、及びこれらの組み合わせ等を挙げることができる。なお、金属部材と組み合わせて用いる成形品においては、金属腐食性の観点から、これら寸法精度向上用充填剤（Ｄ－２）の中に含まれる遊離無機酸の含有量がそれぞれ０．５質量％以下のものであることが好ましい。 Specific examples of the plate-shaped filler include plate-shaped talc, mica, glass flakes, metal pieces and combinations thereof, and specific examples of the spherical filler include glass beads, glass balloons, spherical silica and the like. Examples of the powdery filler include glass powder, talc powder, quartz powder, quartz powder, kaolin, clay, diatomaceous earth, wollastonite, silicon carbide, silicon nitride, metal powder, and inorganic acid metal. Salt (calcium carbonate, zinc borate, calcium borate, zinc tintate, calcium sulfate, barium sulfate, etc.) powder, metal oxide (magnesium oxide, iron oxide, titanium oxide, zinc oxide, alumina, etc.) powder, metal Hydroxide (aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, alumina hydrate (bemite), etc.) powder, metal sulfide (zinc sulfide, molybdenum sulfide, tungsten sulfide, etc.) powder, and combinations thereof, etc. Can be mentioned. In the molded product used in combination with the metal member, the content of the free inorganic acid contained in these dimensional accuracy improving fillers (D-2) is 0.5% by mass, respectively, from the viewpoint of metal corrosiveness. It is preferably as follows.
寸法精度向上用充填剤（Ｄ－２）のサイズについては、反り低減効果と機械的特性や流動性等とのバランスを考慮して適宜選択することができる。例えばタルクとしては、体積平均粒子径が１～１０μｍのタルク、または嵩比重が０．４～１．５の圧縮微粉タルクを好適に用いることができ、マイカとしては、体積平均粒子径が１０～６０μｍのマイカを好適に用いることができる。これら平均粒子径や嵩比重についても、製造元各社が開示するカタログや仕様書の値を用いればよい。 The size of the filler (D-2) for improving dimensional accuracy can be appropriately selected in consideration of the balance between the warp reducing effect and the mechanical properties, fluidity and the like. For example, as talc, talc having a volume average particle diameter of 1 to 10 μm or compressed fine powder talc having a bulk specific density of 0.4 to 1.5 can be preferably used, and as mica, a volume average particle diameter of 10 to 10 to 60 μm mica can be preferably used. For these average particle diameters and bulk specific densities, the values in the catalogs and specifications disclosed by the manufacturers may be used.
これらの寸法精度向上剤（Ｄ－２）は、無機化合物および／または有機化合物で表面処理（表面被覆）されていてもよく、表面処理に用いられる無機化合物としては、例えば、水酸化アルミニウム、アルミナ、シリカ、ジルコニア、水酸化ジルコニウム、ジルコニア水和物、酸化セリウム、酸化セリウム水和物、水酸化セリウム等のアルミニウム、ケイ素、ジルコニウム、セリウム等の無機酸化物、水酸化物が好ましく挙げられる。また、これらの無機化合物は水和物であってもよい。これらの中でも、水酸化アルミニウム、シリカが好ましく、シリカを用いる場合は、ＳｉＯ２・ｎＨ２Ｏで表されるシリカ水和物であることが特に好ましい。また、表面処理に用いられる有機化合物としては、エポキシ化合物やアミン化合物が好ましく、ビスフェノールＡ型エポキシ、ノボラック型エポキシ等のエポキシ化合物およびモノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジクロルヘキシルアミン等のアミン化合物をより好ましい化合物として例示することができる。 These dimensional accuracy improvers (D-2) may be surface-treated (surface-coated) with an inorganic compound and / or an organic compound, and examples of the inorganic compound used for the surface treatment include aluminum hydroxide and alumina. , Silica, zirconia, zirconium hydride, zirconia hydrate, cerium oxide, cerium oxide hydrate, aluminum such as cerium hydroxide, inorganic oxides such as silicon, zirconium hydride and cerium, and hydroxides are preferable. Moreover, these inorganic compounds may be hydrates. Among these, aluminum hydroxide and silica are preferable, and when silica is used, silica hydrate represented by SiO 2 · nH 2 O is particularly preferable. The organic compound used for the surface treatment is preferably an epoxy compound or an amine compound, and an epoxy compound such as bisphenol A type epoxy or novolak type epoxy and an amine compound such as monoethanolamine, diethanolamine, triethanolamine and dichlorhexylamine are preferable. Can be exemplified as a more preferable compound.
寸法精度向上剤（Ｄ－２）の添加量は、ポリブチレンテレフタレート樹脂（Ａ）１００質量部に対し、０～１００質量部であり、５～９０質量部または１０～８０質量部であっても良い。寸法精度向上剤（Ｄ－２）の添加量は、反り低減効果と機械的特性や流動性等とのバランスを考慮して適宜選択することができる。 The amount of the dimensional accuracy improving agent (D-2) added is 0 to 100 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A), and even if it is 5 to 90 parts by mass or 10 to 80 parts by mass. good. The amount of the dimensional accuracy improving agent (D-2) added can be appropriately selected in consideration of the balance between the warp reducing effect and the mechanical properties, fluidity and the like.
上述の寸法精度向上用アロイ樹脂（Ｄ－１）及び／又は寸法精度向上用充填剤（Ｄ－２）からなる寸法精度向上剤（Ｄ）の添加量は、寸法精度向上用アロイ樹脂（Ｄ－１）と寸法精度向上用充填剤（Ｄ－２）の合計として、ポリブチレンテレフタレート樹脂（Ａ）１００質量部に対し、１０～２００質量部であり、２０～１８０質量部または３０～１５０質量部であっても良い。 The amount of the dimensional accuracy improving agent (D) made of the above-mentioned dimensional accuracy improving alloy resin (D-1) and / or the dimensional accuracy improving filler (D-2) is the dimensional accuracy improving alloy resin (D-). The total of 1) and the filler for improving dimensional accuracy (D-2) is 10 to 200 parts by mass, and 20 to 180 parts by mass or 30 to 150 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). It may be.
（その他の成分）
本発明の実施形態のポリブチレンテレフタレート樹脂組成物には、本発明の効果を阻害しない範囲で、その目的に応じた所望の特性を付与するために、一般に熱可塑性樹脂及び熱硬化性樹脂に添加される公知の物質、例えば、酸化防止剤や紫外線吸収剤等の安定剤、円形断面ガラス繊維などの強化用充填剤、帯電防止剤、染料や顔料等の着色剤、離型剤、潤滑剤、結晶化促進剤、結晶核剤等を配合することが可能である。
(Other ingredients)
The polybutylene terephthalate resin composition of the embodiment of the present invention is generally added to a thermoplastic resin and a thermosetting resin in order to impart desired properties according to the purpose thereof without impairing the effect of the present invention. Known substances such as stabilizers such as antioxidants and ultraviolet absorbers, reinforcing fillers such as circular cross-sectional glass fibers, antioxidants, colorants such as dyes and pigments, mold release agents, lubricants, etc. It is possible to add a crystallization accelerator, a crystal nucleating agent, and the like.
（成形品）
本発明の実施形態の成形品は、本発明のポリブチレンテレフタレート樹脂組成物を成形してなるものである。成形方法は特に限定されず、公知の成形方法を採用することができる。例えば、（１）各成分を混合して、一軸又は二軸の押出機により混練し押出してペレットを調製した後、成形する方法、（２）一旦、組成の異なるペレット（マスターバッチ）を調製し、そのペレットを所定量混合（希釈）して成形に供し、所定の組成の成形品を得る方法、（３）成形機に各成分の１又は２以上を直接仕込む方法などで製造できる。なお、ペレットは、例えば、脆性成分（ガラス系補強材など）を除く成分を溶融混合した後に、脆性成分を混合することにより調製してもよい。また、熱可塑性樹脂からなる他の成形品の成形方法もまた、特に限定されず、公知の成形方法を採用することができる。
(Molding)
The molded product of the embodiment of the present invention is obtained by molding the polybutylene terephthalate resin composition of the present invention. The molding method is not particularly limited, and a known molding method can be adopted. For example, (1) a method of mixing each component, kneading and extruding with a uniaxial or biaxial extruder to prepare pellets, and then molding, and (2) once preparing pellets (master batch) having different compositions. , The pellets can be mixed (diluted) in a predetermined amount and subjected to molding to obtain a molded product having a predetermined composition, or (3) one or two or more of each component is directly charged into a molding machine. The pellet may be prepared, for example, by melting and mixing the components excluding the brittle component (glass-based reinforcing material, etc.) and then mixing the brittle component. Further, the molding method of another molded product made of a thermoplastic resin is also not particularly limited, and a known molding method can be adopted.
成形品は、前記樹脂組成物を溶融混練し、押出成形、射出成形、圧縮成形、ブロー成形、真空成形、回転成形、ガスインジェクションモールディングなどの慣用の方法で成形してもよいが、通常、射出成形により成形される。なお、射出成形時の金型温度は、通常４０～９０℃、好ましくは５０～８０℃、さらに好ましくは６０～８０℃程度である。 The molded product may be formed by melt-kneading the resin composition and molding by a conventional method such as extrusion molding, injection molding, compression molding, blow molding, vacuum molding, rotary molding, gas injection molding, etc., but usually injection. It is molded by molding. The mold temperature during injection molding is usually 40 to 90 ° C, preferably 50 to 80 ° C, and more preferably about 60 to 80 ° C.
成形品は、着色剤を含んでいてもよい。前記着色剤としては、無機顔料［カーボンブラック（例えば、アセチレンブラック、ランプブラック、サーマルブラック、ファーネスブラック、チャンネルブラック、ケッチェンブラックなど）などの黒色顔料、酸化鉄赤などの赤色顔料、モリブデートオレンジなどの橙色顔料、酸化チタンなどの白色顔料など］、有機顔料（黄色顔料、橙色顔料、赤色顔料、青色顔料、緑色顔料など）などが挙げられる。カーボンブラックの平均粒子径は、通常、１０～１０００ｎｍ、好ましくは１０～１００ｎｍ程度であってもよい。着色剤の割合は、成形品全体に対して０．１～１０重量％、好ましくは０．３～５重量％（例えば、０．３～３重量％）程度である。 The molded product may contain a colorant. Examples of the colorant include black pigments such as carbon blacks (eg, acetylene black, lamp black, thermal black, furnace black, channel black, Ketjen black, etc.), red pigments such as iron oxide red, and molybdate orange. Orange pigments such as orange pigments, white pigments such as titanium oxide], organic pigments (yellow pigments, orange pigments, red pigments, blue pigments, green pigments, etc.) and the like. The average particle size of carbon black may be usually about 10 to 1000 nm, preferably about 10 to 100 nm. The ratio of the colorant is about 0.1 to 10% by weight, preferably about 0.3 to 5% by weight (for example, 0.3 to 3% by weight) with respect to the entire molded product.
［実施例］
以下、実施例により本発明を具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。
[Example]
Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
＜材料＞
（Ａ）ポリブチレンテレフタレート樹脂（ＰＢＴ）
・ＰＢＴ：ポリプラスチックス社製、末端カルボキシル基量１２ｍｅｑ／ｋｇ、固有粘度０．８７ｄｌ／ｇのポリブチレンテレフタレート樹脂
（Ｂ）エポキシ系樹脂
・エポキシ樹脂：三菱ケミカル社製、エピコートＪＥＲ１００４Ｋ
（Ｃ）第４級アンモニウム塩
・（Ｃ－１）テトラブチルアンモニウムブロミド
・（Ｃ－２）テトラエチルアンモニウムブロミド
・（Ｃ－３）テトラプロピルアンモニウムブロミド
・（Ｃ－４）テトラペンチルアンモニウムブロミド
・（Ｃ－５）テトラヘキシルアンモニウムブロミド
・（Ｃ－６）テトラヘプチルアンモニウムブロミド
・（Ｃ－７）テトラオクチルアンモニウムブロミド
・（Ｃ－８）テトラブチルアンモニウムクロリド
・（Ｃ－９）テトラブチルアンモニウムヨージド
・（Ｃ－１０）テトラブチルアンモニウムテトラフェニルボレート
・（Ｃ－１１）ベンジルトリメチルアンモニウムブロミド
・（Ｃ－１２）ベンジルトリエチルアンモニウムブロミド
・（Ｃ－１３）ベンジルトリエチルアンモニウムクロリド
・（Ｃ－１４）ドデシルトリメチルアンモニウムブロミド
・（Ｃ’－１）セチルジメチルエチルアンモニウムブロミド
・（Ｃ’－２）ステアリルトリメチルアンモニウムブロミド
・（Ｃ’－３）フェニルボロン酸
・（Ｃ’－４）ステアリン酸カルシウム
・（Ｃ’－５）ビス(２，２，６，６－テトラメチル－４－ピペリジル)セバケート
（Ｄ）寸法精度向上剤
（Ｄ－１）寸法精度向上用アロイ樹脂
（Ｄ－１－１）ＡＳ樹脂（Ｎｉｎｇｂｏ ＬＧ Ｙｏｎｇｘｉｎｇ Ｃｈｅｍｉｃａｌ社製、アクリロニトリル－スチレン樹脂 ８０ＨＦ）
（Ｄ－１－２）ＰＣ樹脂（帝人社製、ポリカーボネート樹脂 パンライトＬ－１２２５Ｗ）
（Ｄ－１－３）ＰＥＴ樹脂（帝人社製、ポリエチレンテレフタレート樹脂 ＴＲＮ－８５５０ＦＦ）
（Ｄ－１－４）ＥＥＡ共重合体（ＮＵＣ社製、ＮＵＣ－６５７０）
（Ｄ－２）寸法精度向上用充填剤
（Ｄ－２－１）タルク（松村産業社製、クラウンタルクＰＰ）
（Ｄ－２－２）ガラスフレーク（日本板硝子社製、マイクログラス フレカＲＥＦＧ－３０１）
（Ｄ－２－３）扁平断面ガラス繊維（日東紡社製、ＣＳＧ３ＰＡ８３０（長径２８μｍ、短径７μｍの長円形断面（長径÷短径比＝４）、平均繊維長３ｍｍの長円形断面ガラス繊維））
（その他の成分）
・強化用充填剤：日本電気硝子製、円形断面ガラス繊維 ＥＣＳ０３Ｔ―１２７（平均繊維径１３μｍ、平均繊維長３ｍｍ）
・酸化防止剤：ＢＡＳＦジャパン社製、フェノール系酸化防止剤 イルガノックス１０１０
・滑剤：理研ビタミン社製、ジグリセロールテトラベヘネート リケマールＢ７４
<Material>
(A) Polybutylene terephthalate resin (PBT)
-PBT: Polybutylene terephthalate resin (B) epoxy resin manufactured by Polyplastics, end carboxyl group amount 12meq / kg, intrinsic viscosity 0.87dl / g Epoxy resin: Epicoat JER1004K manufactured by Mitsubishi Chemical Co., Ltd.
(C) Tertiary ammonium salt, (C-1) tetrabutylammonium bromide, (C-2) tetraethylammonium bromide, (C-3) tetrapropylammonium bromide, (C-4) tetrapentylammonium bromide, (C) -5) Tetrahexylammonium bromide, (C-6) tetraheptylammonium bromide, (C-7) tetraoctylammonium bromide, (C-8) tetrabutylammonium chloride, (C-9) tetrabutylammonium iodide, (C-9) C-10) Tetrabutylammonium tetraphenylborate ・ (C-11) benzyltrimethylammonium bromide ・ (C-12) benzyltriethylammonium bromide ・ (C-13) benzyltriethylammonium chloride ・ (C-14) dodecyltrimethylammonium bromide
・ (C'-1) cetyldimethylethylammonium bromide ・ (C'-2) stearyltrimethylammonium bromide ・ (C'-3) phenylboronic acid ・ (C'-4) calcium stearate ・ (C'-5) bis (2,2,6,6-Tetramethyl-4-piperidyl) Sevacate (D) Dimensional accuracy improver (D-1) Alloy resin for improving dimensional accuracy (D-1-1) AS resin (Ningbo LG Yongxing Chemical) Made by Acrylonitrile-Styrene Resin 80HF)
(D-1-2) PC resin (made by Teijin, polycarbonate resin Panlite L-1225W)
(D-1-3) PET resin (made by Teijin, polyethylene terephthalate resin TRN-8550FF)
(D-1-4) EEA copolymer (manufactured by NUC, NUC-6570)
(D-2) Filler for improving dimensional accuracy (D-2-1) Talc (manufactured by Matsumura Sangyo Co., Ltd., Crown Talc PP)
(D-2-2) Glass flakes (Made by Nippon Sheet Glass, Micro Glass Flaca REFG-301)
(D-2-3) Flat cross-section glass fiber (manufactured by Nitto Boseki, CSG3PA830 (major axis 28 μm, minor axis 7 μm oval cross section (major axis ÷ minor axis ratio = 4), oval cross section glass fiber with average fiber length 3 mm)) )
(Other ingredients)
-Reinforcing filler: Nippon Electric Glass, circular cross-section glass fiber ECS03T-127 (average fiber diameter 13 μm, average fiber length 3 mm)
-Antioxidant: Phenolic antioxidant Ilganox 1010 manufactured by BASF Japan Ltd.
・ Lubricants: Diglycerol Tetrabehenate Rikemar B74 manufactured by RIKEN Vitamin Co., Ltd.
＜評価方法＞
（実施例１～２４、比較例１～１１）
各成分を表１、２に示す割合で混合した後、日本製鋼所製ＴＥＸ－３０を用いて、シリンダー温度２６０℃、吐出量１５ｋｇ／ｈ、スクリュ回転数１３０ｒｐｍで溶融混練して押出し、ポリブチレンテレフタレート樹脂組成物からなるペレットを得て、以下の各特性の評価を行った。
<Evaluation method>
(Examples 1 to 24, Comparative Examples 1 to 11)
After mixing each component at the ratios shown in Tables 1 and 2, melt-kneaded and extruded at a cylinder temperature of 260 ° C., a discharge rate of 15 kg / h, and a screw rotation speed of 130 rpm using TEX-30 manufactured by Japan Steel Works, and then polybutylene. Pellets made of a terephthalate resin composition were obtained, and the following characteristics were evaluated.
（溶融粘度）
得られたペレットを１４０℃で３時間乾燥した後、東洋精機製キャピログラフを用い、キャピラリーとして１ｍｍφ×２０ｍｍＬ／フラットダイを使用し、バレル温度２６０℃、滞留時間９分にて、せん断速度１０００ｓｅｃ－１での溶融粘度（Ｐａ・ｓ）を測定した。溶融粘度が１５０Ｐａ・ｓ以下のものを◎、１５０Ｐａ・ｓ超２００Ｐａ・ｓ以下のものを○、２００Ｐａ・ｓ超のものを×として判定した結果を表１、２に示す。
(Melting viscosity)
After drying the obtained pellets at 140 ° C. for 3 hours, a capillograph manufactured by Toyo Seiki Co., Ltd. was used, a 1 mmφ × 20 mmL / flat die was used as a capillary, a barrel temperature of 260 ° C., a residence time of 9 minutes, and a shear rate of 1000 sec -1 . The melt viscosity (Pa · s) was measured in. Tables 1 and 2 show the results of determining a melt viscosity of 150 Pa · s or less as ⊚, a melt viscosity of more than 150 Pa · s of 200 Pa · s or less as ◯, and a melt viscosity of more than 200 Pa · s as x.
（耐加水分解性）
得られたペレットを１４０℃で３時間乾燥した後、シリンダー温度２６０℃、金型温度８０℃で射出成形して、ＩＳＯ３１６７に準拠した１Ａタイプの引張試験片を作製し、得られた試験片について、ＩＳＯ５２７－１，２に準拠し、引張強さの測定を行った。
(Hydrolysis resistance)
The obtained pellets were dried at 140 ° C. for 3 hours and then injection molded at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. to prepare a 1A type tensile test piece compliant with ISO3167. , ISO527-1,2, and the tensile strength was measured.
次いで、同様にして作製した別の引張試験片を、プレッシャークッカー試験（１２１℃×１００％Ｒｈ×２０３ｋＰａ×７５ｈｒ、１００ｈｒ、１２０ｈｒ）にて処理した後、ＩＳＯ５２７－１，２に準拠し、引張強さの測定を行い、未処理品の引張強さに対する比率からそれぞれの強度保持率（％）を算出した。強度保持率が８０％以上のものを◎、５０％以上８０％未満のものを○、３０以上５０％未満のものを△、３０％未満のものを×として判定した結果を表１、２に示す。 Next, another tensile test piece produced in the same manner was treated by a pressure cooker test (121 ° C. × 100% Rh × 203 kPa × 75 hr, 100 hr, 120 hr), and then subjected to ISO527-1 and 2, tensile strength. The strength was measured and the strength retention rate (%) of each was calculated from the ratio to the tensile strength of the untreated product. Tables 1 and 2 show the results of judging that the strength retention rate is 80% or more as ◎, 50% or more and less than 80% as ○, 30 or more and less than 50% as △, and less than 30% as ×. show.
（寸法精度（低反り性））
得られたペレットを１４０℃で３時間乾燥させた後、シリンダ温度２６０℃、金型温度６０℃、保圧６０ＭＰａにて１２０ｍｍ×１２０ｍｍ×２ｍｍの平板状試験片を射出成形した。得られた平板状試験片を２３℃、５０％ＲＨで２４時間静置後、定盤上に載置し、上面の四隅と中心、及び各辺の中央部（４点）の、合計９点についてミツトヨ製ＣＮＣ画像測定機で高さ方向の座標を測定し、最高部と最低部との差から、成形品の反りの発生量を算出した。反りの発生量が５ｍｍ以下である場合を◎、５ｍｍ超１０ｍｍ以下である場合を○、１０ｍｍ超１５ｍｍ以下である場合を△、１５ｍｍ超である場合を×として評価した結果を表１、２に示す。
(Dimensional accuracy (low warpage))
The obtained pellets were dried at 140 ° C. for 3 hours, and then a flat plate-shaped test piece of 120 mm × 120 mm × 2 mm was injection-molded at a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., and a holding pressure of 60 MPa. The obtained flat plate-shaped test piece was allowed to stand at 23 ° C. and 50% RH for 24 hours, and then placed on a surface plate. The coordinates in the height direction were measured with a CNC image measuring machine manufactured by Mitutoyo, and the amount of warpage of the molded product was calculated from the difference between the highest portion and the lowest portion. Tables 1 and 2 show the results of evaluation as ◎ when the amount of warpage generated is 5 mm or less, ◯ when it is more than 5 mm and 10 mm or less, Δ when it is more than 10 mm and 15 mm or less, and × when it is more than 15 mm. show.
表１、２に示した通り、各実施例ではＰＣＴ処理後においても、高い引張強さ保持率を示していた。特に、各実施例ではＰＣＴ処理１００ｈｒ後または１２０ｈｒ後において顕著な優位性が見られることが確認された。これは、本発明の特定の第４級アンモニウム塩が、ポリブチレンテレフタレート樹脂とエポキシ系樹脂を含有するポリブチレンテレフタレート樹脂組成物からなる成形品の加水分解性を向上させていることを示している。 As shown in Tables 1 and 2, each example showed a high tensile strength retention rate even after the PCT treatment. In particular, it was confirmed that in each example, a remarkable superiority was observed after 100 hours or 120 hours of PCT treatment. This indicates that the specific quaternary ammonium salt of the present invention improves the hydrolyzability of a molded product made of a polybutylene terephthalate resin composition containing a polybutylene terephthalate resin and an epoxy resin. ..
また、表１の実施例２１、２４に示した通り、本発明の第４級アンモニウム塩のカチオンを構成する４つのＲのうち、３つがメチル基、他１つがアルキル基、アリール基、アラルキル基から選択される炭素原子数６以上の官能基である場合、ポリブチレンテレフタレート樹脂とエポキシ系樹脂を含有するポリブチレンテレフタレート樹脂組成物の粘度上昇を抑制しつつ、ＰＣＴ１００ｈｒ後または１２０ｈｒ後においても、高い引張強さ保持率を示していた。 Further, as shown in Examples 21 and 24 of Table 1, of the four Rs constituting the cation of the quaternary ammonium salt of the present invention, three are methyl groups and the other one is an alkyl group, an aryl group and an aralkyl group. When the functional group has 6 or more carbon atoms selected from the above, the polybutylene terephthalate resin composition containing the polybutylene terephthalate resin and the epoxy resin is suppressed from increasing in viscosity, and is high even after PCT 100 hr or 120 hr. It showed the tensile strength retention rate.
Claims (20)
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| CN115246980B (en) * | 2022-07-20 | 2023-09-29 | 广东锦湖日丽高分子材料有限公司 | Essential oil-resistant ABS resin and preparation method thereof |
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