JP6828414B2 - Polyarylene sulfide resin composition, molded article and manufacturing method - Google Patents
Polyarylene sulfide resin composition, molded article and manufacturing method Download PDFInfo
- Publication number
- JP6828414B2 JP6828414B2 JP2016247856A JP2016247856A JP6828414B2 JP 6828414 B2 JP6828414 B2 JP 6828414B2 JP 2016247856 A JP2016247856 A JP 2016247856A JP 2016247856 A JP2016247856 A JP 2016247856A JP 6828414 B2 JP6828414 B2 JP 6828414B2
- Authority
- JP
- Japan
- Prior art keywords
- polyarylene sulfide
- sulfide resin
- range
- resin composition
- mass
- 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.)
- Active
Links
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims description 120
- 229920000412 polyarylene Polymers 0.000 title claims description 118
- 239000011342 resin composition Substances 0.000 title claims description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 229920005989 resin Polymers 0.000 claims description 121
- 239000011347 resin Substances 0.000 claims description 121
- 238000002844 melting Methods 0.000 claims description 37
- 230000008018 melting Effects 0.000 claims description 37
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 36
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 36
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 36
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 34
- 238000001953 recrystallisation Methods 0.000 claims description 29
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 20
- 238000000465 moulding Methods 0.000 claims description 17
- 125000000524 functional group Chemical group 0.000 claims description 13
- 238000004898 kneading Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 46
- 239000000047 product Substances 0.000 description 39
- 238000000034 method Methods 0.000 description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- 239000004734 Polyphenylene sulfide Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229920000069 polyphenylene sulfide Polymers 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 11
- -1 alkali metal salt Chemical class 0.000 description 11
- 150000001491 aromatic compounds Chemical class 0.000 description 11
- 239000000155 melt Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 229920002050 silicone resin Polymers 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 230000001771 impaired effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000004434 sulfur atom Chemical group 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 2
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000007864 aqueous solution Substances 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
- 239000011324 bead Substances 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 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
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 125000000816 ethylene group Polymers [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- NNTRMVRTACZZIO-UHFFFAOYSA-N 3-isocyanatopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCN=C=O NNTRMVRTACZZIO-UHFFFAOYSA-N 0.000 description 1
- NMUBRRLYMADSGF-UHFFFAOYSA-N 3-triethoxysilylpropan-1-ol Chemical compound CCO[Si](OCC)(OCC)CCCO NMUBRRLYMADSGF-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- CDPKJZJVTHSESZ-UHFFFAOYSA-N 4-chlorophenylacetic acid Chemical compound OC(=O)CC1=CC=C(Cl)C=C1 CDPKJZJVTHSESZ-UHFFFAOYSA-N 0.000 description 1
- OSSMYOQKNHMTIP-UHFFFAOYSA-N 5-[dimethoxy(methyl)silyl]pentane-1,3-diamine Chemical compound CO[Si](C)(OC)CCC(N)CCN OSSMYOQKNHMTIP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 0 CC*(C)[C@@](CCCCC1)C1N Chemical compound CC*(C)[C@@](CCCCC1)C1N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical compound CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WYZXIJYWXFEAFG-UHFFFAOYSA-N ethyl-(3-isocyanatopropyl)-dimethoxysilane Chemical compound CC[Si](OC)(OC)CCCN=C=O WYZXIJYWXFEAFG-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012803 melt mixture Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 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
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane 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
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- DDBUVUBWJVIGFH-UHFFFAOYSA-N trichloro(3-isocyanatopropyl)silane Chemical compound Cl[Si](Cl)(Cl)CCCN=C=O DDBUVUBWJVIGFH-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical group C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリアリーレンスルフィド樹脂組成物、成形品およびそれらの製造方法に関する。 The present invention relates to polyarylene sulfide resin compositions, molded articles, and methods for producing them.
ポリフェニレンスルフィド（以下ＰＰＳと略すことがある）樹脂に代表されるポリアリーレンスルフィド（以下ＰＡＳと略すことがある）樹脂は、高融点で耐熱性に優れつつ、かつ、機械的強度、耐薬品性、成形加工性、寸法安定性にも優れることが知られている。そこで、一般的には、ＰＡＳ樹脂に、充填剤やエラストマー等の添加剤を配合し、これらがＰＡＳ樹脂からなるマトリックス中に分散されるよう溶融混練してＰＡＳ樹脂組成物とした上で、溶融成形して電気・電子機器部品、自動車部品等として使用される成形品に加工される。 Polyphenylene sulfide (hereinafter sometimes abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin has a high melting point and excellent heat resistance, and has mechanical strength and chemical resistance. It is known to be excellent in moldability and dimensional stability. Therefore, in general, an additive such as a filler or an elastomer is mixed with the PAS resin and melt-kneaded so that these are dispersed in a matrix made of the PAS resin to obtain a PAS resin composition, and then melted. It is molded and processed into molded products used as electrical / electronic equipment parts, automobile parts, etc.
ポリアリーレンスルフィド樹脂等の熱可塑性樹脂の溶融成形には射出成形、押出成形、圧縮成形、ブロー成形等の様々な溶融加工法が採用される。熱可塑性樹脂を溶融加工する場合、樹脂組成物を融点以上の温度に加熱して流動性を高めた上で成形加工する。例えば、射出成形法では、溶融した樹脂を適切な温度に加熱した金型に射出充填し、冷却し固化させて成形物を得る。しかし、ＰＡＳ樹脂組成物は溶融状態から固化（結晶化）する温度（再結晶化温度：Ｔｃ２）が高いため、金型内を充満する前に固化（結晶化）してしまう問題があった。このような問題は、射出成形に限らず、溶融加工全般で見られ、複雑な形状や、肉厚差のある形状の成形品や、さらに大型（樹脂量が多い）成形品では、賦形前に固化（結晶化）してしまい成形不良品の割合が多くなり、歩留り（樹脂組成物の投入量から期待される生産量に対して、実際に得られた製品生産数（量）比率）が低い傾向にあった。このため、より再結晶化温度（Ｔｃ２）の低い、ポリアリーレンスルフィド樹脂を含む樹脂組成物の開発が望まれていた。 Various melt processing methods such as injection molding, extrusion molding, compression molding, and blow molding are adopted for melt molding of a thermoplastic resin such as a polyarylene sulfide resin. When the thermoplastic resin is melt-processed, the resin composition is heated to a temperature equal to or higher than the melting point to increase its fluidity, and then molded. For example, in the injection molding method, a molten resin is injection-filled in a mold heated to an appropriate temperature, cooled and solidified to obtain a molded product. However, since the PAS resin composition has a high temperature at which it solidifies (crystallizes) from the molten state (recrystallization temperature: Tc2), there is a problem that the PAS resin composition solidifies (crystallizes) before filling the inside of the mold. Such problems are seen not only in injection molding but also in general melt processing, and in molded products with complicated shapes, shapes with different wall thicknesses, and larger molded products (with a large amount of resin), before shaping. The ratio of defective molded products increases due to solidification (crystallization), and the yield (ratio of the actual production number (quantity) of the product to the production amount expected from the input amount of the resin composition) becomes It tended to be low. Therefore, it has been desired to develop a resin composition containing a polyarylene sulfide resin having a lower recrystallization temperature (Tc2).
そこで、ポリアリーレンスルフィド樹脂の再結晶化温度を低下させることを目的として、パラジクロロベンゼンとメタジクロロベンゼンとを共重合させる方法が提案されている（特許文献１参照）。しかしながら、該ＰＡＳ樹脂は骨格の一部にメタ体を挿入する方法であるため、用いるＰＡＳ樹脂そのものの再結晶化温度が低下すると伴に、融点（耐熱性）も低下してしまうという性質があった。その結果、当該ＰＡＳ樹脂を用いた樹脂材料は低温成形性に優れる一方で、得られた成形品も、融点（耐熱性）が著しく低下するという性質があった。さらに、ＰＡＳ樹脂の骨格の変更は、コンタミ防止の観点からポリマー製造ラインの洗浄に多大なエネルギーを要するため生産性の低下を招いていた。 Therefore, a method of copolymerizing paradichlorobenzene and metadichlorobenzene has been proposed for the purpose of lowering the recrystallization temperature of the polyarylene sulfide resin (see Patent Document 1). However, since the PAS resin is a method of inserting a meta-body into a part of the skeleton, there is a property that the melting point (heat resistance) also decreases as the recrystallization temperature of the PAS resin used itself decreases. It was. As a result, while the resin material using the PAS resin is excellent in low-temperature moldability, the obtained molded product also has a property that the melting point (heat resistance) is remarkably lowered. Further, the change in the skeleton of the PAS resin requires a large amount of energy for cleaning the polymer production line from the viewpoint of preventing contamination, resulting in a decrease in productivity.
したがって本発明が解決しようとする課題は、再結晶化温度（Ｔｃ２）が低く、かつ成形品とした際の耐熱性にも優れるポリアリーレンスルフィド樹脂組成物、それを成形して得られるポリアリーレンスルフィド樹脂成形品およびそれらの製造方法を提供することにある。 Therefore, the problem to be solved by the present invention is a polyarylene sulfide resin composition having a low recrystallization temperature (Tc2) and excellent heat resistance when made into a molded product, and a polyarylene sulfide obtained by molding the polyarylene sulfide resin composition. It is an object of the present invention to provide resin molded products and methods for producing them.
本発明者は上記課題を解決するために鋭意研究した結果、ポリアリーレンスルフィド樹脂にポリビニルピロリドンおよびカルボキシ基と反応する官能基を有するシランカップリング剤を必須成分として配合して溶融混錬することにより得られる樹脂組成物が、用いるポリアリーレンスルフィド樹脂の骨格を変更することなく、再結晶化温度（Ｔｃ２）が低く、かつ、成形品とした際に耐熱性にも優れることを見出し、上記課題を解決するに至った。 As a result of diligent research to solve the above problems, the present inventor has added polyvinylpyrrolidone and a silane coupling agent having a functional group that reacts with a carboxy group as essential components to a polyarylene sulfide resin and melt-kneaded the resin. We have found that the obtained resin composition has a low recrystallization temperature (Tc2) and is excellent in heat resistance when formed into a molded product without changing the skeleton of the polyarylene sulfide resin used. It came to a solution.
すなわち、本発明は、ポリアリーレンスルフィド樹脂（Ａ）と、ポリビニルピロリドン（Ｂ）と、カルボキシ基と反応する官能基を有するシランカップリング剤（Ｃ）を必須成分として配合してなり、
ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、前記ポリビニルピロリドン（Ｂ）が０．０１〜１００質量部の範囲であり、前記エポキシ基含有シランカップリング剤（Ｃ）が０．０１〜３０質量部の範囲であること、を特徴とするポリアリーレンスルフィド樹脂組成物、に関する。
That is, the present invention comprises a polyarylene sulfide resin (A), polyvinylpyrrolidone (B), and a silane coupling agent (C) having a functional group that reacts with a carboxy group as essential components.
The polyvinylpyrrolidone (B) is in the range of 0.01 to 100 parts by mass and the epoxy group-containing silane coupling agent (C) is 0.01 to 30 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). The present invention relates to a polyarylene sulfide resin composition, which is characterized by a range of parts by mass.
加えて本発明は、前記ポリアリーレンスルフィド樹脂組成物を成形してなる成形品、に関する。 In addition, the present invention relates to a molded product obtained by molding the polyarylene sulfide resin composition.
さらに本発明は、ポリアリーレンスルフィド樹脂（Ａ）と、ポリビニルピロリドン（Ｂ）と、カルボキシ基と反応する官能基を有するシランカップリング剤（Ｃ）を必須成分として、ポリアリーレンスルフィド樹脂（Ａ）の融点以上で溶融混練することを特徴とするポリアリーレンスルフィド樹脂組成物の製造方法、に関する。 Further, the present invention comprises a polyarylene sulfide resin (A), polyvinylpyrrolidone (B), and a silane coupling agent (C) having a functional group that reacts with a carboxy group as essential components of the polyarylene sulfide resin (A). The present invention relates to a method for producing a polyarylene sulfide resin composition, which comprises melt-kneading at a melting point or higher.
また、本発明は、前記の製造方法で得られたポリアリーレンスルフィド樹脂組成物を成形する、成形品の製造方法、に関する。 The present invention also relates to a method for producing a molded product, which forms the polyarylene sulfide resin composition obtained by the above-mentioned production method.
本発明によれば、再結晶化温度（Ｔｃ２）が低く、かつ、成形品とした際の耐熱性にも優れるポリアリーレンスルフィド樹脂組成物、それを成形して得られるポリアリーレンスルフィド樹脂成形品およびそれらの製造方法を提供することができる。 According to the present invention, a polyarylene sulfide resin composition having a low recrystallization temperature (Tc2) and excellent heat resistance when made into a molded product, a polyarylene sulfide resin molded product obtained by molding the polyarylene sulfide resin composition, and a molded product. A method for producing them can be provided.
本発明のポリアリーレンスルフィド樹脂組成物は、ポリアリーレンスルフィド樹脂（Ａ）と、ポリビニルピロリドン（Ｂ）と、カルボキシ基と反応する官能基を有するシランカップリング剤（Ｃ）を必須成分として配合してなり、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、前記ポリビニルピロリドン（Ｂ）が０．０１〜１００質量部の範囲であり、前記シランカップリング剤（Ｃ）が０．０１〜３０質量部の範囲であることを特徴とする。 The polyarylene sulfide resin composition of the present invention contains a polyarylene sulfide resin (A), polyvinylpyrrolidone (B), and a silane coupling agent (C) having a functional group that reacts with a carboxy group as essential components. The polyvinylpyrrolidone (B) is in the range of 0.01 to 100 parts by mass and the silane coupling agent (C) is in the range of 0.01 to 30 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is characterized by being a range of parts.
本発明のポリアリーレンスルフィド樹脂組成物は、ポリアリーレンスルフィド樹脂（Ａ）を必須成分として含有する。本発明で用いるポリアリーレンスルフィド樹脂は、芳香族環と硫黄原子とが結合した構造を繰り返し単位とする樹脂構造を有するものであり、具体的には、下記一般式（２） The polyarylene sulfide resin composition of the present invention contains the polyarylene sulfide resin (A) as an essential component. The polyarylene sulfide resin used in the present invention has a resin structure having a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit. Specifically, the following general formula (2)
ここで、前記一般式（２）で表される構造部位は、特に該式中のＲ１及びＲ２は、前記ポリアリーレンスルフィド樹脂の機械的強度の点から水素原子であることが好ましく、その場合、下記式（４）で表されるパラ位で結合するもの、及び下記式（５）で表されるメタ位で結合するものが挙げられる。 Here, the structural portion represented by the general formula (2) is preferably a hydrogen atom in particular, R 1 and R 2 in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin. In this case, those that are combined at the para position represented by the following formula (4) and those that are combined at the meta position represented by the following formula (5) can be mentioned.
また、前記ポリアリーレンスルフィド樹脂は、前記一般式（２）や（３）で表される構造部位のみならず、下記の構造式（６）〜（９） Further, the polyarylene sulfide resin has not only the structural parts represented by the general formulas (2) and (3) but also the following structural formulas (6) to (9).
また、前記ポリアリーレンスルフィド樹脂は、その分子構造中に、ナフチルスルフィド結合などを有していてもよいが、他の構造部位との合計モル数に対して、３モル％以下が好ましく、特に１モル％以下であることが好ましい。 Further, the polyarylene sulfide resin may have a naphthyl sulfide bond or the like in its molecular structure, but is preferably 3 mol% or less, particularly 1 in terms of the total number of moles with other structural sites. It is preferably mol% or less.
また、ポリアリーレンスルフィド樹脂の物性は、本発明の効果を損ねない限り特に限定されないが、以下の通りである。 The physical characteristics of the polyarylene sulfide resin are not particularly limited as long as the effects of the present invention are not impaired, but are as follows.
（融点（Ｔｍ）と再結晶化温度（Ｔｃ２））
前記樹脂（Ａ）の融点（Ｔｍ）は、耐熱性や機械的強度に優れるポリアリーレンスルフィド樹脂組成物となることから、２７０℃以上の範囲であることが好ましく、さらに２７０〜３００℃の範囲であることがより好ましい。また、前記樹脂（Ａ）の再結晶化温度（Ｔｃ２）は、耐熱性や機械的強度に優れるポリアリーレンスルフィド樹脂組成物となることから、２００〜２６０℃の範囲であることが好ましい。
(Melting point (Tm) and recrystallization temperature (Tc2))
The melting point (Tm) of the resin (A) is preferably in the range of 270 ° C. or higher, and further in the range of 270 to 300 ° C. because it is a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength. More preferably. The recrystallization temperature (Tc2) of the resin (A) is preferably in the range of 200 to 260 ° C. because it is a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength.
（溶融粘度）
本発明に用いるポリアリーレンスルフィド樹脂は、３００℃で測定した溶融粘度（Ｖ６）が２〜１０００〔Ｐａ・ｓ〕の範囲であることが好ましく、さらに流動性および機械的強度のバランスが良好となることから１０〜５００〔Ｐａ・ｓ〕の範囲がより好ましく、特に６０〜２００〔Ｐａ・ｓ〕の範囲であることが特に好ましい。但し、本発明において、溶融粘度（Ｖ６）は、ポリアリーレンスルフィド樹脂を島津製作所製フローテスター、ＣＦＴ−５００Ｄを用い、３００℃、荷重：１．９６×１０６Ｐａ、Ｌ／Ｄ＝１０（ｍｍ）／１（ｍｍ）にて、６分間保持した後に溶融粘度を測定した値とする。
(Melting viscosity)
The polyarylene sulfide resin used in the present invention preferably has a melt viscosity (V6) measured at 300 ° C. in the range of 2 to 1000 [Pa · s], and further improves the balance between fluidity and mechanical strength. Therefore, the range of 10 to 500 [Pa · s] is more preferable, and the range of 60 to 200 [Pa · s] is particularly preferable. However, in the present invention, the melt viscosity (V6) is 300 ° C., load: 1.96 × 10 6 Pa, L / D = 10 (mm) using a polyarylene sulfide resin, a flow tester manufactured by Shimadzu Corporation, CFT-500D. ) / 1 (mm), the melt viscosity is measured after holding for 6 minutes.
（非ニュートン指数）
本発明に用いるポリアリーレンスルフィド樹脂（Ａ）の非ニュートン指数は、本発明の効果を損ねない限り特に限定されないが、０．９０〜２．００の範囲であることが好ましい。リニア型ポリアリーレンスルフィド樹脂を用いる場合には、非ニュートン指数が０．９０〜１．５０の範囲であることが好ましく、さらに０．９５〜１．２０の範囲であることがより好ましい。このようなポリアリーレンスルフィド樹脂は機械的物性、流動性、耐磨耗性に優れる。ただし、非ニュートン指数（Ｎ値）は、キャピログラフを用いて３００℃、オリフィス長（Ｌ）とオリフィス径（Ｄ）の比、Ｌ／Ｄ＝４０の条件下で、剪断速度及び剪断応力を測定し、下記式を用いて算出した値である。
(Non-Newtonian index)
The non-Newtonian index of the polyarylene sulfide resin (A) used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.90 to 2.00. When a linear polyarylene sulfide resin is used, the non-Newtonian index is preferably in the range of 0.99 to 1.50, and more preferably in the range of 0.95 to 1.20. Such a polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, for the non-Newtonian index (N value), the shear rate and shear stress are measured under the conditions of 300 ° C., the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40 using a capillograph. , It is a value calculated by using the following formula.
（末端カルボキシ基）
さらに、本発明のポリアリーレンスルフィド樹脂（Ａ）は、末端にカルボキシ基およびそのアルカリ金属塩を有するものであることが好ましい。その割合については、用途や必須成分の配合の割合に応じて適宜調整すればよく、一概に限定されるべきものではないが、ポリマー末端にカルボキシ基およびそのアルカリ金属塩を樹脂中５〜２００〔μｍｏｌ／ｇ〕の範囲で含有するものであることが好ましく、さらに２０〜１００〔μｍｏｌ／ｇ〕の範囲で含有するものであることがより好ましい。なお、そのカルボキシ基およびそのアルカリ金属塩は、熱水洗工程における熱水温度が高いほど当該樹脂中の末端カルボキシ基数が多くなり、逆に熱水温度が低いほど樹脂中の末端カルボキシ基数も少なくなる傾向となる。したがって、ポリアリーレンスルフィド樹脂（Ａ）中の末端カルボキシ基の具体的な数値について特に限定する必要はないが、当該樹脂中に７０〔μｍｏｌ／ｇ〕以下の割合とすることが好ましく、０〜６０〔μｍｏｌ／ｇ〕の範囲とすることがより好ましくは、５〜５０〔μｍｏｌ／ｇ〕の範囲とすることがさらに好ましい。なお、０〔μｍｏｌ／ｇ〕は好ましくは末端カルボキシ基を含有しないことを意味するが、通常は、検出限界以下であることを意味する。
(Terminal carboxy group)
Further, the polyarylene sulfide resin (A) of the present invention preferably has a carboxy group and an alkali metal salt thereof at the terminal. The ratio may be appropriately adjusted according to the intended use and the mixing ratio of the essential components, and should not be unconditionally limited, but a carboxy group and an alkali metal salt thereof are added to the polymer terminal in an amount of 5 to 200 [ It is preferably contained in the range of [μmol / g], and more preferably contained in the range of 20 to 100 [μmol / g]. As for the carboxy group and its alkali metal salt, the higher the hot water temperature in the hot water washing step, the larger the number of terminal carboxy groups in the resin, and conversely, the lower the hot water temperature, the smaller the number of terminal carboxy groups in the resin. It becomes a tendency. Therefore, the specific value of the terminal carboxy group in the polyarylene sulfide resin (A) is not particularly limited, but it is preferably 70 [μmol / g] or less in the resin, and 0 to 60. The range is more preferably in the range of [μmol / g], and even more preferably in the range of 5 to 50 [μmol / g]. In addition, 0 [μmol / g] preferably means that it does not contain a terminal carboxy group, but usually means that it is below the detection limit.
（製造方法）
前記ポリアリーレンスルフィド樹脂（Ａ）の製造方法としては、特に限定されないが、例えば１）硫黄と炭酸ソーダの存在下でジハロゲノ芳香族化合物を、必要ならばポリハロゲノ芳香族化合物ないしその他の共重合成分を加えて、重合させる方法、２）極性溶媒中でスルフィド化剤等の存在下にジハロゲノ芳香族化合物を、必要ならばポリハロゲノ芳香族化合物ないしその他の共重合成分を加えて、重合させる方法、３）ｐ−クロルチオフェノールを、必要ならばその他の共重合成分を加えて、自己縮合させる方法、等が挙げられる。これらの方法のなかでも、２）の方法が汎用的であり好ましい。反応の際に、重合度を調節するためにカルボン酸やスルホン酸のアルカリ金属塩や、水酸化アルカリを添加しても良い。上記２）方法のなかでも、加熱した有機極性溶媒とジハロゲノ芳香族化合物とを含む混合物に含水スルフィド化剤を水が反応混合物から除去され得る速度で導入し、有機極性溶媒中でジハロゲノ芳香族化合物とスルフィド化剤とを、必要に応じてポリハロゲノ芳香族化合物と加え、反応させること、及び反応系内の水分量を該有機極性溶媒１モルに対して０．０２〜０．５モルの範囲にコントロールすることによりポリアリーレンスルフィド樹脂を製造する方法（特開平０７−２２８６９９号公報参照。）や、固形のアルカリ金属硫化物及び非プロトン性極性有機溶媒の存在下でジハロゲノ芳香族化合物と必要ならばポリハロゲノ芳香族化合物ないしその他の共重合成分を加え、アルカリ金属水硫化物及び有機酸アルカリ金属塩を、硫黄源１モルに対して０．０１〜０．９モルの範囲の有機酸アルカリ金属塩および反応系内の水分量を非プロトン性極性有機溶媒１モルに対して０．０２モル以下の範囲にコントロールしながら反応させる方法（ＷＯ２０１０／０５８７１３号パンフレット参照。）で得られるものが特に好ましい。ジハロゲノ芳香族化合物の具体的な例としては、ｐ−ジハロベンゼン、ｍ−ジハロベンゼン、ｏ−ジハロベンゼン、２，５−ジハロトルエン、１，４−ジハロナフタレン、１−メトキシ−２，５−ジハロベンゼン、４，４’−ジハロビフェニル、３，５−ジハロ安息香酸、２，４−ジハロ安息香酸、２，５−ジハロニトロベンゼン、２，４−ジハロニトロベンゼン、２，４−ジハロアニソール、ｐ，ｐ’−ジハロジフェニルエーテル、４，４’−ジハロベンゾフェノン、４，４’−ジハロジフェニルスルホン、４，４’−ジハロジフェニルスルホキシド、４，４’−ジハロジフェニルスルフィド、及び、上記各化合物の芳香環に炭素原子数１〜１８の範囲のアルキル基を有する化合物が挙げられ、ポリハロゲノ芳香族化合物としては１，２，３−トリハロベンゼン、１，２，４−トリハロベンゼン、１，３，５−トリハロベンゼン、１，２，３，５−テトラハロベンゼン、１，２，４，５−テトラハロベンゼン、１，４，６−トリハロナフタレンなどが挙げられる。また、上記各化合物中に含まれるハロゲン原子は、塩素原子、臭素原子であることが望ましい。
(Production method)
The method for producing the polyarylene sulfide resin (A) is not particularly limited, but for example, 1) a dihalogeno aromatic compound in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogeno aromatic compound or other copolymerization component. In addition, a method of polymerizing, 2) a method of adding a dihalogeno aromatic compound in the presence of a sulfidizing agent or the like in a polar solvent, and if necessary, a polyhalogeno aromatic compound or other copolymerizing component to polymerize, 3) Examples thereof include a method of self-condensing p-chlorothiophenol by adding other copolymerization components if necessary. Among these methods, the method 2) is general and preferable. At the time of the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above 2) methods, a hydrous sulfide agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogeno aromatic compound is introduced in the organic polar solvent. And a sulfide agent, if necessary, with a polyhalogeno aromatic compound to react, and the amount of water in the reaction system is in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent. A method for producing a polyarylene sulfide resin by control (see JP-A-07-228649), or if necessary with a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotonic polar organic solvent. Polyhalogeno aromatic compounds or other copolymerization components are added to add alkali metal hydrosulfides and organic acid alkali metal salts to organic acid alkali metal salts in the range of 0.01 to 0.9 mol per 1 mol of sulfur source. It is particularly preferable to obtain one obtained by a method of reacting while controlling the amount of water in the reaction system to 0.02 mol or less with respect to 1 mol of the aprotonic polar organic solvent (see WO2010 / 058713 pamphlet). Specific examples of dihalogeno aromatic compounds include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4, 4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p '-Dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenylsulfone, 4,4'-dihalodiphenylsulfoxide, 4,4'-dihalodiphenylsulfide, and the above compounds. Examples of the compound having an alkyl group having an alkyl group in the range of 1 to 18 carbon atoms in the aromatic ring of the above are examples, and examples of the polyhalogeno aromatic compound are 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3. Examples thereof include 5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene and 1,4,6-trihalonaphthalene. Further, it is desirable that the halogen atom contained in each of the above compounds is a chlorine atom or a bromine atom.
重合工程により得られたポリアリーレンスルフィド樹脂を含む反応混合物の後処理方法としては、特に制限されるものではないが、例えば、（１）重合反応終了後、先ず反応混合物をそのまま、あるいは酸または塩基を加えた後、減圧下または常圧下で溶媒を留去し、次いで溶媒留去後の固形物を水、反応溶媒（又は低分子ポリマーに対して同等の溶解度を有する有機溶媒）、アセトン、メチルエチルケトン、アルコール類などの溶媒で１回または２回以上洗浄し、更に中和、水洗、濾過および乾燥する方法、或いは、（２）重合反応終了後、反応混合物に水、アセトン、メチルエチルケトン、アルコール類、エーテル類、ハロゲン化炭化水素、芳香族炭化水素、脂肪族炭化水素などの溶媒（使用した重合溶媒に可溶であり、かつ少なくともポリアリーレンスルフィドに対しては貧溶媒である溶媒）を沈降剤として添加して、ポリアリーレンスルフィドや無機塩等の固体状生成物を沈降させ、これらを濾別、洗浄、乾燥する方法、或いは、（３）重合反応終了後、反応混合物に反応溶媒（又は低分子ポリマーに対して同等の溶解度を有する有機溶媒）を加えて撹拌した後、濾過して低分子量重合体を除いた後、水、アセトン、メチルエチルケトン、アルコール類などの溶媒で１回または２回以上洗浄し、その後中和、水洗、濾過および乾燥をする方法、（４）重合反応終了後、反応混合物に水を加えて水洗浄、濾過、必要に応じて水洗浄の時に酸を加えて酸処理し、乾燥をする方法、（５）重合反応終了後、反応混合物を濾過し、必要に応じ、反応溶媒で１回または２回以上洗浄し、更に水洗浄、濾過および乾燥する方法、等が挙げられる。 The method for post-treating the reaction mixture containing the polyarylene sulfide resin obtained in the polymerization step is not particularly limited. For example, (1) after completion of the polymerization reaction, the reaction mixture is first used as it is, or an acid or a base. After adding the solvent, the solvent was distilled off under reduced pressure or normal pressure, and then the solid substance after the solvent was distilled off was water, a reaction solvent (or an organic solvent having equivalent solubility in a low molecular weight polymer), acetone, and methyl ethyl ketone. , Wash once or twice or more with a solvent such as alcohols, and further neutralize, wash with water, filter and dry, or (2) after completion of the polymerization reaction, add water, acetone, methyl ethyl ketone, alcohols, etc. to the reaction mixture. Solvents such as ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (solvents that are soluble in the polymerization solvent used and at least poor for polyarylene sulfide) are used as precipitants. Addition to precipitate solid products such as polyarylene sulfide and inorganic salts, which are separated by filtration, washed and dried, or (3) after completion of the polymerization reaction, a reaction solvent (or low molecular weight) is added to the reaction mixture. An organic solvent having the same solubility as the polymer) is added and stirred, and then filtered to remove the low molecular weight polymer, and then washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc. Then, neutralization, washing with water, filtration and drying are performed. (4) After completion of the polymerization reaction, water is added to the reaction mixture for washing with water, filtration, and if necessary, acid treatment with water at the time of washing with water. , (5) After completion of the polymerization reaction, the reaction mixture is filtered, washed once or twice or more with a reaction solvent, and further washed with water, filtered and dried, and the like. ..
尚、上記（１）〜（５）に例示したような後処理方法において、ポリアリーレンスルフィド樹脂の乾燥は真空中で行なってもよいし、空気中あるいは窒素のような不活性ガス雰囲気中で行なってもよい。 In the post-treatment methods as illustrated in (1) to (5) above, the polyarylene sulfide resin may be dried in vacuum, in air, or in an atmosphere of an inert gas such as nitrogen. You may.
本発明のポリアリーレンスルフィド樹脂組成物は、ポリビニルピロリドン（Ｂ）を必須成分として配合してなる。該ポリビニルピロリドンの平均分子量は特に限定されないが、好ましくは質量平均分子量が３，０００〜２，０００，０００の範囲であり、より好ましくは５００，０００〜１，５００，０００の範囲であり、さらに好ましくは１，０００，０００〜１，２００，０００の範囲である。重合度ｎは質量平均分子量が上記範囲となる値であれば特に限定されないが、好ましくはｎが３０〜１８，０００の範囲であることが好ましく、４，５００〜１３，５００の範囲であることが好ましく、さらに９，０００〜１０８，０００の範囲であることが特に好ましい。なお、質量平均分子量はポリビニルピロリドンのテトラヒドロフラン溶液（０．１ｗｔ％）を調製し、ＴＳＫＧｅｌＧＨｘｌシリーズ５０００、３０００、２０００、１０００カラムおよび示差屈折計（ＲＩ）検出器を備えたＧＰＣ装置（東ソー株式会社製ＨＬＣ−８２２０ＧＰＣ）を用い、試料溶液注入量５０μｌ、テトラヒドロフランを移動相（１ｍｌ／分）とし、４０℃で測定した。質量平均分子量は、標準スチレンからなる検量線から算出した。ただし、質量平均分子量の測定値に実質的な影響を及ぼさない範囲で、測定条件を適宜変更することは可能である。 The polyarylene sulfide resin composition of the present invention contains polyvinylpyrrolidone (B) as an essential component. The average molecular weight of the polyvinylpyrrolidone is not particularly limited, but the mass average molecular weight is preferably in the range of 3,000 to 2,000,000, more preferably in the range of 500,000 to 1,500,000, and further. It is preferably in the range of 1,000,000 to 1,200,000. The degree of polymerization n is not particularly limited as long as the mass average molecular weight is in the above range, but preferably n is in the range of 30 to 18,000 and is in the range of 4,500 to 13,500. Is preferable, and the range is particularly preferably in the range of 9,000 to 108,000. For the mass average molecular weight, a GPC device (manufactured by Toso Co., Ltd.) prepared by preparing a tetrahydrofuran solution (0.1 wt%) of polyvinylpyrrolidone and equipped with a TSKGelGHxl series 5000, 3000, 2000, 1000 columns and a differential refractometer (RI) detector. Using HLC-8220 GPC), the sample solution injection volume was 50 μl, tetrahydrofuran was used as the mobile phase (1 ml / min), and the measurement was performed at 40 ° C. The mass average molecular weight was calculated from a calibration curve made of standard styrene. However, it is possible to appropriately change the measurement conditions within a range that does not substantially affect the measured value of the mass average molecular weight.
ポリビニルピロリドンは直鎖型のものでも架橋型のものでも差し支えない。 Polyvinylpyrrolidone may be linear or crosslinked.
ポリビニルピロリドン（Ｂ）としては、例えば下記一般式（１） Examples of polyvinylpyrrolidone (B) include the following general formula (1).
上記ポリビニルピロリドンの製造方法は、公知の方法を用いることができ、本発明の効果を損ねない限り特に限定されるものではないが、例えば、２−ピロリドンとアセチレンと原料として反応させる方法（レッペ法）や、Ｎ−ヒドロキシエチルピロリドンの脱水反応による方法の他、好ましくは、Ｎ−ヒドロキシエチルピロリドンを気相脱水反応させて得られた、γ−ブチロラクトン含有量が、例えば５００ｐｐｍ以下に低減させたＮ−ビニルピロリドンを、公知の重合開始剤や塩基性ｐＨ調整剤を適宜加えて、ラジカル重合する方法などが挙げられる。 The method for producing polyvinylpyrrolidone can be a known method and is not particularly limited as long as the effect of the present invention is not impaired. For example, a method of reacting 2-pyrrolidone with acetylene as a raw material (Repe method). ) And the method by dehydration reaction of N-hydroxyethylpyrrolidone, preferably N-hydroxyethylpyrrolidone obtained by vapor phase dehydration reaction and having a γ-butyrolactone content reduced to 500 ppm or less, for example. A method of radically polymerizing vinylpyrrolidone by appropriately adding a known polymerization initiator or basic pH adjuster can be mentioned.
ここで、前記Ｎ−ビニルピロリドンは、下記一般式（１０） Here, the N-vinylpyrrolidone is described by the following general formula (10).
本発明で用いるポリビニルピロリドンは、前記Ｎ−ビニルピロリドンを原料とした単独重合物であることが好ましいが、本発明の効果を損ねない範囲で、前記一般式（１０）で表されるＮ−ビニルピロリドン、その他のモノマーを原料とする共重合物であってもよく、その場合、その他のモノマーの使用量は１０質量％以下であることが好ましく、１質量％以下であることがより好ましく、０．１質量％以下であることがさらに好ましい。 The polyvinylpyrrolidone used in the present invention is preferably a copolymer using the N-vinylpyrrolidone as a raw material, but N-vinyl represented by the general formula (10) is used as long as the effects of the present invention are not impaired. A copolymer using pyrrolidone or another monomer as a raw material may be used. In that case, the amount of the other monomer used is preferably 10% by mass or less, more preferably 1% by mass or less, and 0. It is more preferably 1% by mass or less.
その他のモノマーとしては、例えば、下記一般式（１１） Examples of other monomers include the following general formula (11).
本発明で用いるポリビニルピロリドンは、例えば、株式会社日本触媒製「Ｋ−９０」、同「Ｋ−８５」、同「Ｋ−３０」などとして市販のものを用いることができる。 As the polyvinylpyrrolidone used in the present invention, commercially available products such as “K-90”, “K-85” and “K-30” manufactured by Nippon Shokubai Co., Ltd. can be used.
本発明においてポリビニルピロリドン（Ｂ）の配合の割合は、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、０．０１〜１００質量部の範囲であることが好ましく、０．１〜５０質量部の範囲であることがより好ましく、１〜３０質量部の範囲であることがさらに好ましく、２〜２５質量部の範囲であることが最も好ましい。かかる範囲において、本発明のポリアリーレンスルフィド樹脂組成物が低い再結晶化温度を呈しつつ、かつ得られた成形品が良好な耐熱性を呈するため好ましい。 In the present invention, the proportion of polyvinylpyrrolidone (B) to be blended is preferably in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A), and is 0.1 to 50 parts by mass. It is more preferably in the range of 1 to 30 parts by mass, more preferably in the range of 2 to 25 parts by mass. In such a range, the polyarylene sulfide resin composition of the present invention is preferable because it exhibits a low recrystallization temperature and the obtained molded product exhibits good heat resistance.
本発明のポリアリーレンスルフィド樹脂組成物は、カルボキシ基と反応する官能基を有するシランカップリング剤（Ｃ）を必須成分として配合してなる。シランカップリング剤としては、カルボキシ基と反応する官能基を有し、かつ、本発明の効果を損ねなければ特に限定されないが、例えば、エポキシ基、イソシアナト基、アミノ基または水酸基を有するシランカップリング剤が好ましいものとして挙げられる。このようなシランカップリング剤としては、例えば、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ基含有アルコキシシラン化合物、γ−イソシアナトプロピルトリメトキシシラン、γ−イソシアナトプロピルトリエトキシシラン、γ−イソシアナトプロピルメチルジメトキシシラン、γ−イソシアナトプロピルメチルジエトキシシラン、γ−イソシアナトプロピルエチルジメトキシシラン、γ−イソシアナトプロピルエチルジエトキシシラン、γ−イソシアナトプロピルトリクロロシラン等のイソシアナト基含有アルコキシシラン化合物、γ−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン等のアミノ基含有アルコキシシラン化合物、γ−ヒドロキシプロピルトリメトキシシラン、γ−ヒドロキシプロピルトリエトキシシラン等の水酸基含有アルコキシシラン化合物が挙げられる。本発明において該シランカップリング剤の配合の割合は、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、０．０１〜３０質量部の範囲であることが好ましく、さらに０．０５〜１０質量部の範囲であることがより好ましく、さらに０．１〜５質量部の範囲であることが最も好ましい。かかる範囲において、本発明のポリアリーレンスルフィド樹脂組成物が低い再結晶化温度を呈しつつ、かつ得られた成形品が良好な耐熱性を呈するため好ましい。 The polyarylene sulfide resin composition of the present invention contains a silane coupling agent (C) having a functional group that reacts with a carboxy group as an essential component. The silane coupling agent is not particularly limited as long as it has a functional group that reacts with a carboxy group and does not impair the effects of the present invention. For example, a silane coupling agent having an epoxy group, an isocyanato group, an amino group or a hydroxyl group. Agents are preferred. Examples of such a silane coupling agent include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Containing alkoxysilane compound, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane , Γ-Isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane and other isocyanato group-containing alkoxysilane compounds, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) amino Examples thereof include amino group-containing alkoxysilane compounds such as propyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. In the present invention, the proportion of the silane coupling agent blended is preferably in the range of 0.01 to 30 parts by mass, and further 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). The range of parts is more preferable, and the range of 0.1 to 5 parts by mass is most preferable. In such a range, the polyarylene sulfide resin composition of the present invention is preferable because it exhibits a low recrystallization temperature and the obtained molded product exhibits good heat resistance.
本発明のポリアリーレンスルフィド樹脂組成物は、必要に応じて、充填剤を任意成分として含有することができる。これら充填剤としては本発明の効果を損なうものでなければ公知慣用の材料を用いることもでき、例えば、繊維状のものや、粒状や板状などの非繊維状のものなど、さまざまな形状の充填剤等が挙げられる。具体的には、ガラス繊維、炭素繊維、シランガラス繊維、セラミック繊維、アラミド繊維、金属繊維、チタン酸カリウム、炭化珪素、珪酸カルシウム、ワラストナイト等の繊維、天然繊維等の繊維状充填剤が使用でき、またガラスビーズ、ガラスフレーク、硫酸バリウム、クレー、パイロフィライト、ベントナイト、セリサイト、マイカ、雲母、タルク、アタパルジャイト、フェライト、珪酸カルシウム、炭酸カルシウム、炭酸マグネシウム、ガラスビーズ、ゼオライト、ミルドファイバー、硫酸カルシウム等の非繊維状充填剤も使用できる。 The polyarylene sulfide resin composition of the present invention may contain a filler as an optional component, if necessary. As these fillers, known and commonly used materials can be used as long as they do not impair the effects of the present invention, and have various shapes such as fibrous ones and non-fibrous ones such as granular and plate-like ones. Examples include fillers. Specifically, glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium silicate, warastonite and other fibers, and natural fibers and other fibrous fillers are used. Can also be used, glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, mica, talc, attapulsite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, milled fiber , Non-fibrous fillers such as calcium sulfate can also be used.
本発明において充填剤は必須成分ではないが、配合する場合、その配合の割合は本発明の効果を損ねなければ特に限定されるものではなく、また、それぞれの目的に応じて異なり、一概に規定することはできないが、例えば、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、１〜６００質量部の範囲であることが好ましく、さらに１０〜２００質量部の範囲であることがより好ましい。かかる範囲において、樹脂組成物が良好な機械強度と成形性を示すため好ましい。 Although the filler is not an essential component in the present invention, when it is blended, the blending ratio is not particularly limited as long as the effect of the present invention is not impaired, and it varies according to each purpose and is generally defined. However, for example, it is preferably in the range of 1 to 600 parts by mass, and more preferably in the range of 10 to 200 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). In such a range, the resin composition is preferable because it exhibits good mechanical strength and moldability.
本発明のポリアリーレンスルフィド樹脂組成物は、必要に応じて、熱可塑性エラストマーを任意成分として配合することができる。熱可塑性エラストマーとしては、ポリオレフィン系エラストマー、弗素系エラストマーまたはシリコーン系エラストマーが挙げられ、このうちポリオレフィン系エラストマーが好ましいものとして挙げられる。これらのエラストマーを配合する場合、その配合の割合は、本発明の効果を損ねなければ特に限定されなく、また、それぞれの目的に応じて異なり、一概に規定することはできないが、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、０．０１〜１０質量部の範囲であることが好ましく、さらに０．１〜５質量部の範囲であることがより好ましい。かかる範囲において、得られるポリアリーレンスルフィド樹脂組成物の耐衝撃性が向上するため好ましい。 The polyarylene sulfide resin composition of the present invention may contain a thermoplastic elastomer as an optional component, if necessary. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluoroelastomers, and silicone-based elastomers, and among them, polyolefin-based elastomers are preferable. When these elastomers are blended, the blending ratio is not particularly limited as long as the effects of the present invention are not impaired, and the polyallylen sulfide resin is different depending on the respective purposes and cannot be unconditionally specified. (A) The range is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass. In such a range, the impact resistance of the obtained polyarylene sulfide resin composition is improved, which is preferable.
前記ポリオレフィン系エラストマーは、例えば、α−オレフィンの単独重合または異なるα−オレフィン同士の共重合により、さらに、官能基を付与する場合には、α−オレフィンと官能基を有するビニル重合性化合物との共重合により得ることができる。α−オレフィンは、例えば、エチレン、プロピレン及びブテン−１等の炭素原子数２〜８の範囲のものが挙げられる。また、官能基としては、カルボキシ基、式−（ＣＯ）Ｏ（ＣＯ）−で表される酸無水物基、それらのエステル、エポキシ基、アミノ基、水酸基、メルカプト基、イソシアネート基、またはオキサゾリン基などが挙げられる。 The polyolefin-based elastomer is, for example, a homopolymerization of α-olefins or a copolymerization of different α-olefins, and when a functional group is further imparted, the α-olefin and a vinyl polymerizable compound having a functional group are used. It can be obtained by copolymerization. Examples of the α-olefin include those in the range of 2 to 8 carbon atoms such as ethylene, propylene and butene-1. The functional group includes a carboxy group, an acid anhydride group represented by the formula − (CO) O (CO) −, an ester thereof, an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, or an oxazoline group. And so on.
このような官能基を有するビニル重合性化合物の具体例としては、例えば、（メタ）アクリル酸及び（メタ）アクリル酸エステル等のα，β−不飽和カルボン酸及びそのアルキルエステル、マレイン酸、フマル酸、イタコン酸及びその他の炭素原子数４〜１０のα，β−不飽和ジカルボン酸及びその誘導体（モノ若しくはジエステル、及びその酸無水物等）、並びにグリシジル（メタ）アクリレート等が挙げられる。これらの中でも、上述したエポキシ基、カルボキシ基、及び、該酸無水物基からなる群から選ばれる少なくとも１種の官能基を有するエチレン−プロピレン共重合体及びエチレン−ブテン共重合体が、機械的強度、特に靭性及び耐衝撃性の向上の点から好ましい。 Specific examples of the vinyl polymerizable compound having such a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid ester and their alkyl esters, maleic acid and fumaric acid. Examples thereof include acids, itaconic acids and other α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono or diesters and their acid anhydrides, etc.), and glycidyl (meth) acrylates. Among these, ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the group consisting of the above-mentioned epoxy group, carboxy group, and acid anhydride group are mechanically used. It is preferable from the viewpoint of improving strength, particularly toughness and impact resistance.
更に、本発明のポリアリーレンスルフィド樹脂組成物は、上記成分に加えて、さらに用途に応じて、適宜、前記ポリアリーレンスルフィド樹脂及び前記ポリビニルピロリドンを除く他の合成樹脂、例えばポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ポリスルフォン樹脂、ポリエーテルスルフォン樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルケトン樹脂、ポリアリーレン樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリ四弗化エチレン樹脂、ポリ二弗化エチレン樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、フェノール樹脂、ウレタン樹脂、液晶ポリマー等（以下、単に合成樹脂という）を任意成分として配合することができる。本発明において合成樹脂は必須成分ではないが、配合する場合、その配合の割合は本発明の効果を損ねなければ特に限定されるものではなく、また、それぞれの目的に応じて異なり、一概に規定することはできないが、本発明のポリアリーレンスルフィド樹脂組成物中に配合する樹脂成分（前記ポリアリーレンスルフィド樹脂、前記ポリビニルピロリドン及び合成樹脂の合計）の割合としてポリアリーレンスルフィド樹脂及び前記ポリビニルピロリドンの合計が７５．０質量％以上の範囲、好ましくは８０〜９９．９９質量％の範囲となるよう、換言すると、上記の合成樹脂が２５．０質量％以下の範囲、好ましくは０．０１〜２０．０質量％の範囲で、本発明の効果を損なわないよう目的や用途に応じて適宜調整して用いればよい。 Further, in addition to the above components, the polyarylene sulfide resin composition of the present invention further comprises, depending on the intended use, the polyarylene sulfide resin and other synthetic resins other than the polyvinylpyrrolidone, such as polyester resin and polyamide resin. Polyethylene resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyether ketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluorinated ethylene A resin, polydifluorinated ethylene resin, polystyrene resin, ABS resin, phenol resin, urethane resin, liquid crystal polymer and the like (hereinafter, simply referred to as synthetic resin) can be blended as an optional component. Although the synthetic resin is not an essential component in the present invention, when it is blended, the blending ratio is not particularly limited as long as the effect of the present invention is not impaired, and it varies according to each purpose and is generally defined. However, the total amount of the polyarylene sulfide resin and the polyvinylpyrrolidone as the ratio of the resin components (the total of the polyarylene sulfide resin, the polyvinylpyrrolidone and the synthetic resin) to be blended in the polyarylene sulfide resin composition of the present invention. Is in the range of 75.0% by mass or more, preferably in the range of 80 to 99.99% by mass, in other words, the above synthetic resin is in the range of 25.0% by mass or less, preferably 0.01 to 20%. In the range of 0% by mass, it may be appropriately adjusted and used according to the purpose and application so as not to impair the effect of the present invention.
また本発明のポリアリーレンスルフィド樹脂組成物は、その他にも着色剤、帯電防止剤、酸化防止剤、耐熱安定剤、紫外線安定剤、紫外線吸収剤、発泡剤、難燃剤、難燃助剤、防錆剤、およびカップリング剤等の公知慣用の添加剤を必要に応じ、任意成分として配合してもよい。これらの添加剤は必須成分ではないが、配合する場合、その配合の割合は、本発明の効果を損ねなければ特に限定されなく、また、それぞれの目的に応じて異なり、一概に規定することはできないが、例えば、ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、好ましくは０．０１〜１，０００質量部の範囲で、本発明の効果を損なわないよう目的や用途に応じて適宜調整して用いればよい。 In addition, the polyarylene sulfide resin composition of the present invention also has a colorant, an antistatic agent, an antioxidant, a heat-resistant stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, a flame retardant aid, and an anti-inflammatory agent. Known and commonly used additives such as rusting agents and coupling agents may be added as optional components, if necessary. These additives are not essential ingredients, but when they are blended, the blending ratio is not particularly limited as long as the effects of the present invention are not impaired, and they differ according to their respective purposes and can be unconditionally specified. However, for example, with respect to 100 parts by mass of the polyarylene sulfide resin (A), it is appropriately adjusted in the range of 0.01 to 1,000 parts by mass according to the purpose and application so as not to impair the effects of the present invention. And use it.
本発明のポリアリーレンスルフィド樹脂組成物の製造方法は、ポリアリーレンスルフィド樹脂（Ａ）と、前記ポリビニルピロリドン（Ｂ）と前記シランカップリング剤（Ｃ）を必須成分として配合して、ポリアリーレンスルフィド樹脂（Ａ）の融点以上で溶融混練する。 In the method for producing a polyarylene sulfide resin composition of the present invention, a polyarylene sulfide resin (A), the polyvinylpyrrolidone (B), and the silane coupling agent (C) are blended as essential components to form a polyarylene sulfide resin. Melt and knead at a temperature equal to or higher than the melting point of (A).
本発明のポリアリーレンスルフィド樹脂組成物の好ましい製造方法は、上述した配合割合となるよう、ポリアリーレンスルフィド樹脂（Ａ）と、前記ポリビニルピロリドン（Ｂ）と、前記シランカップリング剤（Ｃ）の各必須成分と、必要に応じて、充填剤などの任意成分を、粉末、ペレット、細片など様々な形態でリボンブレンター、ヘンシェルミキサー、Ｖブレンダーなどに投入してドライブレンドした後、バンバリーミキサー、ミキシングロール、単軸または２軸の押出機およびニーダーなどの公知の溶融混練機に投入し、樹脂温度がポリアリーレンスルフィド樹脂の融点以上となる温度範囲、好ましくは融点＋１０℃以上となる温度範囲、より好ましくは融点＋１０℃〜融点＋１００℃となる温度範囲、さらに好ましくは融点＋２０〜融点＋５０℃となる温度範囲で溶融混練する工程を経て製造することができる。溶融混練機への各成分の添加、混合は同時に行ってもよいし、分割して行っても良い。 A preferable method for producing the polyarylene sulfide resin composition of the present invention is to use the polyarylene sulfide resin (A), the polyvinylpyrrolidone (B), and the silane coupling agent (C) so as to have the above-mentioned blending ratio. The essential ingredients and, if necessary, optional ingredients such as fillers are added to a ribbon blender, Henschel mixer, V blender, etc. in various forms such as powder, pellets, and strips for dry blending, and then a Banbury mixer. A temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably a melting point of +10 ° C. or higher, by charging into a known melt-kneader such as a mixing roll, a single-screw or twin-screw extruder and a kneader. It can be produced through a step of melt-kneading more preferably in a temperature range of melting point + 10 ° C. to melting point + 100 ° C., and more preferably in a temperature range of melting point +20 to melting point + 50 ° C. Each component may be added to and mixed with the melt kneader at the same time, or may be divided.
前記溶融混練機としては分散性や生産性の観点から二軸混練押出機が好ましく、例えば、樹脂成分の吐出量５〜５００（ｋｇ／ｈｒ）の範囲と、スクリュー回転数５０〜５００（ｒｐｍ）の範囲とを適宜調整しながら溶融混練することが好ましく、それらの比率（吐出量／スクリュー回転数）が０．０２〜５（ｋｇ／ｈｒ／ｒｐｍ）の範囲となる条件下に溶融混練することがさらに好ましい。また、前記成分のうち、充填剤や添加剤を添加する場合は、前記二軸混練押出機のサイドフィーダーから該押出機内に投入することが分散性の観点から好ましい。かかるサイドフィーダーの位置は、前記二軸混練押出機のスクリュー全長に対する、該押出機樹脂投入部から該サイドフィーダーまでの距離の比率が、０．１〜０．９の範囲であることが好ましい。中でも０．３〜０．７の範囲であることが特に好ましい。 As the melt kneader, a twin-screw kneading extruder is preferable from the viewpoint of dispersibility and productivity. For example, a resin component discharge amount in the range of 5 to 500 (kg / hr) and a screw rotation speed of 50 to 500 (rpm) are preferable. It is preferable to melt-knead while appropriately adjusting the range of, and melt-knead under the condition that the ratio (discharge amount / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). Is even more preferable. Further, when a filler or an additive is added among the components, it is preferable to put the filler into the extruder from the side feeder of the twin-screw kneading extruder from the viewpoint of dispersibility. The position of the side feeder is preferably in the range of 0.1 to 0.9 in the ratio of the distance from the extruder resin input portion to the side feeder with respect to the total screw length of the twin-screw kneading extruder. Above all, the range of 0.3 to 0.7 is particularly preferable.
このように溶融混練して得られる本発明のポリアリーレンスルフィド樹脂組成物は、必須成分であるポリアリーレンスルフィド樹脂（Ａ）と、前記ポリビニルピロリドン（Ｂ）と、前記シランカップリング剤（Ｃ）と、必要に応じて加える任意成分およびそれらの由来成分を含む溶融混合物であり、該溶融混練後に、公知の方法でペレット、チップ、顆粒、粉末等の形態に加工してから、必要に応じて１００〜１５０℃の温度で予備乾燥を施して、各種成形に供することが好ましい。 The polyarylene sulfide resin composition of the present invention obtained by melt-kneading in this manner contains the polyarylene sulfide resin (A), which is an essential component, the polyvinylpyrrolidone (B), and the silane coupling agent (C). It is a melt mixture containing optional components added as necessary and components derived from them, and after the melt kneading, it is processed into pellets, chips, granules, powders, etc. by a known method, and then 100 as required. It is preferable to pre-dry the product at a temperature of about 150 ° C. and use it for various moldings.
上記製造方法により製造される本発明のポリアリーレンスルフィド樹脂組成物は、ポリアリーレンスルフィド樹脂をマトリックスとし、当該マトリックス中に、必須成分である前記ポリビニルピロリドン（Ｂ）と前記シランカップリング剤（Ｃ）と、それらに由来する成分、必要に応じて添加する任意成分が分散したモルフォロジーを形成する。その結果、当該ポリアリーレンスルフィド樹脂組成物が低い再結晶化温度を呈しつつ、かつ得られた成形品が耐熱性、耐薬品性等に優れたものとなり好ましい。ピロリドン骨格に起因してポリアリーレンスルフィド樹脂との相溶性に優れる性質を有するポリビニルピロリドンが、溶融混練時にポリアリーレンスルフィド樹脂の結晶化を遅延させたものと考えられ、さらに、ポリアリーレンスルフィド樹脂の分子鎖同士が、シランカップリング剤の存在下で、分子鎖が延長した効果により、さらに上記の結晶化を遅延させたものと考えられる。 The polyarylene sulfide resin composition of the present invention produced by the above production method uses a polyarylene sulfide resin as a matrix, and the polyvinylpyrrolidone (B) and the silane coupling agent (C), which are essential components, are contained in the matrix. And, the components derived from them and the optional components to be added as needed form a dispersed morphology. As a result, the polyarylene sulfide resin composition is preferable because it exhibits a low recrystallization temperature and the obtained molded product is excellent in heat resistance, chemical resistance and the like. It is considered that polyvinylpyrrolidone, which has excellent compatibility with the polyarylene sulfide resin due to the pyrrolidone skeleton, delayed the crystallization of the polyarylene sulfide resin during melt-kneading, and further, the molecule of the polyarylene sulfide resin. It is considered that the chains further delayed the above crystallization due to the effect of extending the molecular chain in the presence of the silane coupling agent.
本発明のポリアリーレンスルフィド樹脂組成物ないしその成形品の融点（Ｔｍ）は、前記樹脂（Ａ）の融点（Ｔｍ）を維持しつつ、一方で、ポリアリーレンスルフィド樹脂組成物ないしその成形品の再結晶化温度（Ｔｃ２）は、前記樹脂（Ａ）の再結晶化温度（Ｔｃ２）から、さらに低下させることができる。具体的な再結晶化温度（Ｔｃ２）の低下の範囲については、成形品の用途や目的に応じて機械的特性等の他の性質との関係も踏まえて、必須成分や任意成分の配合を決める必要があることから、一概に規定することはできないが、好ましいものでは、ポリアリーレンスルフィド樹脂組成物ないしその成形品の再結晶化温度（Ｔｃ２）として、前記樹脂（Ａ）の再結晶化温度（Ｔｃ２）から２０〜１００℃の範囲で低下させることができ、より好ましいものでは３０〜８０℃の範囲で低下させることができる。すなわち、本発明のポリアリーレンスルフィド樹脂組成物および成形品の融点（Ｔｍ）と再結晶化温度（Ｔｃ２）との差ΔＴを、好ましくは５０℃以上、より好ましくは５０〜１３０℃の範囲、さらに好ましくは６０〜８０℃の範囲とすることもできる。したがって、本発明のポリアリーレンスルフィド樹脂組成物および成形品の融点（Ｔｍ）を、好ましくは２７０〜３００℃の範囲としつつ、本発明のポリアリーレンスルフィド樹脂組成物および成形品の再結晶化温度（Ｔｃ２）を好ましくは２４０℃以下の範囲、より好ましくは１２０〜２４０℃の範囲、さらに好ましくは１６０〜２００℃の範囲のものとすることができる。なお、本発明のポリアリーレンスルフィド樹脂組成物ないしその成形品の融点（Ｔｍ）が、前記樹脂（Ａ）の融点（Ｔｍ）を維持している、とは、実質的に融点が同じであること、好ましくは、ポリアリーレンスルフィド樹脂組成物ないしその成形品のＴｍ（℃）と、必須成分として配合したポリアリーレンスルフィド樹脂（Ａ）のＴｍ（℃）の温度差が１０℃以内、さらに好ましくは、５℃以内であることを意味する。 The melting point (Tm) of the polyarylene sulfide resin composition or the molded product thereof of the present invention maintains the melting point (Tm) of the resin (A), while the polyarylene sulfide resin composition or the molded product thereof is reconstituted. The crystallization temperature (Tc2) can be further lowered from the recrystallization temperature (Tc2) of the resin (A). Regarding the specific range of decrease in recrystallization temperature (Tc2), the composition of essential components and optional components is determined according to the application and purpose of the molded product, taking into consideration the relationship with other properties such as mechanical properties. Since it is necessary, it cannot be unconditionally specified, but preferably, the recrystallization temperature (Tc2) of the polyarylene sulfide resin composition or its molded product is the recrystallization temperature (Tc2) of the resin (A). It can be lowered in the range of 20 to 100 ° C. from Tc2), and more preferably it can be lowered in the range of 30 to 80 ° C. That is, the difference ΔT between the melting point (Tm) and the recrystallization temperature (Tc2) of the polyarylene sulfide resin composition and the molded product of the present invention is preferably in the range of 50 ° C. or higher, more preferably 50 to 130 ° C., and further. It can also be preferably in the range of 60 to 80 ° C. Therefore, while keeping the melting point (Tm) of the polyarylene sulfide resin composition and the molded product of the present invention in the range of preferably 270 to 300 ° C., the recrystallization temperature of the polyarylene sulfide resin composition and the molded product of the present invention ( Tc2) can be preferably in the range of 240 ° C. or lower, more preferably in the range of 120 to 240 ° C., and further preferably in the range of 160 to 200 ° C. The melting point (Tm) of the polyarylene sulfide resin composition of the present invention or a molded product thereof maintains the melting point (Tm) of the resin (A), which means that the melting points are substantially the same. The temperature difference between the Tm (° C.) of the polyarylene sulfide resin composition or its molded product and the Tm (° C.) of the polyarylene sulfide resin (A) blended as an essential component is preferably within 10 ° C., more preferably. It means that it is within 5 ° C.
本発明のポリアリーレンスルフィド樹脂組成物は、射出成形、圧縮成形、コンポジット、シート、パイプなどの押出成形、引抜成形、ブロー成形、トランスファー成形など各種成形に供することが可能であるが、特に離形性にも優れるため射出成形用途に適している。射出成形にて成形する場合、各種成形条件は特に限定されず、通常一般的な方法にて成形することができる。例えば、射出成形機内で、樹脂温度がポリアリーレンスルフィド樹脂の融点以上の温度範囲、好ましくは該融点＋１０℃以上の温度範囲、より好ましくは融点＋１０℃〜融点＋１００℃の温度範囲、さらに好ましくは融点＋２０〜融点＋５０℃の温度範囲で前記ポリアリーレンスルフィド樹脂組成物を溶融する工程を経た後、樹脂吐出口よりを金型内に注入して成形すればよい。その際、金型温度も公知の温度範囲、例えば、室温（２３℃）〜３００℃、好ましくは４０〜１８０℃の範囲に設定することができる。本発明のポリアリーレンスルフィド樹脂組成物は通常の成形温度として好ましい１２０〜１８０℃の温度範囲に設定することもできる上に、上記の通り再結晶化温度（Ｔｃ２）が低く、低温成形性に優れる特徴も有することから、４０℃以上かつ１２０℃未満の範囲といった比較的低温条件の金型温度であっても外観性や充填性等の成形性や機械物性、耐薬品性に優れる成形物を得ることができる。 The polyarylene sulfide resin composition of the present invention can be used for various moldings such as injection molding, compression molding, composite, extrusion molding of sheets, pipes, etc., drawing molding, blow molding, transfer molding, etc. It is also suitable for injection molding because of its excellent properties. When molding by injection molding, various molding conditions are not particularly limited, and molding can usually be performed by a general method. For example, in an injection molding machine, the resin temperature is in a temperature range equal to or higher than the melting point of the polyarylene sulfide resin, preferably in a temperature range of the melting point + 10 ° C. or higher, more preferably in a temperature range of + 10 ° C. to + 100 ° C. After undergoing the step of melting the polyarylene sulfide resin composition in a temperature range of +20 to a melting point of +50 ° C., the polyarylene sulfide resin composition may be injected into a mold from a resin discharge port for molding. At that time, the mold temperature can also be set in a known temperature range, for example, room temperature (23 ° C.) to 300 ° C., preferably 40 to 180 ° C. The polyarylene sulfide resin composition of the present invention can be set in a temperature range of 120 to 180 ° C., which is preferable as a normal molding temperature, and as described above, the recrystallization temperature (Tc2) is low and the low temperature moldability is excellent. Since it also has characteristics, it is possible to obtain a molded product having excellent moldability such as appearance and filling property, mechanical properties, and chemical resistance even at a mold temperature under relatively low temperature conditions such as 40 ° C. or higher and lower than 120 ° C. be able to.
本発明のポリアリーレンスルフィド樹脂組成物を成形してなる成形品は、シリコーン樹脂との接着性に優れつつ、射出成形時のＴＤ方向の機械的強度にも優れるが、さらに前記ポリビニルピロリドン（Ｂ）として質量平均分子量５０，０００〜２，０００，０００の範囲のものを用いた場合には、シリコーン樹脂との接着性および射出成形時のＴＤ方向の機械的強度が特に優れたものとなる。そのため、ポリアリーレンスルフィド樹脂とシリコーン樹脂からなる硬化物とが接着した複合成形品として好適に用いることができる。複合成形品を製造する際に用いるシリコーン樹脂としては、当業者が接着剤として通常用いるシリコーン樹脂であればよく、縮合型シリコーン樹脂、付加型シリコーン樹脂のいずれであってもよく、また一液型および二液型のいずれを用いてもよいが、均一に硬化することから付加型シリコーン樹脂を用いることが好ましい。前記複合成形品の製造方法としては各種成形方法により成形したポリアリーレンスルフィド樹脂成形品にシリコーン樹脂を接触させた後、該シリコーン樹脂を硬化することにより複合成形品を製造する方法を用いることができる。 The molded product obtained by molding the polyarylene sulfide resin composition of the present invention has excellent adhesiveness to a silicone resin and also excellent mechanical strength in the TD direction during injection molding. Further, the polyvinylpyrrolidone (B) When a material having a mass average molecular weight in the range of 50,000 to 2,000,000 is used, the adhesiveness to the silicone resin and the mechanical strength in the TD direction at the time of injection molding are particularly excellent. Therefore, it can be suitably used as a composite molded product in which a cured product made of a polyarylene sulfide resin and a silicone resin is adhered. The silicone resin used in producing the composite molded product may be any silicone resin usually used as an adhesive by those skilled in the art, and may be either a condensation type silicone resin or an addition type silicone resin, or a one-component type. Either the two-component type or the two-component type may be used, but it is preferable to use an addition type silicone resin because it cures uniformly. As a method for producing the composite molded product, a method of producing the composite molded product by bringing the silicone resin into contact with the polyarylene sulfide resin molded product molded by various molding methods and then curing the silicone resin can be used. ..
前記複合成形体の主な用途例としては、各種家電製品、携帯電話、及びＰＣ（Personal Computer）等の電子機器の筐体、箱型の電気・電子部品集積モジュール用保護・支持部材・複数の個別半導体またはモジュール、センサ、ＬＥＤランプ、コネクタ、ソケット、抵抗器、リレーケース、スイッチ、コイルボビン、コンデンサ、バリコンケース、光ピックアップ、発振子、各種端子板、変成器、プラグ、プリント基板、チューナ、スピーカ、マイクロフォン、ヘッドフォン、小型モータ、磁気ヘッドベース、パワーモジュール、端子台、半導体、液晶、ＦＤＤキャリッジ、ＦＤＤシャーシ、モーターブラッシュホルダ、パラボラアンテナ、コンピュータ関連部品等に代表される電気・電子部品；ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤ、炊飯器部品、電子レンジ部品、音響部品、オーディオ・レーザディスク・コンパクトディスク・ＤＶＤディスク・ブルーレイディスク等の音声・映像機器部品、照明部品、冷蔵庫部品、エアコン部品、タイプライタ部品、ワードプロセッサ部品、あるいは給湯機や風呂の湯量、温度センサなどの水回り機器部品等に代表される家庭、事務電気製品部品；オフィスコンピュータ関連部品、電話器関連部品、ファクシミリ関連部品、複写機関連部品、洗浄用治具、モーター部品、ライタ、タイプライタなどに代表される機械関連部品：顕微鏡、双眼鏡、カメラ、時計等に代表される光学機器、精密機械関連部品；オルタネーターターミナル、オルタネーターコネクタ、ブラシホルダー、スリップリング、ＩＣレギュレータ、ライトディヤ用ポテンシオメーターベース、リレーブロック、インヒビタースイッチ、排気ガスバルブ等の各種バルブ、燃料関係・排気系・吸気系各種パイプ、エアーインテークノズルスノーケル、インテークマニホールド、燃料ポンプ、エンジン冷却水ジョイント、キャブレターメインボディ、キャブレタースペーサ、排気ガスセンサ、冷却水センサ、油温センサ、ブレーキパットウェアーセンサ、スロットルポジションセンサ、クランクシャフトポジションセンサ、エアーフローメータ、ブレーキパッド摩耗センサ、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダ、ウォーターポンプインペラ、タービンベイン、ワイパーモーター関係部品、デュストリビュータ、スタータースイッチ、イグニッションコイルおよびそのボビン、モーターインシュレータ、モーターロータ、モーターコア、スターターリレ、トランスミッション用ワイヤーハーネス、ウィンドウォッシャーノズル、エアコンパネルスイッチ基板、燃料関係電磁気弁用コイル、ヒューズ用コネクタ、ホーンターミナル、電装部品絶縁板、ステップモーターロータ、ランプソケット、ランプリフレクタ、ランプハウジング、ブレーキピストン、ソレノイドボビン、エンジンオイルフィルタ、点火装置ケース等の自動車・車両関連部品、その他各種用途にも適用可能である。 Examples of the main applications of the composite molded body include housings for various home appliances, mobile phones, electronic devices such as PCs (Personal Computers), protection / support members for box-shaped electric / electronic component integration modules, and a plurality of. Individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed boards, tuners, speakers , Microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, and other electrical and electronic parts; VTR parts , TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio / video equipment parts such as audio / laser discs / compact discs / DVD discs / Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, Household and office electrical product parts represented by typewriter parts, word processor parts, water volume of water heaters and baths, water supply equipment parts such as temperature sensors; office computer related parts, telephone equipment related parts, facsimile related parts, copying Machine-related parts, cleaning jigs, motor parts, writers, typewriters, and other machine-related parts: microscopes, binoculars, cameras, watches, and other optical equipment, precision machine-related parts; alternator terminals, alternator connectors , Brush holder, slip ring, IC regulator, potential meter base for light die, relay block, inhibitor switch, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, Fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, air conditioner Thermostat base, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dustributor , Starter switch, Ignition coil and its bobbin, Motor insulator, Motor rotor, Motor core, Starter reel, Wire harness for transmission, Window washer nozzle, Air conditioner panel switch board, Fuel related electromagnetic valve coil, Fuse connector, Horn terminal, It can also be applied to automobile / vehicle-related parts such as insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, and ignition device cases, and various other applications.
（ポリフェニレンスルフィド樹脂のカルボキシ基濃度の測定）
ポリフェニレンスルフィド樹脂を３５０℃、荷重１０ＭＰａ、６０秒でプレスしたのち、６０秒かけて２５℃まで急冷することによって非晶性を示すフィルムを作成した。得られた非晶性を示すフィルムを、フーリエ変換赤外分光装置(以下「ＦＴ−ＩＲ装置」と略記する。)を用いて測定した。赤外吸収スペクトルのうち６３０．６ｃｍ−１の吸収に対する１７０５ｃｍ−１の吸収の相対強度を求め、別途後述する方法により作成した検量線を用いて測定サンプル中のカルボキシ基の含有量（以下「カルボキシ基の全含有量」と略記する。）を求めた。カルボキシ基の含有量は樹脂組成物１ｇ中のモル数で示され、その単位はμｍｏｌ／ｇで表される。検量線の作成方法は酸処理を行わずにカルボン酸塩を分子鎖に含有するポリアリーレンスルフィド樹脂３ｇに所定量の４−クロロフェニル酢酸を加え良く混合したのち、前記と同じようにしてフィルムを作成し、ＦＴ−ＩＲ装置で測定を行い、カルボキシ基含有量に対する、前記吸収の相対強度比をプロットした検量線を作成した。
(Measurement of carboxy group concentration of polyphenylene sulfide resin)
A polyphenylene sulfide resin was pressed at 350 ° C., a load of 10 MPa, and 60 seconds, and then rapidly cooled to 25 ° C. over 60 seconds to prepare a film showing amorphousness. The obtained amorphous film was measured using a Fourier transform infrared spectroscope (hereinafter abbreviated as "FT-IR device"). It determined the relative intensity of the absorption of 1705 cm -1 for absorption of 630.6Cm -1 of infrared absorption spectrum, additional content of carboxyl group in the measurement sample using a calibration curve prepared by the method described later (hereinafter "carboxy Abbreviated as "total content of groups"). The content of the carboxy group is represented by the number of moles in 1 g of the resin composition, and the unit thereof is represented by μmol / g. The method for preparing the calibration curve is to add a predetermined amount of 4-chlorophenylacetic acid to 3 g of a polyarylene sulfide resin containing a carboxylate in the molecular chain without performing acid treatment, mix well, and then prepare a film in the same manner as described above. Then, the measurement was carried out with an FT-IR apparatus, and a calibration curve was prepared by plotting the relative intensity ratio of the absorption to the carboxy group content.
（ポリフェニレンスルフィド樹脂の溶融粘度の測定）
参考例で製造したポリフェニレンスルフィド樹脂を島津製作所製フローテスター、ＣＦＴ−５００Ｄを用い、３００℃、荷重：１．９６×１０６Ｐａ、Ｌ／Ｄ＝１０（ｍｍ）／１（ｍｍ）にて、６分間保持した後に測定した。
(Measurement of melt viscosity of polyphenylene sulfide resin)
The polyphenylene sulfide resin produced in the reference example was used in a flow tester manufactured by Shimadzu Corporation, CFT-500D, at 300 ° C., a load of 1.96 × 10 6 Pa, and L / D = 10 (mm) / 1 (mm). It was measured after holding for 6 minutes.
（ＰＰＳ樹脂およびＰＰＳ樹脂組成物の融点（Ｔｍ）、再結晶化温度（Ｔｃ２）の測定）
参考例、比較参考例で得られたポリアリーレンスルフィド樹脂及び実施例、比較例で得られたポリアリーレンスルフィド樹脂組成物に係る融点（Ｔｍ）、再結晶化温度（Ｔｃ２）は、樹脂又は樹脂組成物を３５０℃にて溶融させた後、急冷させて非晶性フィルムを作製し、このフィルムからおよそ４ｍｇはかりとり、示差走査熱量計（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製『ＤＳＣ８５００』）を用いて測定した。
(Measurement of melting point (Tm) and recrystallization temperature (Tc2) of PPS resin and PPS resin composition)
The melting point (Tm) and recrystallization temperature (Tc2) of the polyarylene sulfide resin obtained in Reference Example and Comparative Reference Example and the polyarylene sulfide resin composition obtained in Examples and Comparative Examples are the resin or resin composition. The material was melted at 350 ° C. and then rapidly cooled to prepare an amorphous film, and about 4 mg of the film was weighed and measured using a differential scanning calorimeter (“DSC8500” manufactured by Perkin Elmer).
（参考例１）カルボキシ基含有ポリフェニレンスルフィド樹脂（ＰＰＳ−１）の製造
圧力計、温度計、コンデンサ、デカンター、精留塔を連結した撹拌翼付き１５０リットルオートクレーブにｐ−ジクロロベンゼン（以下、「ｐ−ＤＣＢ」と略記する。）３３．２２２ｋｇ（２２６モル）、ＮＭＰ２．２８０ｋｇ（２３モル）、４７．２３質量％ＮａＳＨ水溶液２７．３００ｋｇ（ＮａＳＨとして２３０モル）、及び４９．２１質量％ＮａＯＨ水溶液１８．５３３ｇ（ＮａＯＨとして２２８モル）を仕込み、撹拌しながら窒素雰囲気下で１７３℃まで５時間掛けて昇温して、水２７．３００ｋｇを留出させた後、オートクレーブを密閉した。脱水時に共沸により留出したｐ−ＤＣＢはデカンターで分離して、随時オートクレーブ内に戻した。脱水終了後のオートクレーブ内は微粒子状の無水硫化ナトリウム組成物がｐ−ＤＣＢ中に分散した状態であった。この組成物中のＮＭＰ含有量は０．０６９ｋｇ（０．７モル）であったことから、仕込んだＮＭＰの９７モル％（２２．３モル）がＮＭＰの開環体（４−（メチルアミノ）酪酸）のナトリウム塩（以下、「ＳＭＡＢ」と略記する。）に加水分解されていることが示された。オートクレーブ内のＳＭＡＢ量は、オートクレーブ中に存在する硫黄原子１モル当たり０．０９７モルであった。仕込んだＮａＳＨとＮａＯＨが全量、無水Ｎａ２Ｓに変わる場合の理論脱水量は２７．９２１ｇであることから、オートクレーブ内の残水量６２１ｇ（３４．５モル）の内、４０１ｇ（２２．３モル）はＮＭＰとＮａＯＨとの加水分解反応に消費されて、水としてオートクレーブ内に存在せず、残りの２２０ｇ（１２．２モル）は水、あるいは結晶水の形でオートクレーブ内に残留していることを示していた。オートクレーブ内の水分量はオートクレーブ中に存在する硫黄原子１モル当たり０．０５３モルであった。
(Reference Example 1) Production of carboxy group-containing polyphenylene sulfide resin (PPS-1) p-dichlorobenzene (hereinafter, "p-dichlorobenzene") is placed in a 150-liter autoclave with a stirring blade in which a pressure gauge, a thermometer, a capacitor, a decanter, and a rectification tower are connected. -DCB ".) 33.222 kg (226 mol), NMP 2.280 kg (23 mol), 47.23 mass% NaSH aqueous solution 27.300 kg (230 mol as NaSH), and 49.21 mass% NaOH aqueous solution 18 .533 g (228 mol of NaOH) was charged, and the temperature was raised to 173 ° C. over 5 hours under a nitrogen atmosphere with stirring to distill 27.300 kg of water, and then the autoclave was sealed. The p-DCB distilled by azeotrope during dehydration was separated by a decanter and returned to the autoclave at any time. In the autoclave after the completion of dehydration, the anhydrous sodium sulfide composition in the form of fine particles was dispersed in p-DCB. Since the NMP content in this composition was 0.069 kg (0.7 mol), 97 mol% (22.3 mol) of the charged NMP was an open ring of NMP (4- (methylamino)). It was shown that it was hydrolyzed to a sodium salt of (butyric acid) (hereinafter abbreviated as "SMAB"). The amount of SMAB in the autoclave was 0.097 mol per mole of sulfur atoms present in the autoclave. The charged NaSH and NaOH is the total amount, since the theoretical amount of dehydration may change anhydrous Na 2 S is 27.921G, among residual water content in the autoclave 621 g (34.5 moles), 401 g (22.3 mol) Is consumed in the hydrolysis reaction of NMP and NaOH and does not exist in the autoclave as water, and the remaining 220 g (12.2 mol) remains in the autoclave in the form of water or water of crystallization. Was showing. The water content in the autoclave was 0.053 mol per mol of sulfur atoms present in the autoclave.
上記脱水工程終了後に、内温を１６０℃に冷却し、ＮＭＰ４７．４９２ｋｇ（４７９モル）に含む溶液を仕込み、１８５℃まで昇温した。オートクレーブ内の水分量は、工程２で仕込んだＮＭＰ１モル当たり０．０２５モルであった。ゲージ圧が０．００ＭＰａに到達した時点で、精留塔を連結したバルブを開放し、内温２００℃まで１時間掛けて昇温した。この際、精留塔出口温度が１１０℃以下になる様に冷却とバルブ開度で制御した。留出したｐ−ＤＣＢと水の混合蒸気はコンデンサで凝縮し、デカンターで分離して、ｐ−ＤＣＢはオートクレーブへ戻した。留出水量は１７９ｇ（９．９モル）で、オートクレーブ内水分量は４１ｇ（２．３モル）で、脱水後に仕込んだＮＭＰ１モル当たり０．００５モルで、オートクレーブ中に存在する硫黄原子１モル当たり０．０１０モルであった。オートクレーブ内のＳＭＡＢ量は脱水時と同じく、オートクレーブ中に存在する硫黄原子１モル当たり０．０９７モルであった。 After the completion of the dehydration step, the internal temperature was cooled to 160 ° C., a solution contained in 47.492 kg (479 mol) of NMP was charged, and the temperature was raised to 185 ° C. The amount of water in the autoclave was 0.025 mol per 1 mol of NMP charged in step 2. When the gauge pressure reached 0.00 MPa, the valve connected to the rectification column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, cooling and valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower. The distilled steam of mixed p-DCB and water was condensed by a condenser, separated by a decanter, and the p-DCB was returned to the autoclave. The amount of distilled water was 179 g (9.9 mol), the water content in the autoclave was 41 g (2.3 mol), 0.005 mol per 1 mol of NMP charged after dehydration, and 1 mol of sulfur atoms present in the autoclave. It was 0.010 mol. The amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave, as in the case of dehydration.
次いで、内温２００℃から２３０℃まで３時間掛けて昇温し、２３０℃で１時間撹拌した後、２５０℃まで昇温し、１時間撹拌した。内温２００℃時点のゲージ圧は０．０３ＭＰａで、最終ゲージ圧は０．３０ＭＰａであった。冷却後、得られたスラリーの内、６．５ｋｇを３０リットルの８０℃温水に注いで１時間撹拌した後、濾過した。このケーキを再び３０リットルの温水で１時間撹拌し、洗浄した後、濾過した。次に、得られたケーキに３０リットルの水を加え、酢酸でｐＨを４．５に調整し、常温で１時間撹拌したのち、濾過した。さらに得られたケーキに３０リットルの温水を加え、１時間撹拌したのち、ろ過する操作を２回繰返して、熱風循環乾燥機を用い１２０℃で一晩乾燥して白色粉末上のカルボキシ基含有ＰＰＳ樹脂（以下、ＰＰＳ−１）を得た。得られたポリマーの溶融粘度は９８Ｐａ・ｓで、カルボキシ基含有量は５５．４μｍｏｌ／gであった。また、融点（Ｔｍ）は２８２℃、再結晶化温度（Ｔｃ２）は２０３℃であった。 Then, the temperature was raised from 200 ° C. to 230 ° C. over 3 hours, and the mixture was stirred at 230 ° C. for 1 hour, then raised to 250 ° C. and stirred for 1 hour. The gauge pressure at an internal temperature of 200 ° C. was 0.03 MPa, and the final gauge pressure was 0.30 MPa. After cooling, 6.5 kg of the obtained slurry was poured into 30 liters of warm water at 80 ° C., stirred for 1 hour, and then filtered. The cake was stirred again with 30 liters of warm water for 1 hour, washed and then filtered. Next, 30 liters of water was added to the obtained cake, the pH was adjusted to 4.5 with acetic acid, the mixture was stirred at room temperature for 1 hour, and then filtered. Further, 30 liters of warm water was added to the obtained cake, and after stirring for 1 hour, the operation of filtering was repeated twice, dried overnight at 120 ° C. using a hot air circulation dryer, and carboxy group-containing PPS on a white powder. A resin (hereinafter, PPS-1) was obtained. The melt viscosity of the obtained polymer was 98 Pa · s, and the carboxy group content was 55.4 μmol / g. The melting point (Tm) was 282 ° C. and the recrystallization temperature (Tc2) was 203 ° C.
（参考例２）カルボキシ基含有ポリフェニレンスルフィド樹脂（ＰＰＳ−２）の製造
圧力計、温度計、コンデンサを連結した撹拌翼および底弁付き１５０リットルオートクレーブに、４５％水硫化ソーダ（４７．５５質量％ＮａＳＨ）１４．１４８ｋｇ、４８％苛性ソーダ（４８．７質量％ＮａＯＨ）９．４７４ｋｇと、Ｎ−メチル−２−ピロリドン３８．０ｋｇを仕込んだ。窒素気流下攪拌しながら２０９℃まで昇温して、水１２．１５０ｋｇを留出させた（残存する水分量はＮａＳＨ１モル当り１．１３モル）。その後、オートクレーブを密閉して１８０℃まで冷却し、パラジクロロベンゼン１７．１２９ｋｇ及びＮ−メチル−２−ピロリドン１６．０ｋｇを仕込んだ。液温１５０℃で窒素ガスを用いてゲージ圧で０．１ＭＰａに加圧して昇温を開始した。液温２２０℃で４時間撹拌したのち、昇温して２６０℃になった時点でオートクレーブ上部を散水することで冷却しながら、２６０℃で３時間反応した。オートクレーブ上部を冷却中、液温が下がらないように一定に保持した。次に降温させると共にオートクレーブ上部の冷却を止めた。反応中の最高圧力は、０．８７ＭＰａであった。反応後、冷却し、１００℃で底弁を開き、反応スラリーを１５０リットル平板ろ過機に移送し１２０℃で加圧ろ過した。得られたケーキに７０℃温水５０ｋｇを加え撹拌したのち、濾過し、さらに温水２５ｋｇを加え濾過した。次に温水２５ｋｇを加え、酢酸でｐＨを４．５に調整し、１時間撹拌し、濾過したのち、温水２５ｋｇを加え、濾過した。さらに、温水２５ｋｇを加え１時間撹拌し、濾過したのち、温水２５ｋｇを加えろ過する操作を２回繰り返した。得られたケーキを熱風循環乾燥機を用いて１２０℃で１５時間乾燥し、ＰＰＳ−２を得た。得られたポリマーの溶融粘度１０８Ｐａ・ｓで、カルボキシ基含有量は７４．５μｍｏｌ／ｇであった。また、融点（Ｔｍ）は２７８℃、再結晶化温度（Ｔｃ２）は２４０℃であった。
(Reference Example 2) Production of carboxy group-containing polyphenylene sulfide resin (PPS-2) 45% sodium hydrosulfide (47.55% by mass) in a 150-liter autoclave with a stirring blade and bottom valve connected to a pressure gauge, thermometer, and capacitor. 14.148 kg of NaSH), 9.474 kg of 48% caustic soda (48.7 mass% NaOH), and 38.0 kg of N-methyl-2-pyrrolidone were charged. The temperature was raised to 209 ° C. with stirring under a nitrogen stream, and 12.150 kg of water was distilled off (the amount of residual water was 1.13 mol per 1 mol of NaSH). Then, the autoclave was sealed and cooled to 180 ° C., and 17.129 kg of paradichlorobenzene and 16.0 kg of N-methyl-2-pyrrolidone were charged. The temperature was started by pressurizing the liquid temperature to 0.1 MPa with a gauge pressure using nitrogen gas at a liquid temperature of 150 ° C. After stirring at a liquid temperature of 220 ° C. for 4 hours, the reaction was carried out at 260 ° C. for 3 hours while cooling by sprinkling water on the upper part of the autoclave when the temperature was raised to 260 ° C. While cooling the upper part of the autoclave, the liquid temperature was kept constant so as not to drop. Next, the temperature was lowered and the cooling of the upper part of the autoclave was stopped. The maximum pressure during the reaction was 0.87 MPa. After the reaction, the mixture was cooled, the bottom valve was opened at 100 ° C., the reaction slurry was transferred to a 150 liter flat plate filter, and pressure filtered at 120 ° C. To the obtained cake, 50 kg of warm water at 70 ° C. was added and stirred, and then the cake was filtered. Further, 25 kg of warm water was added and filtered. Next, 25 kg of warm water was added, the pH was adjusted to 4.5 with acetic acid, the mixture was stirred for 1 hour, filtered, and then 25 kg of warm water was added and filtered. Further, 25 kg of warm water was added, the mixture was stirred for 1 hour, filtered, and then 25 kg of warm water was added and filtered, and the operation was repeated twice. The obtained cake was dried at 120 ° C. for 15 hours using a hot air circulation dryer to obtain PPS-2. The melt viscosity of the obtained polymer was 108 Pa · s, and the carboxy group content was 74.5 μmol / g. The melting point (Tm) was 278 ° C., and the recrystallization temperature (Tc2) was 240 ° C.
（参考例３）カルボキシ基含有ポリフェニレンスルフィド樹脂（ＰＰＳ−３）の製造
「次いで、内温２００℃から２３０℃まで３時間掛けて昇温し、２３０℃で１時間撹拌した後、２５０℃まで昇温し、１時間撹拌した。」ところを、「次いで、内温２００℃から２３０℃まで３時間掛けて昇温し、２３０℃で３時間撹拌した後、２５０℃まで昇温し、１時間撹拌した。」としたこと、「次に、得られたケーキに３０リットルの水を加え、酢酸でｐＨを４．５に調整し、常温で１時間撹拌したのち、濾過した。」ところを「次に、得られたケーキに３０リットルの水を加え、炭酸水でｐＨを６．０に調整し、常温で１時間撹拌したのち、濾過した。」としたことの２点以外は参考例１と同様に行い、ＰＰＳ−３を得た。得られたポリマーの溶融粘度は１７１Ｐａ・ｓで、カルボキシ基含有量は３４．１μｍｏｌ／ｇであった。また、融点（Ｔｍ）は２８０℃、再結晶化温度（Ｔｃ２）は２１１℃であった。
(Reference Example 3) Production of carboxy group-containing polyphenylene sulfide resin (PPS-3) “Next, the temperature is raised from 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 1 hour, and then raised to 250 ° C. "Warm and stirred for 1 hour.""Then, the temperature was raised from 200 ° C. to 230 ° C. over 3 hours, and after stirring at 230 ° C. for 3 hours, the temperature was raised to 250 ° C. and stirred for 1 hour.""Next, 30 liters of water was added to the obtained cake, the pH was adjusted to 4.5 with acetic acid, the mixture was stirred at room temperature for 1 hour, and then filtered." In addition, 30 liters of water was added to the obtained cake, the pH was adjusted to 6.0 with carbonated water, the mixture was stirred at room temperature for 1 hour, and then filtered. ”Except for the two points mentioned in Reference Example 1. The same procedure was carried out to obtain PPS-3. The melt viscosity of the obtained polymer was 171 Pa · s, and the carboxy group content was 34.1 μmol / g. The melting point (Tm) was 280 ° C., and the recrystallization temperature (Tc2) was 211 ° C.
（参考例４）
パラジクロロベンゼンと同時に１，３，５−トリクロロベンゼン６５．３ｇ（ＮａＳＨ１モルに対して０．３ｍｏｌ％）を添加した以外は参考例２と同様に行い、カルボキシ基含有ポリフェニレンスルフィド樹脂（ＰＰＳ−４）を得た。得られたポリマーは溶融粘度２８４０Ｐａ・ｓ、カルボキシ基濃度は６６．９μｍｏｌ／ｇであった。また、融点（Ｔｍ）は２８４℃、再結晶化温度（Ｔｃ２）は２３０℃であった。
(Reference example 4)
The same procedure as in Reference Example 2 was carried out except that 65.3 g of 1,3,5-trichlorobenzene (0.3 mol% with respect to 1 mol of NaSH) was added at the same time as paradichlorobenzene, and a carboxy group-containing polyphenylene sulfide resin (PPS-4) was used. Got The obtained polymer had a melt viscosity of 2840 Pa · s and a carboxy group concentration of 66.9 μmol / g. The melting point (Tm) was 284 ° C., and the recrystallization temperature (Tc2) was 230 ° C.
（比較参考例１）
パラジクロロベンゼン１７．１２９ｋｇの変わりに、パラジクロロベンゼンを１４．５５９ｋｇ、メタジクロロベンゼンを２．５６９ｋｇ加えた以外は参考例２と同様に行い、カルボキシ基含有ポリフェニレンスルフィド樹脂（ＰＰＳ−Ｃ１）を得た。得られたポリマーは溶融粘度１０Ｐａ・ｓ、カルボキシ基濃度は３２．1μｍｏｌ／ｇであった。また、融点（Ｔｍ）は２４２℃、再結晶化温度（Ｔｃ２）は１４６℃であった。
(Comparative Reference Example 1)
The same procedure as in Reference Example 2 was carried out except that 14.559 kg of paradichlorobenzene and 2.569 kg of metadichlorobenzene were added instead of 17.129 kg of paradichlorobenzene to obtain a carboxy group-containing polyphenylene sulfide resin (PPS-C1). The obtained polymer had a melt viscosity of 10 Pa · s and a carboxy group concentration of 32.1 μmol / g. The melting point (Tm) was 242 ° C, and the recrystallization temperature (Tc2) was 146 ° C.
＜実施例１〜５及び比較例１〜２＞
表１〜２に記載する組成成分および配合量（全て質量部）に従い、各材料をタンブラーで均一に混合した。その後、東芝機械株式会社製ベント付き２軸押出機「ＴＥＭ−３５Ｂ」に前記配合材料を投入し、樹脂成分吐出量２５ｋｇ／ｈｒ、スクリュー回転数２５０ｒｐｍ、樹脂成分の吐出量（ｋｇ／ｈｒ）とスクリュー回転数（ｒｐｍ）との比率（吐出量／スクリュー回転数）＝０．１（ｋｇ／ｈｒ・ｒｐｍ）、設定樹脂温度３３０℃で溶融混練して樹脂組成物のペレットを得た。このペレットを用いて融点（Ｔｍ）、再結晶化温度（Ｔｃ２）を測定、両者の差ΔＴを算出した。結果を表１〜２に示す。
<Examples 1 to 5 and Comparative Examples 1 to 2>
Each material was uniformly mixed with a tumbler according to the composition components and blending amounts (all by mass) shown in Tables 1 and 2. After that, the compounded material was put into a twin-screw extruder "TEM-35B" with a vent manufactured by Toshiba Machine Co., Ltd., and the resin component discharge amount was 25 kg / hr, the screw rotation speed was 250 rpm, and the resin component discharge amount (kg / hr). Pellets of the resin composition were obtained by melt-kneading at a ratio (discharge amount / screw rotation speed) = 0.1 (kg / hr · rpm) to the screw rotation speed (rpm) and a set resin temperature of 330 ° C. Using this pellet, the melting point (Tm) and the recrystallization temperature (Tc2) were measured, and the difference ΔT between the two was calculated. The results are shown in Tables 1-2.
※１ ΔＴｃ２は、各実施例で得られた試験片（ＰＰＳ樹脂成形品）のＴｃ２（℃）から、各実施例で原料の用いたＰＰＳ樹脂のＴｃ２（℃）を差し引いた値。
また、表中の各原料は以下の通り。
* 1 ΔTc2 is a value obtained by subtracting Tc2 (° C.) of the PPS resin used as the raw material in each example from Tc2 (° C.) of the test piece (PPS resin molded product) obtained in each example.
In addition, each raw material in the table is as follows.
ビニルピロリドン系添加材
ＰＶＰ−１ ポリビニルピロリドン樹脂 株式会社日本触媒製「Ｋ−９０」（質量平均分子量：１０５００００〜１２０００００）
ＰＶＰ−２ ポリビニルピロリドン樹脂 株式会社日本触媒製「Ｋ−８５」（質量平均分子量：９０００００〜１０５００００）
ＰＶＰ−３ ポリビニルピロリドン樹脂 株式会社日本触媒製「Ｋ−３０」（質量平均分子量：８００００〜１２００００）
ＰＶＰ−４ ポリビニルピロリドン樹脂 第一工業製薬株式会社製「ピッツコールＫ−１７Ｌ」（質量平均分子量：９０００〜１２００００）
Vinylpyrrolidone-based additive PVP-1 Polyvinylpyrrolidone resin "K-90" manufactured by Nippon Shokubai Co., Ltd. (mass average molecular weight: 105,000 to 1200000)
PVP-2 Polyvinylpyrrolidone Resin "K-85" manufactured by Nippon Shokubai Co., Ltd. (mass average molecular weight: 900,000 to 1050,000)
PVP-3 Polyvinylpyrrolidone Resin "K-30" manufactured by Nippon Shokubai Co., Ltd. (mass average molecular weight: 80,000 to 120,000)
PVP-4 Polyvinylpyrrolidone Resin "Pittscol K-17L" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (mass average molecular weight: 9000 to 120,000)
エポキシシラン ３−グリシドキシプロピルトリメトキシシラン ダウ・コーニング株式会社製「ＳＨ−６０４０」 Epoxysilane 3-glycidoxypropyltrimethoxysilane Dow Corning Co., Ltd. "SH-6040"
Claims (12)
ポリアリーレンスルフィド樹脂（Ａ）１００質量部に対して、前記ポリビニルピロリドン（Ｂ）が０．０１〜１００質量部の範囲であり、前記シランカップリング剤（Ｃ）が０．０１〜３０質量部の範囲であること、を特徴とするポリアリーレンスルフィド樹脂組成物。 A polyarylene sulfide resin (A), polyvinylpyrrolidone (B), and a silane coupling agent (C) having a functional group that reacts with a carboxy group are blended as essential components.
The polyvinylpyrrolidone (B) is in the range of 0.01 to 100 parts by mass and the silane coupling agent (C) is in the range of 0.01 to 30 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). A polyarylene sulfide resin composition characterized by being in the range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016247856A JP6828414B2 (en) | 2016-12-21 | 2016-12-21 | Polyarylene sulfide resin composition, molded article and manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016247856A JP6828414B2 (en) | 2016-12-21 | 2016-12-21 | Polyarylene sulfide resin composition, molded article and manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018100364A JP2018100364A (en) | 2018-06-28 |
| JP6828414B2 true JP6828414B2 (en) | 2021-02-10 |
Family
ID=62715108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016247856A Active JP6828414B2 (en) | 2016-12-21 | 2016-12-21 | Polyarylene sulfide resin composition, molded article and manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6828414B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6950281B2 (en) * | 2017-05-26 | 2021-10-13 | Dic株式会社 | Polyarylene sulfide resin composition, molded article, metal / resin composite structure and manufacturing method |
| CN113980466B (en) * | 2021-10-29 | 2023-06-13 | 金发科技股份有限公司 | Polyphenylene sulfide composition and preparation method and application thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07309957A (en) * | 1994-05-16 | 1995-11-28 | Polyplastics Co | Polyarylene sulfide resin molding excellent in surface property |
| JP3487378B2 (en) * | 1995-03-09 | 2004-01-19 | 大日本インキ化学工業株式会社 | Method for producing polyarylene sulfide resin molded article |
| JP2001300969A (en) * | 2000-04-21 | 2001-10-30 | Polyplastics Co | Molded article having weld part |
| TWI428394B (en) * | 2008-01-31 | 2014-03-01 | Dainippon Ink & Chemicals | Polyarylene sulfide resin composition, manufacturing method thereof and surface-mount electronic element |
| JP5821213B2 (en) * | 2011-02-25 | 2015-11-24 | 東レ株式会社 | Method for producing polyphenylene sulfide resin fine particle dispersion |
| JP5970793B2 (en) * | 2011-11-30 | 2016-08-17 | Dic株式会社 | Resin composition, method for producing the same, molded product, and method for producing the same |
| JPWO2017069109A1 (en) * | 2015-10-20 | 2018-06-21 | Dic株式会社 | Polyarylene sulfide resin composition, molded article, and production method thereof |
| CN106269840A (en) * | 2016-08-29 | 2017-01-04 | 付融冰 | A kind of electrode restorative procedure of contaminated soil or subsoil water |
| JP6797360B2 (en) * | 2016-10-21 | 2020-12-09 | Dic株式会社 | Polyarylene sulfide resin composition, molded article and manufacturing method |
| JP7047248B2 (en) * | 2016-12-21 | 2022-04-05 | Dic株式会社 | Polyarylene sulfide resin composition, molded product and manufacturing method |
-
2016
- 2016-12-21 JP JP2016247856A patent/JP6828414B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018100364A (en) | 2018-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6797350B2 (en) | Polyarylene sulfide resin composition, molded article and manufacturing method | |
| KR102570939B1 (en) | Polyarylene sulfide resin composition and molded product thereof, method for producing polyarylene sulfide resin composition, and method for producing molded product | |
| JP7047248B2 (en) | Polyarylene sulfide resin composition, molded product and manufacturing method | |
| JP6950281B2 (en) | Polyarylene sulfide resin composition, molded article, metal / resin composite structure and manufacturing method | |
| WO2017069109A1 (en) | Polyarylene sulfide resin composition, molded product, and methods for producing said composition and product | |
| JP6797360B2 (en) | Polyarylene sulfide resin composition, molded article and manufacturing method | |
| JP6828414B2 (en) | Polyarylene sulfide resin composition, molded article and manufacturing method | |
| JP7024932B1 (en) | Polyarylene sulfide resin compositions, molded articles and methods for producing them | |
| KR102499526B1 (en) | Resin composition and molded product thereof | |
| JP7070811B1 (en) | Polyarylene sulfide resin compositions, molded articles and methods for producing them | |
| JP6866609B2 (en) | Polyarylene sulfide resin compositions, molded articles and methods for producing them | |
| JP7136394B1 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| JP7298797B1 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| JP7180814B2 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| JP7311051B2 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| WO2023157411A1 (en) | Polyarylene sulfide resin composition, molded article, and production methods for same | |
| JP7197066B1 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| JP7136372B2 (en) | Polyarylene sulfide resin composition, molded article and method for producing the same | |
| JP2017088878A (en) | Polyarylene sulfide resin composition and molded article | |
| WO2022215395A1 (en) | Polyarylene sulfide resin composition, molded article, and methods for producing said polyarylene sulfide resin composition and molded article | |
| WO2023074035A1 (en) | Polyarylene sulfide resin composition, molded article, and methods for producing these | |
| JP2024040672A (en) | Polyarylene sulfide resin composition, molded article, and production methods of these | |
| TW202400923A (en) | Gear mechanism, arm mechanism for robot, and robot | |
| EP3785905A1 (en) | Poly(arylene sulfide) resin composition, molded article, composite molded article, and methods respectively for producing said products | |
| JP2017088877A (en) | Polyarylene sulfide resin composition and molded article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20180220 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20190624 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20191029 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200630 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200728 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200924 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201222 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210104 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6828414 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |