JPS63286467A - Polyphenylene sulfide resin composition - Google Patents
Polyphenylene sulfide resin compositionInfo
- Publication number
- JPS63286467A JPS63286467A JP12274387A JP12274387A JPS63286467A JP S63286467 A JPS63286467 A JP S63286467A JP 12274387 A JP12274387 A JP 12274387A JP 12274387 A JP12274387 A JP 12274387A JP S63286467 A JPS63286467 A JP S63286467A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- melt
- parts
- weight
- curing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 42
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 42
- 239000011342 resin composition Substances 0.000 title claims description 9
- 229920005989 resin Polymers 0.000 claims abstract description 85
- 239000011347 resin Substances 0.000 claims abstract description 85
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 229920003986 novolac Polymers 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000155 melt Substances 0.000 claims abstract description 14
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 12
- 239000005011 phenolic resin Substances 0.000 claims abstract description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 4
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims description 31
- 238000000691 measurement method Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 150000001408 amides Chemical class 0.000 abstract description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract 3
- 238000010438 heat treatment Methods 0.000 abstract 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 15
- 238000005452 bending Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000002989 phenols Chemical class 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- -1 fluorophenol Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 229920013632 Ryton Polymers 0.000 description 3
- 239000004736 Ryton® Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- FIWYWGLEPWBBQU-UHFFFAOYSA-N 2-heptylphenol Chemical compound CCCCCCCC1=CC=CC=C1O FIWYWGLEPWBBQU-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- QPVRKFOKCKORDP-UHFFFAOYSA-N 1,3-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC(C)(O)CC=C1 QPVRKFOKCKORDP-UHFFFAOYSA-N 0.000 description 1
- AQFCDVGUEQOTAC-UHFFFAOYSA-N 2,5-diethylphenol Chemical compound CCC1=CC=C(CC)C(O)=C1 AQFCDVGUEQOTAC-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 1
- ABMULKFGWTYIIK-UHFFFAOYSA-N 2-hexylphenol Chemical compound CCCCCCC1=CC=CC=C1O ABMULKFGWTYIIK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- RDCHMDPGLCHQQM-UHFFFAOYSA-N 2-methyl-3-phenylphenol Chemical compound CC1=C(O)C=CC=C1C1=CC=CC=C1 RDCHMDPGLCHQQM-UHFFFAOYSA-N 0.000 description 1
- CAPGYRYSLXORFK-UHFFFAOYSA-N 2-methyl-5-phenylphenol Chemical compound C1=C(O)C(C)=CC=C1C1=CC=CC=C1 CAPGYRYSLXORFK-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- PFBHMJJMZWUEAI-UHFFFAOYSA-N 3,5-di(butan-2-yl)phenol Chemical compound CCC(C)C1=CC(O)=CC(C(C)CC)=C1 PFBHMJJMZWUEAI-UHFFFAOYSA-N 0.000 description 1
- PZFMWYNHJFZBPO-UHFFFAOYSA-N 3,5-dibromophenol Chemical compound OC1=CC(Br)=CC(Br)=C1 PZFMWYNHJFZBPO-UHFFFAOYSA-N 0.000 description 1
- MFQKPJOZPDGWLO-UHFFFAOYSA-N 3,5-dioctylphenol Chemical compound CCCCCCCCC1=CC(O)=CC(CCCCCCCC)=C1 MFQKPJOZPDGWLO-UHFFFAOYSA-N 0.000 description 1
- ZDWSNKPLZUXBPE-UHFFFAOYSA-N 3,5-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1 ZDWSNKPLZUXBPE-UHFFFAOYSA-N 0.000 description 1
- ZVUDLZCSBFUWEO-UHFFFAOYSA-N 3-(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=CC(O)=C1 ZVUDLZCSBFUWEO-UHFFFAOYSA-N 0.000 description 1
- SJTBRFHBXDZMPS-UHFFFAOYSA-N 3-fluorophenol Chemical compound OC1=CC=CC(F)=C1 SJTBRFHBXDZMPS-UHFFFAOYSA-N 0.000 description 1
- BHUODJHOUAFKAS-UHFFFAOYSA-N 3-methyl-4-phenylphenol Chemical compound CC1=CC(O)=CC=C1C1=CC=CC=C1 BHUODJHOUAFKAS-UHFFFAOYSA-N 0.000 description 1
- MPWGZBWDLMDIHO-UHFFFAOYSA-N 3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1 MPWGZBWDLMDIHO-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920006364 Rulon (plastic) Polymers 0.000 description 1
- 241001290864 Schoenoplectus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008430 aromatic amides Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229940118056 cresol / formaldehyde Drugs 0.000 description 1
- 238000005520 cutting process Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- USEUJPGSYMRJHM-UHFFFAOYSA-N formaldehyde;4-methylphenol Chemical compound O=C.CC1=CC=C(O)C=C1 USEUJPGSYMRJHM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 230000013011 mating Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明はポリフェニレンサルファイド樹組成物に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a polyphenylene sulfide tree composition.
ポリフェニレンサルファイド〔ＰＰＳ〕樹脂は、耐熱性
、成形性、耐薬品性に優れているが、ＰＰＳ樹脂単独で
は伸びが少なく、脆弱であり、エンジニアリング・プラ
スチックとして電子・電気機器部品、事務機器部品、音
響機器部品、その他機械部品等の分野で使用されるため
には、曲げ強度等の機械的強度が小さく、熱膨張率は太
き（、耐摩耗性が劣るなどの多（の問題点を改善する必
要がある。そこで、ＰＰＳ樹脂にガラス繊維、炭素繊維
等の繊維状強化剤（充填剤）またはシリカ粉、マイカ粉
等の粉末状充填剤を配合して強度、熱膨張率、耐摩耗性
を改善しようとする試みがなされている、しかし、これ
ら無機充填剤を多量配合すると、溶融成形性が悪化した
り、特に繊維状充填剤を多く配合したときには強度また
は寸法に大きい異方性を生じたり、潤滑性を要求される
部品などに用いたとき相手材を著しく損傷させたりする
が、一方無機充填剤の量が少な過ぎるときまたは有機充
填剤の盪が多いときには、強化の効果が充分得られなか
ったり、成形収縮率が大きく、また成形品にひけ、そり
等の現象が目立つようになって好ましくない。Polyphenylene sulfide [PPS] resin has excellent heat resistance, moldability, and chemical resistance, but PPS resin alone has low elongation and is brittle, and is used as an engineering plastic for electronic and electrical equipment parts, office equipment parts, and acoustics. In order to be used in the field of equipment parts and other mechanical parts, it is necessary to improve the problems of low mechanical strength such as bending strength, high coefficient of thermal expansion, and poor wear resistance. Therefore, PPS resin is blended with fibrous reinforcing agents (fillers) such as glass fibers and carbon fibers, or powdered fillers such as silica powder and mica powder to improve strength, thermal expansion coefficient, and abrasion resistance. Attempts have been made to improve the process, but when large amounts of these inorganic fillers are blended, melt moldability deteriorates, and especially when large amounts of fibrous fillers are blended, large anisotropy occurs in strength or dimensions. When used in parts that require lubricity, it can cause significant damage to the mating material, but on the other hand, when the amount of inorganic filler is too small or when the amount of organic filler is too much, the reinforcing effect cannot be obtained sufficiently. This is undesirable because the molding shrinkage rate is high, and phenomena such as shrinkage and warpage become noticeable in the molded product.
特に成形性または脆弱性を改善するために、ＰＰＳ樹脂
と各種の熱可塑性樹脂（たとえばポリアリ−レート、ポ
リスルホン、ポリフェニレンオキサイド、ポリエーテル
ケトン、ポリアミドイミドなど）とをブレンドすること
もよく知られているが、これらブレンド品のほとんどは
相溶性が充分でなく、そのために曲げ強度等の機械的性
質は改善されておらず、成形収縮率、そり、ひけ等の寸
法精度、摺動特性等は改善というよりはむしろ低下する
場合が多い。It is also well known to blend PPS resins with various thermoplastic resins (e.g. polyarylates, polysulfones, polyphenylene oxides, polyetherketones, polyamideimides, etc.), particularly to improve moldability or brittleness. However, most of these blended products do not have sufficient compatibility, and therefore mechanical properties such as bending strength have not been improved, while molding shrinkage, dimensional accuracy such as warpage and sink marks, and sliding properties have not been improved. In many cases, it actually decreases.
上記方法のほかに、熱硬化性樹脂を用いて改質する方法
が提案されている。たとえば特公昭５３−１３３９１号
公報には無機充填剤を含有するＰＰＳ樹脂に未硬化すな
わち溶融成形可能なエポキシ（ＥＰ）樹脂を配合するこ
とによって機械的強度および熱変形温度等を改善するこ
とが提案されている。そして、この方法ではＥＰ樹脂主
剤に対して硬化剤を併用することについては全く言及さ
れていないが、硬化剤を使用しないときには成形加工性
が優れているが、ＥＰＩ脂のブリード現象によって成形
品表面の外観を損ねたり、成形収縮率、そり、ひけ等の
寸法精度、摺動特性等については、はとんど改善されな
いで逆に低下する傾向にある。また硬化剤を使用すると
きは場合によってＥＰ樹脂自身の架橋三次元化の進行に
伴って溶融流動性が著しく低下して、金型への樹脂の安
定供給が不可能となり、特に強度的改善度の高いＥＰ樹
脂の高充填の場合にこのような現象が顕著である。In addition to the above methods, a method of modifying using a thermosetting resin has been proposed. For example, Japanese Patent Publication No. 53-13391 proposes to improve mechanical strength, heat distortion temperature, etc. by blending uncured, ie, melt moldable, epoxy (EP) resin with PPS resin containing an inorganic filler. has been done. In this method, there is no mention of using a curing agent in combination with the EP resin base resin, but when no curing agent is used, moldability is excellent, but the EPI resin bleeds, causing the molded product to There is a tendency for the appearance of the material to deteriorate, the molding shrinkage rate, dimensional accuracy such as warpage and sink marks, sliding characteristics, etc. to be deteriorated without being improved. In addition, when using a curing agent, in some cases, as the EP resin itself progresses to three-dimensional crosslinking, the melt fluidity decreases significantly, making it impossible to stably supply the resin to the mold, especially in terms of strength improvement. This phenomenon is noticeable when the EP resin is highly filled.
また、特開昭５９−３３３６０号公報には、無機充填剤
を含有するＰＰＳ樹脂にＢＰ樹脂硬化物を配合すること
によって、°前記特公昭５３−１３３９１号公報に開示
された方法の問題点を改善する方法が提案されているが
、この方法では溶融成形性、機械的強度に対しては改善
されるが、成形品の寸法精度向上のためには、かなりの
無機充填剤をさらに添加しなければならず、そのための
前記弊害が生ずるようになる。さらに、特開昭５９−５
１９４４号公報、同５９−５１９４５号公報においては
酸化架橋していない低粘度のＰＰＳ樹脂にＥＰ樹脂を反
応させて高分子量化させることによって溶融粘度を安定
化させ、成形加工性に優れた組成物を提案しているが、
これらによって得られる組成物は摺動特性に劣るという
欠点を存している。Furthermore, JP-A No. 59-33360 discloses that the problems of the method disclosed in JP-A-53-13391 can be solved by blending a cured BP resin with a PPS resin containing an inorganic filler. A method has been proposed to improve melt formability and mechanical strength, but in order to improve the dimensional accuracy of the molded product, a considerable amount of inorganic filler must be added. As a result, the above-mentioned disadvantages occur. Furthermore, JP-A-59-5
No. 1944 and No. 59-51945 disclose compositions that stabilize melt viscosity and have excellent moldability by reacting low-viscosity PPS resin that is not oxidatively crosslinked with EP resin to increase the molecular weight. However, we are proposing
The compositions obtained by these methods have the disadvantage of poor sliding properties.
このように、従来の技術においては、ＰＰＳ樹脂本来の
機械的緒特性、耐熱性等の優れた性質を保持し、しかも
溶融成形性、寸法精度および摺動特性に優れた実用性の
大きい加熱溶融成形用ＰＰＳ樹脂組成物は得られないと
いう問題点があった。As described above, in the conventional technology, PPS resin retains its original mechanical properties, heat resistance, and other excellent properties, and has excellent melt formability, dimensional accuracy, and sliding properties, making it highly practical. There was a problem that a PPS resin composition for molding could not be obtained.
上記の問題点を解決するために、この発明はメルトフロ
ーレイト（内径２．０９ｍｍ、長さ８．００ｍｍのオリ
フィスを用い、温度３００℃、保持時間６分間、荷重５
０００ ｇのＡＳＴＭ−０１２３８に基づく測定法によ
る値）が２００ｇ／１０分以下であるポリフェニト窪ル
ファイド〔ＰＰＳ〕樹脂１００重量部と加熱溶融成形可
能な耐熱性エポキシ（ＥＰ）樹脂（主剤および硬化剤）
１０〜１００重量部と充填剤０〜２５０重量部、好まし
くは３０〜２５０重量部、とを配合した組成物であって
、ＰＰＳ樹脂とＢＰ樹脂との溶融配合物の保持時間６分
間および３０分間としたときのメルトフローレイト（保
持時間以外の条件は前記条件と同一）の差が保持時間を
６分間としたときの値に対して０．７以下であるＰＰＳ
樹脂組成物とする手段を採用したものである。以下その
詳細を述べる。In order to solve the above problems, this invention uses a melt flow rate (orifice with an inner diameter of 2.09 mm and a length of 8.00 mm, a temperature of 300°C, a holding time of 6 minutes, a load of 5
100 parts by weight of polyphenylphide [PPS] resin with a measurement method based on ASTM-01238 of 200 g/10 minutes or less and a heat-resistant epoxy (EP) resin (base resin and curing agent) that can be heat-melted and molded.
A composition containing 10 to 100 parts by weight of a filler and 0 to 250 parts by weight, preferably 30 to 250 parts by weight, wherein the holding time of the melt blend of PPS resin and BP resin is 6 minutes and 30 minutes. PPS where the difference in melt flow rate (conditions other than holding time are the same as above) is 0.7 or less compared to the value when holding time is 6 minutes.
This method employs a method of forming a resin composition. The details will be described below.
まず、この発明で使用するＰＰＳ樹脂は、一般式
で表わされる繰返し単位からなる重合体であって、特に
この繰返し単位を９０モル％以上含むものが特性上好ま
しいが、９０モル％未満では期待する性質の組成物は得
難くなる。そしてこのような重合体を得る方法は公知の
種々の方法を採用することが出来るが、硫化ナトリウム
とｐ−ジクロルヘンゼンとをＮメチルピロリドン、ジメ
チルアセトアミドなどのアミド系溶媒やスルホランなど
のスルホン系溶媒中で反応させるのが好適である。共重
合成分として１０モル％未満であって、重合体の結晶性
に影響を与えない範囲で、たとえば
などの共重合成分を含んでいてもよい、このようなＰＰ
Ｓ樹脂はたとえば特公昭４４−２７６７１号公報および
同４５−３３６８号公報に開示されているようなハロゲ
ン置換芳香族化合物と硫化アルカリとの反応、特公昭４
６−２７２５５号に開示されているような芳香族化合物
を塩化硫黄とのルイス酸触媒共存下における縮合反応、
または米国特許第３２７４１６５号に開示されているよ
うなチオフェノール類のアルカリ触媒もしくは銅塩等の
共存下における縮合反応等によって合成されるが、目的
に応じて具体的な方法を任意に選択することが出来る。First, the PPS resin used in this invention is a polymer consisting of repeating units represented by the general formula, and it is particularly preferable in terms of properties that it contains 90 mol% or more of this repeating unit, but if it is less than 90 mol%, the expected Compositions of this nature become difficult to obtain. Various known methods can be used to obtain such a polymer, including sodium sulfide and p-dichlorohenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide, or a sulfone solvent such as sulfolane. It is preferable to react with Such PP may contain a copolymerization component such as less than 10 mol% as a copolymerization component and within a range that does not affect the crystallinity of the polymer.
S resin is produced by the reaction of a halogen-substituted aromatic compound with an alkali sulfide as disclosed in Japanese Patent Publications No. 44-27671 and No. 45-3368,
A condensation reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst as disclosed in No. 6-27255,
Alternatively, it can be synthesized by a condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt as disclosed in U.S. Pat. No. 3,274,165, but a specific method can be arbitrarily selected depending on the purpose. I can do it.
ＰＰＳ樹脂は上記のような縮合等の反応直後においては
白色に近い未架橋品であって、このままでは低分子量で
低粘度であることから、押出成形、射出成形などの用途
に用いるために、空気中において融点以下に加熱し、酸
化架橋させてまたは縮合反応の工程で分子量を高め、押
出成形、射出成形等に適する溶媒粘度のものに変化させ
る。分子量が小さ過ぎるとたとえＥＰ樹脂主剤と反応さ
せて高分子量化させたとしても摺動特性、特に潤滑性が
悪いので、この発明において望ましいＰＰＳ樹脂の溶融
粘度はＡＳＴＭ−ロＩ２３８に規定された３００℃、保
持時間６分間、荷重５０００ ｇの条件下におけるメル
トフローレイト（オリフィス内径２．０９１＋１．長さ
８．００ｍ）が２００ ｇ ／１０分以下のものである
。Immediately after the above-mentioned condensation reaction, PPS resin is an uncrosslinked product that is nearly white in color and has a low molecular weight and low viscosity. The polymer is heated to below its melting point in the mold, and the molecular weight is increased through oxidative crosslinking or a condensation reaction process, and the solvent viscosity is changed to be suitable for extrusion molding, injection molding, etc. If the molecular weight is too small, the sliding properties, especially the lubricity, will be poor even if the molecular weight is increased by reacting with the EP resin base material. Therefore, the melt viscosity of the PPS resin desired in this invention is 300 as specified in ASTM-Ro I238. The melt flow rate (orifice inner diameter 2.091+1. length 8.00 m) under the conditions of 5000 g load at 6 minutes holding time at 200 g/10 minutes or less.
つぎにこの発明で使用するＥＰ樹脂は溶融成形の可能な
未硬化樹脂で、前記のＰＰＳ樹脂との溶融配合物の保持
時間６分間および３０分間としたときのメルトフローレ
イト（保持時間以外の条件は前記の条件と同じ）の差が
保持時間を６分間としたときの値に対して０．７以下で
あることが望ましい。なぜならば、０．７を越えるとそ
の溶融配合物の溶融流動性は著しく低下して好ましくな
いからである。そしてＥＰ樹脂の主剤自体の種類はビス
フェノール系、脂環族系、ノボラック系などエポキシ基
を有するものであればいずれでもよいが、硬化剤として
はアミン類、酸無水物、多硫化物、フェノール樹脂など
のうち、高分子量ノボラック型フェノール系樹脂を特に
好ましいものとして推奨することが出来る。なお硬化反
応を促進するために、イミダソール類その他の促進剤を
添加してもよい。Next, the EP resin used in this invention is an uncured resin that can be melt-molded, and the melt flow rate (conditions other than the holding time) when the melt blend with the PPS resin is held for 6 minutes and 30 minutes is as follows. (same as the above conditions) is desirably 0.7 or less with respect to the value when the holding time is 6 minutes. This is because if it exceeds 0.7, the melt fluidity of the melt blend will drop significantly, which is undesirable. The main resin itself for EP resin may be any type that has an epoxy group, such as bisphenol, alicyclic, or novolac, but the curing agent may be amines, acid anhydrides, polysulfides, or phenolic resins. Among these, high molecular weight novolak type phenolic resins can be recommended as particularly preferred. In addition, in order to accelerate the curing reaction, imidasoles and other accelerators may be added.
この発明の樹脂組成物に硬化剤として配合される高分子
量ノボラック型フェノール系樹脂は構成フェノール類成
分として二官能性フェノール類成分（二官能性フェノー
ル類は通常７０〜１００モル％、好ましくは８０〜１０
０モル％）を主体とし、数平均分子量（Ｍｎ）が１５０
０以上であり、かつ実質上線状の高分子量ノボラック型
フェノール系樹脂である。このような高分子量ノボラッ
ク型フェノール系樹脂は、すべて実質上線状のノボラッ
ク反復単位からなっても、また数平均分子量が２５０〜
１２００のノボラック型反復単位のブロック毎に２価の
炭化水素基からなる鎖延長基をこのブロック１モル当り
０．５ないし１モル未満、特に０．６ないし１モル未満
となる割合いで交互に含む高分子量ノボラツク型フェノ
ール系樹脂であっても良い０重要なことはこの高分子量
ノボラック型樹脂が実質上線状でしかも１５００以上、
好ましくは１７００〜１５０００の範囲の数平均分子量
（Ｍｎ）を有することである。The high molecular weight novolak type phenolic resin blended as a curing agent in the resin composition of the present invention has a difunctional phenol component as a constituent phenol component (the difunctional phenol is usually 70 to 100 mol%, preferably 80 to 100% by mole). 10
0 mol%) with a number average molecular weight (Mn) of 150
0 or more, and is a substantially linear high molecular weight novolak type phenolic resin. Such high molecular weight novolak-type phenolic resins may consist entirely of substantially linear novolac repeating units or may have a number average molecular weight of 250 to 250.
Each block of 1200 novolak-type repeating units alternately contains chain extending groups consisting of divalent hydrocarbon groups in a proportion of 0.5 to less than 1 mol, especially 0.6 to less than 1 mol, per mol of this block. It may be a high molecular weight novolak type phenolic resin. The important thing is that this high molecular weight novolak type resin is substantially linear and has a molecular weight of 1500 or more.
Preferably, it has a number average molecular weight (Mn) in the range of 1,700 to 15,000.
ここで数平均分子量（Ｍｎ）はＮ、Ｎ−ジメチルアセト
アミド溶媒中で蒸気圧浸透圧法によって測定した値であ
る。また、前記した実質上線状とは、重合体鎖が直鎖状
または分枝鎖状の線状構造のものであり、網状構造すな
わちゲル化物を実質的に含まないことを意味している。Here, the number average molecular weight (Mn) is a value measured by vapor pressure osmosis method in N,N-dimethylacetamide solvent. Furthermore, the above-mentioned "substantially linear" means that the polymer chain has a linear or branched linear structure, and that it does not substantially contain a network structure, that is, a gelled product.
そして数平均分子量（Ｍｎ）が大きくなると硬化型樹脂
に配合した場合に耐熱性、機械的特性および難燃性の優
れた組成物が得られるようになるので好ましく、また分
子量分布はＭｎが２０００以上の帰脂成分の含を率が通
常５０重量％以上であり、好ましくは６０重量％以上で
あり、特に７０重量％以上が好ましい、さらに、ゲルパ
ーミニ−シランクロマトグラフィーで測定した数平均分
子量（Ｍｎ）に対する重量平均分子量（Ｍｗ）の比、す
なわちＭ ｗ ／ Ｍ ｎで表わした分子量分布は好ま
しくは１．８〜２０．０、特に２〜１０の範囲が好まし
い。またこの高分子量ノボラック型樹脂の融点は通常１
２０℃以上、好ましくは１５０℃以上である。A large number average molecular weight (Mn) is preferable because a composition with excellent heat resistance, mechanical properties, and flame retardancy can be obtained when blended into a curable resin, and the molecular weight distribution is such that Mn is 2000 or more. The content of fat-reducing components is usually 50% by weight or more, preferably 60% by weight or more, particularly preferably 70% by weight or more, and the number average molecular weight (Mn) measured by gel perminisilane chromatography. The ratio of weight average molecular weight (Mw) to Mw, that is, the molecular weight distribution expressed as Mw/Mn, is preferably in the range of 1.8 to 20.0, particularly 2 to 10. In addition, the melting point of this high molecular weight novolac type resin is usually 1
The temperature is 20°C or higher, preferably 150°C or higher.
前記の高分子量ノボラック型フェノール系樹脂を構成す
るノボラック型反復単位として、さらに具体的にはこれ
を構成するフェノール類成分が、Ｒ＋
で表わされる少なくとも１種の二官能性フェノール類成
分が７０〜１００モル％、好ましくは８０〜１００モル
％、さらに好ましくは９０〜！００モル％のｉ囲および
三官能性フェノール類成分が０〜３０モル％、好ましく
は０〜２０モル％、さらに好ましくは０〜ｌＯモル％の
範囲（ただし、両フェノール類成分の合計が１００モル
％になるように選ぶ）からなるフェノール類成分である
上記一般式において、３個のＲ１のうちの２個は水素原
子であり、他の１個は炭素数１〜８のアルキル基、炭素
数６〜ＩＯのアリール基、ハロゲン原子または水酸基、
好ましくは炭素数１〜８のアルキル基、を示し、さらに
好ましくはエチル基、エチル基、トプロピル基、５ｅｃ
−ブチル基、Ｌａｒｔ−ブチル基およびオクチル基から
なる群の中から選ばれた１種の置換基を示し、特に好ま
しくはメチル基である。また、２個のＲは水素原子、炭
素数１〜８のアルキル基、ハロゲン原子および水酸基か
らなる群の中から選ばれた同一もしくは異種の基を表わ
し、好ましくは２個のうち１個が水素原子、他の１個が
水素原子もしくは炭素数１〜Ｂのアルキル基、さらに好
ましくは２個のＲが共に水素原子である。The novolak repeating unit constituting the high molecular weight novolak phenolic resin, more specifically, the phenol component constituting this is such that at least one difunctional phenol component represented by R+ has a molecular weight of 70 to 100%. Mol%, preferably 80-100 mol%, more preferably 90-! 00 mol% of i and trifunctional phenolic components are in the range of 0 to 30 mol%, preferably 0 to 20 mol%, more preferably 0 to 10 mol% (provided that the total of both phenolic components is 100 mol%) In the above general formula, two of the three R1 are hydrogen atoms, and the other one is an alkyl group having 1 to 8 carbon atoms, 6 to IO aryl group, halogen atom or hydroxyl group,
Preferably an alkyl group having 1 to 8 carbon atoms, more preferably an ethyl group, an ethyl group, a topropyl group, a 5ec
represents one type of substituent selected from the group consisting of -butyl group, lart-butyl group, and octyl group, and particularly preferably methyl group. Further, the two R's represent the same or different groups selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, and a hydroxyl group, and preferably one of the two R's is hydrogen. The other one of the atoms is a hydrogen atom or an alkyl group having 1 to B carbon atoms, and more preferably both R atoms are hydrogen atoms.
したがって、前記高分子量ノボラック型フェノール系樹
脂を構成するフェノール類成分のうちで、二官能性フェ
ノール類成分の一つは、上記一般式のベンゼン核上に、
１損反応に対して活性のある２個の水素原子を有するフ
ェノール類、たとえばヒドロキシル基に対してオルトも
しくはパラの位置に炭素数１〜８のアルキル基、炭素数
６〜１０のアリール基、ハロゲンまたは水酸基を有する
フェノール類すなわちフェノール類のオルト異性体もし
くはパラ異性体であり、具体例としてクレゾール、エチ
ルフェノール、ｎ−プロピルフェノール、ｉ−プロピル
フェノール、ローブチルフェノール、５ｅＣ−ブチルフ
ェノール、ｔｅｒｔ−ブチルフェノール、５ｅｃ−アミ
ルフェノール、ｔｅｒｔ−アミルフェノール、ヘキシル
フェノール、ヘプチルフェノール、オクチルフェノール
などのアルキルフェノール類、クロロフェノール、ブロ
モフェノールなどのハロゲン化フェノール、フェニルフ
ェノール、トリルフェノールなどのアリールフェノール
類等のオルト型もしくはパラ型のフェノール異性体を挙
げることが出来る。また、これら以外の二官能性フェノ
ール類成分としては、２．３−キシレノール、３．４−
キシレノール、２１５−キシレノール、２．３−ジエチ
ルフェノール、３．４−ジエチルフェノール、２，５−
ジエチルフェノール、２．３−ジイソプロピルフェノー
ル、３．４−ジイソプロピルフェノール、２．５−ジイ
ソプロピルフェノール、２．３−ジクロロフェノール、
３．４−ジクロロフェノール、２．５−ジクロロフェノ
ール、２−メチル−３−フェニルフェノール、３−メチ
ル−４−フェニルフェノール、２−メチル−５−フェニ
ルフェなくとも１種類であって、２種以上の混合物であ
っても支障はない。Therefore, among the phenolic components constituting the high molecular weight novolak type phenolic resin, one of the bifunctional phenolic components is on the benzene nucleus of the general formula,
Phenols having two hydrogen atoms that are active in one-loss reactions, such as alkyl groups with 1 to 8 carbon atoms, aryl groups with 6 to 10 carbon atoms, halogens in the ortho or para position to the hydroxyl group. or phenols having a hydroxyl group, that is, ortho-isomers or para-isomers of phenols; specific examples include cresol, ethylphenol, n-propylphenol, i-propylphenol, lobethylphenol, 5eC-butylphenol, tert-butylphenol, 5ec - Alkylphenols such as amylphenol, tert-amylphenol, hexylphenol, heptylphenol, and octylphenol; halogenated phenols such as chlorophenol and bromophenol; and arylphenols such as phenylphenol and tolylphenol; Mention may be made of phenol isomers. In addition, other bifunctional phenol components include 2,3-xylenol, 3,4-
Xylenol, 215-xylenol, 2.3-diethylphenol, 3.4-diethylphenol, 2,5-
diethylphenol, 2.3-diisopropylphenol, 3.4-diisopropylphenol, 2.5-diisopropylphenol, 2.3-dichlorophenol,
3.4-dichlorophenol, 2.5-dichlorophenol, 2-methyl-3-phenylphenol, 3-methyl-4-phenylphenol, 2-methyl-5-phenylphenol, at least one type, but two types There is no problem even if the above mixture is used.
また、前記高分子量ノボラック型フェノール系樹脂を構
成するフェノール類成分のうちで、三官能性フェノール
類成分は、ベンゼン核上に置換反応に対して活性のある
３個の水素原子を有するフェノール類であり、具体的に
はフェノール、フェノールの両メタ置換体、フェノール
の３．５−１［Ｃである。そしてこれらの三官能性フェ
ノール類が両メタ位もしくは、３．５の位置に有する置
換基としては、通常、アルキル基、ハロゲンもしくは水
酸基であって、これら三官能性フェノール類のうちで、
好ましいものは、一般式
（ここで式中のＲは前記のＲと同じ）
で表されるフェノール類であって、具体例としてはフェ
ノール、トクレゾール、トエチルフェノール、 ｍ−ｎ
−プロピルフェノール、トイソプロビルフェノール、ａ
＋−ｎ−７’チルフエノール、 ｓ＋−５ｅｃ−７’チ
ルフエノール、■−ｔｅｒｔ−ブチルフェノール、トｎ
−アミルフェノール、ａ＋−５ｅｃ−アミルフェノール
、ｍ−ｔｅｒｔ−アミルフェノール
トヘプチルフェノール、−オクチルフェノール−フロロ
フェノール、トクロロフェノール、ｍ−フロロフェノー
ル、レゾルシンなどのメタ置換フェノール１９、３．５
−キシレノール、３．５−ジエチルフェノール、３．５
−ジイソプロピルフェノール、３，５−ジーｓｅｃーブ
チルフェノール、３，５−ジーｔｅｒｔーブチルフェノ
ール、３．５−ジーｓｅｃーアミルフェノール・３，５
−ジーｔｅｒｔーアミルフェノール、３．５−ジエチル
フェノール、３．５−ジエチルフェノール、３，５−ジ
オクチルフェノール、３．５−ジクロロフェノール、３
．５−ジクロロフェノール、３．５−ジブロモフェノー
ル、３、５−ショートフェノールなどの３．５−ジ置換
フェノール類などを挙げることが出来る°。Furthermore, among the phenolic components constituting the high molecular weight novolak type phenolic resin, the trifunctional phenol component is a phenol having three hydrogen atoms active for substitution reactions on the benzene nucleus. Specifically, it is phenol, both meta-substituted products of phenol, and 3.5-1[C of phenol. The substituents that these trifunctional phenols have at both meta positions or the 3.5 position are usually alkyl groups, halogens, or hydroxyl groups, and among these trifunctional phenols,
Preferred are phenols represented by the general formula (where R is the same as R above), and specific examples include phenol, tocresol, toethylphenol, m-n
-propylphenol, toisopropylphenol, a
+-n-7'tylphenol, s+-5ec-7'tylphenol, ■-tert-butylphenol, t-n
-Amylphenol, a+-5ec-amylphenol, m-tert-amylphenol, heptylphenol, -octylphenol - meta-substituted phenols such as fluorophenol, tochlorophenol, m-fluorophenol, resorcinol, etc. 19, 3.5
-xylenol, 3.5-diethylphenol, 3.5
-diisopropylphenol, 3,5-di-sec-butylphenol, 3,5-di-tert-butylphenol, 3,5-di-sec-amylphenol 3,5
-di-tert-amylphenol, 3.5-diethylphenol, 3.5-diethylphenol, 3,5-dioctylphenol, 3.5-dichlorophenol, 3
．． Examples include 3,5-disubstituted phenols such as 5-dichlorophenol, 3,5-dibromophenol, and 3,5-short phenol.
以上述べたＥＰ樹脂（主剤および硬化剤）の添加量は、
充填剤の量および用途によって異なるが、ＰＰＳ樹脂１
００重量部に対して１０〜１００重量部とする．なぜな
らば添加量が１０重量部未満の少量では、そり、ひけ、
成形収縮率など寸法精度に関係の深い因子を押えること
が出来ず、また逆に１００重量部を越える量では、機械
的強度の低下またはＥＰ樹脂の種類によっては成形品表
面へのブリードによる摺動特性の低下、さらには溶融流
動安定性への悪影響などを起こし好ましくないからであ
る．一般にＥＰ樹脂の主剤はＰＰＳ樹脂の末端基等と反
応するが、この発明の重要な目的の一つが、寸法精度の
向上であることから、硬化剤としてのアミン類、酸無水
物、多硫化物またはフェノール樹脂等を配合して、ＰＰ
Ｓ樹脂のマトリックス中にＢＰ樹脂の三次元架橋構造を
形成させることが望ましく、このような構造にすれば低
分子量のＰＰＳ樹脂とＥＰ樹脂（主剤のみもしくは硬化
剤を併用するとしてもきわめて少量の場合）とから得ら
れる組成物に比較して、摺動特性特に潤滑性が優れてい
る．その理由は明らかではないが、この発明の樹脂組成
物の組織においては、せん断強さが小さくて潤滑性には
好適であるというＰＰＳ樹脂本来の性質が殆んど阻害さ
れていないからではないかと推測される。The amount of the EP resin (base resin and curing agent) mentioned above is as follows:
Depending on filler amount and application, PPS resin 1
00 parts by weight to 10 to 100 parts by weight. This is because if the amount added is less than 10 parts by weight, warpage, sink marks, etc.
Factors closely related to dimensional accuracy, such as molding shrinkage rate, cannot be suppressed, and conversely, if the amount exceeds 100 parts by weight, mechanical strength may decrease or, depending on the type of EP resin, sliding may occur due to bleeding on the surface of the molded product. This is because it is undesirable because it causes a decrease in properties and also has an adverse effect on melt flow stability. Generally, the main resin of EP resin reacts with the end groups of PPS resin, but since one of the important objectives of this invention is to improve dimensional accuracy, amines, acid anhydrides, and polysulfides are used as curing agents. Or, by blending phenol resin etc., PP
It is desirable to form a three-dimensional crosslinked structure of BP resin in the matrix of S resin, and with this structure, low molecular weight PPS resin and EP resin (even if only the main resin or a curing agent is used together, if only in a very small amount) ) has superior sliding properties, especially lubricity. The reason for this is not clear, but it is thought that the structure of the resin composition of the present invention is not inhibited by the inherent properties of PPS resin, which have low shear strength and are suitable for lubricity. Guessed.
さらに、この発明に使用される充填剤は、ＰＰＳ樹脂を
溶豫成形する際に加熱される温度に耐えるものであれば
特に種類を限定するものではなく、目的、用途に応じて
取捨選択すれば良い．ここに充填剤としては、ポリエー
テルケトン、ポリイミド、シリコーン、フッ素樹脂等の
耐熱性高分子材料を始めとし、ガラス繊維、炭素繊維、
グラファイト繊維、ウオラストナイト、チタン酸カリウ
ムホイスカー、銅線、銅線、ステンレス線などの耐熱性
無機単一繊維、タングステン心線もしくは炭素繊維など
にボロンもしくは炭化珪素などを蒸着。Furthermore, the filler used in this invention is not particularly limited in type as long as it can withstand the temperature heated when PPS resin is molded, and can be selected depending on the purpose and use. good. Fillers include heat-resistant polymer materials such as polyetherketone, polyimide, silicone, and fluororesin, as well as glass fiber, carbon fiber,
Boron or silicon carbide is deposited on heat-resistant inorganic single fibers such as graphite fibers, wollastonite, potassium titanate whiskers, copper wires, copper wires, stainless steel wires, tungsten core wires, or carbon fibers.
したいわゆるボロン繊維もしくはた炭化珪素繊維などの
耐熱性無機複合繊維、芳香族アミド繊維などの耐熱性有
機繊維、グラファイトまたは亜鉛、アルミニウム、マグ
ネシウム等の金属もしくはこれらの酸化物などの熱伝導
改良用無機粉末、ガラスピーズ、シリカバルーン、珪藻
土、石綿、炭酸マグネシウムなどの断熱性向上用の無機
粉末、二硫化モリブデン、グラファイト、カーボン、マ
イカ、タルク等の潤滑性向上用の無機粉末、および酸化
鉄、硫化カドミウム、セレン化カドミウム、カーボンブ
ラック等の着色用の無機粉末など数多くのものを例示す
ることが出来る。そしてこの発明におけるこれら充填剤
の添加量は、ＰＰＳ樹脂１００重量部に対して、０〜２
５０重量部、好ましくは３０〜２５０重量部である。な
ぜならば充填剤が３０重量部未満の少量では熱膨張率が
少し大きく、曲げ強度等の機械的強度も少し低く、逆に
２５０重量部を越える多量では曲げ強度等の機械的強度
が著しく低下するからである。heat-resistant inorganic composite fibers such as so-called boron fibers or silicon carbide fibers, heat-resistant organic fibers such as aromatic amide fibers, inorganic materials for improving heat conduction such as graphite or metals such as zinc, aluminum, and magnesium, or their oxides. Inorganic powders for improving heat insulation such as powder, glass peas, silica balloons, diatomaceous earth, asbestos, magnesium carbonate, etc., inorganic powders for improving lubricity such as molybdenum disulfide, graphite, carbon, mica, talc, iron oxide, sulfide, etc. Many examples include inorganic powders for coloring such as cadmium, cadmium selenide, and carbon black. The amount of these fillers added in this invention is 0 to 2 parts by weight per 100 parts by weight of PPS resin.
The amount is 50 parts by weight, preferably 30 to 250 parts by weight. This is because if the amount of filler is less than 30 parts by weight, the coefficient of thermal expansion will be a little high and the mechanical strength such as bending strength will be a little low, whereas if the amount is more than 250 parts by weight, the mechanical strength such as bending strength will be significantly reduced. It is from.
以上述べたＰＰＳ樹脂、ＥＰ樹脂、充填剤などの諸原料
を混合する方法は特に限定されるものではなく、たとえ
ばＰＰＳ樹脂とＥＰ樹脂および充填剤を個別にもしくは
ヘンシェルミキサー、ボールミル、タンブラ−ミキサー
等の混合機を用いて乾式混合した後に、熱口・−ル、ニ
ーダ、バンバリーミキサ−１溶融押出機などで溶融混合
（たとえば造粒）したものを所定の形状に溶融成形すれ
ばよい、この際の溶融混合する温度は、ＰＰＳ樹脂が溶
融する温度以上、具体的には２８０〜４００°Ｃ１好ま
しくは２８０〜３５０°Ｃである。なぜならばＰＰＳ樹
脂が溶融しない２８０°Ｃ未満の低温またはＥＰ樹脂が
短時間のうちに硬化する４００″Ｃを越えるような高温
では、二つの樹脂の均一分散が望めないからである。The method of mixing the various raw materials such as the PPS resin, EP resin, and filler described above is not particularly limited, and for example, the PPS resin, EP resin, and filler may be mixed individually, or using a Henschel mixer, a ball mill, a tumbler mixer, etc. After dry mixing using a mixer, the mixture may be melt-mixed (e.g., granulated) using a hot hole, kneader, Banbury mixer 1 melt extruder, etc., and then melt-molded into a predetermined shape. The temperature at which the PPS resin is melted and mixed is higher than the temperature at which the PPS resin melts, specifically 280 to 400°C, preferably 280 to 350°C. This is because uniform dispersion of the two resins cannot be expected at low temperatures below 280°C where the PPS resin does not melt or at high temperatures above 400''C where the EP resin hardens within a short time.
実施例および比較例に使用した原材料を一括して示すと
次のとおりである。なお〔〕内に略号を示した。これら
原材料の配合割合はすべて重量部である。The raw materials used in the Examples and Comparative Examples are listed below. Abbreviations are shown in brackets. All blending ratios of these raw materials are parts by weight.
（１）ポリフェニレンサルファイド〔ＰＰＳ〕樹脂、■
（ｐｐｓ−１３（米国フィリップス・ペトローリアム・
インターナショナル社製：ライトンＰ−４）、■（ＰＰ
Ｓ−２） （同上社製：ライトンＰＩ？０６ ”）、
■（ＰＰＳ−３） （同上社製：ライトンＶ−１）、
■（ＰＰＳ−４） （呉羽化学社製： ＫＰＳ−＃２
００）、（２）エポキシ（Ｅ！Ｐ）樹脂、
■（ＥＰ−１） （日本化薬社製：エボキシ化フェノ
ールノボラックＥＰＰＮ−２０１”）、■（ＥＰ−２３
（三井石油化学エポキシ社製： ビスフェノールＡ型エ
ポキシ樹脂ＥＰＯＭＩＫ Ｒ−１４０）、（３）硬化剤
（各硬化剤の性状を一括して第１表に示す）、
■〔硬化剤−１〕（高分子量ノボラック型Ｐ−クレゾー
ル・ホルムアルデヒド樹脂）、
■〔硬化剤−２〕（高分子量ノボラック型Ｐ−クレゾー
ル・トクレゾール・ホルムアルデヒ ド樹脂）、
■〔硬化剤−３〕（高分子量ノボラック型Ｐ−クレゾー
ル・ホルムアルデヒド樹脂）、
［相］〔硬化剤−４〕（ノボラック型フェノール・ホル
ムアルデヒド樹脂）、
■〔硬化剤−５〕（ノボラック型Ｐ−クレゾール・ホル
ムアルデヒド樹脂）、
■〔硬化促進剤］ （ＢＦ３・２−メチルイミダゾー
ル錯体）、
第 １ 表
（４）充填剤
■炭素繊維（東邦レーヨン社製：チョツプドファイバー
、径７ｎ、長さ６Ｍ、収束剤エポキシ系）、
■硝子繊維（旭ファイバーグラス社！！！：チョップド
ストランド、径１３１１ｍ、長さ３ｍｍ、アミノシラン
カップリング処理品）、
［相］マイカ（カナダマイカ社製：マイカＳ−３２５）
、実施例１〜６：
諸原料を第２表に示す配合割合で予め乾式混合した後、
二軸押出ｉ（部員鉄工社製： ＰＣＭ−３０）に供給し
、シリンダ一温度３００°Ｃ，スクリュー回転数５０ｒ
ｐ■の条件で押出し造粒した。得られたペレットをシリ
ンダ一温度３２０″Ｃ１射出圧９００ｋｇ／ｃｄ、金型
温度１３０°Ｃの条件のもとに射出成形し、円筒（外径
２３ｍ、内径１４ｍ、長さ１３■）、板（幅１２．７印
、長さ１２６Ｍ、厚さ３．２ｍ）、寸法精度測定用円板
１ （外径２０閤、厚さ３ＩＩＩｌの円板の両面に外径
８ｍ、高さ３■の突出部２が同軸状に形成され、それら
の軸芯部に径２ＩＩＩＩの穴３が貫通したもの、第１図
および第２図参照）および流れ性測定用のくし流れ試験
片（幅５ＩＩＩ１１、厚さ０．４１１ＩＩおよび０，６
閣）などを得た。さらに、前記板材から線膨張係数測定
用の角柱（断面３ ｍ Ｘ ３ ｍ、長さ８閣）を、ま
た板材成形時の樹脂の流れ方向およびその直角方向の二
方向がそれぞれ長手方向になるような試験片を切削加工
によって作製した。得られた各種試験片に対して、くし
流れ試験（溶融成形安定性）、曲げ強度、曲げ弾性率、
熱膨張率、寸法精度（円筒内径の真円度およびひけ）、
摺動特性などを測定し評価した。評価の方法は以下のと
おりである。すなわち、
（１）＜Ｌ流れ試験：
厚さ０．４閣および０．６ｏｓで幅各５■のくし流れ試
験用金型を用いて一定条件で射出成形し、各厚みの流れ
た長さを測定し、１００個の試験片の最大値と最小値と
を取って溶融成形安定性の目安とした。(1) Polyphenylene sulfide [PPS] resin, ■
(pps-13 (Philips Petroleum, U.S.)
Manufactured by International: Ryton P-4), ■(PP
S-2) (manufactured by the same company: Ryton PI?06”),
■(PPS-3) (manufactured by the same company: Ryton V-1),
■(PPS-4) (manufactured by Kureha Chemical Co., Ltd.: KPS-#2
00), (2) Epoxy (E!P) resin, ■(EP-1) (manufactured by Nippon Kayaku Co., Ltd.: Eboxidized phenol novolak EPPN-201''), ■(EP-23)
(manufactured by Mitsui Petrochemical Epoxy Co., Ltd.: bisphenol A type epoxy resin EPOMIK R-140), (3) Curing agent (the properties of each curing agent are shown in Table 1), ■ [Curing agent-1] (High (molecular weight novolak type P-cresol/formaldehyde resin), ■ [Curing agent-2] (high molecular weight novolac type P-cresol/tocresol/formaldehyde resin), ■ [Curing agent-3] (high molecular weight novolac type P-cresol・Formaldehyde resin), [Phase] [Curing agent-4] (Novolak type phenol formaldehyde resin), ■ [Curing agent-5] (Novolak type P-cresol formaldehyde resin), ■ [Curing accelerator] (BF3. 2-methylimidazole complex), Table 1 (4) Filler ■Carbon fiber (manufactured by Toho Rayon Co., Ltd.: chopped fiber, diameter 7n, length 6M, binder epoxy system), ■Glass fiber (Asahi Fiberglass Co., Ltd.) !!!: Chopped strand, diameter 1311 m, length 3 mm, aminosilane coupling treated product), [Phase] Mica (manufactured by Mica Canada: Mica S-325)
, Examples 1 to 6: After dry mixing the various raw materials in the proportions shown in Table 2,
Supplied to a twin-screw extruder i (manufactured by Bumen Tekko Co., Ltd.: PCM-30), the cylinder temperature was 300°C, and the screw rotation speed was 50r.
Extrusion granulation was carried out under the conditions of p■. The obtained pellets were injection molded under the conditions of cylinder temperature 320'' C1 injection pressure 900 kg/cd and mold temperature 130°C to form a cylinder (outer diameter 23 m, inner diameter 14 m, length 13 cm), plate ( Width: 12.7 m, length: 126 m, thickness: 3.2 m), dimensional accuracy measurement disc 1 (outer diameter: 8 m, height: 3 cm protrusions on both sides of a disc with an outer diameter of 20 m and a thickness of 3 mm) 2 are formed coaxially, and a hole 3 with a diameter of 2III is penetrated through their axial center (see Figures 1 and 2), and a comb flow test piece for flowability measurement (width: 5III:11, thickness: 0) .411II and 0,6
(Kaku) etc. Furthermore, a rectangular column (3 m x 3 m in cross section, 8 cm length) for measuring the coefficient of linear expansion was made from the plate material, and the two directions, the flow direction of the resin during molding the plate material and the direction perpendicular thereto, were the longitudinal directions. A test piece was prepared by cutting. The various test pieces obtained were tested for comb flow test (melt molding stability), bending strength, bending modulus,
Thermal expansion coefficient, dimensional accuracy (roundness of cylinder inner diameter and sink mark),
The sliding characteristics were measured and evaluated. The evaluation method is as follows. That is, (1) <L flow test: Injection molding was performed under certain conditions using a comb flow test mold with a thickness of 0.4 cm and a width of 0.6 os and a width of 5 cm, and the length of flow for each thickness was calculated. The maximum and minimum values of 100 test pieces were taken as a measure of melt molding stability.
（２）曲げ強度および曲げ弾性率： ＡＳＴＭ−［１７
９０による。(2) Bending strength and bending modulus: ASTM-[17
According to 90.
（３）熱膨張率：
ＴＭＡ法（島津製作所熱機械分析装置）によって、成形
時の樹脂の流れ方向またはその直角方向がそれぞれ長手
方向に（るような角柱（３閣角、長さ８■）を使って、
０〜９０℃の範囲の熱膨張率を求める。(3) Coefficient of thermal expansion: The TMA method (Shimadzu's thermomechanical analyzer) was used to measure the shape of a rectangular column (three squares, length 8 cm) in which the flow direction of the resin during molding or the direction perpendicular thereto is in the longitudinal direction, respectively. using
The coefficient of thermal expansion is determined in the range of 0 to 90°C.
第 ２ 表
（４）寸法精度（真円度およびひけ）：真円度は英国ラ
ンクテーラーホブソン社製のタリロンド２００を用いて
軸方向中央部を測定し、ひけは小板研究所製サーフコー
ダーモデル５Ｒ−３Ｅを用いて、第２図→印のように各
対角に４カ所内径２１１１１の穴３の内径形状を軸方向
に測定し、穴３の軸方間両入口部を結ぶ線を基準として
その凹凸の絶対値の最大のものをひけとして求める。Table 2 (4) Dimensional accuracy (roundness and sink marks): Roundness was measured at the center in the axial direction using Talyrond 200 manufactured by Rank Taylor Hobson Co., Ltd., and sink marks were measured using a surfcorder model manufactured by Koita Research Institute. 5R-3E, measure the inner diameter shape of the hole 3 with an inner diameter of 21111 in the axial direction at four locations on each diagonal as shown in Fig. 2 →, and use the line connecting both axial entrances of the hole 3 as the reference The maximum absolute value of the unevenness is determined as the sink mark.
（５）摺動特性（動摩擦係数および摩耗係数）：内径１
４−１外径２３■、長さ１３ｍの試験片を用い、スラス
ト型摩擦摩耗試験機を使用して荷重１ｋｇ／ｄ、速度１
００ｍ／分の条件で軸受Ｘ （ＳＵＪ２）を相手材とし
て１時間摺動後の値を動摩擦係数とし、また摩耗係数に
ついては１００時間摺動前後の重量変化を求めその値か
ら算出する。(5) Sliding characteristics (dynamic friction coefficient and wear coefficient): Inner diameter 1
4-1 Using a test piece with an outer diameter of 23cm and a length of 13m, a load of 1kg/d and a speed of 1 were measured using a thrust type friction and wear tester.
The dynamic friction coefficient is the value after 1 hour of sliding with Bearing
以上の各測定方法によって得られた結果を第３表にまと
めた。The results obtained by each of the above measurement methods are summarized in Table 3.
比較例１〜７：
諸原料を第４表に示す割合で配合した以外は実施例１と
全く同じ操作を行なって各種試験片を作製し、同じ緒特
性について評価を行ない、得られた結果を第５表にまと
めた。Comparative Examples 1 to 7: Various test specimens were prepared in exactly the same manner as in Example 1, except that the raw materials were blended in the proportions shown in Table 4, and the same properties were evaluated. The results are summarized in Table 5.
第 ３ 表
第 ４ 表
第３表および第５表を比較すると、実施例１〜７はくし
流れ試験のバラツキが少なく、溶融成形安定性が良く、
曲げ強度および曲げ弾性率も良好な値を示している。ま
た、熱膨張率の異方性も小さく、寸法精度および摺動特
性も良好であるが、耐熱性のＥＰ−１樹脂を使用しても
メルトフローレイトの大きいＰＰＳ樹脂を用いた比較例
１は、同じ充填剤を同量配合した実施例３または４に比
べて寸法精度も摺動特性も共に悪く、またＥＰ樹脂主剤
を用いても硬化剤を用いなかった比較例２も、比較例１
と同様に寸法精度も摺動特性も悪いばかりか、熱膨張率
の異方性も大きい値を示して、ＥＰ樹脂添加の効果が全
く認められなかった。また添加したＥＰ樹脂の耐熱性が
、実施例で使用したものよりも劣る比較例３および４に
おいては、くし流れ試験のバラツキが大きく、溶融成形
安定性に欠け、寸法精度、摺動特性においても不満足な
ものであった。また耐熱性ＥＰ樹脂の配合量の少ない比
較例５は、ＥＰ樹脂添加の効果が認められず寸法精度、
耐摩耗性、熱膨張率の異方性などいずれも劣っている。Comparing Tables 3 and 5, Examples 1 to 7 have little variation in the comb flow test, good melt molding stability,
The bending strength and bending modulus also show good values. In addition, the anisotropy of the coefficient of thermal expansion is small, and the dimensional accuracy and sliding properties are also good, but even if heat-resistant EP-1 resin is used, Comparative Example 1 using PPS resin has a large melt flow rate. Both dimensional accuracy and sliding properties were worse than those of Examples 3 and 4, in which the same amount of filler was blended, and Comparative Example 2, in which an EP resin base material was used but no curing agent was used, was also worse than Comparative Example 1.
Similarly, not only the dimensional accuracy and sliding properties were poor, but also the anisotropy of the coefficient of thermal expansion was large, and no effect of the addition of the EP resin was observed. In addition, in Comparative Examples 3 and 4, in which the heat resistance of the added EP resin is inferior to that used in the Examples, the variation in the comb flow test is large, the melt molding stability is lacking, and the dimensional accuracy and sliding properties are also poor. It was unsatisfactory. In addition, in Comparative Example 5, which has a small amount of heat-resistant EP resin, no effect of the addition of EP resin was observed, resulting in poor dimensional accuracy.
It is inferior in both wear resistance and anisotropy of thermal expansion coefficient.
逆に耐熱性ＥＰ樹脂の配合量が多過ぎる比較例６および
充填剤の多過ぎる比較例７はいずれも曲げ強度の低下が
著しく摺動特性も不満足なものであった。なお、充填剤
を添加していない実施例８は充填剤を３帽１部以上添加
している実施例１〜７と比べると曲げ強度や熱膨張率の
値が少し劣っているが、同じように充填剤を添加してい
ない比較例８と比べると、すべての物性において上回っ
ており、特に寸法精度、摺動特性に優れていることがわ
かった。On the contrary, both Comparative Example 6, which contained too much heat-resistant EP resin, and Comparative Example 7, which contained too much filler, had a significant decrease in bending strength and unsatisfactory sliding properties. In addition, Example 8, in which no filler was added, had slightly inferior bending strength and thermal expansion coefficient values compared to Examples 1 to 7, in which 3 parts or more of filler was added, but they were similar. Compared with Comparative Example 8 in which no filler was added, it was found that all physical properties were superior, and in particular, dimensional accuracy and sliding properties were excellent.
この発明のＰＰＳ樹脂組成物は溶融成形性に優れるばか
りではなく、これを溶融成形して得られる成形品は、Ｐ
ＰＳ樹脂特有の優れた耐熱性、耐薬品性、低摩擦性を保
有し、しかも優れた機械的強度、耐摩耗性、寸法精度を
も兼ね備えていることから、たとえば、自動車用、航空
・宇宙機器用、一般産業機械用、事務機器用および光・
電気・電子用などその他あらゆる分野の部品として広く
利用することが出来るが、各種軸受類、スラストワッシ
ャー、ギヤ、カム、ピストンリング、コンプレッサーベ
ーン、各種バルブ、ハウジング、コネクタ、ソケット、
保持体、トレイ、ケース、マウント、ヒユーズ等の部品
および自動車、宇宙・航空機分野のエンジン周辺の各部
分品に使用すれば特に優れた寸法精度と摺動特性を充分
に発揮させることが出来るので、この発明の意義はきわ
めて大きいといえる。The PPS resin composition of the present invention not only has excellent melt moldability, but also the molded product obtained by melt molding the PPS resin composition.
It has excellent heat resistance, chemical resistance, and low friction properties unique to PS resin, and also has excellent mechanical strength, abrasion resistance, and dimensional accuracy, so it is suitable for use in automobiles, aerospace equipment, etc. for general industrial machinery, office equipment, and optical/
It can be widely used as parts for all kinds of fields, including electrical and electronic applications, including various bearings, thrust washers, gears, cams, piston rings, compressor vanes, various valves, housings, connectors, sockets, etc.
When used in parts such as holders, trays, cases, mounts, fuses, and parts around engines in the automobile, space, and aircraft fields, it can fully demonstrate particularly excellent dimensional accuracy and sliding characteristics. It can be said that the significance of this invention is extremely large.
第１図は寸法精度測定用円板の断面図、第２図はその平
面図である。
１・・・・・・円板、２・・・・・・突出部、３・・・
・・・穴。
特許出願人 洋ベア・ルーロン工業株式会社岡 三井
石油化学工業株式会社
同 代理人 鎌 １） 文 二第１図
第２図FIG. 1 is a sectional view of the dimensional accuracy measuring disk, and FIG. 2 is a plan view thereof. 1... Disk, 2... Protrusion, 3...
···hole. Patent Applicant: Yobea Rulon Kogyo Co., Ltd. Oka Mitsui Petrochemical Industries Co., Ltd. Agent: Kama 1) Text 2 Figure 1 Figure 2
Claims (1)
００ｍｍのオリフィスを用い、温度３００℃、保持時間
６分間、荷重５０００ｇのＡＳＴＭ−Ｄ１２３８に基づ
く測定法による値）が２００ｇ／１０分以下であるポリ
フェニレンサルファイド〔ＰＰＳ〕樹脂１００重量部と
加熱溶融成形可能な耐熱性エポキシ〔ＥＰ〕樹脂（主剤
および硬化剤）１０〜１００重量部と充填剤０〜２５０
重量部、好ましくは３０〜２５０重量部、とを配合した
組成物であって、ＰＰＳ樹脂とＥＰ樹脂との溶融配合物
の保持時間６分間および３０分間としたときのメルトフ
ローレイト（保持時間以外の条件は前記条件と同一）の
差が保持時間を６分間としたときの値に対して０．７以
下であることを特徴とするポリフェニレンサルファイド
樹脂組成物。 ２）加熱溶融成形可能な耐熱性エポキシ〔ＥＰ〕樹脂（
主剤および硬化剤）が硬化剤として高分子量ノボラック
型フェノール系樹脂を含有するエポキシ樹脂である特許
請求の範囲第１項記載のポリフェニレンサルファイド樹
脂組成物。[Claims] 1) Melt flow rate (inner diameter 2.09 mm, length 8.
Can be heat-melted and molded with 100 parts by weight of polyphenylene sulfide [PPS] resin with a value of 200 g/10 minutes or less using a 00 mm orifice, a temperature of 300 °C, a holding time of 6 minutes, a load of 5000 g, and a measurement method based on ASTM-D1238. 10 to 100 parts by weight of heat-resistant epoxy [EP] resin (base resin and curing agent) and 0 to 250 parts by weight of filler.
parts by weight, preferably 30 to 250 parts by weight, and the melt flow rate (other than the holding time) when the melt blend of PPS resin and EP resin is held for 6 minutes and 30 minutes. The polyphenylene sulfide resin composition has a difference of 0.7 or less with respect to the value when the holding time is 6 minutes. 2) Heat-resistant epoxy [EP] resin that can be heat-melted and molded (
2. The polyphenylene sulfide resin composition according to claim 1, wherein the main agent and curing agent) is an epoxy resin containing a high molecular weight novolak type phenolic resin as a curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62122743A JP2524593B2 (en) | 1987-05-19 | 1987-05-19 | Polyphenylene sulfide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62122743A JP2524593B2 (en) | 1987-05-19 | 1987-05-19 | Polyphenylene sulfide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63286467A true JPS63286467A (en) | 1988-11-24 |
| JP2524593B2 JP2524593B2 (en) | 1996-08-14 |
Family
ID=14843499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62122743A Expired - Fee Related JP2524593B2 (en) | 1987-05-19 | 1987-05-19 | Polyphenylene sulfide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2524593B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007512406A (en) * | 2003-11-21 | 2007-05-17 | チェイル インダストリーズ インコーポレイテッド | Polyphenylene sulfide thermoplastic resin composition |
| JP2008248048A (en) * | 2007-03-30 | 2008-10-16 | Shin Kobe Electric Mach Co Ltd | Molding material of high heat conductive thermoplastic resin |
| CN109535716A (en) * | 2018-10-18 | 2019-03-29 | 江苏澳盛复合材料科技有限公司 | A kind of and good polyphenylene sulfide/carbon fibre composite of metal adhesion |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS568359A (en) * | 1979-06-29 | 1981-01-28 | Standard Oil Co | Manufacture of heterocyclic compound |
| JPS59164360A (en) * | 1983-03-10 | 1984-09-17 | Dainippon Ink & Chem Inc | Resin composition |
| JPS6153356A (en) * | 1984-08-22 | 1986-03-17 | Dainippon Ink & Chem Inc | Polyphenylene sulfide resin composition |
| JPS63161057A (en) * | 1986-12-25 | 1988-07-04 | Dainippon Ink & Chem Inc | Resin composition |
-
1987
- 1987-05-19 JP JP62122743A patent/JP2524593B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS568359A (en) * | 1979-06-29 | 1981-01-28 | Standard Oil Co | Manufacture of heterocyclic compound |
| JPS59164360A (en) * | 1983-03-10 | 1984-09-17 | Dainippon Ink & Chem Inc | Resin composition |
| JPS6153356A (en) * | 1984-08-22 | 1986-03-17 | Dainippon Ink & Chem Inc | Polyphenylene sulfide resin composition |
| JPS63161057A (en) * | 1986-12-25 | 1988-07-04 | Dainippon Ink & Chem Inc | Resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007512406A (en) * | 2003-11-21 | 2007-05-17 | チェイル インダストリーズ インコーポレイテッド | Polyphenylene sulfide thermoplastic resin composition |
| JP2008248048A (en) * | 2007-03-30 | 2008-10-16 | Shin Kobe Electric Mach Co Ltd | Molding material of high heat conductive thermoplastic resin |
| CN109535716A (en) * | 2018-10-18 | 2019-03-29 | 江苏澳盛复合材料科技有限公司 | A kind of and good polyphenylene sulfide/carbon fibre composite of metal adhesion |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2524593B2 (en) | 1996-08-14 |
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