CN115702206B - Liquid crystalline resin composition for ball bearing sliding wear member and ball bearing sliding wear member using same - Google Patents
Liquid crystalline resin composition for ball bearing sliding wear member and ball bearing sliding wear member using same Download PDFInfo
- Publication number
- CN115702206B CN115702206B CN202180043329.4A CN202180043329A CN115702206B CN 115702206 B CN115702206 B CN 115702206B CN 202180043329 A CN202180043329 A CN 202180043329A CN 115702206 B CN115702206 B CN 115702206B
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- China
- Prior art keywords
- ball bearing
- sliding wear
- mass
- liquid crystalline
- resin composition
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 title claims description 52
- 229920006038 crystalline resin Polymers 0.000 title claims description 51
- 239000000945 filler Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 125000003700 epoxy group Chemical group 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 23
- 230000002087 whitening effect Effects 0.000 abstract description 14
- 239000000428 dust Substances 0.000 abstract description 13
- 230000001629 suppression Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 24
- -1 aromatic hydroxycarboxylic acids Chemical class 0.000 description 21
- 238000000465 moulding Methods 0.000 description 20
- 239000000835 fiber Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 239000000155 melt Substances 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 6
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 235000012222 talc Nutrition 0.000 description 5
- 239000010456 wollastonite Substances 0.000 description 5
- 229910052882 wollastonite Inorganic materials 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000000378 calcium silicate Substances 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012765 fibrous filler Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 229920006249 styrenic copolymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 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
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- SXQXMCWCWVCFPC-UHFFFAOYSA-N aluminum;potassium;dioxido(oxo)silane Chemical compound [Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O SXQXMCWCWVCFPC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- CCPVLWRYBOQDFU-UHFFFAOYSA-N cobalt(3+);pentane-2,4-dione Chemical compound [Co+3].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O CCPVLWRYBOQDFU-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- BPILDHPJSYVNAF-UHFFFAOYSA-M sodium;diiodomethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(I)I BPILDHPJSYVNAF-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/02—Parts of sliding-contact bearings
- F16C33/04—Brasses; Bushes; Linings
- F16C33/20—Sliding surface consisting mainly of plastics
Abstract
Providing: a liquid crystal resin composition for manufacturing a ball bearing sliding wear member, which is excellent in balance among surface whitening suppression, mechanical strength, dimensional accuracy, and low dust generation, has reduced ball bearing sliding wear properties, and maintains impact resistance. The liquid crystal resin composition for a ball bearing sliding wear resistant member of the present invention comprises: the liquid crystal resin (A), the granular filler (B) having a median particle diameter of 0.3 to 5.0 [ mu ] m, the granular filler (B) having a content of 7.5 to 22.5 mass%, the whisker (C) having a content of 2.5 to 17.5 mass%, and the whisker (C) having a total content of 12.5 to 32.5 mass%.
Description
Technical Field
The present invention relates to a liquid crystal resin composition for a ball bearing sliding wear resistant member and a ball bearing sliding wear resistant member using the same.
Background
Liquid crystalline resins, such as liquid crystalline polyester resins, have excellent mechanical strength, heat resistance, chemical resistance, electrical properties, and the like, and also have excellent dimensional stability, and therefore, are widely used as high-functional engineering plastics. Recently, liquid crystalline resins have been used for precision instrument parts by taking advantage of their features.
Examples of the member using the liquid crystal resin include a connector such as an FPC connector; sockets such as a memory card socket; a component for a lens holder and other camera modules; and a relay. These components are required to have excellent surface whitening suppression, mechanical strength, dimensional accuracy, and low dust generation, and in addition, 2 or more members are sometimes used in a dynamic contact state, so that sliding wear properties (that is, ease of wear when 2 or more members are in dynamic contact) are also required to be reduced. For example, patent document 1 discloses a liquid crystal resin composition containing a liquid crystal resin and talc having a specific volume average particle diameter in a specific ratio, with a view to providing a molded article made of a liquid crystal resin composition having excellent surface appearance and excellent sliding properties.
Among the above-mentioned members, in particular, in the case of a member used in a form in which a molded body formed of a liquid crystalline resin composition is in dynamic contact with a ball bearing, it is required to reduce sliding wear properties of the ball bearing (i.e., ease of wear upon dynamic contact with the ball bearing). In addition, when the member is impacted, there is a concern that the molded body is not easily restored when dents are easily generated in the molded body and defects are generated in dynamic contact between the molded body and the ball bearing. Accordingly, the above-mentioned members are required to have impact resistance, that is, to have a property of easily recovering even if a dent is generated by an impact. Patent document 2 describes a camera module member that is used in a state of dynamic contact with a ball bearing.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 5087958
Patent document 2: specification of European patent No. 2938063
Disclosure of Invention
Problems to be solved by the invention
However, according to the studies by the present inventors, in the conventional liquid crystalline resin composition, the sliding wear of the ball bearing is reduced, but the impact resistance is rather deteriorated. The present invention has been made to solve the above problems, and an object thereof is to provide: a liquid crystal resin composition for manufacturing a ball bearing sliding wear resistant member, which is excellent in balance among surface whitening suppression, mechanical strength, dimensional accuracy, and low dust generation, has reduced ball bearing sliding wear properties, and maintains impact resistance.
Solution for solving the problem
The present inventors have made intensive studies to solve the above problems. The result shows that: the present invention has been completed by solving the above problems by using a liquid-crystalline resin composition containing a liquid-crystalline resin, a particulate filler and whiskers, wherein the median particle diameter of the particulate filler is within a predetermined range, and the content of the particulate filler, whiskers, and the total of these is within a predetermined range. More specifically, the present invention provides the following.
(1) A liquid crystalline resin composition for a ball bearing sliding wear resistant member, comprising: the liquid crystal resin (A), the granular filler (B) having a median particle diameter of 0.3 to 5.0 [ mu ] m, the granular filler (B) having a content of 7.5 to 22.5 mass%, the whisker (C) having a content of 2.5 to 17.5 mass%, and the whisker (C) having a total content of 12.5 to 32.5 mass%.
(2) The composition according to (1), wherein the particulate filler (B) is 1 or more selected from the group consisting of silica and barium sulfate.
(3) The composition according to (1) or (2), which further comprises (D) an epoxy group-containing copolymer, wherein the content of the epoxy group-containing copolymer (D) is 1 to 5% by mass.
(4) A ball bearing sliding wear resistant member comprising the composition of any one of (1) to (3).
ADVANTAGEOUS EFFECTS OF INVENTION
When the liquid crystal resin composition for a ball bearing sliding wear member of the present invention is used as a raw material for producing a ball bearing sliding wear member, a ball bearing sliding wear member which is excellent in balance among suppression of surface whitening, mechanical strength, dimensional accuracy, and low dust generation property, has reduced ball bearing sliding wear property, and maintains impact resistance can be obtained.
Drawings
Fig. 1 (a) is a plan view showing a molded body molded for measuring the depth of a recess in the embodiment, and fig. 1 (b) is a longitudinal sectional view showing a BB section part of fig. 1 (a). Unless otherwise specified, the numerical values in the drawings are in mm.
Fig. 2 (a) is a perspective view showing a コ -type liquid crystalline resin molded body used for evaluation of the camber deformation in the examples, and fig. 2 (b) is a side view showing the コ -type liquid crystalline resin molded body.
Fig. 3 is a diagram for explaining a method of evaluating the sliding wear amount.
Detailed Description
Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.
Liquid crystalline resin composition for ball bearing sliding wear resistant member
The liquid crystal resin composition for a ball bearing sliding wear resistant member of the present invention comprises: a liquid crystalline resin (A), a granular filler (B), and whiskers (C).
[ (A) liquid crystalline resin ]
The liquid crystalline resin (a) used in the present invention is a melt processable polymer having a property of forming an optically anisotropic melt phase. The properties of the anisotropic melt phase can be confirmed by a conventional polarization detection method using an orthogonal polarizer. More specifically, the confirmation of the anisotropic melt phase may be performed as follows: the molten sample placed on the Leitz hot stage was observed under a nitrogen atmosphere at a magnification of 40 times using a Leitz polarizing microscope, and this was performed. When the liquid crystalline polymer which can be used in the present invention is detected between orthogonal polarizers, polarized light is generally transmitted even in a molten state of rest, and optically anisotropic is exhibited.
The type of the liquid crystalline resin (a) is not particularly limited, but aromatic polyesters and/or aromatic polyester amides are preferable. In addition, polyesters comprising partially aromatic polyesters and/or aromatic polyester amides in the same molecular chain are also within this range. As the liquid crystalline resin (A), it is preferable to use: when dissolved in pentafluorophenol at a concentration of 0.1 mass% at 60 ℃, it preferably has a logarithmic viscosity (i.v.) of at least about 2.0dl/g, more preferably 2.0 to 10.0 dl/g.
The aromatic polyester or aromatic polyester amide of the (a) liquid crystalline resin which can be used in the present invention is particularly preferably an aromatic polyester or aromatic polyester amide having 1 or more than 2 kinds of repeating units derived from an aromatic hydroxycarboxylic acid and its derivative as constituent components.
More specifically, the process is carried out,
(1) Polyesters mainly comprising 1 or more than 2 kinds of repeating units derived from aromatic hydroxycarboxylic acids and derivatives thereof;
(2) A polyester mainly comprising (a) 1 or more than 2 kinds of repeating units derived from an aromatic hydroxycarboxylic acid and a derivative thereof, and (b) 1 or more than 2 kinds of repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof;
(3) A polyester mainly comprising (a) 1 or 2 or more repeating units derived from an aromatic hydroxycarboxylic acid and a derivative thereof, (b) 1 or 2 or more repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof, and (c) at least 1 or 2 or more repeating units derived from an aromatic diol, an alicyclic diol, an aliphatic diol, and a derivative thereof;
(4) A polyester amide mainly comprising (a) 1 or 2 or more repeating units derived from an aromatic hydroxycarboxylic acid and its derivative, (b) 1 or 2 or more repeating units derived from an aromatic hydroxylamine, an aromatic diamine, and its derivative, and (c) 1 or 2 or more repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and its derivative;
(5) Mainly comprising (a) 1 or 2 or more repeating units derived from an aromatic hydroxycarboxylic acid and a derivative thereof, (b) 1 or 2 or more repeating units derived from an aromatic hydroxylamine, an aromatic diamine, and a derivative thereof, (c) 1 or 2 or more repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof, and (d) a polyesteramide derived from at least 1 or 2 or more repeating units derived from an aromatic diol, an alicyclic diol, an aliphatic diol, and a derivative thereof, and the like. Further, a molecular weight regulator may be used in combination with the above components as required.
As a specific example of the compound constituting the (A) liquid crystalline resin which can be used in the present invention, aromatic hydroxycarboxylic acids such as parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; aromatic diols such as 2, 6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 4' -dihydroxybiphenyl, hydroquinone, resorcinol, a compound represented by the following general formula (I), and a compound represented by the following general formula (II); aromatic dicarboxylic acids such as 1, 4-phenylene dicarboxylic acid, 1, 3-phenylene dicarboxylic acid, 4' -diphenyl dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, and a compound represented by the following general formula (III); aromatic amines such as p-aminophenol, p-phenylenediamine, and N-acetyl-p-aminophenol.
(X is selected from alkylene (C) 1 ～C 4 ) Alkylidene, -O-, -SO 2 -, -S-, and-CO-
(Y is selected from- (CH) 2 ) n - (n=1 to 4) and-O (CH) 2 ) n O- (n=1 to 4). )
The liquid crystalline resin (a) used in the present invention can be produced from the above-mentioned monomer compound (or mixture of monomers) by a known method such as a direct polymerization method or an ester exchange method, and usually by a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or the like, or a combination of 2 or more of these, preferably by a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method. The above-mentioned compounds having an ester-forming ability may be used directly for polymerization, or may be modified from a precursor to a derivative having an ester-forming ability at a stage before polymerization. In the polymerization, various catalysts can be used, and typical catalysts include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and cobalt (III) tris (2, 4-pentanedione), and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The amount of the catalyst to be used is usually preferably about 0.001 to 1% by mass, particularly preferably about 0.01 to 0.2% by mass, relative to the total mass of the monomers. The polymer produced by these polymerization methods can be further increased in molecular weight by a solid-phase polymerization method in which heating is performed under reduced pressure or in an inert gas, as needed.
The melt viscosity of the liquid crystalline resin (a) obtained by the above method is not particularly limited. Melt viscosity at the molding temperature at a shear rate of 1000 seconds can be generally used -1 The lower range is 3 Pa.s to 500 Pa.s. However, when the viscosity is too high, fluidity is extremely deteriorated, which is not preferable. The liquid crystal property (A)The resin may be a mixture of 2 or more kinds of liquid crystalline resins.
In the liquid crystalline resin composition of the present invention, the content of the liquid crystalline resin (a) is preferably 67.5 to 87.5 mass% or 66.5 to 82.5 mass%, more preferably 69 to 84 mass% or 67 to 80 mass%. (A) The content of the component (A) is preferably within the above range in terms of fluidity, heat resistance and the like.
[ (B) granular filler ]
(B) The component (B) is a granular filler, and the median particle diameter of the component (B) is 0.3-5.0 mu m. When the median particle diameter is 0.3 μm or more, the impact resistance of the molded article can be easily maintained. When the median diameter is 5.0 μm or less, the surface whitening suppression effect of the molded article tends to be high. The median particle diameter is preferably 0.5 to 5.0. Mu.m, more preferably 0.5 to 4.0. Mu.m. In the present specification, the median particle diameter of the component (B) means a volume-based median value measured by a laser diffraction/scattering particle size distribution measurement method. The median particle diameter of the component (B) in the liquid crystalline resin composition can be measured as follows: the component (B) remaining in the liquid crystal resin composition after ashing was measured by heating at 600℃for 2 hours by the method described above. (B) The components may be used alone or in combination of 2 or more.
Examples of the particulate filler as the component (B) include metal oxides such as silica, quartz powder, glass beads, glass powder, potassium aluminum silicate, diatomaceous earth, iron oxide, titanium oxide, zinc oxide, and aluminum oxide; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; phosphates such as calcium pyrophosphate and anhydrous calcium dihydrogen phosphate; silicon carbide; silicon nitride; boron nitride, and the like. In the present invention, from the viewpoint of suppressing surface whitening of the molded article and low dust generation of the molded article, it is preferable to use 1 or more selected from the group consisting of silica and barium sulfate as the component (B), and it is more preferable to use silica.
(B) The content of the component (A) in the liquid crystal composition of the present invention is 7.5 to 22.5% by mass. (B) If the content of the component is 7.5 mass% or more, the dimensional accuracy of the molded article tends to be high, and a molded article having reduced sliding wear properties of the ball bearing tends to be obtained. (B) If the content of the component is 22.5 mass% or less, the surface whitening suppression effect of the molded article tends to be high, and the impact resistance of the molded article tends to be maintained. The preferable content of the component (B) is 8.5 to 21 mass%.
[ (C) whisker ]
The liquid crystalline resin composition of the present invention contains whiskers. By including whiskers in the liquid crystalline resin composition of the present invention, the mechanical strength of the molded article can be easily improved, and a molded article having reduced sliding wear properties of a ball bearing can be easily obtained. In the present specification, whiskers refer to mineral fibers, and more specifically, pointer-shaped single crystals. The whisker may be used alone or in combination of 2 or more.
(C) The average fiber length of the whiskers is preferably 5 to 200. Mu.m, more preferably 7 to 170. Mu.m, still more preferably 9 to 150. Mu.m. If the average fiber length is within the above range, the mechanical strength of the molded article can be more easily improved. In the present specification, as the average fiber length of the whiskers (C), an average value of fiber lengths was measured for 100 whiskers, that is, for a total of 1000 whiskers in each 1 solid microscope image by collecting 10 solid microscope images of whiskers from a CCD camera to a PC and using an image measuring machine according to an image processing method. The average fiber length of the whiskers of (C) in the liquid crystalline resin composition was measured as follows: the whisker remaining from the liquid crystalline resin composition after ashing was measured by heating at 600℃for 2 hours by the method described above.
(C) The average fiber diameter of the whiskers is preferably 0.2 to 15 μm or less, more preferably 0.25 to 10 μm. When the average fiber diameter is within the above range, the mechanical strength of the molded article can be more easily improved. In the present specification, as the average fiber diameter of the whiskers (C), an average of values obtained by measuring fiber diameters of 30 whiskers observed with a scanning electron microscope was used. The average fiber diameter of the whiskers of (C) in the liquid crystalline resin composition was measured as follows: the whisker remaining from the liquid crystalline resin composition after ashing was measured by heating at 600℃for 2 hours by the method described above.
The aspect ratio of the whiskers (C), that is, the value of the average fiber length/average fiber diameter, is preferably 8 or more, more preferably 10to 100, still more preferably 15 to 75, from the viewpoint of the mechanical strength of a molded article such as a ball bearing sliding wear member comprising the liquid crystalline resin composition of the present invention.
The whisker (C) is not particularly limited, and examples thereof include potassium titanate whisker, calcium silicate whisker (wollastonite), calcium carbonate whisker, zinc oxide whisker, aluminum borate whisker, silicon nitride whisker, basic magnesium sulfate whisker, barium titanate whisker, silicon carbide whisker, and boron whisker, and potassium titanate whisker, calcium silicate whisker (wollastonite), calcium carbonate whisker, zinc oxide whisker, aluminum borate whisker, and the like are preferable in terms of availability, and potassium titanate whisker, calcium silicate whisker (wollastonite) and the like are more preferable.
(C) The content of the component (A) in the liquid crystalline resin composition of the present invention is 2.5 to 17.5% by mass. (C) If the content of the component is 2.5 mass% or more, the mechanical strength is easily improved, and a molded article having reduced sliding wear properties of the ball bearing is easily obtained. (C) If the content of the component (A) is 17.5% by mass or less, the impact resistance of the molded article can be easily maintained. The content of the component (C) is preferably 4.5 to 14% by mass.
Further, the total content of the component (B) and the component (C) in the liquid crystalline resin composition of the present invention is 12.5 to 32.5% by mass, preferably 16 to 31% by mass. If the total content is 12.5 mass% or more, the dimensional accuracy of the molded article tends to be high, and a molded article having reduced sliding wear properties of the ball bearing tends to be obtained. If the total content is 32.5 mass% or less, the surface whitening suppressing effect of the molded article and the low dust generation property of the molded article are liable to be high, and the impact resistance of the molded article is liable to be maintained.
[ (D) epoxy group-containing copolymer ]
The liquid crystalline composition of the present invention may contain (D) an epoxy group-containing copolymer. (D) The epoxy group-containing copolymer may be used singly or in combination of 2 or more. The epoxy group-containing copolymer (D) is not particularly limited, and examples thereof include at least 1 selected from the group consisting of an epoxy group-containing olefin copolymer (D1) and an epoxy group-containing styrene copolymer (D2). (D) The epoxy group-containing copolymer is advantageous in reducing the sliding wear of ball bearings of molded articles obtained from the liquid crystalline resin composition of the present invention.
Examples of the epoxy group-containing olefin copolymer (D1) include copolymers composed of repeating units derived from an α -olefin and repeating units derived from a glycidyl ester of an α, β -unsaturated acid.
The α -olefin is not particularly limited, and examples thereof include ethylene, propylene, butene, and the like, and among them, ethylene is preferably used. The glycidyl ester of an α, β -unsaturated acid is represented by the following general formula (IV). The glycidyl ester of an α, β -unsaturated acid is, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate or the like, and glycidyl methacrylate is particularly preferred.
(D1) In the epoxy group-containing olefin copolymer, the content of the repeating unit derived from an α -olefin is preferably 87 to 98% by mass, and the content of the repeating unit derived from a glycidyl ester of an α, β -unsaturated acid is preferably 13 to 2% by mass.
The epoxy group-containing olefin copolymer (D1) used in the present invention may contain, as the 3 rd component, not only the 2 kinds of components described above, but also 1 or more than 2 kinds of repeating units derived from an olefinically unsaturated ester such as acrylonitrile, acrylic acid ester, methacrylic acid ester, α -methylstyrene, maleic anhydride, etc., in an amount of 0to 48 parts by mass relative to 100 parts by mass of the 2 kinds of components, within a range not detrimental to the present invention.
The epoxy group-containing olefin-based copolymer as the component (D1) of the present invention can be easily produced by using monomers corresponding to the respective components and a radical polymerization catalyst and according to a usual radical polymerization method. More specifically, it can be generally manufactured by the following method: the alpha-olefin is copolymerized with a glycidyl ester of an alpha, beta-unsaturated acid in the presence of a radical generator, at 500 to 4000 atmospheres, 100 to 300 ℃, in the presence or absence of a suitable solvent, chain transfer agent. In addition, the method can also be used for manufacturing the alloy wire: the alpha-olefin is mixed with a glycidyl ester of an alpha, beta-unsaturated acid and a radical generator, and melt graft copolymerized in an extruder.
Examples of the epoxy group-containing styrene-based copolymer (D2) include copolymers composed of repeating units derived from styrene-based monomers and repeating units derived from glycidyl esters of α, β -unsaturated acids. The glycidyl esters of α, β -unsaturated acids are the same as those described for the component (D1), and therefore, description thereof is omitted.
As the styrenes, styrene, α -methylstyrene, brominated styrene, divinylbenzene, and the like can be mentioned, and styrene is preferably used.
The epoxy group-containing styrenic copolymer (D2) used in the present invention may be a multipolymer containing 1 or 2 or more kinds of repeating units derived from other vinyl monomers as the 3 rd component in addition to the above 2 components. The 3 rd component is preferably a repeating unit derived from 1 or 2 or more kinds of olefinically unsaturated esters such as acrylonitrile, acrylic acid ester, methacrylic acid ester, maleic anhydride and the like. An epoxy group-containing styrene copolymer containing 40 mass% or less of these repeating units in the copolymer is preferable as the component (D2).
(D2) In the epoxy group-containing styrenic copolymer, the content of the repeating unit derived from the glycidyl ester of an α, β -unsaturated acid is preferably 2 to 20% by mass, and the content of the repeating unit derived from the styrenic is preferably 80 to 98% by mass.
(D2) The epoxy group-containing styrenic copolymer can be prepared according to a usual radical polymerization method by using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, it can be generally manufactured by the following method: the glycidyl esters of styrene and alpha, beta-unsaturated acids are copolymerized in the presence of a free radical generator at 500 to 4000 atmospheres and 100 to 300 ℃ in the presence or absence of a suitable solvent, chain transfer agent. In addition, the method can also be used for manufacturing the alloy wire: styrene is mixed with glycidyl esters of alpha, beta-unsaturated acids and free radical generators and melt graft copolymerized in an extruder.
The epoxy group-containing copolymer (D) is preferably an epoxy group-containing olefin copolymer (D1) in terms of heat resistance. In the case of using the component (D1) and the component (D2) in combination, the ratio of these components to each other can be appropriately selected according to the desired characteristics.
(D) The content of the epoxy group-containing copolymer in the liquid crystalline resin composition of the present invention may be, for example, 0to 5% by mass, and preferably 1 to 5% by mass. (D) If the content of the component is within the above range, a molded article having reduced sliding wear properties of the ball bearing without impairing the fluidity of the liquid crystalline resin composition can be easily obtained. More preferably, the content is 2 to 4% by mass.
[ (E) carbon black ]
The carbon black (E) used as an optional component in the present invention is not particularly limited as long as it is a generally available one used for coloring resins. Generally, the carbon black (E) contains a lump of primary particles, but if the lump is not significantly contained with a size of 50 μm or more, a large amount of coarse particles (fine coarse protrusions (fine irregularities) of the carbon black) are not likely to be generated on the surface of the molded article obtained by molding the resin composition of the present invention. If the content of the particles having a particle diameter of 50 μm or more is 20ppm or less, the fuzzing inhibition effect on the surface of the molded article tends to be high. The preferable content is 5ppm or less. (E) The components may be used alone or in combination of 2 or more.
The amount of the carbon black to be blended in the liquid crystalline resin composition may be, for example, in the range of 0to 5% by mass, preferably 0.5 to 5% by mass. If the amount of carbon black is 0.5 mass% or more, the black paint property of the obtained resin composition is not easily lowered, and the light-shielding property is not easily unstable. If the compounding amount of carbon black is 5 mass% or less, it is not easy to become uneconomical and coarse matters are not easy to be generated.
[ (F) Release agent ]
The release agent (F) used as an optional component in the present invention is not particularly limited as long as it is usually available, and examples thereof include fatty acid esters, fatty acid metal salts, fatty acid amides, low molecular weight polyolefin, and the like, preferably fatty acid esters of pentaerythritol (for example, pentaerythritol tetrastearate). (F) The components may be used alone or in combination of 2 or more.
The amount of the release agent (F) to be blended may be, for example, 0to 3% by mass, preferably 0.1 to 3% by mass, in the liquid crystal resin composition. If the amount of the release agent is 0.1 mass% or more, the releasability at the time of molding is improved, and a molded article having reduced sliding wear properties of the ball bearing can be easily obtained. If the compounding amount of the mold release agent is 3 mass% or less, the mold deposit (i.e., referred to as deposit on a mold during molding, hereinafter also referred to as "MD") tends to be reduced.
[ other Components ]
The liquid crystal resin composition of the present invention may be added as appropriate according to the desired properties within a range that does not hinder the effects of the present invention: other polymers, other fillers, and known substances generally added to synthetic resins, that is, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, crystallization accelerators, and other components such as crystallization nucleating agents. The other components may be used alone or in combination of 1 or more than 2.
The other filler is a filler other than the (B) granular filler, (C) whisker, and (E) carbon black, and examples thereof include a granular filler other than the (B) component; a plate-like filler; fibrous filler other than component (C). The other fillers may be used alone or in combination of 2 or more. Examples of the particulate filler other than the component (B) include those having a median particle diameter of less than 0.3 μm or more than 5.0. Mu.m. Examples of the plate-like filler include mica and talc. Examples of the fibrous filler other than the component (C) include glass fibers. However, from the viewpoint of impact resistance and the like of the molded article, the liquid crystalline resin composition of the present invention preferably does not contain a plate-like filler. In addition, from the viewpoints of impact resistance of the molded article, low dust generation of the molded article, and the like, the liquid crystalline resin composition of the present invention preferably does not contain a fibrous filler other than the component (C).
[ method for producing liquid crystalline resin composition for ball bearing sliding wear Member ]
The method for producing the liquid crystal resin composition for a ball bearing sliding wear member of the present invention is not particularly limited. For example, the liquid crystal resin composition for a ball bearing sliding wear resistant member is prepared by mixing the components (a) to (C) and at least 1 of any of the components (D) to (F) and other components, and melt-kneading them with a single screw or twin screw extruder.
[ liquid Crystal resin composition for sliding wear Member of ball bearing ]
The liquid crystal resin composition of the present invention obtained as described above preferably has a melt viscosity of 90pa·s or less, more preferably 80pa·s or less, from the viewpoints of fluidity at the time of melting and moldability. In the present specification, as the melt viscosity, the following are used: at a barrel temperature of 10to 20 ℃ higher than the melting point of the liquid crystalline resin and a shearing speed of 1000 seconds -1 Using the values obtained according to the measurement method of ISO 11443.
Ball bearing sliding wear resistant component
The liquid crystalline resin composition of the present invention is used to produce a ball bearing sliding wear resistant member. The ball bearing sliding wear resistant member of the present invention is excellent in balance among suppression of surface whitening, mechanical strength, dimensional accuracy, and low dust generation property, while reducing the ball bearing sliding wear property and maintaining impact resistance. The ball bearing sliding wear resistant member of the present invention can be used for a component that is in dynamic contact with a ball bearing at the time of use, specifically, for example, a component for a lens holder or other camera module that is used in a state of dynamic contact with a ball bearing.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
< liquid crystalline resin >)
Liquid crystalline polyester amide resin
After the following raw materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140℃and reacted at 140℃for 1 hour. Thereafter, the temperature was further raised to 340℃over 4.5 hours, and then reduced to 10Torr (i.e., 1330 Pa) over 15 minutes, and melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride, and other low boiling fractions. After the stirring torque reached a predetermined value, nitrogen gas was introduced and the pressure was increased from a reduced pressure state to a pressurized state, and the polymer was discharged from the lower part of the polymerization vessel and the strand was pelletized to obtain pellets. The obtained pellets were subjected to heat treatment at 300℃for 2 hours under a nitrogen gas stream to obtain a target polymer. The melting point of the obtained polymer was 336℃and the melt viscosity at 350℃was 19.0 Pa.s. The melt viscosity of the polymer was measured in the same manner as the measurement method of the melt viscosity described later.
(I) 4-hydroxybenzoic acid (HBA); 1380g (60 mol%)
(II) 2-hydroxy-6-naphthoic acid (HNA); 157g (5 mol%)
(III) 1, 4-phenylene dicarboxylic acid (TA); 484g (17.5 mol%)
(IV) 4,4' -dihydroxybiphenyl (BP); 388g (12.5 mole%)
(V) N-acetyl-para-aminophenol (APAP); 126g (5 mol%)
Metal catalysts (potassium acetate catalysts); 110mg
Acylating agents (acetic anhydride); 1659g
< materials other than liquid crystalline resin >)
Silica 1: admafine SO-C2 (manufactured by Admatechs, inc., silica, median particle size 0.5 μm)
Silica 2: admafine SO-C6 (manufactured by Admatechs, inc., silica, median particle diameter 2.0 μm)
Silica 3: denka fused silica FB-5SDC (manufactured by Denka Corporation, silica, median particle size 4.0 μm)
Mica: AB-25S (YAMAGUCHI MICACO., LTD. Manufactured by Mirabilite, median particle size 25.0 μm)
Talc: CROWN TALC PP (Talcum, median particle size 14.6 μm, manufactured by Songcun industries Co., ltd.)
Potassium titanate: tismo N-102 (Potassium titanate whisker (Potassium titanate fiber, manufactured by Otsuka chemical Co., ltd.), average fiber diameter of 0.3 to 0.6 μm, average fiber length of 10to 20 μm)
Wollastonite: nyglos 8 (manufactured by NYCO Materials Co., ltd., calcium silicate whisker (wollastonite), average fiber length 136 μm, average fiber diameter 8 μm)
Glass fiber: ECS03T-786H (manufactured by Nitro Kabushiki Kaisha, japan, chopped strands, fiber diameter 10 μm, length 3 mm)
Epoxy group-containing olefin copolymer: bond First 2C (ethylene-glycidyl methacrylate copolymer, 6% by mass of glycidyl methacrylate, manufactured by Sumitomo chemical Co., ltd.)
Carbon black: VULCAN XC305 (Cabot Japan Co., ltd., average particle diameter 20nm, proportion of particles having particle diameter of 50 μm or more is 20ppm or less)
Mold release agent: pentaerythritol tetrastearate (Emery Oreo Chemicals Japan Co., ltd.)
Production of liquid Crystal resin composition for ball bearing sliding wear Member
The above components were melt kneaded at a barrel temperature of 350℃in a twin screw extruder (TEX 30. Alpha. Type manufactured by Japanese Steel Co., ltd.) at the proportions shown in Table 1, table 2 or Table 3 to obtain pellets of the liquid crystal resin composition for ball bearing sliding wear members.
< surface whitening >)
The pellets of examples and comparative examples were molded under the following molding conditions using a molding machine (Sumitomo heavy machinery Co., ltd. "SE30 DUZ"), to obtain test pieces (12.5 mm. Times.120 mm. Times.0.8 mm). The test piece for measurement was applied to an ultrasonic cleaner (power 300W, frequency 45 kHz) in water (80 ml) at room temperature for 3 minutes. Then, the surface of the test piece for measurement was visually observed. The surface whitening of the test piece for measurement was evaluated on the basis of the following criteria. The results are shown in tables 1 to 3.
O (good): whitening was not observed over the entire surface of the test piece.
X (bad): obvious whitening was confirmed in the smooth portion of the test piece
[ Molding conditions ]
Barrel temperature: 350 DEG C
Mold temperature: 80 DEG C
Injection rate: 100 mm/sec
< bending test >)
The pellets of examples and comparative examples were molded using a molding machine (SE 100DU manufactured by sumitomo heavy machinery industries, ltd.) under the following molding conditions to obtain an ISO test piece a shape. The test piece was cut out to obtain a test piece for measurement (80 mm. Times.10 mm. Times.4 mm). Using this test piece for measurement, the flexural strength, flexural strain, and flexural modulus were measured according to ISO 178. Among them, the measurement results of the bending strength were evaluated on the following criteria. The results are shown in tables 1 to 3.
O (good): the bending strength is 150MPa or more.
X (bad): the bending strength is lower than 150MPa.
[ Molding conditions ]
Barrel temperature: 350 DEG C
Mold temperature: 90 DEG C
Injection rate: 33 mm/sec
Ball bearing sliding wear Property
The pellets of examples and comparative examples were molded under the following molding conditions using a molding machine (SE 100DU manufactured by sumitomo heavy machinery industries, ltd.) to obtain test pieces (80 mm×80mm×1 mm). With a light load reciprocating tester, as shown in fig. 3, a ball 4 (diameter 5mm, SUS) at the tip of an arm 3 was loaded with grease 2 on a test piece 1 for measurement, and after the reciprocating sliding test was performed under the following reciprocating sliding conditions, the width of the ball bearing sliding mark remaining on the test piece 1 for measurement was measured with a solid microscope, and the ball bearing sliding wear was evaluated on the following basis. The results are shown in tables 1 to 3.
O (good): the width of the ball bearing sliding mark is less than 540 μm.
X (bad): the width of the ball bearing sliding trace exceeds 540 μm.
[ Molding conditions ]
Barrel temperature: 350 DEG C
Mold temperature: 80 DEG C
Injection rate: 33 mm/sec
[ reciprocating sliding conditions ]
Sliding speed: 5 cm/sec
Stroke: 20mm of
Load: 29.6N (3 kg heavy)
Number of reciprocations: 1000 times
And (3) lubricating grease: DOW CORNING TORAY CO., LTD. Monostaro EM-30L
< depth of recess >
The liquid crystalline resin composition was injection molded under the following molding conditions (gate: pin gate, gate size:) The molded article shown in fig. 1 (a) and 1 (b) was obtained.
[ Molding conditions ]
And (3) a forming machine: sumitomo heavy machinery industries Co., ltd., SE30DUZ
Barrel temperature: 350 DEG C
Mold temperature: 90 DEG C
Injection rate: 200 mm/sec
The depth of the recess remaining in the molded article was measured by a laser microscope after dropping the weight from the top surface of the molded article using a Dupont drop impact tester (manufactured by the company An Tian refiner) under the following conditions. The depth of the recess was used as an index indicating the impact resistance of the molded article. The results are shown in tables 1 to 3.
[ test conditions ]
Drop height: 15mm of
Dropping the heavy hammer: 75g
Shooting type: diameter of 0.75mm
< evaluation of inward-tilting deformation >)
The liquid crystalline resin composition was injection molded under the following molding conditions to obtain コ -shaped liquid crystalline resin molded articles (thickness: 0.5 mm) shown in fig. 2 (a) and 2 (B), and the angle a (gate side) and the angle B (back gate side) shown in fig. 2 (B) were measured using a Keyence Corporation image size measuring apparatus IM-6020. The average of the angles a and B is calculated and used as an index indicating the dimensional accuracy of the molded article. The results are shown in tables 1 to 3.
[ Molding conditions ]
And (3) a forming machine: sumitomo heavy machinery industry, SE30DUZ
Barrel temperature: 350 DEG C
Mold temperature: 90 DEG C
Injection rate: 100 mm/sec
< dust Generation count >)
The pellets of examples and comparative examples were molded by a molding machine (product of Sumitomo heavy machinery Co., ltd. "SE30 DUZ") under the following molding conditions to obtain molded articles of 12.5 mm. Times.120 mm. Times.0.8 mm. The molded article was used as a test piece.
[ Molding conditions ]
Barrel temperature: 350 DEG C
Mold temperature: 80 DEG C
Injection rate: 100 mm/sec
[ evaluation ]
The test piece was applied to an ultrasonic cleaner (power 300W, frequency 45 kHz) in water (80 ml) at room temperature for 3 minutes. Thereafter, the number of particles of 2 μm or more present in the water was measured by a Particle Counter (Particle Counter KL-11A (PARTICLECOUNTER), manufactured by RION Co., ltd.) and evaluated as a dust generation number based on the following criteria. The results are shown in tables 1 to 3.
O (good): the dust generation number is 60000/80 ml or less.
X (bad): dust generation number exceeds 60000/80 ml.
TABLE 1
TABLE 2
TABLE 3
From the results shown in tables 1 to 3, it was confirmed that the molded articles of examples were excellent in balance among suppression of surface whitening, mechanical strength, dimensional accuracy, and low dust generation property, and the ball bearing sliding wear property was reduced while maintaining impact property.
Claims (3)
1. A liquid crystalline resin composition for a ball bearing sliding wear resistant member, comprising:
(A) A liquid crystalline resin,
(B) Granular filler
(C) The crystal whisker is arranged on the surface of the crystal whisker,
the liquid crystalline resin (A) is an aromatic polyester or an aromatic polyester amide having 1 or more than 2 repeating units derived from an aromatic hydroxycarboxylic acid and a derivative thereof as a constituent component,
the granular filler (B) is 1 or more selected from the group consisting of silica and barium sulfate,
the median particle diameter of the granular filler (B) is 0.3-5.0 mu m,
the content of the granular filler (B) is 7.5 to 22.5 mass%,
the content of the whisker (C) is 4.5 to 14 mass percent,
the total content of the granular filler (B) and the whisker (C) is 12.5 to 32.5 mass%.
2. The composition of claim 1, further comprising (D) an epoxy-containing copolymer,
the content of the epoxy group-containing copolymer (D) is 1 to 5% by mass.
3. A ball bearing sliding wear resistant member comprising the composition of claim 1 or 2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020112583 | 2020-06-30 | ||
| JP2020-112583 | 2020-06-30 | ||
| PCT/JP2021/023996 WO2022004553A1 (en) | 2020-06-30 | 2021-06-24 | Liquid crystalline resin composition for ball bearing anti-sliding wear member, and ball bearing anti-sliding wear member using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115702206A CN115702206A (en) | 2023-02-14 |
| CN115702206B true CN115702206B (en) | 2023-12-12 |
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| CN202180043329.4A Active CN115702206B (en) | 2020-06-30 | 2021-06-24 | Liquid crystalline resin composition for ball bearing sliding wear member and ball bearing sliding wear member using same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7200435B2 (en) |
| KR (1) | KR102545958B1 (en) |
| CN (1) | CN115702206B (en) |
| TW (1) | TW202204522A (en) |
| WO (1) | WO2022004553A1 (en) |
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| WO2020071495A1 (en) * | 2018-10-05 | 2020-04-09 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for ball bearing anti-sliding-abrasion member, and ball bearing anti-sliding-abrasion member using same |
| CN110997820A (en) * | 2017-09-12 | 2020-04-10 | 宝理塑料株式会社 | Liquid crystalline resin composition for sliding wear resistant member and sliding wear resistant member using same |
| CN111253716A (en) * | 2019-05-17 | 2020-06-09 | 住友化学株式会社 | Particle mixture and injection molded body |
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| JP3044491B2 (en) * | 1991-01-25 | 2000-05-22 | 日本石油化学株式会社 | bearing |
| DE69534461T2 (en) * | 1994-03-18 | 2006-06-29 | Mitsubishi Denki K.K. | RESIN COMPOSITION FOR FORMING PRECISION PARTS, SLEEVES AND CONNECTORS PRODUCED HEREOF |
| JP5092324B2 (en) * | 2006-09-08 | 2012-12-05 | 東レ株式会社 | Liquid crystalline polyester composition |
| JP5087958B2 (en) | 2007-03-07 | 2012-12-05 | 東レ株式会社 | Molded product comprising liquid crystalline resin composition |
| TWI586750B (en) * | 2011-02-28 | 2017-06-11 | 住友化學股份有限公司 | Liquid crystal polyester composition and process for producing the same |
| EP2921525B1 (en) * | 2012-11-19 | 2017-07-19 | Mitsui Chemicals, Inc. | Polyester resin composition, manufacturing method therefor, and camera module containing said polyester resin composition |
| WO2015016370A1 (en) * | 2013-07-31 | 2015-02-05 | 住友化学株式会社 | Liquid crystalline polyester composition |
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| JP6063373B2 (en) * | 2013-12-03 | 2017-01-18 | Ｊｘエネルギー株式会社 | Liquid crystal polyesteramide resin composition, and camera module component including the injection molded body as a constituent member |
| US9618770B2 (en) | 2014-04-11 | 2017-04-11 | Samsung Electro-Mechanics Co., Ltd. | Camera module with function of auto-focus and image stabilize |
| JP2018104527A (en) * | 2016-12-26 | 2018-07-05 | 東レ株式会社 | Liquid crystal polyester resin composition and molded article made of the same |
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| CN114502657B (en) * | 2019-10-03 | 2023-05-26 | 宝理塑料株式会社 | Liquid crystalline resin composition for ball bearing sliding wear member and ball bearing sliding wear member using same |
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2021
- 2021-06-24 WO PCT/JP2021/023996 patent/WO2022004553A1/en active Application Filing
- 2021-06-24 KR KR1020227043936A patent/KR102545958B1/en active IP Right Grant
- 2021-06-24 CN CN202180043329.4A patent/CN115702206B/en active Active
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| TW202204522A (en) | 2022-02-01 |
| JPWO2022004553A1 (en) | 2022-01-06 |
| KR102545958B1 (en) | 2023-06-22 |
| WO2022004553A1 (en) | 2022-01-06 |
| KR20230008223A (en) | 2023-01-13 |
| CN115702206A (en) | 2023-02-14 |
| JP7200435B2 (en) | 2023-01-06 |
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