JP7518742B2 - Particles and their uses - Google Patents
Particles and their uses Download PDFInfo
- Publication number
- JP7518742B2 JP7518742B2 JP2020197606A JP2020197606A JP7518742B2 JP 7518742 B2 JP7518742 B2 JP 7518742B2 JP 2020197606 A JP2020197606 A JP 2020197606A JP 2020197606 A JP2020197606 A JP 2020197606A JP 7518742 B2 JP7518742 B2 JP 7518742B2
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- weight
- particles
- meth
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002245 particle Substances 0.000 title claims description 147
- 239000000178 monomer Substances 0.000 claims description 98
- 239000000314 lubricant Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 39
- 239000003921 oil Substances 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 13
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 150000002825 nitriles Chemical class 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 59
- 238000011156 evaluation Methods 0.000 description 33
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 18
- -1 carboxyethyl Chemical group 0.000 description 17
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 14
- 230000007774 longterm Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000003381 stabilizer Substances 0.000 description 12
- 239000002612 dispersion medium Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 230000005484 gravity Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229920000554 ionomer Polymers 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000002459 sustained effect Effects 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
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WPUKZOKYKHYASK-UHFFFAOYSA-N bis(11-methyldodecyl) hexanedioate Chemical compound CC(C)CCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCC(C)C WPUKZOKYKHYASK-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010696 ester oil Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000012905 visible particle Substances 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- OIXSXGIGQZSWJN-UHFFFAOYSA-N 1,4-dichloro-1,1,2,2-tetrafluorobutane Chemical compound FC(F)(Cl)C(F)(F)CCCl OIXSXGIGQZSWJN-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- RCSKFKICHQAKEZ-UHFFFAOYSA-N 1-ethenylindole Chemical compound C1=CC=C2N(C=C)C=CC2=C1 RCSKFKICHQAKEZ-UHFFFAOYSA-N 0.000 description 1
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 1
- YFMDXYVZWMHAHJ-UHFFFAOYSA-N 1-pentaphen-1-yloxypentaphene Chemical compound C1=CC=CC2=CC3=C(C=C4C(OC=5C6=CC7=C8C=C9C=CC=CC9=CC8=CC=C7C=C6C=CC=5)=CC=CC4=C4)C4=CC=C3C=C21 YFMDXYVZWMHAHJ-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- RVBFWXYFXKDVKG-UHFFFAOYSA-N 2-ethoxyprop-2-enenitrile Chemical compound CCOC(=C)C#N RVBFWXYFXKDVKG-UHFFFAOYSA-N 0.000 description 1
- LLEFDCACDRGBKD-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;nonanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCCC(O)=O LLEFDCACDRGBKD-UHFFFAOYSA-N 0.000 description 1
- CWTQBXKJKDAOSQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;octanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCC(O)=O CWTQBXKJKDAOSQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- LIFFBWPIGFQNHW-UHFFFAOYSA-N 6-(4-hydroxyhex-5-enoxy)hex-1-en-3-ol Chemical compound C=CC(O)CCCOCCCC(O)C=C LIFFBWPIGFQNHW-UHFFFAOYSA-N 0.000 description 1
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- DJBVDAUKGXUPLO-QEMDMZNVSA-N C(C)C(C(=O)O)CCCC.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O Chemical compound C(C)C(C(=O)O)CCCC.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O DJBVDAUKGXUPLO-QEMDMZNVSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- SMYKBXMWXCZOLU-UHFFFAOYSA-N tris-decyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCCCC)C(C(=O)OCCCCCCCCCC)=C1 SMYKBXMWXCZOLU-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Images
Landscapes
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、粒子、及びその用途に関する。 The present invention relates to particles and their uses.
ゴムや樹脂は、自動車、建材、家電、ＯＡ機器等の部材として、様々な分野・用途で使用されている。部材によっては、摩擦抵抗が少なく、摺動性に優れることが求められる。
摺動性を付与する方法としては、部材に潤滑剤を直接塗布する方法、潤滑性のフィルムを部材に接着させる方法、基材と潤滑剤の混合物を成形して部材を作成する方法等があげられる。例えば、熱可塑性樹脂等の基材に、ウレタン系塗料やシリコン系塗料等を塗布して潤滑性被膜を形成する方法がある。しかし、形成される潤滑性被膜が基材と比べて硬いという問題があり、また、有機溶剤の使用制限や、多くの手間がかかる等の問題がある。
特許文献１には、摺動耐久性に優れた潤滑被膜形成用樹脂組成物として、液体潤滑剤を内包する熱硬化性樹脂からなるマイクロカプセルを含有する潤滑被膜形成用樹脂組成物が例示されている。しかし、特許文献１における方法においても、上記問題は解決できておらず、さらに、摺動性が長期間維持できない問題がある。また、熱可塑性樹脂等にシリコーンオイル等の滑剤を添加し、成形して得られる摺動部材が提案されているが、部材表面に滑剤がブリードアウトしやすく、時間経過とともに外観が損なわれ、また、繰り返し摩擦により、滑剤が除去され、摺動性が低下するという問題がある。
Rubber and resin are used in a variety of fields and applications as components for automobiles, building materials, home appliances, office automation equipment, etc. Depending on the component, low friction resistance and excellent sliding properties are required.
Methods for imparting slidability include a method of directly applying a lubricant to a member, a method of adhering a lubricating film to a member, and a method of forming a member by molding a mixture of a substrate and a lubricant. For example, there is a method of forming a lubricating coating by applying a urethane-based paint or a silicone-based paint to a substrate such as a thermoplastic resin. However, there are problems in that the formed lubricating coating is harder than the substrate, and there are also problems such as restrictions on the use of organic solvents and a lot of effort.
Patent Document 1 exemplifies a resin composition for forming a lubricating film, which contains microcapsules made of a thermosetting resin containing a liquid lubricant, as a resin composition for forming a lubricating film having excellent sliding durability. However, the method in Patent Document 1 does not solve the above problems, and there is also a problem that the sliding properties cannot be maintained for a long period of time. In addition, a sliding member obtained by adding a lubricant such as silicone oil to a thermoplastic resin and molding the resin has been proposed, but the lubricant is likely to bleed out on the surface of the member, which impairs the appearance over time, and the lubricant is removed by repeated friction, which reduces the sliding properties.
特許文献２には、基材であるＰＰとＥＰＤＭにＰＥ粒子を混練した摺動材が例示されている。ＰＥ粒子により、摺動材表面が凹凸化し、接触面を減らすため、摩擦係数や摩耗量が減少し、摺動性が良好となる。しかし、粒子の分散性が悪く、摺動性は十分とは言えず、また、摺動材の柔軟性に劣るという問題がある。
特許文献３には、熱可塑性樹脂中にシリコーンオイルおよび／またはシリコーンポリマーとシリコーンパウダーとを混在させたことを特徴とする耐摩耗性熱可塑性樹脂組成物が例示されている。シリコーンパウダーを混在させることにより、シリコーンオイルがシリコーンパウダーに吸収されブリードアウトが抑制される。しかし、特許文献３においては、摺動性を長期間持続できないという問題がある。 Patent Document 3 exemplifies an abrasion-resistant thermoplastic resin composition characterized by mixing silicone oil and/or silicone polymer with silicone powder in a thermoplastic resin. By mixing in silicone powder, the silicone oil is absorbed into the silicone powder, suppressing bleeding out. However, Patent Document 3 has the problem that the sliding properties cannot be maintained for a long period of time.
そこで、本発明の目的は、摺動性を付与することができ、かつ、摺動性の長期持続性に優れる粒子、及びその用途を提供する。 The object of the present invention is to provide particles that can impart sliding properties and have excellent long-term durability of the sliding properties, and uses thereof.
本発明者らは鋭意検討を行った結果、特定の重合性成分の重合体からなる外殻と、その外殻に内包される特定の内包物とから構成される粒子であれば、上記課題を解決できることを見出し、本発明に到達した。 As a result of intensive research, the inventors discovered that the above problems could be solved by particles that are composed of an outer shell made of a polymer of a specific polymerizable component and a specific inclusion contained within the outer shell, and thus arrived at the present invention.
すなわち本発明は、単量体（Ａ）と単量体（Ｂ）を含む重合性成分の重合体からなる外殻と、前記外殻に内包される内包物とから構成される粒子であって、前記単量体（Ａ）が重合性炭素－炭素二重結合を１つ有する単量体であり、前記単量体（Ｂ）が重合性炭素－炭素二重結合を少なくとも２つ有する単量体であり、前記内包物が潤滑剤を含む、粒子である。 That is, the present invention provides particles that are composed of an outer shell made of a polymer of polymerizable components including monomer (A) and monomer (B) and inclusions encapsulated in the outer shell, where monomer (A) is a monomer having one polymerizable carbon-carbon double bond, monomer (B) is a monomer having at least two polymerizable carbon-carbon double bonds, and the inclusions include a lubricant.
本発明の粒子は、前記重合性成分に占める前記単量体（Ａ）の重量割合が５０～９９．９９９重量％であり、前記重合性成分に占める前記単量体（Ｂ）の重量割合が０．００１～５０重量％であると、好ましい。
本発明の粒子は、前記単量体（Ａ）が単量体（ａ１）を含み、前記単量体（ａ１）がカルボキシル基を有する単量体、ニトリル系単量体、アミド基を有する単量体、（メタ）アクリル酸エステル、塩化ビニリデン、ビニルエステル系単量体、及びスチレン系単量体から選ばれる少なくとも１つであると、好ましい。
本発明の粒子は、前記潤滑剤の２５℃における動粘度が１０～１０００００ｍｍ２／ｓであると、好ましい。
本発明の粒子は、前記潤滑剤が、シリコーン系オイル、フッ素系オイル、エステル系オイル、及び炭化水素系オイルから選ばれる少なくとも１種を含むと、好ましい。
本発明の粒子は、内径（ｄ１）と外径（ｄ２）の比（ｄ１／ｄ２）が０．０５～０．９９９であると、好ましい。
In the particles of the present invention, it is preferable that the weight ratio of the monomer (A) in the polymerizable component is 50 to 99.999% by weight, and the weight ratio of the monomer (B) in the polymerizable component is 0.001 to 50% by weight.
In the particles of the present invention, it is preferable that the monomer (A) contains a monomer (a1), and the monomer (a1) is at least one selected from a monomer having a carboxyl group, a nitrile monomer, a monomer having an amide group, a (meth)acrylic acid ester, vinylidene chloride, a vinyl ester monomer, and a styrene monomer.
In the particles of the present invention, the kinetic viscosity of the lubricant at 25° C. is preferably 10 to 100,000 mm 2 /s.
In the particles of the present invention, it is preferable that the lubricant contains at least one oil selected from the group consisting of silicone-based oil, fluorine-based oil, ester-based oil, and hydrocarbon-based oil.
The particles of the present invention preferably have a ratio (d1/d2) of the inner diameter (d1) to the outer diameter (d2) of 0.05 to 0.999.
本発明の組成物は、上記粒子と、基材成分を含む。
本発明の成形体は、上記組成物を成形してなるものである。
The composition of the present invention contains the above-mentioned particles and a substrate component.
The molded article of the present invention is obtained by molding the above composition.
本発明の粒子は、摺動性を付与し、摺動性の長期持続性に優れ、分散性に優れる。
本発明の組成物は、上記粒子を含んでいるため、摺動性を有し、摺動性が長期間持続し、優れた外観を有する成形体を得ることができる。
本発明の成形体は、上記組成物を成形して得られるので、摺動性を有し、摺動性が長期間持続し、優れた外観を有する。
The particles of the present invention impart sliding properties, are excellent in long-term durability of the sliding properties, and are excellent in dispersibility.
Since the composition of the present invention contains the above-mentioned particles, it is possible to obtain a molded article that has sliding properties, that sliding properties are maintained for a long period of time, and that has an excellent appearance.
The molded article of the present invention is obtained by molding the above-mentioned composition, and therefore has slidability, the slidability is sustained for a long period of time, and has an excellent appearance.
〔粒子〕
本発明の粒子は、重合体からなる外殻と、その外殻に内包される内包物とから構成され、かつ内包物は潤滑剤を含有しており、摺動性を付与することができるものである。
本発明の粒子は、摺動性の長期持続性の効果をより高めるには、内部に１つ以上の独立した孔を有する構造であると好ましく、内部の孔に潤滑剤を含む粒子であると好ましい。特に、図１に示すように、重合体からなる外殻（シェル）１とそれに内包された内包物（コア）２とから構成されるコア－シェル構造を有する粒子であると、高い摺動特性が得られ、好ましい。また、外殻が連続した重合体であると好ましい。
本発明の粒子において、構成する外殻は単量体（Ａ）と単量体（Ｂ）を含む重合性成分の重合体であり、単量体（Ａ）が（ラジカル）重合性炭素－炭素二重結合を１つ有する単量体であり、単量体（Ｂ）が（ラジカル）重合性炭素－炭素二重結合を少なくとも２つ有する単量体である。
〔particle〕
The particles of the present invention are composed of an outer shell made of a polymer and an inclusion contained in the outer shell, and the inclusion contains a lubricant and can impart sliding properties.
In order to further enhance the effect of long-term durability of sliding properties, the particles of the present invention are preferably structured to have one or more independent holes inside, and are preferably particles containing a lubricant in the internal holes. In particular, as shown in Figure 1, particles having a core-shell structure consisting of an outer shell (shell) 1 made of a polymer and an inclusion (core) 2 contained therein are preferable because they can provide high sliding properties. In addition, it is preferable that the outer shell is a continuous polymer.
In the particles of the present invention, the outer shell is a polymer of polymerizable components containing monomer (A) and monomer (B), monomer (A) is a monomer having one (radically) polymerizable carbon-carbon double bond, and monomer (B) is a monomer having at least two (radically) polymerizable carbon-carbon double bonds.
外殻が、単量体（Ａ）と単量体（Ｂ）を含む重合性成分の重合体であることで、重合体の緻密性が向上し、多量の潤滑剤の染み出しや、特に成形加工時の粒子の潰れが抑制でき、好ましい。 The outer shell is preferably a polymer of polymerizable components including monomer (A) and monomer (B), which improves the density of the polymer and suppresses the seepage of a large amount of lubricant and the crushing of particles, particularly during molding.
また成形体においては表面付近が、通常、摺動時の摩擦等の外力を受けるが、その際に、単量体（Ａ）と単量体（Ｂ）を含む重合性成分の重合体を外殻とする本発明の粒子は、外力により潤滑剤を放出し、さらにその量を制御できるため、摺動性の長期持続性に優れる。 In addition, the surface of a molded product is usually subjected to external forces such as friction during sliding. In this case, the particles of the present invention, which have an outer shell made of a polymer of polymerizable components containing monomer (A) and monomer (B), release a lubricant in response to external forces and the amount of the lubricant can be controlled, resulting in excellent long-term durability of sliding properties.
単量体（Ａ）としては、例えば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、シトラコン酸、カルボキシエチル（メタ）アクリレート等のカルボキシル基を有する単量体；グリシジル（メタ）アクリレート、アリルグリシジルエーテル等のグリシジル基を有する単量体；アクリロニトリル、メタクリロニトリル、α－クロルアクリロニトリル、α－エトキシアクリロニトリル、フマロニトリル等のニトリル系単量体；アクリルアミド、置換アクリルアミド、メタクリルアミド、置換メタクリルアミド等のアクリルアミド系単量体や、Ｎ－フェニルマレイミド、Ｎ－（２－クロロフェニル）マレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ラウリルマレイミド等のマレイミド系単量体等のアミド結合を有する単量体；メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、ドデシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、２－クロルエチル（メタ）アクリレート、フェニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等の（メタ）アクリル酸エステル系単量体；塩化ビニリデン；酢酸ビニル、プロピオン酸ビニル、酪酸ビニル等のビニルエステル系単量体；スチレン、α－メチルスチレン、ｐ－メチルスチレン、クロロスチレン等のスチレン系単量体；塩化ビニル、臭化ビニル、弗化ビニル等のハロゲン化ビニル系単量体；エチレン、プロピレン、ブチレン、イソブチレン等の不飽和モノオレフイン系単量体；ビニルメチルエーテル、ビニルエチルエーテル、ビニルプロピルエーテル、ビニルイソプロピルエーテル、ビニルブチルエーテル、ビニルイソブチルエーテル、ビニル－２－エチルヘキシルエーテル、ビニルシクロヘキシルエーテル、ビニル－４－ヒドロキシブチルエーテル等のビニルエーテル系単量体；ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトン等のビニルケトン系単量体；Ｎ－ビニルピロール、Ｎ－ビニルカルバゾール、Ｎ－ビニルインドール、Ｎ－ビニルピロリドン等のＮ－ビニル系単量体、ビニルナフタリン塩等が挙げられる。カルボキシル基を有する単量体については、一部または全部のカルボキシル基が重合時に中和されていてもよい。なお本発明では、（メタ）アクリルは、アクリルまたはメタクリルを意味し、（メタ）アクリレートは、アクリレートまたはメタクリレートを意味する。また上記単量体（Ａ）は、１種または２種以上を併用してもよい。 Examples of the monomer (A) include monomers having a carboxyl group, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and carboxyethyl (meth)acrylate; monomers having a glycidyl group, such as glycidyl (meth)acrylate and allyl glycidyl ether; nitrile monomers, such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, and fumaronitrile; acrylamide monomers, such as acrylamide, substituted acrylamide, methacrylamide, and substituted methacrylamide; and N-phenylmaleimide, N Monomers having an amide bond, such as maleimide-based monomers such as -(2-chlorophenyl)maleimide, N-cyclohexylmaleimide, and N-laurylmaleimide; methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, propyl (meth)acrylate, n-octyl (meth)acrylate, dodecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, 2-chloroethyl (meth)acrylate, phenyl (meth)acrylate, (Meth)acrylic acid ester monomers such as isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; vinylidene chloride; vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl butyrate; styrene monomers such as styrene, α-methylstyrene, p-methylstyrene, and chlorostyrene; halogenated vinyl monomers such as vinyl chloride, vinyl bromide, and vinyl fluoride; unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene. In-based monomers: vinyl ether-based monomers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isopropyl ether, vinyl butyl ether, vinyl isobutyl ether, vinyl-2-ethylhexyl ether, vinyl cyclohexyl ether, and vinyl-4-hydroxybutyl ether; vinyl ketone-based monomers such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl-based monomers such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone, and vinylnaphthalene salts. For monomers having a carboxyl group, some or all of the carboxyl groups may be neutralized during polymerization. In the present invention, (meth)acrylic means acrylic or methacrylic, and (meth)acrylate means acrylate or methacrylate. The above-mentioned monomer (A) may be used alone or in combination of two or more.
重合性成分に占める単量体（Ａ）の重量割合は、特に限定はないが、好ましくは５０～９９．９９９重量％である。単量体（Ａ）の重量割合が５０重量％未満であると、内包する潤滑剤が粒子の外へ放出されないことがあり、単量体（Ａ）の重量割合が９９．９９９重量％超であると、重合体の緻密性が低下することがある。単量体（Ａ）の重量割合の上限は、（１）９９．９９重量％、（２）９９．９重量％、（３）９９．７重量％、（４）９９．５重量％、（５）９９重量％の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。単量体（Ａ）の重量割合の下限は、（１）６０重量％、（２）７０重量％、（３）８０重量％、（４）８５重量％、（５）９０重量％、（６）９３重量％の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。 The weight percentage of monomer (A) in the polymerizable component is not particularly limited, but is preferably 50 to 99.999% by weight. If the weight percentage of monomer (A) is less than 50% by weight, the encapsulated lubricant may not be released outside the particles, and if the weight percentage of monomer (A) is more than 99.999% by weight, the density of the polymer may decrease. The upper limit of the weight percentage of monomer (A) is preferably (1) 99.99% by weight, (2) 99.9% by weight, (3) 99.7% by weight, (4) 99.5% by weight, and (5) 99% by weight (the larger the number in parentheses, the more preferable it is). The lower limit of the weight ratio of monomer (A) is preferably (1) 60% by weight, (2) 70% by weight, (3) 80% by weight, (4) 85% by weight, (5) 90% by weight, and (6) 93% by weight (the larger the number in parentheses, the more preferable it is).
単量体（Ａ）は、カルボキシル基を有する単量体、ニトリル系単量体、アミド基を有する単量体、（メタ）アクリル酸エステル、塩化ビニリデン、ビニルエステル系単量体、及びスチレン系単量体から選ばれる少なくとも１つである単量体（ａ１）を含むと、外殻の強度が向上する点で好ましい。
単量体（Ａ）が単量体（ａ１）を含む場合、単量体（Ａ）に占める単量体（ａ１）の重量割合としては、特に限定はないが、好ましくは１０重量％以上である。単量体（ａ１）の重量割合の上限は、好ましくは１００重量％、より好ましくは９７重量％、さらに好ましくは９５重量％、特に好ましくは９０重量％、最も好ましくは８５重量％である。一方、単量体（ａ１）の重量割合の下限は、より好ましくは２０重量％、さらに好ましくは３０重量％、特に好ましくは５０重量％、最も好ましくは７０重量％である。
The monomer (A) preferably contains at least one monomer (a1) selected from a monomer having a carboxyl group, a nitrile monomer, a monomer having an amide group, a (meth)acrylic acid ester, vinylidene chloride, a vinyl ester monomer, and a styrene monomer, in terms of improving the strength of the outer shell.
When the monomer (A) contains the monomer (a1), the weight ratio of the monomer (a1) in the monomer (A) is not particularly limited, but is preferably 10% by weight or more. The upper limit of the weight ratio of the monomer (a1) is preferably 100% by weight, more preferably 97% by weight, even more preferably 95% by weight, particularly preferably 90% by weight, and most preferably 85% by weight. On the other hand, the lower limit of the weight ratio of the monomer (a1) is more preferably 20% by weight, even more preferably 30% by weight, particularly preferably 50% by weight, and most preferably 70% by weight.
単量体（Ａ）がカルボキシル基を有する単量体及び／またはニトリル系単量体を含むと、耐熱性の点で好ましい。
単量体（Ａ）がカルボキシル基を有する単量体及びニトリル系単量体を含む場合、カルボキシル基を有する単量体とニトリル系単量体の合計重量に占めるニトリル系単量体の重量割合は、好ましくは５～９５重量％である。ニトリル系単量体の重量割合の上限は、より好ましくは９０重量％、さらに好ましくは８５重量％、特に好ましくは８０重量％、最も好ましくは７５重量％である。一方、ニトリル系単量体の重量割合の下限は、より好ましくは１０重量％、さらに好ましくは１５重量％、特に好ましくは２０重量％、最も好ましくは２５重量％である。
It is preferable from the viewpoint of heat resistance that the monomer (A) contains a monomer having a carboxyl group and/or a nitrile monomer.
When the monomer (A) contains a monomer having a carboxyl group and a nitrile monomer, the weight ratio of the nitrile monomer to the total weight of the monomer having a carboxyl group and the nitrile monomer is preferably 5 to 95% by weight. The upper limit of the weight ratio of the nitrile monomer is more preferably 90% by weight, even more preferably 85% by weight, particularly preferably 80% by weight, and most preferably 75% by weight. On the other hand, the lower limit of the weight ratio of the nitrile monomer is more preferably 10% by weight, even more preferably 15% by weight, particularly preferably 20% by weight, and most preferably 25% by weight.
重合性成分に必須に含まれる単量体（Ｂ）は、得られる重合体に橋掛け構造（架橋構造）を導入する。これにより、重合体は緻密性が向上し、内包する潤滑剤の放出を制御できる。
単量体（Ｂ）としては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ＰＥＧ＃２００ジ（メタ）アクリレート、ＰＥＧ＃４００ジ（メタ）アクリレート、ＰＥＧ＃６００ジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート等のジ（メタ）アクリレート類、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリストールトリ（メタ）アクリレート等のトリ（メタ）アクリレート類；ジビニルベンゼン、ジビニルナフタレン等の芳香族ジビニル化合物、ブタジエン等を挙げることができる。なお本発明では、また上記単量体（Ｂ）は、１種または２種以上を併用してもよい。また上記で、「ＰＥＧ＃○○○ジ（メタ）アクリレート」と表記されている一連の化合物は、ポリエチレングリコールジ（メタ）アクリレートで、そのポリエチレングリコール部分の平均分子量が○○○であることを意味する。
The monomer (B) which is essentially contained in the polymerizable component introduces a cross-linked structure into the resulting polymer, which improves the density of the polymer and enables the release of the encapsulated lubricant to be controlled.
Examples of the monomer (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol ... triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, triethylene Examples of the di(meth)acrylates include methylolpropane di(meth)acrylate, PEG#200 di(meth)acrylate, PEG#400 di(meth)acrylate, PEG#600 di(meth)acrylate, neopentyl glycol di(meth)acrylate, and other di(meth)acrylates; trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and other tri(meth)acrylates; aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; butadiene, and the like. In the present invention, the monomer (B) may be used alone or in combination of two or more. In addition, the series of compounds described above as "PEG#○○○di(meth)acrylate" means that the polyethylene glycol di(meth)acrylate has an average molecular weight of ○○○ in the polyethylene glycol portion.
重合性成分に占める単量体（Ｂ）の重量割合は、特に限定はないが、好ましくは０．００１～５０重量％である。単量体（Ｂ）の重量割合が０．００１重量％未満であると、有機樹脂の緻密性が低下することがあり、単量体（Ｂ）の重量割合が５０重量％超であると、内包する潤滑剤が粒子の外へ放出されないことがある。単量体（Ｂ）の重量割合の上限は、（１）４０重量％、（２）３０重量％、（３）２０重量％、（４）１５重量％、（５）１０重量％、（６）７重量％の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。単量体（Ｂ）の重量割合の下限は、（１）０．０１重量％、（２）０．１重量％、（３）０．３重量％、（４）０．５重量％、（５）１重量％の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。 The weight percentage of the monomer (B) in the polymerizable component is not particularly limited, but is preferably 0.001 to 50% by weight. If the weight percentage of the monomer (B) is less than 0.001% by weight, the denseness of the organic resin may decrease, and if the weight percentage of the monomer (B) is more than 50% by weight, the encapsulated lubricant may not be released outside the particles. The upper limit of the weight percentage of the monomer (B) is preferably (1) 40% by weight, (2) 30% by weight, (3) 20% by weight, (4) 15% by weight, (5) 10% by weight, and (6) 7% by weight (the larger the number in parentheses, the more preferable). The lower limit of the weight percentage of the monomer (B) is preferably (1) 0.01% by weight, (2) 0.1% by weight, (3) 0.3% by weight, (4) 0.5% by weight, and (5) 1% by weight (the larger the number in parentheses, the more preferable).
本発明の粒子において、内包物に含まれる潤滑剤は粒子から放出されることで、摺動性を付与することができる成分である。
潤滑剤としては、例えば、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイル、変性シリコーンオイル等のシリコーン系オイル；フルオロエチレン、３フッ素塩化エチレン、パーフルオロポリエーテル、パーフルオロポリアルキルエーテル等のフッ素系オイル；ジブチルセバケート、ジ（２－エチルヘキシル）セバケート、ジオクチルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、ジイソトリデシルアジペート、ジトリデシルグルタレート、メチルアセチルリシノレート等のジエステルオイル、トリオクチルトリメリテート、トリデシルトリメリテート、テトラオクチルピロメリテート、トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール－２－エチルヘキサノエート、ペンタエリスリトールペラルゴネート、一塩基酸及び二塩基酸の混合脂肪酸と多価アルコールとのオリゴエステルであるコンプレックスエステルオイル等のエステル系オイル；ノルマルパラフィン、イソパラフィン、ポリブテン、ポリイソブチレン、１－デセンオリゴマー、１－デセンとエチレンとのコオリゴマー、モノアルキルベンゼン、ジアルキルベンゼン、ポリアルキルベンゼン、モノアルキルナフタレン、ジアルキルナフタレン、ポリアルキルナフタレン等の炭化水素系オイル；ポリエチレングリコール、ポリプロピレングリコール、ポリエチレングリコールモノエーテル、ポリプロピレングリコールモノエーテル、モノアルキルトリフェニルエーテル、アルキルジフェニルエーテル、ジアルキルジフェニルエーテル、テトラフェニルエーテル、ペンタフェニルエーテル、モノアルキルテトラフェニルエーテル、ジアルキルテトラフェニルエーテル等のエーテル系オイル；グラファイト；二硫化モリブデン（ＭｏＳ２）；二硫化タングステン（ＷＳ２）；窒化ホウ素（ＢＮ）；ポリテトラフルオロエチレン等が挙げられる。
また潤滑剤としては、上記オイルと増ちょう剤を含んだグリースを用いてもよい。増ちょう剤は、例えば、石鹸、ウレア、ナトリウムテレフタラート、有機ベントナイト、シリカゲル等の一般的なものが挙げられる。上記潤滑剤は、1種または２種以上を併用してもよい。
In the particles of the present invention, the lubricant contained in the inclusions is a component that can impart sliding properties when released from the particles.
Examples of the lubricant include silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, and modified silicone oil; fluorine oils such as fluoroethylene, trifluoroethylene chloride, perfluoropolyether, and perfluoropolyalkyl ether; diester oils such as dibutyl sebacate, di(2-ethylhexyl) sebacate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate, diisotridecyl adipate, ditridecyl glutarate, and methyl acetyl ricinoleate; trioctyl trimellitate, tridecyl trimellitate, tetraoctyl pyromellitate, trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, monobasic acids, and dibasic acids. ester-based oils such as complex ester oils which are oligoesters of mixed fatty acids and polyhydric alcohols; hydrocarbon-based oils such as normal paraffin, isoparaffin, polybutene, polyisobutylene, 1-decene oligomer, 1-decene and ethylene co-oligomer, monoalkylbenzene, dialkylbenzene, polyalkylbenzene, monoalkylnaphthalene, dialkylnaphthalene, and polyalkylnaphthalene; ether-based oils such as polyethylene glycol, polypropylene glycol, polyethylene glycol monoether, polypropylene glycol monoether, monoalkyltriphenyl ether, alkyldiphenyl ether, dialkyldiphenyl ether, tetraphenyl ether, pentaphenyl ether, monoalkyltetraphenyl ether, and dialkyltetraphenyl ether; graphite; molybdenum disulfide (MoS 2 ); tungsten disulfide (WS 2 ); boron nitride (BN); and polytetrafluoroethylene.
As the lubricant, a grease containing the above-mentioned oil and a thickener may be used. Examples of the thickener include common ones such as soap, urea, sodium terephthalate, organic bentonite, and silica gel. The above-mentioned lubricants may be used alone or in combination of two or more kinds.
潤滑剤は、シリコーン系オイル、フッ素系オイル、エステル系オイル、炭化水素系オイル、及びエーテル系オイルから選ばれる少なくとも１種を含むと、摺動性を持続する点で好ましい。
シリコーン系オイル、フッ素系オイル、エステル系オイル、炭化水素系オイル、及びエーテル系オイルから選ばれる少なくとも１種を含む場合、潤滑剤全体に占める重量割合は、特に限定はないが、好ましくは１０重量％以上、より好ましくは２０重量％以上、さらに好ましくは３０重量％以上、特に好ましくは４０重量％以上、最も好ましくは５０重量％以上であり、上限は１００重量％である。
The lubricant preferably contains at least one oil selected from the group consisting of silicone-based oil, fluorine-based oil, ester-based oil, hydrocarbon-based oil, and ether-based oil, in terms of sustaining slidability.
When at least one oil selected from silicone-based oils, fluorine-based oils, ester-based oils, hydrocarbon-based oils, and ether-based oils is contained, the weight percentage of the entire lubricant is not particularly limited, but is preferably 10% by weight or more, more preferably 20% by weight or more, even more preferably 30% by weight or more, particularly preferably 40% by weight or more, and most preferably 50% by weight or more, with the upper limit being 100% by weight.
潤滑剤の２５℃における動粘度は、特に限定はないが、好ましくは１０～１０００００ｍｍ２／ｓである。潤滑剤の動粘度が１０ｍｍ２／ｓ未満であると、潤滑剤が漏出しやすく、長期持続性に劣ることがある。一方、潤滑剤の動粘度が１０００００ｍｍ２／ｓ超であると、粒子から潤滑剤を漏出するために強い外力が必要となり、十分な摺動性が得られないことがある。潤滑剤の動粘度の上限は、（１）５００００ｍｍ２／ｓ、（２）２５０００ｍｍ２／ｓ、（３）１００００ｍｍ２／ｓ、（４）５０００ｍｍ２／ｓの順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。一方、潤滑剤の動粘度の下限は、（１）５０ｍｍ２／ｓ、（２）１００ｍｍ２／ｓ、（３）２００ｍｍ２／ｓ、（４）５００ｍｍ２／ｓ、（５）７００ｍｍ２／ｓ、（６）１０００ｍｍ２／ｓの順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。動粘度の異なる２種類以上の潤滑剤を併用してもよく、併用した際の動粘度が上記範囲であると好ましい。なお潤滑剤の２５℃における動粘度は、例えば、ウベローデ粘度計を用いて測定することができる。 The kinetic viscosity of the lubricant at 25°C is not particularly limited, but is preferably 10 to 100,000 mm 2 /s. If the kinetic viscosity of the lubricant is less than 10 mm 2 /s, the lubricant may leak easily and may not last long. On the other hand, if the kinetic viscosity of the lubricant is more than 100,000 mm 2 /s, a strong external force is required to leak the lubricant from the particles, and sufficient sliding properties may not be obtained. The upper limit of the kinetic viscosity of the lubricant is preferably (1) 50,000 mm 2 /s, (2) 25,000 mm 2 /s, (3) 10,000 mm 2 /s, and (4) 5,000 mm 2 /s (the larger the number in parentheses, the more preferable it is). On the other hand, the lower limit of the kinetic viscosity of the lubricant is preferably in the order of (1) 50 mm 2 /s, (2) 100 mm 2 /s, (3) 200 mm 2 /s, (4) 500 mm 2 /s, (5) 700 mm 2 /s, and (6) 1000 mm 2 /s (the larger the number in parentheses, the more preferable it is). Two or more lubricants with different kinetic viscosities may be used in combination, and it is preferable that the kinetic viscosity when used in combination is within the above range. The kinetic viscosity of the lubricant at 25°C can be measured, for example, using an Ubbelohde viscometer.
本発明の粒子は、内包物として、潤滑剤以外に、加熱することで気化する成分（以下、気化成分ということがある）を含むと、粒子が加熱により膨張する性質（熱膨張性）を有し、加熱による膨張により粒子の外殻の厚みを調整できる点で好ましい。また粒子が加熱により膨張する性質を利用し、成形体を軽量化できたり、成形体に柔軟性を付与することができ、好ましい。
加熱することで気化する成分としては、例えば、プロパン、（イソ）ブタン、（イソ）ペンタン、（イソ）ヘキサン、（イソ）ヘプタン、（イソ）オクタン等の炭化水素；塩化メチル、塩化メチレン、クロロホルム、四塩化炭素等の炭化水素のハロゲン化物；アゾジカルボンアミド、Ｎ，Ｎ’－ジニトロソペンタメチレンテトラミン、４，４’－オキシビス（ベンゼンスルホニルヒドラジド）等の加熱により熱分解してガスを生成する化合物等が挙げられる。
The particle of the present invention is preferable in that, when it contains, other than lubricant, a component that evaporates when heated (hereinafter, sometimes referred to as vaporizing component), the particle has the property of expanding when heated (thermal expansion), and the thickness of the shell of the particle can be adjusted by the expansion caused by heating.In addition, by utilizing the property of the particle that expands when heated, the molded body can be made lighter and the molded body can be given flexibility, which is preferable.
Examples of components that vaporize when heated include hydrocarbons such as propane, (iso)butane, (iso)pentane, (iso)hexane, (iso)heptane, and (iso)octane; hydrocarbon halides such as methyl chloride, methylene chloride, chloroform, and carbon tetrachloride; and compounds that decompose thermally when heated to generate gas, such as azodicarbonamide, N,N'-dinitrosopentamethylenetetramine, and 4,4'-oxybis(benzenesulfonylhydrazide).
気化成分が沸点を有する場合、気化成分の沸点は、特に限定はないが、好ましくは－３０～３００℃である。気化成分の沸点が上記範囲であると、粒子の外殻の厚みを効率的に調整することができる傾向がある。気化成分の沸点の上限は、（１）２７０℃、（２）２００℃、（３）１５０℃、（４）１３０℃、（５）１１０℃、（６）１００℃、の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。一方、気化成分の沸点の下限は、（１）－１５℃、（２）－５℃、（３）０℃、（４）５℃の順で好ましい（括弧内の数字が大きくなるにつれ好ましい） When the vaporized component has a boiling point, the boiling point of the vaporized component is not particularly limited, but is preferably -30 to 300°C. When the boiling point of the vaporized component is in the above range, the thickness of the outer shell of the particle tends to be efficiently adjusted. The upper limit of the boiling point of the vaporized component is preferably (1) 270°C, (2) 200°C, (3) 150°C, (4) 130°C, (5) 110°C, (6) 100°C (the larger the number in parentheses, the more preferable). On the other hand, the lower limit of the boiling point of the vaporized component is preferably (1) -15°C, (2) -5°C, (3) 0°C, (4) 5°C (the larger the number in parentheses, the more preferable).
粒子全体に占める内包物の重量割合（以下、単に内包物の内包率ということもある）は、特に限定はないが、好ましくは５～８０重量％である。内包物の内包率が５重量％未満であると、十分な摺動性を付与できないことがある。一方、内包物の内包率が８０重量％超であると、摺動性の長期持続性が劣ることがある。内包率の上限は、（１）７０重量％、（２）６０重量％、（３）５５重量％、（４）５０重量％、（５）４５重量％、（６）４０重量％の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。一方、内包率の下限は、（１）１０重量％、（２）１３重量％、（３）１５重量％、（４）１８重量％、（５）２０重量％の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。なお本発明の粒子に占める内包物の重量割合は、実施例に記載の方法で測定されたものを意味する。 The weight ratio of the inclusions to the entire particle (hereinafter, sometimes simply referred to as the inclusion ratio of the inclusions) is not particularly limited, but is preferably 5 to 80% by weight. If the inclusion ratio is less than 5% by weight, sufficient sliding properties may not be imparted. On the other hand, if the inclusion ratio is more than 80% by weight, the long-term durability of the sliding properties may be poor. The upper limit of the inclusion ratio is preferably (1) 70% by weight, (2) 60% by weight, (3) 55% by weight, (4) 50% by weight, (5) 45% by weight, and (6) 40% by weight (the larger the number in parentheses, the more preferable). On the other hand, the lower limit of the inclusion ratio is preferably (1) 10% by weight, (2) 13% by weight, (3) 15% by weight, (4) 18% by weight, and (5) 20% by weight (the larger the number in parentheses, the more preferable). The weight ratio of the inclusions to the particles of the present invention means that measured by the method described in the Examples.
内包物に占める潤滑剤の重量割合は、特に限定はないが、好ましくは２０～１００重量％である。内包物に占める潤滑剤の重量割合が２０重量％未満であると、十分な摺動性を付与できないことがある。内包物に占める潤滑剤の重量割合の下限は、（１）３０重量％、（２）４０重量％、（３）５０重量％の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。一方、内包物に占める潤滑剤の重量割合の上限は、（１）９９重量％、（２）９７量％、（３）９５重量％、（４）９３重量％、（５）９０重量％の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。 The weight percentage of the lubricant in the inclusions is not particularly limited, but is preferably 20 to 100% by weight. If the weight percentage of the lubricant in the inclusions is less than 20% by weight, sufficient sliding properties may not be imparted. The lower limit of the weight percentage of the lubricant in the inclusions is preferably (1) 30% by weight, (2) 40% by weight, and (3) 50% by weight (the larger the number in parentheses, the more preferable). On the other hand, the upper limit of the weight percentage of the lubricant in the inclusions is preferably (1) 99% by weight, (2) 97% by weight, (3) 95% by weight, (4) 93% by weight, and (5) 90% by weight (the larger the number in parentheses, the more preferable).
内包物に占める気化成分の重量割合は、特に限定はないが、好ましくは０～８０重量％である。内包物に占める気化成分の重量割合が８０重量％超であると、十分な摺動性を付与できないことがある。内包物に占める気化成分の重量割合の上限は、（１）７０重量％、（２）６０重量％、（３）５０重量％の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。一方、内包物に占める気化成分の重量割合の下限は、（１）１重量％、（２）３重量％、（３）５重量％、（４）７重量％、（５）１０重量％の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。 The weight percentage of the vaporized component in the inclusion is not particularly limited, but is preferably 0 to 80% by weight. If the weight percentage of the vaporized component in the inclusion exceeds 80% by weight, sufficient sliding properties may not be imparted. The upper limit of the weight percentage of the vaporized component in the inclusion is preferably (1) 70% by weight, (2) 60% by weight, and (3) 50% by weight (the larger the number in parentheses, the more preferable). On the other hand, the lower limit of the weight percentage of the vaporized component in the inclusion is preferably (1) 1% by weight, (2) 3% by weight, (3) 5% by weight, (4) 7% by weight, and (5) 10% by weight (the larger the number in parentheses, the more preferable).
本発明の粒子は、加熱により膨張させてなる粒子でもよい。
粒子の真比重は、特に限定はないが、好ましくは０．０２～２．０ｇ／ｃｍ３である。真比重が０．０２ｇ／ｃｍ３未満であると、粒子の強度が十分ではなく、摺動性の長期持続性が劣ることがある。一方２．０ｇ／ｃｍ３超であると、粒子を配合した成形体の比重が大きくなることがある。粒子の真比重の上限は、（１）１．７０ｇ／ｃｍ３、（２）１．６５ｇ／ｃｍ３、（３）１．５０ｇ／ｃｍ３、（４）１．４５ｇ／ｃｍ３、（５）１．３０ｇ／ｃｍ３、（６）１．２５ｇ／ｃｍ３の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。一方、粒子の真比重の下限は、（１）０．０３０ｇ／ｃｍ３、（２）０．０４５ｇ／ｃｍ３、（３）０．０６０ｇ／ｃｍ３、（４）０．１０ｇ／ｃｍ３、（５）０．１５ｇ／ｃｍ３、（６）０．２０ｇ／ｃｍ３の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。
The particles of the present invention may be particles expanded by heating.
The true density of the particles is not particularly limited, but is preferably 0.02 to 2.0 g/cm 3. If the true density is less than 0.02 g/cm 3 , the strength of the particles may be insufficient, and the long-term durability of the sliding properties may be poor. On the other hand, if it exceeds 2.0 g/cm 3 , the specific gravity of a molded body containing the particles may be high. The upper limit of the true density of the particles is preferably in the following order (1) 1.70 g/cm 3 , (2) 1.65 g/cm 3 , (3) 1.50 g/cm 3 , (4) 1.45 g/cm 3 , (5) 1.30 g/cm 3 , and (6) 1.25 g/cm 3 (the larger the number in parentheses, the more preferable it is). On the other hand, the lower limit of the true specific gravity of the particles is preferably in the order of (1) 0.030 g/cm 3 , (2) 0.045 g/cm 3 , (3) 0.060 g/cm 3 , (4) 0.10 g/cm 3 , (5) 0.15 g/cm 3 , and (6) 0.20 g/cm 3 (the larger the number in parentheses, the more preferable it is).
本発明の粒子の平均粒子径は、特に限定はないが、好ましくは０．１～２００μｍである。粒子の平均粒子径が０．１μｍ未満であると、十分な摺動性を付与できないことがある。一方、粒子の平均粒子径が２００μｍ超であると、摺動性の長期持続性が劣ることがある。粒子の平均粒子径の上限は、（１）１５０μｍ、（２）１２０μｍ、（３）１００μｍ、（４）７５μｍ、（５）６０μｍ、（６）５０μｍ、（７）４５μｍの順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。一方、粒子の平均粒子径の下限は、（１）０．５μｍ、（２）１μｍ、（３）３μｍ、（４）５μｍ、（５）１０μｍの順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。なお本発明の粒子の平均粒子径は、実施例に記載の方法で測定されたものを意味する。 The average particle size of the particles of the present invention is not particularly limited, but is preferably 0.1 to 200 μm. If the average particle size of the particles is less than 0.1 μm, sufficient sliding properties may not be imparted. On the other hand, if the average particle size of the particles is more than 200 μm, the long-term durability of the sliding properties may be poor. The upper limit of the average particle size of the particles is preferably (1) 150 μm, (2) 120 μm, (3) 100 μm, (4) 75 μm, (5) 60 μm, (6) 50 μm, and (7) 45 μm (the larger the number in parentheses, the more preferable). On the other hand, the lower limit of the average particle size of the particles is preferably (1) 0.5 μm, (2) 1 μm, (3) 3 μm, (4) 5 μm, and (5) 10 μm (the larger the number in parentheses, the more preferable). The average particle size of the particles of the present invention means the one measured by the method described in the examples.
本発明の粒子の内径（ｄ１）と外径（ｄ２）の比（ｄ１／ｄ２）は、特に限定はないが、好ましくは０．０５～０．９９９である。粒子のｄ１／ｄ２が０．０５未満であると、十分な摺動性を付与できないことがあり、ｄ１／ｄ２が０．９９９超であると、粒子が潰れやすく、摺動性の長期持続性が劣ることがある。ｄ１／ｄ２の上限は、（１）０．９９５（２）０．９９０、（３）０．９５、（４）０．９０、（５）０．８５、（６）０．８０の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。一方、ｄ１／ｄ２の下限は、（１）０．１０、（２）０．２０、（３）０．３０、（４）０．４０、（５）０．４５の順で好ましい（括弧内の数字が大きくなるにつれ好ましい）。なお本発明の粒子のｄ１／ｄ２は、実施例に記載の方法で測定されたものを意味する。 The ratio (d1/d2) of the inner diameter (d1) to the outer diameter (d2) of the particles of the present invention is not particularly limited, but is preferably 0.05 to 0.999. If the d1/d2 of the particles is less than 0.05, sufficient sliding properties may not be imparted, and if the d1/d2 is more than 0.999, the particles may be easily crushed and the long-term durability of the sliding properties may be poor. The upper limit of d1/d2 is preferably (1) 0.995, (2) 0.990, (3) 0.95, (4) 0.90, (5) 0.85, and (6) 0.80 (the larger the number in parentheses, the more preferable). On the other hand, the lower limit of d1/d2 is preferably (1) 0.10, (2) 0.20, (3) 0.30, (4) 0.40, and (5) 0.45 (the larger the number in parentheses, the more preferable). The d1/d2 of the particles of the present invention is measured using the method described in the Examples.
〔粒子の製造方法〕
本発明の粒子について、その製造方法は特に限定はないが、水性分散媒中に、重合性炭素－炭素二重結合を１つ有する単量体である単量体（Ａ）と重合性炭素－炭素二重結合を少なくとも２つ有する単量体である単量体（Ｂ）を含む重合性成分と、潤滑剤とを分散させて、重合性成分を重合させる工程（重合工程）を含む方法であると、好ましい。重合工程は水性分散媒中に重合性成分と潤滑剤を含む油性混合物を分散させ、重合性成分を重合させる工程であり、油性混合物は、重合性成分と潤滑剤以外に、気化成分を含んでいてもよい。
[Method of producing particles]
The method for producing the particles of the present invention is not particularly limited, but is preferably a method including a step (polymerization step) of dispersing a polymerizable component including a monomer (A) having one polymerizable carbon-carbon double bond and a monomer (B) having at least two polymerizable carbon-carbon double bonds in an aqueous dispersion medium, and polymerizing the polymerizable component. The polymerization step is a step of dispersing an oily mixture including a polymerizable component and a lubricant in an aqueous dispersion medium, and polymerizing the polymerizable component, and the oily mixture may include a vaporizing component in addition to the polymerizable component and the lubricant.
重合工程では、重合性成分を重合開始剤の存在下で重合させることが好ましい。重合開始剤は、油性混合物に含まれるとよい。
重合開始剤としては、例えば、パーオキシジカーボネート、パーオキシエステル、ジアシルパーオキサイド等の過酸化物；アゾニトリル、アゾエステル、アゾアミド、アゾアルキル、高分子アゾ開始剤等のアゾ化合物；レドックス開始剤等を挙げることができる。これらの重合開始剤は、１種または２種以上を併用してもよい。なお重合開始剤としては、重合性成分に対して可溶な油溶性の重合開始剤が好ましい。
使用する重合開始剤の量は、特に限定はないが、重合性成分１００重量部に対して、好ましく０．０５～１０重量部、より好ましくは０．１～８重量部、さらに好ましくは０．２～５重量部である。
In the polymerization step, the polymerizable components are preferably polymerized in the presence of a polymerization initiator. The polymerization initiator may be contained in the oil mixture.
Examples of the polymerization initiator include peroxides such as peroxydicarbonate, peroxyester, and diacyl peroxide; azo compounds such as azonitrile, azoester, azoamide, azoalkyl, and polymeric azo initiator; and redox initiators. These polymerization initiators may be used alone or in combination of two or more. The polymerization initiator is preferably an oil-soluble polymerization initiator that is soluble in the polymerizable component.
The amount of the polymerization initiator used is not particularly limited, but is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, and even more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymerizable component.
水性分散媒は、例えば、水（イオン交換水）に、必要に応じて、分散安定剤、分散安定補助剤、重合助剤、電解質等を配合して調製される。
本発明の粒子について、その製造方法としては、液滴を安定させ、粒子径を制御するために、分散安定剤を添加することが好ましい。分散安定剤としては、特に限定はないが、有機系分散安定剤及び／又は無機系分散安定剤であると好ましい。
有機系分散安定剤としては、例えば、微粒子安定剤や水溶性高分子、ナノセルロース等が挙げられる。微粒子安定剤としては、例えば、ピッカリングエマルションに用いられているものが挙げられる。水溶性高分子としては、例えば、ポリビニルアルコール、メチルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース、ポリアクリル酸等が挙げられる。
無機系分散安定剤としては、例えば、粘土鉱物、第三リン酸カルシウム、複分解生成法により得られるピロリン酸マグネシウム、ピロリン酸カルシウムや、コロイダルシリカ、アルミナゾル、水酸化マグネシウム等の無機化合物が挙げられる。
これらの分散安定剤は、１種または２種以上を併用してもよい。使用する分散安定剤の量は、油性混合物１００重量部に対して、好ましくは０．０５～１００重量部、さらに好ましくは０．２～７０重量部である。
The aqueous dispersion medium is prepared, for example, by mixing water (ion-exchanged water) with a dispersion stabilizer, a dispersion stabilization assistant, a polymerization aid, an electrolyte, etc., as necessary.
In the method for producing the particles of the present invention, it is preferable to add a dispersion stabilizer in order to stabilize the droplets and control the particle size. The dispersion stabilizer is not particularly limited, but is preferably an organic dispersion stabilizer and/or an inorganic dispersion stabilizer.
Examples of organic dispersion stabilizers include particulate stabilizers, water-soluble polymers, nanocellulose, etc. Examples of particulate stabilizers include those used in Pickering emulsions. Examples of water-soluble polymers include polyvinyl alcohol, methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, polyacrylic acid, etc.
Examples of inorganic dispersion stabilizers include clay minerals, tricalcium phosphate, magnesium pyrophosphate obtained by a double decomposition method, calcium pyrophosphate, colloidal silica, alumina sol, magnesium hydroxide, and other inorganic compounds.
These dispersion stabilizers may be used alone or in combination of two or more. The amount of the dispersion stabilizer used is preferably 0.05 to 100 parts by weight, more preferably 0.2 to 70 parts by weight, based on 100 parts by weight of the oil mixture.
液滴の安定性および粒子径の制御のために、さらに分散安定補助剤を併用してもよい。分散安定補助剤としては、高分子タイプの分散安定補助剤、カチオン性界面活性剤、アニオン性界面活性剤、両性イオン界面活性剤、ノニオン性界面活性剤等の界面活性剤を挙げることができる。これらの分散安定補助剤は、１種または２種以上を併用してもよい。 A dispersion stabilization assistant may be used in combination to control the stability and particle size of the droplets. Examples of the dispersion stabilization assistant include polymer-type dispersion stabilization assistants, and surfactants such as cationic surfactants, anionic surfactants, zwitterionic surfactants, and nonionic surfactants. These dispersion stabilization assistants may be used alone or in combination of two or more.
水性分散媒は、電解質を含有してもよい。電解質としては、例えば、塩化ナトリウム、塩化マグネシウム、塩化カルシウム、硫酸ナトリウム、硫酸マグネシウム、硫酸アンモニウム、炭酸ナトリウム等が挙げられる。これらの電解質は、１種または２種以上を併用してもよい。
電解質の含有量は、特に限定はないが、水性分散媒１００重量部に対して、好ましくは０．１～５０重量部である。
The aqueous dispersion medium may contain an electrolyte. Examples of the electrolyte include sodium chloride, magnesium chloride, calcium chloride, sodium sulfate, magnesium sulfate, ammonium sulfate, sodium carbonate, etc. These electrolytes may be used alone or in combination of two or more.
The content of the electrolyte is not particularly limited, but is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the aqueous dispersion medium.
水性分散媒は、重合助剤を含有してもよい。重合助剤を含有することで、粒子の凝集や重合反応器内のスケール発生（具体的には、重合性成分の重合において、重合物が粒子の外殻表面に強固に付着することによる凝集体や、重合反応器内壁への重合物の付着）を抑制することができる。
重合助剤としては、例えば、亜硝酸塩、亜硫酸ナトリウム、塩化銅、塩化鉄、重クロム酸塩、塩化第二スズ、ヒドロキノン、エチレンジアミン四酢酸塩、水溶性アスコルビン酸類、水溶性ポリフェノール類、水溶性ビタミンＢ類等が挙げられる。これらの重合助剤は１種または２種以上を併用してもよい。
The aqueous dispersion medium may contain a polymerization aid, which can suppress particle aggregation and scale generation in a polymerization reactor (specifically, aggregation caused by the polymerized product firmly adhering to the outer shell surface of the particles during polymerization of the polymerizable component, and adhesion of the polymerized product to the inner wall of the polymerization reactor).
Examples of the polymerization aid include nitrite, sodium sulfite, copper chloride, iron chloride, dichromate, stannic chloride, hydroquinone, ethylenediaminetetraacetate, water-soluble ascorbic acids, water-soluble polyphenols, water-soluble vitamin B, etc. These polymerization aids may be used alone or in combination of two or more.
重合工程では、所定粒子径の球状油滴が調製されるように油性混合物を水性分散媒中に分散させる。油性混合物を分散させる方法としては、例えば、ホモミキサー（例えば、プライミクス社製）等により攪拌する方法や、スタティックミキサー（例えば、株式会社ノリタケエンジニアリング社製）等の静止型分散装置を用いる方法、膜懸濁法、超音波分散法等の一般的な分散方法を挙げることができる。
次いで、油性混合物が球状油滴として水性分散媒に分散された分散液を加熱することにより、重合を行う。重合反応中は、分散液を攪拌するのが好ましく、その攪拌は、例えば、油性混合物や重合後の粒子の浮上や沈降を防止できる程度に緩く行えばよい。
In the polymerization step, the oil mixture is dispersed in the aqueous dispersion medium so as to prepare spherical oil droplets of a predetermined particle size. Examples of the method for dispersing the oil mixture include a method of stirring with a homomixer (e.g., manufactured by Primix Corporation), a method using a static type dispersion device such as a static mixer (e.g., manufactured by Noritake Engineering Co., Ltd.), a membrane suspension method, an ultrasonic dispersion method, and other general dispersion methods.
Next, the dispersion in which the oily mixture is dispersed in the aqueous dispersion medium as spherical oil droplets is heated to polymerize. During the polymerization reaction, it is preferable to stir the dispersion, and the stirring may be performed, for example, gently enough to prevent the oily mixture or the particles after polymerization from floating up or sinking.
重合温度は、重合開始剤の種類によって自由に設定されるが、好ましくは３０～１００℃、より好ましくは４０～９０℃の範囲で制御されるとよい。反応温度を保持する時間は、１～２０時間程度が好ましい。重合初期圧力については、特に限定はないが、ゲージ圧で好ましくは０～５ＭＰａ、より好ましくは０．０２～３ＭＰａの範囲であるとよい。 The polymerization temperature can be freely set depending on the type of polymerization initiator, but is preferably controlled within the range of 30 to 100°C, and more preferably 40 to 90°C. The reaction temperature is preferably maintained for about 1 to 20 hours. There are no particular limitations on the initial polymerization pressure, but it is preferably in the range of 0 to 5 MPa, and more preferably 0.02 to 3 MPa, in terms of gauge pressure.
本発明の粒子は、スラリーの状態でもよく、湿粉の状態でもよく、乾燥した粉末の状態でもよい。本発明の粒子が湿粉の状態のものである場合、例えば、上記製造方法によって得られた粒子を含有するスラリーを遠心分離機、加圧プレス機、真空脱水機等を用いて脱水し、得ることができる。このような湿粉の含水率は、特に限定はないが、通常１０～５０重量％、好ましくは１５～４５重量％、より好ましくは２０～４０重量％である。
また、上記で得られた湿粉を、棚型乾燥機、間接加熱乾燥機、流動乾燥機、真空乾燥機、振動乾燥機、気流乾燥機等により乾燥し、乾燥粉末とすることができる。また、スラリーを噴霧乾燥機、流動乾燥機等により乾燥し、乾燥した粉末を得てもよい。
The particles of the present invention may be in the form of a slurry, a wet powder, or a dry powder. When the particles of the present invention are in the form of a wet powder, they can be obtained, for example, by dehydrating the slurry containing the particles obtained by the above-mentioned production method using a centrifuge, a pressure press, a vacuum dehydrator, or the like. The moisture content of such wet powder is not particularly limited, but is usually 10 to 50% by weight, preferably 15 to 45% by weight, and more preferably 20 to 40% by weight.
The wet powder obtained above can be dried to a dry powder using a tray dryer, an indirect heating dryer, a fluidized bed dryer, a vacuum dryer, a vibration dryer, an airflow dryer, etc. The slurry can also be dried to a dry powder using a spray dryer, a fluidized bed dryer, etc.
本発明の粒子について、その製造方法は上記で説明した方法以外にも、例えば、界面重合法、逆相乳化法、乳化重合法等が挙げられる。また水性分散媒中で液滴を作製しない方法として、例えば、液中乾燥法、コアセルベーション法、噴霧乾燥法、乾式混合法等で製造することも可能であると考えられる。 In addition to the above-described methods, the particles of the present invention can also be produced by other methods, such as interfacial polymerization, reverse phase emulsification, and emulsion polymerization. It is also possible to produce the particles by methods that do not produce droplets in an aqueous dispersion medium, such as submerged drying, coacervation, spray drying, and dry mixing.
〔組成物〕
本発明の組成物は、上記粒子と基材成分を含むものであり、摺動性を有し、摺動性が長期間持続し、且つ優れた外観を有する成形体を得ることができる。
基材成分としては、例えば、天然ゴム、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン－ブタジエンゴム（ＳＢＲ）、クロロプレンゴム（ＣＲ）、ニトリルゴム（ＮＢＲ）、ブチルゴム、シリコンゴム、アクリルゴム、ウレタンゴム、フッ素ゴム、ポリエーテルゴム、エチレン－プロピレンゴム（ＥＰＭ）、エチレン－プロピレン－ジエンゴム（ＥＰＤＭ）等のゴム類；エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ポリウレタン、ポリイミド、ポリアミドイミド等の熱硬化性樹脂；ポリエチレンワックス、パラフィンワックス等のワックス類；エチレン－酢酸ビニル共重合体（ＥＶＡ）、ポリエチレン（ＰＥ）、変性ポリエチレン、ポリプロピレン（ＰＰ）、変性ポリプロピレン、変性ポリオレフィン、ポリ塩化ビニル（ＰＶＣ）、アクリル樹脂、熱可塑性ポリウレタン、アクリロニトリル－スチレン共重合体（ＡＳ樹脂）、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）、ポリスチレン（ＰＳ）、（メタ）アクリレート・スチレン共重合体、ポリアミド樹脂（ナイロン６、ナイロン６６等）、変性ポリアミド、ポリカーボネート、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリアセタール（ＰＯＭ）、ポリフェニレンサルファイド（ＰＰＳ）、ポリフェニレンエーテル（ＰＰＥ）、変性ポリフェニレンエーテル、フッ素樹脂等の熱可塑性樹脂；エチレン系アイオノマー、ウレタン系アイオノマー、スチレン系アイオノマー、フッ素系アイオノマー等のアイオノマー樹脂；オレフィン系エラストマー、スチレン系エラストマー、ウレタン系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、フッ素系エラストマー等の熱可塑性エラストマー；ポリ乳酸（ＰＬＡ）、酢酸セルロース、ＰＢＳ、ＰＨＡ、澱粉樹脂等のバイオプラスチック等が挙げられる。これらの基材成分は、１または２種以上を併用してもよい。
本発明の組成物は、粒子と基材成分以外に、用途に応じて、難燃剤、酸化防止剤、紫外線吸収剤、安定剤、充填剤、可塑剤、顔料、帯電防止剤等の添加剤、溶剤、潤滑剤、本発明の粒子以外の粒子、有機粉末、無機粉末等を含んでいてもよい。
〔Composition〕
The composition of the present invention contains the above-mentioned particles and a base component, and can give a molded article that has sliding properties, maintains the sliding properties for a long period of time, and has an excellent appearance.
Examples of the base material component include rubbers such as natural rubber, isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), butyl rubber, silicone rubber, acrylic rubber, urethane rubber, fluororubber, polyether rubber, ethylene-propylene rubber (EPM), and ethylene-propylene-diene rubber (EPDM); thermosetting resins such as epoxy resins, phenolic resins, unsaturated polyester resins, polyurethanes, polyimides, and polyamideimides; waxes such as polyethylene wax and paraffin wax; ethylene-vinyl acetate copolymers (EVA), polyethylene (PE), modified polyethylene, polypropylene (PP), modified polypropylene, modified polyolefins, polyvinyl chloride (PVC), acrylic resins, thermoplastic polyurethanes, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene rubbers, and the like. Examples of the base material include thermoplastic resins such as styrene-styrene copolymers (ABS resins), polystyrene (PS), (meth)acrylate-styrene copolymers, polyamide resins (nylon 6, nylon 66, etc.), modified polyamides, polycarbonates, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetal (POM), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified polyphenylene ether, and fluororesins; ionomer resins such as ethylene-based ionomers, urethane-based ionomers, styrene-based ionomers, and fluorine-based ionomers; thermoplastic elastomers such as olefin-based elastomers, styrene-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and fluorine-based elastomers; and bioplastics such as polylactic acid (PLA), cellulose acetate, PBS, PHA, and starch resins. These base material components may be used alone or in combination of two or more kinds.
In addition to the particles and base material components, the composition of the present invention may contain additives such as flame retardants, antioxidants, UV absorbers, stabilizers, fillers, plasticizers, pigments, and antistatic agents, solvents, lubricants, particles other than the particles of the present invention, organic powders, inorganic powders, and the like, depending on the application.
本発明の組成物に含まれる粒子の量は、特に限定はないが、基材成分１００重量部に対して、好ましくは０．１～４００重量部である。粒子の含有量の下限は、より好ましくは０．３重量部、さらに好ましくは０．５重量部、特に好ましくは１重量部である。粒子の含有量の上限は、より好ましくは２５０重量部、さらに好ましくは１５０重量部、特に好ましくは１００重量部である。粒子の含有量が上記範囲内であると、十分な摺動性を有し、摺動性の長期持続性に優れる成形体を得ることができるため好ましい。 The amount of particles contained in the composition of the present invention is not particularly limited, but is preferably 0.1 to 400 parts by weight relative to 100 parts by weight of the base component. The lower limit of the particle content is more preferably 0.3 parts by weight, even more preferably 0.5 parts by weight, and particularly preferably 1 part by weight. The upper limit of the particle content is more preferably 250 parts by weight, even more preferably 150 parts by weight, and particularly preferably 100 parts by weight. It is preferable that the particle content is within the above range, since it is possible to obtain a molded product that has sufficient sliding properties and excellent long-term durability of sliding properties.
本発明の組成物は、粒子と基材成分および必要に応じて各種添加剤を混合することで得られる。また、粒子と基材成分を含む組成物を作成した後、さらに基材成分と混合して組成物とすることもできる。粒子と比較的融点の低い基材成分を含む組成物を作成した後、さらに基材成分と混合して組成物とすることで、粒子の分散性に優れ、好ましい。比較的低い融点としては、特に限定はないが、好ましくは５０～２００℃、より好ましくは５０～１７０℃、さらに好ましくは５０～１４０℃、特に好ましくは５０～１１０℃、最も好ましくは５０～８０℃である。
混合方法は、例えば、混合攪拌機、ミキサー、ヘンシェルミキサー、スーパーミキサー、リボンミキサー、リボンブレンダー、ニーダー、ロール、ミキシングロール、単軸混練機、二軸混練機、多軸混練機等により混合することができる。
The composition of the present invention can be obtained by mixing particles, a base component, and various additives as necessary. In addition, after preparing a composition containing particles and a base component, it can be further mixed with the base component to form a composition. After preparing a composition containing particles and a base component having a relatively low melting point, it is preferable to further mix the base component to form a composition, which has excellent particle dispersibility. There is no particular limit to the relatively low melting point, but it is preferably 50 to 200°C, more preferably 50 to 170°C, even more preferably 50 to 140°C, particularly preferably 50 to 110°C, and most preferably 50 to 80°C.
The mixing method may include, for example, mixing with a mixer, mixer, Henschel mixer, super mixer, ribbon mixer, ribbon blender, kneader, roll, mixing roll, single-shaft kneader, twin-shaft kneader, multi-shaft kneader, etc.
本発明の成形体は、上記組成物を成形してなるものである。
成形方法としては、熱可塑性樹脂と熱硬化性樹脂の違いにより、押出成形法、射出成形法、真空成形法、ブロー成形法、圧縮成形法、トランスファー成形法、ＲＩＭ成形、注型成形法、等の、広く一般的に用いられている成形方法を採用することができる。
本発明の成形体に含まれる前記粒子の量は、特に限定はないが、基材成分１００重量部に対して、好ましくは０．１～２０重量部、より好ましくは０．３～１５重量部、さらに好ましくは０．５～１０重量部、特に好ましくは１～８重量部である。
本発明の成形体は、優れた摺動性を有するため、自動車分野、建材分野、ＯＡ機器分野、家電、電子機器分野等の様々な部材として、工業的に広く利用することができる。中でも、車両用シール材や建築用シール材として好適に用いることができる。
The molded article of the present invention is obtained by molding the above composition.
As the molding method, depending on the difference between thermoplastic resin and thermosetting resin, a molding method that is widely and commonly used, such as extrusion molding, injection molding, vacuum molding, blow molding, compression molding, transfer molding, RIM molding, cast molding, etc., can be used.
The amount of the particles contained in the molded product of the present invention is not particularly limited, but is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 15 parts by weight, even more preferably 0.5 to 10 parts by weight, and particularly preferably 1 to 8 parts by weight, relative to 100 parts by weight of the base component.
Since the molded article of the present invention has excellent sliding properties, it can be widely used industrially as various members in the fields of automobiles, building materials, office automation equipment, home appliances, electronic devices, etc. In particular, it can be suitably used as a sealing material for vehicles and a sealing material for construction.
以下に、本発明の粒子の実施例について、具体的に説明する。なお本発明はこれらの実施例に限定されるものではない。実施例及び比較例における物性の測定方法、評価項目と評価方法は以下に示す通りである。以下では、「％」および「部」は、それぞれ「重量％」および「重量部」ということがある。 Below, examples of the particles of the present invention are specifically described. Note that the present invention is not limited to these examples. The measurement methods of physical properties, evaluation items and evaluation methods in the examples and comparative examples are as follows. In the following, "%" and "parts" may be referred to as "% by weight" and "parts by weight", respectively.
＜粒子の平均粒子径＞
レーザー回折散乱式粒度分析計（Ｍｉｃｒｏｔｒａｃ ＡＳＶＲ、日機装株式会社製）を用いて測定し、体積基準の累積５０％粒子径（Ｄ５０）を平均粒子径とした。
<Average particle size of particles>
The particle size was measured using a laser diffraction scattering particle size analyzer (Microtrac ASVR, manufactured by Nikkiso Co., Ltd.), and the cumulative 50% particle size (D50) on a volume basis was taken as the average particle size.
＜粒子全体に占める内包物の重量割合（内包物の内包率）＞
粒子１．０ｇを直径８０ｍｍ、深さ１５ｍｍのステンレス製蒸発皿に入れ、その重量を測定した（Ｗ１（ｇ））。アセトニトリル３０ｍＬを加え均一に分散させ、２４時間室温で放置した後に、１３０℃で２時間減圧乾燥した。減圧乾燥後の試料をヘキサン３０ｍＬで３回洗浄後、１００℃で１０分乾燥し、その重量）を測定した（Ｗ２（ｇ））。
またカールフィッシャー水分計（ＭＫＡ－５１０Ｎ型、京都電子工業株式会社製）を用いて粒子の含水率を測定し、Ｃｗ（重量％）とした。
上記Ｗ１、Ｗ２、Ｃｗより、粒子における内包物の内包率（Ｃ（重量％））を下記式（１）から算出した。
Ｃ＝１００×［（Ｗ１―Ｗ２）－ＣＷ／１００］／（１．０－ＣＷ／１００） （１）
<Weight ratio of inclusions to the entire particle (inclusion rate)>
1.0 g of particles was placed in a stainless steel evaporating dish with a diameter of 80 mm and a depth of 15 mm, and its weight was measured ( W1 (g)). 30 mL of acetonitrile was added to disperse the particles uniformly, and the particles were left at room temperature for 24 hours, and then dried under reduced pressure at 130°C for 2 hours. After drying under reduced pressure, the sample was washed three times with 30 mL of hexane, and then dried at 100°C for 10 minutes, and its weight was measured ( W2 (g)).
The moisture content of the particles was measured using a Karl Fischer moisture meter (Model MKA-510N, manufactured by Kyoto Electronics Manufacturing Co., Ltd.) and was taken as C w (wt %).
From the above W 1 , W 2 and Cw , the inclusion ratio (C (wt %)) of the particles was calculated according to the following formula (1).
C=100×[(W 1 - W 2 )-C W /100]/(1.0-C W /100) (1)
＜粒子の内径（ｄ１）と外径（ｄ２）との比（ｄ１／ｄ２）＞
上記Ｃより、粒子の内径（ｄ１）と外径（ｄ２）との比（ｄ１／ｄ２）を下記式（２）から算出した。
ｄ１／ｄ２＝（Ｃ／１００）１／３ （２）
<Ratio (d1/d2) of inner diameter (d1) to outer diameter (d2) of particle>
From the above C, the ratio (d1/d2) of the inner diameter (d1) to the outer diameter (d2) of the particle was calculated from the following formula (2).
d1/d2=(C/100) 1/3 (2)
＜粒子の真比重（Ｄ１）＞
イソプロピルアルコールを用いて、浸液式ピクノメータ法により２５℃における粒子の真比重を測定した（Ｄ１）。
<True specific gravity of particles (D 1 )>
The true specific gravity of the particles at 25° C. was measured (D 1 ) by an immersion pycnometer method using isopropyl alcohol.
＜成形体中の粒子の平均粒子径＞
作成した成形体の断面を電子顕微鏡にて粒子が５０個以上画面上に入る倍率で撮影し、画像解析により平均粒子径を求めた。
<Average particle size of particles in molded body>
The cross section of the produced molded article was photographed with an electron microscope at a magnification such that 50 or more particles were included on the screen, and the average particle size was determined by image analysis.
＜成形体中の粒子の真比重＞
作成した成形体中の粒子の真比重については、作成した成形体の比重より換算した（Ｄ２）。なお、成形品比重は測定液にイオン交換水を用い、２５℃でアルキメデス法により測定した。
<True specific gravity of particles in compact>
The true specific gravity of the particles in the produced molded body was calculated from the specific gravity of the produced molded body (D 2 ).The specific gravity of the molded product was measured by Archimedes' method at 25° C. using ion-exchanged water as the measuring liquid.
＜成形体中の粒子の内径（ｄ１）と外径（ｄ２）との比（ｄ１／ｄ２）＞
上記Ｃ、Ｄ１、Ｄ２より、作成した成形体中の粒子の内径（ｄ１）と外径（ｄ２）との比（ｄ１／ｄ２）を下記式（３）から算出した。
ｄ１／ｄ２＝［{（Ｄ１／Ｄ２）－１＋（Ｃ／１００）}／（Ｄ１／Ｄ２）］１／３ （３）
<Ratio (d1/d2) of inner diameter (d1) to outer diameter (d2) of particles in compact>
From the above C, D 1 and D 2 , the ratio (d1/d2) of the inner diameter (d1) to the outer diameter (d2) of the particles in the produced molded body was calculated according to the following formula (3).
d1/d2=[{(D 1 /D 2 )-1+(C/100)}/(D 1 /D 2 )] 1/3 (3)
＜摺動性付与評価＞
製造した粒子３部とミラストマー８０３２ＢＳ（三井化学株式会社製、熱可塑性オレフィン系エラストマー）９７部を混合し、組成物を得た。
次に、ラボプラストミル（２軸押出成形機ＭＥ－２５、東洋精機工業株式会社製）およびＴダイ（リップ幅１５０ｍｍ、厚み０．７ｍｍ）を用いて、押出成形機およびＴダイの設定温度（成形温度）を１８０℃に設定し、スクリュー回転数を５０ｒｐｍに設定した。
得られた組成物をラボプラストミルの原料ホッパーから投入し、成形体であるシートを作成した。作成したシートの動摩擦係数を、摩擦測定器（ＦＲＩＣＴＩＯＮ ＴＥＳＴＥＲ ＴＲ－２、東洋精機工業株式会社製）を用いて測定速度１００ｍｍ／分で測定し、以下の基準より粒子の摺動性付与評価を行った。なお、粒子を含有していないシートの動摩擦係数は０．９２であった。
○○○：動摩擦係数が０．５未満で、摺動性付与効果に優れる。
○○：動摩擦係数が０．５以上０．６５未満で、摺動性付与効果が良い。
○：動摩擦係数が０．６５以上０．８未満で、摺動性付与効果がやや良い。
×：動摩擦係数が０．８以上で、摺動性付与効果に劣る。
<Evaluation of Sliding Property>
3 parts of the produced particles and 97 parts of Milastomer 8032BS (a thermoplastic olefin-based elastomer manufactured by Mitsui Chemicals, Inc.) were mixed to obtain a composition.
Next, using a Labo Plastomill (twin-screw extruder ME-25, manufactured by Toyo Seiki Kogyo Co., Ltd.) and a T-die (lip width 150 mm, thickness 0.7 mm), the set temperatures (molding temperatures) of the extruder and T-die were set to 180°C, and the screw rotation speed was set to 50 rpm.
The obtained composition was charged from the raw material hopper of a Labo Plastomill to prepare a sheet as a molded body. The dynamic friction coefficient of the prepared sheet was measured at a measurement speed of 100 mm/min using a friction tester (FRICTION TESTER TR-2, manufactured by Toyo Seiki Kogyo Co., Ltd.), and the sliding property imparted by the particles was evaluated according to the following criteria. The dynamic friction coefficient of the sheet not containing particles was 0.92.
◯◯◯: The dynamic friction coefficient is less than 0.5, and the effect of imparting sliding properties is excellent.
◯: The dynamic friction coefficient is 0.5 or more and less than 0.65, and the effect of imparting sliding properties is good.
◯: The dynamic friction coefficient is 0.65 or more and less than 0.8, and the effect of imparting sliding properties is somewhat good.
×: The dynamic friction coefficient is 0.8 or more, and the effect of imparting sliding properties is poor.
＜摺動性持続評価１＞
上記摺動性付与評価にて評価したシートの表面を、上記摺動性付与評価にて使用した摩擦測定器にて、測定速度１００ｍｍ／分における動摩擦係数が０．８５～０．９５になるまで乾布で拭取り、４０℃で１ヶ月間保管した。保管後のシートの動摩擦係数を上記摺動性付与評価にて使用した摩擦測定器により、測定速度１００ｍｍ／分で測定し、以下の基準より粒子の摺動性持続評価（摺動性持続評価１）を行った。なお、摺動性持続係数を下記にて算出した。摺動性持続係数は、数値が小さいほど、摺動性持続に優れることを示す。
摺動性持続係数１＝［１ヵ月後の動摩擦係数／初期の動摩擦係数（上記摺動性付与評価時の動摩擦係数）］×１００
○○：摺動性持続係数１が９０未満で、摺動性持続効果に優れる。
○：摺動性持続係数１が９０以上１３０未満で、摺動性持続効果にやや優れる。
△：摺動性持続係数１が１３０以上１８０未満で、摺動性持続効果にやや劣る。
×：摺動性持続係数１が１８０以上で、摺動性持続効果に劣る。
<Sliding property sustained evaluation 1>
The surface of the sheet evaluated in the above evaluation of sliding property imparting was wiped with a dry cloth until the dynamic friction coefficient at a measurement speed of 100 mm/min reached 0.85 to 0.95 using the friction meter used in the above evaluation of sliding property imparting, and then stored at 40° C. for one month. The dynamic friction coefficient of the sheet after storage was measured at a measurement speed of 100 mm/min using the friction meter used in the above evaluation of sliding property imparting, and the sliding property duration of the particles was evaluated (sliding property duration evaluation 1) according to the following criteria. The sliding property duration coefficient was calculated as follows. The smaller the value of the sliding property duration coefficient, the better the sliding property duration.
Slidability durability coefficient 1=[dynamic friction coefficient after 1 month/initial dynamic friction coefficient (dynamic friction coefficient at the time of evaluating the above-mentioned sliding property)]×100
◯: The sliding property durability coefficient 1 is less than 90, and the sliding property durability effect is excellent.
◯: The sliding property durability coefficient 1 is 90 or more and less than 130, and the sliding property durability effect is somewhat excellent.
Δ: The sliding property durability coefficient 1 is 130 or more and less than 180, and the sliding property durability effect is somewhat poor.
×: The sliding property durability coefficient 1 is 180 or more, and the sliding property durability is poor.
＜摺動性持続評価２＞
上記摺動性持続評価１にて評価したシートの表面を、上記摺動性付与評価にて使用した摩擦測定器にて、測定速度１００ｍｍ／分における動摩擦係数が０．８５～０．９５になるまで乾布で拭取り、４０℃で１ヶ月間保管した。保管後のシートの動摩擦係数を上記摺動性付与評価にて使用した摩擦測定器により、測定速度１００ｍｍ／分で測定し、以下の基準より粒子の摺動性持続評価（摺動性持続評価２）を行った。なお、摺動性持続係数を下記にて算出した。摺動性持続係数は、数値が小さいほど、摺動性の長期持続性に優れることを示す。
摺動性持続係数２＝［２ヵ月後の動摩擦係数／初期の動摩擦係数（上記摺動性付与評価時の動摩擦係数）］×１００
○○：摺動性持続係数２が９０未満で、摺動性持続効果に優れる。
○：摺動性持続係数２が９０以上１３０未満で、摺動性持続効果にやや優れる。
△：摺動性持続係数２が１３０以上１８０未満で、摺動性持続効果にやや劣る。
×：摺動性持続係数２が１８０以上で、摺動性持続効果に劣る。
<Sliding property sustained
The surface of the sheet evaluated in the above-mentioned sliding property durability evaluation 1 was wiped with a dry cloth until the dynamic friction coefficient at a measurement speed of 100 mm/min reached 0.85 to 0.95 using the friction meter used in the above-mentioned evaluation of sliding property impartation, and then stored at 40°C for one month. The dynamic friction coefficient of the sheet after storage was measured at a measurement speed of 100 mm/min using the friction meter used in the above-mentioned evaluation of sliding property impartation, and the sliding property durability evaluation of the particles (sliding property durability evaluation 2) was performed according to the following criteria. The sliding property durability coefficient was calculated as follows. The smaller the sliding property durability coefficient value, the better the long-term durability of sliding property.
◯: The sliding
◯: The sliding
Δ: The sliding
×: The sliding
＜粒子の分散性評価＞
作成したシートの状態を目視で確認し、粒子の分散性を以下の基準より評価した。
○：粒子が凝集して視認できる粒子塊が確認されない。
×：粒子が凝集して視認できる粒子塊が多く確認される。
<Evaluation of particle dispersibility>
The state of the prepared sheet was visually inspected, and the dispersibility of the particles was evaluated according to the following criteria.
◯: No visible particle agglomerates due to particle aggregation were observed.
x: Particles are aggregated and many visible particle agglomerates are observed.
＜成形体の外観評価＞
作成したシートを４０℃で２ヶ月保管した。２ヶ月保管後のシート表面を目視で確認し、成形体の外観を以下の基準より評価した。なお、ブランクとは、粒子を含有していないシートである。
○：ブランクの外観と差がなく、外観性に優れる。
△：テカリや液体による濡れが確認され、外観性にやや劣る。
×：白化などの色目の変化が確認され、外観性に劣る。
<Appearance Evaluation of Molded Product>
The prepared sheet was stored for 2 months at 40° C. After the 2-month storage, the surface of the sheet was visually inspected and the appearance of the molded product was evaluated according to the following criteria. Note that a blank sheet is a sheet that does not contain particles.
◯: No difference in appearance from the blank, excellent appearance.
Δ: Shiny or wet with liquid was observed, and the appearance was somewhat poor.
×: A change in color such as whitening was observed, and the appearance was poor.
（実施例１）
メタクリル酸メチル１４０部、ジメタクリル酸エチレングリコール２部、ジラウロリルパーオキサイド１．５部、ジメチルポリシロキサン（シリコーンＫＦ－９６－１００ｃｓ、信越化学工業株式会社製、２５℃における動粘度１００ｍｍ２／ｓ）６３部を混合し、油性混合物を調製した。
これとは別に、イオン交換水５５０部、塩化ナトリウム１１０部、ポリビニルピロリドン０．８部、有効成分２０重量％であるコロイダルシリカ６０部を加え、ｐＨ２～４に調整し、水性分散媒を調製した。
水性分散媒と油性混合物を混合し、得られた混合液をホモミキサーで攪拌し、懸濁液を調製した。この懸濁液を窒素ガスで０．３ＭＰａに加圧した重合容器内で、７０℃で６時間重合させた。
重合後に得られた生成物から粒子をろ過、乾燥して、粒子を製造した。製造した粒子の物性の測定と、粒子の評価を上記に示す方法にて実施した。結果を表１、３に示す。
Example 1
140 parts of methyl methacrylate, 2 parts of ethylene glycol dimethacrylate, 1.5 parts of dilauroyl peroxide, and 63 parts of dimethylpolysiloxane (silicone KF-96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd., kinetic viscosity at 25° C. 100 mm 2 /s) were mixed to prepare an oily mixture.
Separately, 550 parts of ion-exchanged water, 110 parts of sodium chloride, 0.8 parts of polyvinylpyrrolidone, and 60 parts of colloidal silica containing 20% by weight of active ingredient were added and adjusted to pH 2-4 to prepare an aqueous dispersion medium.
The aqueous dispersion medium and the oil mixture were mixed, and the resulting mixture was stirred with a homomixer to prepare a suspension. The suspension was polymerized at 70° C. for 6 hours in a polymerization vessel pressurized to 0.3 MPa with nitrogen gas.
The product obtained after polymerization was filtered and dried to produce particles. The physical properties of the produced particles were measured and the particles were evaluated by the methods described above. The results are shown in Tables 1 and 3.
（実施例２～１３、比較例１、２）
油性混合物を表１～２に示すものに変更すること以外は実施例１と同様にして粒子をそれぞれ製造した。製造した粒子の物性の測定及び評価を実施例１と同様に行った。結果を表１～４に示す。なお、実施例１１にて使用した潤滑剤の２５℃における動粘度は４００ｍｍ２／ｓであった。
(Examples 2 to 13, Comparative Examples 1 and 2)
Particles were produced in the same manner as in Example 1, except that the oil mixture was changed to that shown in Tables 1 and 2. The physical properties of the produced particles were measured and evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 4. The kinetic viscosity of the lubricant used in Example 11 at 25° C. was 400 mm 2 /s.
表１～２に記載の使用原料の略号の詳細を以下に示す。
ＥＤＭＡ：ジメタクリル酸エチレングリコール
ＴＭＰ：トリメチロールプロパントリメタクリレート
１，９ＮＤ－Ａ：１，９－ノナンジオールジアクリレート
ＫＦ－９６－１００ｃｓ：シリコーンＫＦ－９６－１００ｃｓ、ジメチルポリシロキサン、信越化学工業株式会社製、２５℃における動粘度が１００ｍｍ２／ｓ
ＫＦ－９６－１０００ｃｓ：シリコーンＫＦ－９６－１０００ｃｓ、ジメチルポリシロキサン、信越化学工業株式会社製、２５℃における動粘度が１０００ｍｍ２／ｓ
ＫＦ－９６Ｈ－１万ｃｓ：シリコーンＫＦ－９６Ｈ－１万ｃｓ、ジメチルポリシロキサン、信越化学工業株式会社製、２５℃における動粘度が１００００ｍｍ２／ｓ
ＫＦ－９６Ｈ－１０万ｃｓ：シリコーンＫＦ－９６Ｈ－１０万、ジメチルポリシロキサン、信越化学工業株式会社製、２５℃における動粘度が１０００００ｍｍ２／ｓ
フッ素オイル：１，１，２，２－テトラフルオロエチル－２，２，２－トリフルオロエチルエーテル、
エステルオイル：ジイソトリデシルアジペート、２５℃における動粘度が２５０ｍｍ２／ｓ
なお上記略号は以下の記載においても、それぞれの原料を示す。
Details of the abbreviations for the raw materials used in Tables 1 and 2 are shown below.
EDMA: ethylene glycol dimethacrylate TMP: trimethylolpropane trimethacrylate 1,9ND-A: 1,9-nonanediol diacrylate KF-96-100cs: silicone KF-96-100cs, dimethylpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., having a kinetic viscosity of 100 mm 2 /s at 25° C.
KF-96-1000cs: Silicone KF-96-1000cs, dimethylpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., having a kinetic viscosity of 1000 mm 2 /s at 25°C.
KF-96H-10,000cs: Silicone KF-96H-10,000cs, dimethylpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity at 25°C is 10,000mm 2 /s
KF-96H-100,000cs: Silicone KF-96H-100,000, dimethylpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., having a kinetic viscosity of 100,000 mm 2 /s at 25°C.
Fluorine oil: 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether,
Ester oil: diisotridecyl adipate, kinematic viscosity at 25°C of 250 mm2 /s
The above abbreviations also represent the respective raw materials in the following description.
（実施例１４）
ミラストマー８０３２ＢＳを８５部と実施例１で製造した粒子１５部を二軸混練機にて混練し、ペレット状に裁断して、マスターバッチを作成した。次に、ミラストマー８０３２ＢＳを８０部と作成したマスターバッチ２０部を混合し、混合物を得た。得られた混合物を使用して、上記摺動性付与評価に記載された方法と同様にして成形し、シートを作成した。作成したシートの摺動性付与評価、摺動性持続評価１、摺動性持続評価２及び成形体の外観評価と、粒子の分散性評価を実施例１と同様にして行った。結果を表４に示す。
(Example 14)
85 parts of Milastomer 8032BS and 15 parts of the particles produced in Example 1 were kneaded in a twin-screw kneader and cut into pellets to prepare a master batch. Next, 80 parts of Milastomer 8032BS and 20 parts of the prepared master batch were mixed to obtain a mixture. The obtained mixture was molded in the same manner as described in the above-mentioned evaluation of the sliding property to prepare a sheet. The evaluation of the sliding property of the prepared sheet, the evaluation of the sliding property duration 1, the evaluation of the sliding
（比較例３）
ポリエチレン無水マレイン酸３．５ｇをイオン交換水５０ｇに溶解した後、ｐＨを約４に調整し、水性混合液を得た。この水性混合液にジメチルポリシロキサン（ＫＦ－９６－１０００ｃｓ）３５ｇを加え、攪拌し、乳化液を調整した。この乳化液に、ｐＨ１２に調整したメラミン６ｇ、３７％ホルムアルデヒド水溶液１１ｇの混合溶液を添加し、ｐＨを約４に調整した。８０℃で３時間界面重合を実施し、重合後に得られた生成物から粒子をろ過、乾燥して、粒子を製造した。製造した粒子の平均粒子径は８μｍであった。
製造した粒子を使用して、上記摺動性付与評価に記載された方法と同様にして成形し、シートを作成した。作成したシートの摺動性付与評価、摺動性持続評価１、摺動性持続評価２及び成形体の外観評価と、粒子の分散性評価を実施例１と同様にして行った。結果を表４に示す。なお、成形体中の粒子については、均一な粒子形状を有しておらず、粒子径の算出ができなかった。
(Comparative Example 3)
3.5 g of polyethylene maleic anhydride was dissolved in 50 g of ion-exchanged water, and the pH was adjusted to about 4 to obtain an aqueous mixture. 35 g of dimethylpolysiloxane (KF-96-1000cs) was added to this aqueous mixture, and the mixture was stirred to prepare an emulsion. A mixed solution of 6 g of melamine, adjusted to pH 12, and 11 g of a 37% aqueous formaldehyde solution was added to this emulsion, and the pH was adjusted to about 4. Interfacial polymerization was carried out at 80° C. for 3 hours, and particles were filtered and dried from the product obtained after polymerization to produce particles. The average particle size of the produced particles was 8 μm.
The produced particles were molded in the same manner as described in the above evaluation of the sliding property to produce a sheet. The evaluation of the sliding property of the produced sheet, the evaluation of the sliding property duration 1, the evaluation of the sliding
（比較例４）
９９部のミラストマー８０３２ＢＳと、１部のＫＦ－９６－１００ｃｓを混合して、混合物を得た。得られた混合物を使用して、上記摺動性付与評価に記載された方法と同様にして成形し、シートを作成した。作成したシートの摺動性付与評価、摺動性持続評価１、摺動性持続評価２及び成形体の外観評価を実施例１と同様にして行った。結果を表４に示す。
(Comparative Example 4)
A mixture was obtained by mixing 99 parts of Milastomer 8032BS and 1 part of KF-96-100cs. The mixture was molded to prepare a sheet in the same manner as described in the above evaluation of the sliding property imparted. The evaluation of the sliding property imparted to the prepared sheet, the evaluation of the sliding property sustainment 1, the evaluation of the sliding
表３～４より、単量体（Ａ）と単量体（Ｂ）を含む重合性成分の重合体からなる外殻と、それに内包される内包物とから構成され、内包物が潤滑剤を含む粒子であれは、摺動性を付与し、摺動性の長期持続性に優れ、分散性に優れる。また、気化成分をさらに内包すると、軽量な成形体を作成することもできる。
一方、潤滑剤を含有していない比較例１では、十分な摺動性が得られない。また、単量体（Ｂ）を含まない比較例２や、熱硬化性樹脂からなる潤滑剤内包粒子である比較例３では、初期の摺動性には、優れているものの、長期持続性は十分ではない。
From Tables 3 and 4, it is seen that the inclusions are composed of an outer shell made of a polymer of a polymerizable component containing a monomer (A) and a monomer (B), and the inclusions are particles containing a lubricant, and the inclusions impart sliding properties, have excellent long-term durability of sliding properties, and are excellent in dispersibility. In addition, if a vaporizable component is further included, a lightweight molded body can be produced.
On the other hand, in Comparative Example 1, which does not contain a lubricant, sufficient sliding properties are not obtained. In Comparative Example 2, which does not contain the monomer (B), and Comparative Example 3, which is a lubricant-containing particle made of a thermosetting resin, the initial sliding properties are excellent, but the long-term durability is not sufficient.
１ 重合体からなる外殻
２ 内包物
1.
Claims (8)
前記単量体（Ａ）が重合性炭素－炭素二重結合を１つ有する単量体であり、前記単量体（Ｂ）が重合性炭素－炭素二重結合を少なくとも２つ有する単量体であり、
前記内包物が潤滑剤を含む、粒子。 A particle comprising an outer shell made of a polymer of a polymerizable component containing a monomer (A) and a monomer (B), and an inclusion contained in the outer shell,
the monomer (A) is a monomer having one polymerizable carbon-carbon double bond, and the monomer (B) is a monomer having at least two polymerizable carbon-carbon double bonds,
The inclusions comprise a lubricant.
A molded article obtained by molding the composition according to claim 7.
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