WO2022181018A1 - 表面処理ゾルゲルシリカ粒子の製造方法、表面処理ゾルゲルシリカ粒子、及び静電荷像現像用トナー外添剤 - Google Patents
表面処理ゾルゲルシリカ粒子の製造方法、表面処理ゾルゲルシリカ粒子、及び静電荷像現像用トナー外添剤 Download PDFInfo
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- WO2022181018A1 WO2022181018A1 PCT/JP2021/047477 JP2021047477W WO2022181018A1 WO 2022181018 A1 WO2022181018 A1 WO 2022181018A1 JP 2021047477 W JP2021047477 W JP 2021047477W WO 2022181018 A1 WO2022181018 A1 WO 2022181018A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silica particles
- group
- gel silica
- sol
- units
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 239000002245 particle Substances 0.000 title claims abstract description 51
- 239000000654 additive Substances 0.000 title claims abstract description 34
- 230000000996 additive effect Effects 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 18
- 238000011161 development Methods 0.000 title claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 48
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 17
- 125000005372 silanol group Chemical group 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- -1 silane compound Chemical class 0.000 claims description 36
- 229910000077 silane Inorganic materials 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 20
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 239000012046 mixed solvent Substances 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 239000007859 condensation product Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 238000002296 dynamic light scattering Methods 0.000 claims description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- APDDLLVYBXGBRF-UHFFFAOYSA-N [diethyl-(triethylsilylamino)silyl]ethane Chemical compound CC[Si](CC)(CC)N[Si](CC)(CC)CC APDDLLVYBXGBRF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 14
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 10
- 241000519995 Stachys sylvatica Species 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 108091008695 photoreceptors Proteins 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HIMXYMYMHUAZLW-UHFFFAOYSA-N [[[dimethyl(phenyl)silyl]amino]-dimethylsilyl]benzene Chemical compound C=1C=CC=CC=1[Si](C)(C)N[Si](C)(C)C1=CC=CC=C1 HIMXYMYMHUAZLW-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GXGDLEBZHWVDTF-UHFFFAOYSA-N 1-[[[butyl(dimethyl)silyl]amino]-dimethylsilyl]butane Chemical compound CCCC[Si](C)(C)N[Si](C)(C)CCCC GXGDLEBZHWVDTF-UHFFFAOYSA-N 0.000 description 1
- CNNPULJFGORMOI-UHFFFAOYSA-N 1-[[[dimethyl(octyl)silyl]amino]-dimethylsilyl]octane Chemical compound CCCCCCCC[Si](C)(C)N[Si](C)(C)CCCCCCCC CNNPULJFGORMOI-UHFFFAOYSA-N 0.000 description 1
- XNVKQSYMDNUWNH-UHFFFAOYSA-N 1-[[[dimethyl(propyl)silyl]amino]-dimethylsilyl]propane Chemical compound CCC[Si](C)(C)N[Si](C)(C)CCC XNVKQSYMDNUWNH-UHFFFAOYSA-N 0.000 description 1
- SJXRYSFPMDJANJ-UHFFFAOYSA-N 1-[[[hexyl(dimethyl)silyl]amino]-dimethylsilyl]hexane Chemical compound CCCCCC[Si](C)(C)N[Si](C)(C)CCCCCC SJXRYSFPMDJANJ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- YVHUUEPYEDOELM-UHFFFAOYSA-N 2-ethylpropanedioic acid;piperidin-1-id-2-ylmethylazanide;platinum(2+) Chemical compound [Pt+2].[NH-]CC1CCCC[N-]1.CCC(C(O)=O)C(O)=O YVHUUEPYEDOELM-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- MHRNQQUEUYMEEH-UHFFFAOYSA-N [[[ethyl(dimethyl)silyl]amino]-dimethylsilyl]ethane Chemical compound CC[Si](C)(C)N[Si](C)(C)CC MHRNQQUEUYMEEH-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VNVRPYPOLKSSCA-UHFFFAOYSA-N butyl-methoxy-dimethylsilane Chemical compound CCCC[Si](C)(C)OC VNVRPYPOLKSSCA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000012730 carminic acid Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NUFVQEIPPHHQCK-UHFFFAOYSA-N ethenyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C=C NUFVQEIPPHHQCK-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- SUHRFYWSDBWMFS-UHFFFAOYSA-N ethyl-methoxy-dimethylsilane Chemical compound CC[Si](C)(C)OC SUHRFYWSDBWMFS-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- MLOOSKOYXCDAIJ-UHFFFAOYSA-N hexyl-methoxy-dimethylsilane Chemical compound CCCCCC[Si](C)(C)OC MLOOSKOYXCDAIJ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- BAXHQTUUOKMMGV-UHFFFAOYSA-N methoxy-dimethyl-octylsilane Chemical compound CCCCCCCC[Si](C)(C)OC BAXHQTUUOKMMGV-UHFFFAOYSA-N 0.000 description 1
- REQXNMOSXYEQLM-UHFFFAOYSA-N methoxy-dimethyl-phenylsilane Chemical compound CO[Si](C)(C)C1=CC=CC=C1 REQXNMOSXYEQLM-UHFFFAOYSA-N 0.000 description 1
- LTJUCEWBHDKRBL-UHFFFAOYSA-N methoxy-dimethyl-propan-2-ylsilane Chemical compound CO[Si](C)(C)C(C)C LTJUCEWBHDKRBL-UHFFFAOYSA-N 0.000 description 1
- NCHMPORHGFKNSI-UHFFFAOYSA-N methoxy-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)OC NCHMPORHGFKNSI-UHFFFAOYSA-N 0.000 description 1
- 125000004370 n-butenyl group Chemical group [H]\C([H])=C(/[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09716—Inorganic compounds treated with organic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09725—Silicon-oxides; Silicates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
Definitions
- the present invention relates to surface-treated sol-gel silica particles, a method for producing the same, and an external toner additive for developing electrostatic images used for developing electrostatic images in electrophotography, electrostatic recording, and the like.
- Dry developers used in electrophotography and the like can be broadly classified into one-component developers that use toner itself in which a coloring agent is dispersed in a binder resin, and two-component developers that mix the toner with a carrier.
- the developers When these developers are used for copying operations, the developers must be excellent in fluidity, caking resistance, fixability, chargeability, cleanability, etc. in order to have process suitability. .
- inorganic fine particles are often used as external toner additives.
- Patent Documents 1 and 2 there has been proposed a technology for suppressing deterioration of toner using a spacer effect of an external additive for toner having a large particle size.
- toner external additives a small particle size toner external additive and a large particle size toner external additive are often used together. Due to the presence of the external toner additive with a large particle diameter adhering to the surface of the toner particles, the frequency with which the external external additive with a small particle diameter adhering to the surface of the toner particles in the vicinity thereof is subjected to external forces such as direct shear force and impact force is reduced. Since it is possible to prevent the toner external additive having a small particle size from being buried in the toner particle surface due to the external force (spacer effect), deterioration of the toner can be suppressed.
- the toner becomes easier to separate from the photoreceptor, and the toner on the photoreceptor is quickly transferred to the paper, and the transfer efficiency can be maintained at a high level. It is believed that the large particle size toner external additive also functions as a transfer aid.
- the small particle size silica used at this time is often used mainly as a fluidizing agent, but until now, fumed silica particles produced by the combustion method have been mainly used.
- fumed silica particles certainly improve the fluidity, there is a tendency to increase the amount of addition in order to improve the fluidity of recent toners with small particle diameters.
- transferability and cleanability have been required more strictly, and there has been a demand for toners free from aggregates and excellent in dispersibility.
- fumed silica particles as described above are used for the purpose of improving charging characteristics, etc., but generally the surface is not sufficiently hydrophobized, and silanol groups remain on the surface. There is a problem that it is difficult to control charging, and there has been a demand for silica particles with a small particle size that are excellent in both fluidity and charging control.
- the present invention has been made in view of the above circumstances, and the surface-treated sol-gel silica particles that can impart good fluidity when added to toner and have little charge change when the environment changes, a method for producing the same, and the surface
- An object of the present invention is to provide an external additive for toner comprising treated sol-gel silica particles.
- a method for producing surface-treated sol-gel silica particles comprising: (A1) A hydrophilic sol-gel silica having silanol groups on the surface and substantially consisting of SiO2 units is obtained by hydrolyzing and condensing a tetrafunctional silane compound, a partial hydrolysis condensation product thereof, or a mixture thereof.
- the hydrophilic sol-gel silica particles have (C 2 H 5 ) 3 Si—groups or R 1 R 2 2 Si—groups (wherein R 1 is an alkyl or alkenyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 8 carbon atoms, and R 2 is the same or different substituted or unsubstituted alkyl group having 1 to 4 carbon atoms) to obtain the hydrophilic sol-gel silica particles.
- the step (A1) is represented by the general formula (i): Si( OR4)4 ( i) (Wherein, each R 4 is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms)
- a tetrafunctional silane compound represented by, a partial hydrolysis condensation product thereof or a mixture thereof in the presence of a basic substance in a mixture of a hydrophilic organic solvent and water on the surface
- a step of obtaining a mixed solvent dispersion of hydrophilic sol - gel silica particles having silanol groups and substantially consisting of SiO units The step (A2) is applied to the obtained mixed solvent dispersion of the hydrophilic sol-gel silica particles with the general formula (ii): R1R22SiNHSiR1R22 ( ii ) _ _ (Wherein, R 1 and R 2 are as defined above)
- the step (A3) is applied to the obtained mixed solvent dispersion of the pretreated silica particles with the general formula (iv): R33SiNHSiR333 ( iv ) ( Wherein, R3 is as defined above)
- /2 units R3 is as described above) to obtain surface-treated sol-gel silica particles.
- the method for producing surface-treated sol-gel silica particles of the present invention can be such a production method.
- R 1 is an alkyl group having 6 to 8 carbon atoms, phenyl group or vinyl group
- R 2 is methyl group, ethyl group, propyl group or isopropyl group
- R 3 is methyl group or ethyl group. It is preferable to
- the hydrophilic sol-gel silica particles are preferably surface-treated using such a compound.
- R 1 R 2 2 SiO 1/2 units (wherein R 1 is an alkyl or aryl group having 6 to 8 carbon atoms or a vinyl group, and R 2 is the same or different and has 1 to 2 carbon atoms) 4) and R 3 3 SiO 1/2 units (wherein R 3 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms).
- a surface-treated sol-gel silica particle that is The median diameter in the dynamic light scattering method is 5 nm to 99 nm, The average circularity is 0.8 to 1.0, has a refractive index of 1.38 to 1.42; A true density of 1.7 g/cm 3 or more and less than 1.9 g/cm 3 , The ratio represented by water vapor adsorption specific surface area/nitrogen adsorption specific surface area is 0.4 to 1.9, Provided are surface-treated sol-gel silica particles having a methanol hydrophobicity of 67% or more and 75% or less.
- surface-treated sol-gel silica particles having such properties can be used.
- R 1 is an alkyl group having 6 to 8 carbon atoms, a phenyl group, or a vinyl group
- R 2 is a methyl group, an ethyl group, a propyl group, or an isopropyl group
- R 3 is a methyl group. or preferably an ethyl group.
- the surface-treated sol-gel silica particles of the present invention are preferably subjected to such surface treatment.
- the present invention also provides a toner external additive for electrostatic charge image development containing the surface-treated sol-gel silica particles.
- the surface-treated sol-gel silica particles of the present invention can impart good fluidity and printing properties to the toner when used as a toner external additive.
- surface-treated sol-gel silica particles capable of improving charging abnormalities and toner fluidity due to environmental changes that occur when conventional small-diameter fumed silica is used as an external additive. It is possible to provide a toner external additive for developing an electrostatic charge image and a toner for developing an electrostatic charge image comprising the above.
- the present inventors have found that by surface-treating spherical silica particles obtained by a sol-gel method with a specific organosilicon compound, good fluidity can be achieved when added to toner. can be imparted, and surface-treated sol-gel silica particles with little change in charge amount when the environment changes can be obtained, and the present invention has been completed.
- a method for producing surface-treated sol-gel silica particles comprising: (A1) A hydrophilic sol-gel silica having silanol groups on the surface and substantially consisting of SiO2 units is obtained by hydrolyzing and condensing a tetrafunctional silane compound, a partial hydrolysis condensation product thereof, or a mixture thereof.
- the hydrophilic sol-gel silica particles have (C 2 H 5 ) 3 Si—groups or R 1 R 2 2 Si—groups (wherein R 1 is an alkyl or alkenyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 8 carbon atoms, and R 2 is the same or different substituted or unsubstituted alkyl group having 1 to 4 carbon atoms) to obtain the hydrophilic sol-gel silica particles.
- Step (A1) Synthesis step of hydrophilic sol-gel silica particles Step (A1) involves hydrolyzing and condensing a tetrafunctional silane compound, a partial hydrolysis condensation product thereof, or a mixture thereof to form silanol groups on the surface. and substantially consisting of SiO 2 units.
- the hydrophilic sol-gel silica particles “substantially consist of SiO2 units” means that the particles are basically composed of SiO2 units but composed only of SiO2 units. Rather, it means that at least the surface may have a large number of silanol groups as is commonly known. In some cases, a small amount of hydrolyzable groups (hydrocarbyloxy groups) derived from the raw material tetrafunctional silane compound and/or a partial hydrolysis condensation product thereof are not converted into silanol groups, and the particles are used as they are. It means that it may remain on the surface or inside.
- the small-diameter sol-gel method silica particles obtained by hydrolysis of a tetrafunctional silane compound such as tetraalkoxysilane in the step (A1) are used as the silica raw material (silica particles before hydrophobization treatment).
- the particle size after the hydrophobization treatment maintains the primary particle size of the silica raw material, is not aggregated, and has a small particle size, Surface-treated sol-gel silica particles that are excellent as an external additive for toner can be obtained.
- Step (A1) comprises general formula (i): Si( OR4)4 ( i) (Wherein, each R 4 is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms)
- a tetrafunctional silane compound represented by, a partial hydrolysis condensation product thereof or a mixture thereof in the presence of a basic substance in a mixture of a hydrophilic organic solvent and water hydrophilic It is preferably a step of obtaining a mixed solvent dispersion of sol-gel silica particles.
- R 4 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms. be.
- Examples of the monovalent hydrocarbon group represented by R 4 include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; and aryl groups such as phenyl group, preferably methyl group, Ethyl group, propyl group or butyl group, particularly preferably methyl group or ethyl group.
- Examples of the tetrafunctional silane compound represented by the general formula (i) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; and tetraphenoxysilane, preferably , tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, particularly preferably tetramethoxysilane and tetraethoxysilane.
- Partial hydrolysis condensation products of the tetrafunctional silane compound represented by formula (i) include, for example, alkyl silicates such as methyl silicate and ethyl silicate.
- the hydrophilic organic solvent is not particularly limited as long as it dissolves the tetrafunctional silane compound represented by the general formula (i), the partial hydrolysis condensation product thereof, and water.
- cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and cellosolve acetate; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and tetrahydrofuran; alcohols and cellosolves are particularly preferred; Alcohols are mentioned.
- R5OH (vi) (Wherein, R 5 is a monovalent hydrocarbon group having 1 to 6 carbon atoms)
- the alcohol represented by is mentioned.
- R 5 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms. be.
- Examples of the monovalent hydrocarbon group represented by R 5 include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group, preferably methyl group, ethyl , propyl and isopropyl groups, more preferably methyl and ethyl groups.
- Examples of the alcohol represented by the general formula (vi) include methanol, ethanol, propanol, isopropanol, butanol and the like, preferably methanol and ethanol.
- methanol is preferred for obtaining silica particles with a small particle size.
- the basic substance examples include ammonia, dimethylamine, diethylamine, etc., preferably ammonia and diethylamine, particularly preferably ammonia.
- the resulting aqueous solution may be mixed with the hydrophilic organic solvent.
- the basic substance is used in an amount of 0.01 to 2 mol per 1 mol of hydrocarbyloxy groups in the tetrafunctional silane compound represented by general formula (i) and/or its partial hydrolysis condensation product. is preferred, 0.02 to 0.5 mol is more preferred, and 0.04 to 0.12 mol is particularly preferred. At this time, the smaller the amount of the basic substance, the smaller the silica particles.
- the amount of water used in the above hydrolysis and condensation is 0.00 to 1 mol of total hydrocarbyloxy groups of the tetrafunctional silane compound represented by general formula (i) and/or its partial hydrolysis condensation product. It is preferably 1 to 2 mol, more preferably 0.1 to 1 mol.
- the ratio of the hydrophilic organic solvent to water is preferably 0.2-10, more preferably 0.3-5, by mass. The larger the amount of the hydrophilic organic solvent, the smaller the silica particles obtained.
- Hydrolysis and condensation of a tetrafunctional silane compound and the like can be performed by a known method, that is, by adding a tetrafunctional silane compound and a basic substance to a mixture of a hydrophilic organic solvent and water.
- the temperature during hydrolysis and condensation is preferably 20 to 50°C, and the higher the temperature, the smaller the silica particles obtained.
- the concentration of the hydrophilic sol-gel silica particles obtained in this step (A1) in the mixed solvent dispersion is generally 3-15% by mass, preferably 5-10% by mass.
- Step (A2) comprises adding (C 2 H 5 ) 3 Si— groups or R 1 R 2 2 to the hydrophilic sol-gel silica particles obtained in the above step (A1).
- Si—group wherein R 1 is an alkyl or alkenyl group having 2 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms, and R 2 is the same or different substituted or unsubstituted carbon atom (C 2 H 5 ) 3 SiO 1/2 units or R 1 R 2 2 SiO 1/2 units (wherein R 1 and R 2 are as defined above) to obtain pretreated silica particles.
- the surface treatment in the following step (A3) proceeds more uniformly and to a high degree.
- step (A2) general formula (ii): R1R22SiNHSiR1R22 ( ii ) _ _ (Wherein, R 1 and R 2 are as defined above)
- the alkyl group having 2 to 8 carbon atoms for R 1 includes ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, cyclo An octyl group and the like can be mentioned.
- the alkenyl group having 2 to 8 carbon atoms includes vinyl group, allyl group, n-butenyl group, n-hexenyl group, n-octenyl group and the like.
- aryl group having 6 to 8 carbon atoms examples include a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2 , 6-dimethylphenyl group and the like.
- R 1 is preferably an alkyl group having 6 to 8 carbon atoms, a phenyl group or a vinyl group, particularly preferably an n-octyl group, a phenyl group or a vinyl group.
- Examples of the alkyl group having 1 to 4 carbon atoms represented by R 2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group and the like, preferably Methyl group, ethyl group, propyl group and isopropyl group, more preferably methyl group and ethyl group.
- Some or all of the hydrogen atoms in these alkyl groups may be substituted with halogen atoms such as fluorine, chlorine and bromine atoms, preferably fluorine atoms.
- R 2 is a group different from R 1 above.
- hydrolyzable group represented by X examples include chlorine atom, alkoxy group, amino group and acyloxy group, preferably alkoxy group or amino group, particularly preferably alkoxy group.
- Silazane compounds represented by formula (ii) include 1,3-diethyltetramethyldisilazane, 1,3-di-n-propyltetramethyldisilazane, and 1,3-di-n-butyltetramethyldisilazane. , 1,3-di-n-hexyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyl-tetramethyldisilazane, 1,3-divinyltetramethyldisilazane, 1,3-diallyltetramethyldisilazane and the like.
- Examples of the monofunctional silane compound represented by formula (iii-1) include ethyldimethylmethoxysilane, n-propyldimethylmethoxysilane, isopropyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-hexyldimethylmethoxysilane, n -monoalkoxysilanes such as octyldimethylmethoxysilane, phenyldimethylmethoxysilane, and vinyldimethylmethoxysilane, and their silanol and monochloro silanes.
- Examples of the monofunctional silane compound represented by the general formula (iii-2) include monoalkoxysilanes such as triethylmethoxysilane, and silanol and monochloro silanes thereof.
- the total addition amount of the silazane compound represented by the general formula (ii), hexaethyldisilazane, and the monofunctional silane compounds represented by the general formulas (iii-1) and (iii-2) is the hydrophilic sol-gel silica particles. 0.001 to 1 mol, more preferably 0.02 to 0.5 mol, and particularly preferably 0.05 to 0.3 mol per 1 mol of SiO 2 units in the mixture. Within such a range, the surface treatment efficiency in step (A3) can be improved.
- reaction temperature of the surface treatment in step (A2) is not particularly limited, but is preferably 20 to 80°C, more preferably 40 to 60°C.
- Step (A3) includes adding R 3 3 Si— groups (wherein R 3 is substituted or unsubstituted is a C 1-6 monovalent hydrocarbon group) to form R 3 3 SiO 1/2 units (wherein R 3 is as defined above) on the surface of the pretreated silica particles. ) is introduced to obtain surface-treated sol-gel silica particles. In this step, R 3 3 SiO 1/2 units are introduced in the form of triorganosilylation of the silanol groups remaining on the surface of the pretreated silica particles, resulting in more highly surface treated sol-gel silica particles.
- step (A3) general formula (iv): R33SiNHSiR333 ( iv ) ( Wherein, R3 is as defined above)
- the step is to introduce R 3 3 SiO 1/2 units (where R 3 is as defined above) into the surface to obtain surface-treated sol-gel silica particles.
- R 3 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms.
- monovalent hydrocarbon groups represented by R 3 include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group; vinyl group, allyl group and the like.
- phenyl group preferably methyl group or ethyl group, more preferably methyl group.
- some or all of the hydrogen atoms in these groups may be substituted with halogen atoms such as fluorine, chlorine and bromine atoms, preferably fluorine atoms.
- silazane compound represented by the general formula (iv) examples include hexamethyldisilazane, hexaethyldisilazane and the like, with hexamethyldisilazane being preferred.
- Examples of monofunctional silane compounds represented by general formula (v) include monosilanol compounds such as trimethylsilanol and triethylsilanol; monochlorosilanes such as trimethylchlorosilane and triethylchlorosilane; monoalkoxy compounds such as trimethylmethoxysilane and trimethylethoxysilane; Silanes; monoaminosilanes such as trimethylsilyldimethylamine and trimethylsilyldiethylamine; and monoacyloxysilanes such as trimethylacetoxysilane, preferably trimethylsilanol, trimethylmethoxysilane or trimethylsilyldiethylamine, particularly preferably trimethylsilanol or trimethylmethoxysilane. be done.
- monosilanol compounds such as trimethylsilanol and triethylsilanol
- monochlorosilanes such as trimethylchlorosilane
- the total addition amount of the silazane compound represented by general formula (iv) and the monofunctional silane compound represented by general formula (v) is preferably 5 to 50 mol per 1 mol of SiO 2 units in the pretreated silica particles, More preferably 10 to 30 mol. Within such a range, aggregation of particles is unlikely to occur, and surface-treated sol-gel silica particles having excellent dispersibility in toner can be obtained.
- the number of SiO 2 units in the pretreated silica particles is the same as the number of SiO 2 units in the hydrophilic sol-gel silica particles used as raw materials.
- reaction temperature of the surface treatment in step (A3) is not particularly limited, but is preferably 20 to 80°C, more preferably 50 to 70°C.
- the unit introduced onto the surface of the hydrophilic sol-gel silica particles in step (A2) differs from the unit introduced onto the surface of the pretreated silica particles in step (A3). That is, when (C 2 H 5 ) 3 SiO 1/2 units are introduced onto the surface of the hydrophilic sol-gel silica particles in step (A2), (C 2 H 5 ) introducing units other than 3 SiO 1/2 units.
- the above surface-treated sol-gel silica particles can be obtained as powder by ordinary methods such as normal pressure drying and reduced pressure drying.
- the surface-treated sol-gel silica particles obtained by the method for producing surface-treated sol-gel silica particles of the present invention are R 1 R 2 2 SiO 1/2 units (wherein R 1 is an alkyl or aryl group having 6 to 8 carbon atoms or a vinyl group, and R 2 is the same or different and has 1 to 2 carbon atoms) 4) and R 3 3 SiO 1/2 units (wherein R 3 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms).
- a surface-treated sol-gel silica particle that is (1) the median diameter in the dynamic light scattering method is 5 nm to 99 nm; (2) an average circularity of 0.8 to 1.0, (3) a refractive index of 1.38 to 1.42; (4) a true density of 1.7 g/cm 3 or more and less than 1.9 g/cm 3 ; (5) the ratio represented by water vapor adsorption specific surface area/nitrogen adsorption specific surface area is 0.4 to 1.9; (6) Surface-treated sol-gel silica particles having a methanol hydrophobicity of 67% or more and 75% or less.
- R 1 to R 3 are the same as those described above.
- the median diameter of the surface-treated sol-gel silica particles of the present invention in dynamic light scattering method is preferably 10 nm to 70 nm. If the median diameter is less than 5 nm, a large amount of silica particles are embedded in the toner particles, and when used as an external additive to toner, the required addition amount increases, which is not preferable. On the other hand, if the median diameter exceeds 99 nm, the fluidity is lowered, the charge amount is lowered due to the decrease in the surface area, and the adhesion to the toner particles is lowered.
- the median diameter can be obtained from the particle size distribution of the surface-treated sol-gel silica particles measured by the dynamic light scattering method.
- the dynamic light scattering method uses a dynamic light scattering particle size distribution analyzer (for example, NanotracWave II-Ex150 manufactured by Microtrack Bell) to irradiate a dispersion of silica particles with a laser beam, and measures the scattered light obtained. This is a method of determining the particle size distribution obtained from the scattering intensity by utilizing the fact that the scattering intensity varies depending on the particle size of silica-based fine particles.
- the circularity of the surface-treated sol-gel silica particles of the present invention is defined by (perimeter of a circle with an area equal to the particle area/perimeter of the particle) when the particles are projected two-dimensionally.
- the average is between 0.92 and 1. If the average circularity is less than 0.8, the proportion of irregularly shaped particles increases, which is not preferable because toner contamination tends to occur.
- the refractive index indicates voids inside the surface-treated sol-gel silica particles. If the refractive index is less than 1.38, it means that there are many voids and the crosslinked structure of the sol-gel silica particles is fragile, which is not preferable. On the other hand, if the refractive index exceeds 1.42, the voids are small and the specific gravity is large, so that the charge amount may be lowered and the adhesive force to the toner particles may be lowered, which is not preferable.
- the refractive index of the surface-treated sol-gel silica particles is determined by adding and dispersing the surface-treated sol-gel silica particles in a mixed solvent of toluene (refractive index: 1.4962) and methyl isobutyl ketone (refractive index: 1.3958).
- the refractive index is adjusted by adjusting the blending ratio of the solvent, and the refractive index of the mixed solvent is defined as the point at which the dispersion becomes transparent at 25° C. (the point where the refractive indices of the mixed solvent and the surface-treated silica fine particles match).
- the true density is preferably 1.75 g/cm 3 to 1.85 g/cm 3 . If the true density is less than 1.7 g/cm 3 , the strength of the surface-treated sol-gel silica particles may decrease, which is not preferable. In addition, those having a true density of 1.9 g/cm 3 or more are preferable in that the weight per silica particle increases, so that when used as a toner external additive, the impact on the toner particles increases. do not have.
- Water vapor adsorption specific surface area/nitrogen adsorption specific surface area The ratio of water vapor adsorption specific surface area/nitrogen adsorption specific surface area is a measure of hygroscopicity, and the adsorption specific surface area of each gas can be obtained by the BET method. Water molecules (approximately 2 ⁇ ) are smaller than nitrogen molecules (approximately 3 ⁇ ), so the water vapor adsorption specific surface area/nitrogen adsorption specific surface area ratio is small. indicates that there is a gap of
- the ratio of water vapor adsorption specific surface area/nitrogen adsorption specific surface area is preferably 0.5 to 1.5. If the specific surface area ratio is more than 1.9, the hygroscopicity is too high, and the charge amount of the toner is greatly affected by humidity, which is not preferable.
- Methanol Hydrophobicity indicates the hydrophobicity of the surface-treated sol-gel silica particles.
- the charge amount of the toner is greatly affected by humidity, which is not preferable.
- the silica fine particles tend to aggregate with each other, resulting in poor dispersibility in the toner, poor fluidity of the toner, and poor print image quality.
- the degree of hydrophobicity of methanol exceeds 75%, the charge amount of the toner may become too high when added to the toner.
- the degree of hydrophobicity of methanol in the present invention is measured under the following conditions.
- the transmittance is measured by irradiating the aqueous solution with light having a wavelength of 780 nm, and the volume concentration (%) of methanol in the aqueous methanol solution when the silica particles are suspended and sedimented and the transmittance reaches 80% is the methanol hydrophobicity. degrees.
- the present invention also provides a toner external additive for electrostatic charge image development, which contains the surface-treated sol-gel silica particles.
- the surface-treated sol-gel silica particles of the present invention when used as a toner external additive, impart good fluidity and printing properties to the toner.
- Step (A1) 793.0 g of methanol, 32.1 g of water, and 40.6 g of 28% aqueous ammonia were added and mixed in a 3-liter glass reactor equipped with a stirrer, a dropping funnel, and a thermometer. This solution was adjusted to 45° C., and while stirring, 160.9 g of 5.5% aqueous ammonia and 646.5 g of tetramethoxysilane were simultaneously started dropwise, the former over 4 hours and the latter over 6 hours. After the dropwise addition of tetramethoxysilane was completed, hydrolysis was continued for 0.5 hour to obtain a suspension of hydrophilic sol-gel silica particles.
- Step (A2) 2.0 g of 1,3-divinyl-1,1,3,3 - tetramethyldisilazane (per 0.26 mol equivalent) was added and stirred at 50° C. for 1 hour to obtain a dispersion of pretreated silica particles whose surfaces were dimethylvinylsilylated.
- Step (A3) After dropping 205.3 g of hexamethyldisilazane (equivalent to 30 mol per 1 mol of SiO 2 ) at 25° C. over 0.5 hour to the dispersion liquid obtained in the above step (A2), By reacting at 60° C. for 8 hours, a dispersion liquid of surface-treated sol-gel silica particles whose surfaces were further trimethylsilylated was obtained. Then, the dispersion medium in this dispersion was distilled off at 130° C. under reduced pressure (6650 Pa) to obtain 271 g of white powder of surface-treated sol-gel silica particles (I).
- Example 1-2 272 g of white powder of surface-treated sol-gel silica particles (II) was obtained in the same manner as in Example 1-1, except that the reaction temperature in step (A1) was changed to 35°C.
- Example 1-3 269 g of white powder of surface-treated sol-gel silica particles (III) was obtained in the same manner as in Example 1-1, except that the reaction temperature in step (A1) was changed to 27°C.
- Example 1-4 In Example 1-1, 273 g of white powder of surface-treated sol-gel silica particles (IV) was obtained in the same manner as in Example 1-1, except that the reaction temperature in step (A1) was changed to 25°C.
- Example 1-5 In Example 1-1, 1,3-diphenyl-1,1,3,3-tetramethyldisilazane was substituted for 1,3-divinyl-1,1,3,3-tetramethyldisilazane in step (A2). 274 g of white powder of surface-treated sol-gel silica particles (V) was obtained in the same manner as in Example 1-1, except that 3.1 g of silazane (equivalent to 0.26 mol per 1 mol of SiO 2 ) was used. .
- Example 1-6 In Example 1-1, 1,3-di-n-octyl-1,1,3,3 was substituted for 1,3-divinyl-1,1,3,3-tetramethyldisilazane in step (A2).
- White powder of surface-treated sol-gel silica particles (VI) was prepared in the same manner as in Example 1-1 except that 3.9 g of -tetramethyldisilazane (equivalent to 0.26 mol per 1 mol of SiO 2 ) was used. 275 g was obtained.
- Example 1-1 In Example 1-1, step (A1) was performed, step (A2) was not performed, and 205.3 g of hexamethyldisilazane was added to the suspension obtained in step (A1) at 25° C. as step (A3). (equivalent to 30 mol per 1 mol of SiO 2 ) was added dropwise over 0.5 hours, followed by reaction at 60° C. for 8 hours to obtain a dispersion of surface-treated sol-gel silica particles whose surfaces were trimethylsilylated. . Then, the dispersion medium in this dispersion was distilled off at 130° C. under reduced pressure (6650 Pa) to obtain 268 g of white powder of surface-treated sol-gel silica particles (VII).
- Example 1-3 In Example 1-3, step (A1) was performed, step (A2) was not performed, and 205.3 g of hexamethyldisilazane was added to the suspension obtained in step (A1) at 25° C. as step (A3). (equivalent to 30 mol per 1 mol of SiO 2 ) was added dropwise over 0.5 hours, followed by reaction at 60° C. for 8 hours to obtain a dispersion of surface-treated sol-gel silica particles whose surfaces were trimethylsilylated. . Then, the dispersion medium in this dispersion was distilled off at 130° C. under reduced pressure (6650 Pa) to obtain 268 g of white powder of surface-treated sol-gel silica particles (VIII).
- Table 1 shows the results of measuring the surface-treated sol-gel silica particles (I) to (VIII) obtained by the above steps according to the following measurement methods (1) to (6).
- [Measuring method] Median diameter in dynamic light scattering method 0.1 g of surface-treated sol-gel silica particles and 19.9 g of methanol were placed in a glass bottle, placed in an ultrasonic cleaner, and irradiated with ultrasonic waves at an output of 30 W / L for 10 minutes. Silica particles were dispersed in methanol. The median diameter of the dispersion was measured using a dynamic light scattering particle size distribution analyzer (NanotracWave II-Ex150 manufactured by Microtrack Bell).
- Refractive index Surface-treated sol-gel silica particles are added and dispersed in a mixed solvent of toluene (refractive index 1.4962) and methyl isobutyl ketone (refractive index 1.3958), and the refractive index is adjusted by the blending ratio of the above solvents.
- the refractive index of the mixed solvent at the point where the dispersion becomes transparent was taken as the refractive index of the surface-treated sol-gel silica particles.
- the refractive index of the mixed solvent is a value at 25° C. measured using a digital refractometer (RX-9000 ⁇ manufactured by Atago Co., Ltd.).
- the true density of the surface-treated sol-gel silica particles was measured using an automatic true density measuring device (Auto True Denser MAT-7000 manufactured by Seishin Enterprise Co., Ltd.) using a liquid phase substitution method.
- the surface-treated sol-gel silica particles of Examples 1-1 to 1-6 exhibited a high degree of methanol hydrophobization, and their surfaces were highly hydrophobized. On the other hand, in Comparative Examples 1-1 and 1-2, the hydrophobization of the surface was insufficient.
- Aggregation degree (%) (W 1 + 0.6 x W 2 + 0.2 x W 3 )/5 x 100
- W 1 Amount remaining on 150 ⁇ m mesh sieve
- W 2 Amount remaining on 75 ⁇ m mesh sieve
- W 3 Amount remaining on 45 ⁇ m mesh sieve
- the external additive-mixed toners of Examples 2-1 to 2-6 have low agglomeration degrees, indicating that the surface-treated sol-gel silica particles of the present invention can be suitably used as external toner additives.
- the surface treatment of the silica particles was not sufficient, resulting in a high degree of agglomeration.
- the presence or absence of image defects (white spots) in the image of the printed matter 2 obtained above was evaluated according to the following criteria.
- the two-component developer using the surface-treated sol-gel silica particles obtained in Examples 1-1 to 1-6 as a toner external additive has a small change in the toner charge amount depending on the environment. There were no print image defects.
- the toner using the surface-treated sol-gel silica particles obtained in Comparative Examples 1-1 and 1-2 had a large fluctuation in the toner charge amount depending on the environment, and was inferior in printing characteristics.
- the present invention is not limited to the above embodiments.
- the above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. included in the technical scope of
Abstract
Description
表面処理ゾルゲルシリカ粒子の製造方法であって、
(A1)4官能性シラン化合物、その部分加水分解縮合生成物又はこれらの混合物を加水分解及び縮合することによって、表面にシラノール基を有し、かつ実質的にSiO2単位からなる親水性ゾルゲルシリカ粒子を得る工程、
(A2)前記親水性ゾルゲルシリカ粒子に(C2H5)3Si-基又はR1R2 2Si-基(式中、R1は炭素原子数2~8のアルキル基もしくはアルケニル基、又は炭素原子数6~8のアリール基であり、R2は同一又は異種の置換又は非置換の炭素原子数1~4のアルキル基である)を有する化合物を添加して、前記親水性ゾルゲルシリカ粒子の表面に(C2H5)3SiO1/2単位又はR1R2 2SiO1/2単位(式中、R1及びR2は前記の通りである)を導入して予備処理シリカ粒子を得る工程、及び
(A3)前記予備処理シリカ粒子にR3 3Si-基(式中、R3は置換又は非置換の炭素原子数1~6の一価炭化水素基である)を有する化合物を添加して、前記予備処理シリカ粒子の表面に更にR3 3SiO1/2単位(式中、R3は前記の通りである)を導入して表面処理ゾルゲルシリカ粒子を得る工程を含み、かつ、
前記工程(A2)で前記親水性ゾルゲルシリカ粒子の表面に導入する単位と、前記工程(A3)で前記予備処理シリカ粒子の表面に導入する単位はそれぞれ異なる表面処理ゾルゲルシリカ粒子の製造方法を提供する。
Si(OR4)4 (i)
(式中、各R4は同一又は異種の炭素原子数1~6の一価炭化水素基である)
で示される4官能性シラン化合物、その部分加水分解縮合生成物又はこれらの混合物を、塩基性物質の存在下、親水性有機溶媒と水の混合液中で加水分解及び縮合することによって、表面にシラノール基を有し、かつ実質的にSiO2単位からなる親水性ゾルゲルシリカ粒子の混合溶媒分散液を得る工程とし、
前記工程(A2)を、得られた前記親水性ゾルゲルシリカ粒子の混合溶媒分散液に、一般式(ii):
R1R2 2SiNHSiR1R2 2 (ii)
(式中、R1及びR2は前記の通りである)
で示されるシラザン化合物、ヘキサエチルジシラザン、一般式(iii-1):
R1R2 2SiX (iii-1)
(式中、R1及びR2は前記の通りであり、XはOH基又は加水分解性基である)
で示される1官能性シラン化合物、一般式(iii-2):
(C2H5)3SiX (iii-2)
(式中、Xは前記の通りである)
で示される1官能性シラン化合物、又はこれらの混合物を、前記親水性ゾルゲルシリカ粒子中のSiO2単位1モルあたり0.001~1モルを添加して、前記親水性ゾルゲルシリカ粒子の表面に(C2H5)3SiO1/2単位又はR1R2 2SiO1/2単位(R1及びR2は前記の通りである)を導入して予備処理シリカ粒子の混合溶媒分散液を得る工程とし、
前記工程(A3)を、得られた前記予備処理シリカ粒子の混合溶媒分散液に、一般式(iv):
R3 3SiNHSiR3 3 (iv)
(式中、R3は前記の通りである)
で示されるシラザン化合物、一般式(v):
R3 3SiX (v)
(式中、R3及びXは前記の通りである)
で示される1官能性シラン化合物、又はこれらの混合物を、前記予備処理シリカ粒子中のSiO2単位1モルあたり5~50モルを添加して、前記予備処理シリカ粒子の表面にR3 3SiO1/2単位(R3は前記の通りである)を導入して表面処理ゾルゲルシリカ粒子を得る工程とすることが好ましい。
表面にR1R2 2SiO1/2単位(式中、R1は炭素原子数6~8のアルキル基もしくはアリール基、又はビニル基であり、R2は同一又は異種の炭素原子数1~4のアルキル基である)及びR3 3SiO1/2単位(式中、R3は同一又は異種の置換又は非置換の炭素原子数1~6の1価炭化水素基である)を有するものである表面処理ゾルゲルシリカ粒子であって、
動的光散乱法におけるメジアン径が5nm~99nmであり、
平均円形度が0.8~1.0であり、
屈折率が1.38~1.42であり、
真密度が1.7g/cm3以上1.9g/cm3未満であり、
水蒸気吸着比表面積/窒素吸着比表面積で表される比が0.4~1.9であり、
メタノール疎水化度が67%以上75%以下
のものである表面処理ゾルゲルシリカ粒子を提供する。
表面処理ゾルゲルシリカ粒子の製造方法であって、
(A1)4官能性シラン化合物、その部分加水分解縮合生成物又はこれらの混合物を加水分解及び縮合することによって、表面にシラノール基を有し、かつ実質的にSiO2単位からなる親水性ゾルゲルシリカ粒子を得る工程、
(A2)前記親水性ゾルゲルシリカ粒子に(C2H5)3Si-基又はR1R2 2Si-基(式中、R1は炭素原子数2~8のアルキル基もしくはアルケニル基、又は炭素原子数6~8のアリール基であり、R2は同一又は異種の置換又は非置換の炭素原子数1~4のアルキル基である)を有する化合物を添加して、前記親水性ゾルゲルシリカ粒子の表面に(C2H5)3SiO1/2単位又はR1R2 2SiO1/2単位(式中、R1及びR2は前記の通りである)を導入して予備処理シリカ粒子を得る工程、及び
(A3)前記予備処理シリカ粒子にR3 3Si-基(式中、R3は置換又は非置換の炭素原子数1~6の一価炭化水素基である)を有する化合物を添加して、前記予備処理シリカ粒子の表面に更にR3 3SiO1/2単位(式中、R3は前記の通りである)を導入して表面処理ゾルゲルシリカ粒子を得る工程を含み、かつ、
前記工程(A2)で前記親水性ゾルゲルシリカ粒子の表面に導入する単位と、前記工程(A3)で前記予備処理シリカ粒子の表面に導入する単位はそれぞれ異なる表面処理ゾルゲルシリカ粒子の製造方法である。
・工程(A1):親水性ゾルゲルシリカ粒子の合成工程
工程(A1)は、4官能性シラン化合物、その部分加水分解縮合生成物又はこれらの混合物を加水分解及び縮合することによって、表面にシラノール基を有し、かつ実質的にSiO2単位からなる親水性ゾルゲルシリカ粒子を得る工程である。
Si(OR4)4 (i)
(式中、各R4は同一又は異種の炭素原子数1~6の一価炭化水素基である)
で示される4官能性シラン化合物、その部分加水分解縮合生成物又はこれらの混合物を、塩基性物質の存在下、親水性有機溶媒と水の混合液中で加水分解及び縮合することによって、親水性ゾルゲルシリカ粒子の混合溶媒分散液を得る工程であることが好ましい。
R5OH (vi)
(式中、R5は炭素原子数1~6の1価炭化水素基である)
で示されるアルコールが挙げられる。
工程(A2)は、上記工程(A1)で得られた親水性ゾルゲルシリカ粒子に(C2H5)3Si-基又はR1R2 2Si-基(式中、R1は炭素原子数2~8のアルキル基もしくはアルケニル基、又は炭素原子数6~8のアリール基であり、R2は同一又は異種の置換又は非置換の炭素原子数1~4のアルキル基である)を有する化合物を添加して、親水性ゾルゲルシリカ粒子の表面に(C2H5)3SiO1/2単位又はR1R2 2SiO1/2単位(式中、R1及びR2は前記の通りである)を導入して予備処理シリカ粒子を得る工程である。本工程により、下記工程(A3)における表面処理がより均一に、且つ高度に進行する。
R1R2 2SiNHSiR1R2 2 (ii)
(式中、R1及びR2は前記の通りである)
で示されるシラザン化合物、ヘキサエチルジシラザン、一般式(iii-1):
R1R2 2SiX (iii-1)
(式中、R1及びR2は前記の通りであり、XはOH基又は加水分解性基である)
で示される1官能性シラン化合物、一般式(iii-2):
(C2H5)3SiX (iii-2)
(式中、Xは前記の通りである)
で示される1官能性シラン化合物、又はこれらの混合物を添加して、親水性ゾルゲルシリカ粒子の表面を上記シラザン化合物、上記1官能性シラン化合物、またはこれらの混合物により処理して、親水性ゾルゲルシリカ粒子の表面に(C2H5)3SiO1/2単位又はR1R2 2SiO1/2単位(R1及びR2は前記の通りである)を導入して予備処理シリカ粒子の混合溶媒分散液を得る工程であることが好ましい。
工程(A3)は、(A2)工程で得られた予備処理シリカ粒子にR3 3Si-基(式中、R3は置換又は非置換の炭素原子数1~6の一価炭化水素基である)を有する化合物を添加して、予備処理シリカ粒子の表面にR3 3SiO1/2単位(式中、R3は前記の通りである)を導入して表面処理ゾルゲルシリカ粒子を得る工程である。この工程では、予備処理シリカ粒子表面に残存するシラノール基をトリオルガノシリル化する形でR3 3SiO1/2単位が導入され、より高度に表面処理されたゾルゲルシリカ粒子が得られる。
R3 3SiNHSiR3 3 (iv)
(式中、R3は前記の通りである)
で示されるシラザン化合物、一般式(v):
R3 3SiX (v)
(式中、R3及びXは前記の通りである)
で示される1官能性シラン化合物、又はこれらの混合物を添加して、予備処理シリカ粒子の表面を上記シラザン化合物、上記1官能性シラン化合物、またはこれらの混合物により処理して、予備処理シリカ粒子の表面にR3 3SiO1/2単位(R3は前記の通りである)を導入して表面処理ゾルゲルシリカ粒子を得る工程であることが好ましい。
本発明の表面処理ゾルゲルシリカ粒子の製造方法により得られる表面処理ゾルゲルシリカ粒子は、
表面にR1R2 2SiO1/2単位(式中、R1は炭素原子数6~8のアルキル基もしくはアリール基、又はビニル基であり、R2は同一又は異種の炭素原子数1~4のアルキル基である)及びR3 3SiO1/2単位(式中、R3は同一又は異種の置換又は非置換の炭素原子数1~6の1価炭化水素基である)を有するものである表面処理ゾルゲルシリカ粒子であって、
(1)動的光散乱法におけるメジアン径が5nm~99nmであり、
(2)平均円形度が0.8~1.0であり、
(3)屈折率が1.38~1.42であり、
(4)真密度が1.7g/cm3以上1.9g/cm3未満であり、
(5)水蒸気吸着比表面積/窒素吸着比表面積で表される比が0.4~1.9であり、
(6)メタノール疎水化度が67%以上75%以下
のものである表面処理ゾルゲルシリカ粒子である。
本発明の表面処理ゾルゲルシリカ粒子の動的光散乱法におけるメジアン径は、好ましくは、10nm~70nmである。メジアン径が5nmを下回ると、トナー粒子中に埋没するシリカ粒子が多くなり、トナー外添剤として用いた場合に、必要な添加量が増えるため好ましくない。また、メジアン径が99nmを超えると、流動性の低下、表面積の減少による帯電量の低下、トナー粒子への付着力が低下する等好ましくない。
本発明の表面処理ゾルゲルシリカ粒子の円形度は、粒子を二次元に投影した時の、(粒子面積と等しい面積の円の周囲長/粒子周囲長)で定義され、その平均が0.92~1であることが好ましい。平均円形度が0.8を下回ると不規則形状の粒子の割合が多くなり、トナーの汚染を引き起こしやすくなるため好ましくない。
屈折率は表面処理ゾルゲルシリカ粒子内部の空隙を示し、屈折率が1.38より小さいと、空隙が多く存在しゾルゲルシリカ粒子の架橋構造が脆いことを意味するため好ましくない。また、屈折率が1.42を超えると空隙が少なく比重が大きくなるため、帯電量が低下したり、トナー粒子への付着力が低下する場合があるため好ましくない。
真密度は、好ましくは、1.75g/cm3~1.85g/cm3である。真密度が1.7g/cm3未満であると、表面処理ゾルゲルシリカ粒子の強度が低下する場合があるため好ましくない。また、真密度が1.9g/cm3以上であるものは、シリカ粒子1個当たりの重量が重くなるため、トナー外添剤として用いた場合に、トナー粒子へ与える衝撃が大きくなる点で好ましくない。
水蒸気吸着比表面積/窒素吸着比表面積の比は、吸湿性を示す尺度であり、各気体の吸着比表面積はBET法により求めることができる。水分子(約2Å)の方が窒素分子(約3Å)より小さいため、水蒸気吸着比表面積/窒素吸着比表面積比が小さいということは、即ち、水分子は通過しにくいが、窒素は通過する程度の空隙があることを示す。
メタノール疎水化度は表面処理ゾルゲルシリカ粒子の疎水性を示し、メタノール疎水化度が67%未満であると、シリカ表面の残存シラノール基により、静電荷像現像用トナー外添剤としてトナーに添加した場合、トナーの帯電量が湿度の影響を大きく受けるため好ましくない。また、シリカ微粒子同士の凝集が起きやすくなり、トナーへの分散性が劣り、トナーの流動性および印刷画質に劣るものとなる。メタノール疎水化度が75%を超えると、トナーに添加した場合、トナーの帯電量が高くなりすぎる場合がある。なお、本発明におけるメタノール疎水化度は、以下の条件で測定したものを指す。
体積濃度50%(温度25℃)のメタノール水溶液60mlに表面処理ゾルゲルシリカ粒子を0.2g添加し、撹拌子で攪拌し、次いでシリカ粒子が表面に浮遊した液中にメタノールを滴下しながら、メタノール水溶液に波長780nmの光を照射して透過率を測定し、シリカ粒子が懸濁・沈降して、透過率が80%になったときのメタノール水溶液中のメタノール体積濃度(%)をメタノール疎水化度とする。
また本発明では、上記の表面処理ゾルゲルシリカ粒子を含有するものである静電荷像現像用トナー外添剤を提供する。本発明の表面処理ゾルゲルシリカ粒子は、トナー外添剤として用いた場合、トナーに良好な流動性および印刷特性を与える。
[実施例1-1]
工程(A1):撹拌機、滴下ロート、温度計を備えた3リットルのガラス製反応器にメタノール793.0g、水32.1g、28%アンモニア水40.6gを添加して混合した。この溶液を45℃に調整し、撹拌しながら5.5%アンモニア水160.9gおよびテトラメトキシシラン646.5gを同時に滴下を開始し、前者は4時間、後者は6時間かけて滴下した。テトラメトキシシランの滴下が終了した後も、さらに0.5時間撹拌を継続して加水分解を行うことにより、親水性ゾルゲルシリカ粒子の懸濁液を得た。
実施例1-1において、工程(A1)の反応温度を35℃とした以外は実施例1-1と同様にして、表面処理ゾルゲルシリカ粒子(II)の白色粉体272gを得た。
実施例1-1において、工程(A1)の反応温度を27℃とした以外は実施例1-1と同様にして、表面処理ゾルゲルシリカ粒子(III)の白色粉体269gを得た。
実施例1-1において、工程(A1)の反応温度を25℃とした以外は実施例1-1と同様にして、表面処理ゾルゲルシリカ粒子(IV)の白色粉体273gを得た。
実施例1-1において、工程(A2)の1,3-ジビニル-1,1,3,3-テトラメチルジシラザンに代えて1,3-ジフェニル-1,1,3,3-テトラメチルジシラザン3.1g(SiO21モルに対して0.26モル相当量)を用いた以外は実施例1-1と同様にして、表面処理ゾルゲルシリカ粒子(V)の白色粉体274gを得た。
実施例1-1において、工程(A2)の1,3-ジビニル-1,1,3,3-テトラメチルジシラザンに代えて1,3-ジ-n-オクチル-1,1,3,3-テトラメチルジシラザン3.9g(SiO21モルに対して0.26モル相当量)を用いた以外は実施例1-1と同様にして、表面処理ゾルゲルシリカ粒子(VI)の白色粉体275gを得た。
実施例1-1において、工程(A1)を行い、工程(A2)を行わず、工程(A3)として、工程(A1)で得られた懸濁液に25℃でヘキサメチルジシラザン205.3g(SiO21モルに対して30モル相当量)を0.5時間かけて滴下後、60℃で8時間反応させることにより、表面がトリメチルシリル化された表面処理ゾルゲルシリカ粒子の分散液を得た。次いで、この分散液中の分散媒を130℃、減圧下(6650Pa)で留去することにより、表面処理ゾルゲルシリカ粒子(VII)の白色粉体268gを得た。
実施例1-3において、工程(A1)を行い、工程(A2)を行わず、工程(A3)として、工程(A1)で得られた懸濁液に25℃でヘキサメチルジシラザン205.3g(SiO21モルに対して30モル相当量)を0.5時間かけて滴下後、60℃で8時間反応させることにより、表面がトリメチルシリル化された表面処理ゾルゲルシリカ粒子の分散液を得た。次いで、この分散液中の分散媒を130℃、減圧下(6650Pa)で留去することにより、表面処理ゾルゲルシリカ粒子(VIII)の白色粉体268gを得た。
(1)動的光散乱法におけるメジアン径
表面処理ゾルゲルシリカ粒子0.1g及びメタノール19.9gをガラス瓶に入れ、超音波洗浄機に入れて、出力30W/Lの超音波を10分間照射させてメタノール中にシリカ粒子を分散させた。その分散液について動的光散乱法粒度分布測定装置(マイクロトラックベル社製NanotracWave II-Ex150)を用いてメジアン径を測定した。
表面処理ゾルゲルシリカ粒子を電子顕微鏡(日立製作所製、S-4700、倍率:10万倍)を用いて撮影し、粒子を二次元に投影した時の円形度(粒子面積と等しい面積の円の周囲長/粒子周囲長)を画像解析式粒度分布測定ソフト(株式会社マウンテック製Mac-View Ver.5)で評価した。なお、円形度は1次粒子100個を測定した平均値を用いた。
トルエン(屈折率1.4962)とメチルイソブチルケトン(屈折率1.3958)との混合溶媒に表面処理ゾルゲルシリカ粒子を添加し分散させ、上記溶媒の配合比率により屈折率を調整し、分散液が透明になる点(混合溶媒と表面処理シリカ微粒子の屈折率が合致する点)における混合溶媒の屈折率を表面処理ゾルゲルシリカ粒子の屈折率とした。なお、混合溶媒の屈折率はデジタル屈折計(株式会社アタゴ製RX-9000α)を用いて測定した25℃における値である。
液相置換法を用いた自動真密度測定装置(株式会社セイシン企業製オートトゥルーデンサーMAT-7000)を用いて、表面処理ゾルゲルシリカ粒子の真密度を測定した。
高精度ガス吸着量測定装置(マイクロトラックベル社製BELSORP MAX II)を用いて、BET1点法により水蒸気媒体及び窒素媒体それぞれに対する表面処理ゾルゲルシリカ粒子の比表面積を測定し、水蒸気吸着比表面積/窒素吸着比表面積の比を求めた。
粉体濡れ性試験機(株式会社レスカ製WET101P)を用い、体積濃度50%(温度25℃)のメタノール水溶液60mlに表面処理ゾルゲルシリカ粒子を0.2g添加し、撹拌子で攪拌した。次いでシリカ粒子が表面に浮遊した液中にメタノールを滴下しながら、メタノール水溶液に波長780nmの光を照射して透過率を測定した。表面処理ゾルゲルシリカ粒子が懸濁・沈降して、透過率が80%になったときのメタノール水溶液中のメタノール体積濃度(%)をメタノール疎水化度とした。
[実施例2-1~2-6、比較例2-1,2-2]
Tg60℃、軟化点110℃のポリエステル樹脂96重量部と色剤としてカーミン6BC(住化カラー(株)製)4重量部を溶融混練、粉砕、分級後、体積メジアン径7μmのトナーを得た。このトナー10gと実施例1-1~1-6、及び比較例1-1、1-2で得られた表面処理ゾルゲルシリカ粒子0.2gとをサンプルミルにて混合し、外添剤混合トナーを得た。これらについて下記(7)の方法による評価を行った。
20mlポリエチレン容器に、外添剤混合トナー10gを入れ、容器の蓋を開けた状態で60℃、30%RHの恒温恒湿条件に100時間曝露した後、トナー5gを、粉体特性評価装置(ホソカワミクロン株式会社製パウダーテスターPT-X)を使用して、篩の目開きが上から150μm、75μm、45μm、振動幅1mm、振動数1Hzで60秒間振動させた後、篩上に残った量を測定し、凝集度を下式にて算出した。その結果を表2に示す。
凝集度(%)=(W1+0.6×W2+0.2×W3)/5×100
W1:150μm目開き篩上の残存量(g)
W2:75μm目開き篩上の残存量(g)
W3:45μm目開き篩上の残存量(g)
[実施例3-1~3-6、比較例3-1,3-2]
実施例2-1~2-6、比較例2-1、2-2の外添剤混合トナー3質量部と、キャリアである標準フェライトL(日本画像学会)97質量部とを混合して二成分現像剤を調製した。上記工程により得られた二成分現像剤について、下記の方法(8)~(12)に従って測定を行った結果を表3に示す。
上記二成分現像剤を高温高湿(30℃、90%RH)、中温中湿(25℃、55%RH)及び低温低湿(10℃、15%RH)の各条件下に1日間曝露した後、同一条件下でそれぞれの試料を摩擦帯電した際の帯電量をブローオフ粉体帯電量測定装置(東芝ケミカル(株)製、TB-200)を用いて測定した。
上記二成分現像剤を、有機感光体を備えた現像機に入れ、25℃、50%RH環境下で30,000枚のプリントテストを実施した。このとき、感光体へのトナーの付着は、全ベタ画像での白抜けとして感知できる。ここで、白抜けの程度は、1cm2あたりの白抜け個所の数が10個以上を「多い」、1~9個を「少ない」、0個を「なし」と評価した。
上記(9)のプリントテストにおいて、画像の乱れとして検出される感光体摩耗について、下記基準で評価した。
A:画像の乱れのないもの
B:大きな画像の乱れのないもの
C:画像の乱れがあるもの
上記二成分現像剤を30℃、90%RHの環境に1日間曝露し、その後20cm四方のベタ印刷(画像濃度100%)を5,000枚連続印刷を行った後、再び上記二成分現像剤を30℃、90%RH環境下で静置した。これを60回繰返し、合計300,000枚の印刷を行った。初日の10枚目の印刷物を印刷物1、最終日の最終印刷物を印刷物2とした。
A:目視で画像欠損なし(白点なし)
B:目視で白点(粒子状に白く抜けた画像)が1個以上4個以下
C:目視で白点が5個以上9個以下
D:目視で白点が10個以上
上記印刷物1に対する印刷物2の濃度変化について、反射濃度計X-rite938(X-rite社製)を使用し、JIS Z 8781-5に準拠してCIE1976(L*a*b*)色空間における色差(ΔE)を測定し、下記基準により評価した。
A:ΔE差が1未満
B:ΔE差が1以上2.5未満
C:ΔE差が2.5以上3.0未満
D:ΔE差が3.0以上
Claims (6)
- 表面処理ゾルゲルシリカ粒子の製造方法であって、
(A1)4官能性シラン化合物、その部分加水分解縮合生成物又はこれらの混合物を加水分解及び縮合することによって、表面にシラノール基を有し、かつ実質的にSiO2単位からなる親水性ゾルゲルシリカ粒子を得る工程、
(A2)前記親水性ゾルゲルシリカ粒子に(C2H5)3Si-基又はR1R2 2Si-基(式中、R1は炭素原子数2~8のアルキル基もしくはアルケニル基、又は炭素原子数6~8のアリール基であり、R2は同一又は異種の置換又は非置換の炭素原子数1~4のアルキル基である)を有する化合物を添加して、前記親水性ゾルゲルシリカ粒子の表面に(C2H5)3SiO1/2単位又はR1R2 2SiO1/2単位(式中、R1及びR2は前記の通りである)を導入して予備処理シリカ粒子を得る工程、及び
(A3)前記予備処理シリカ粒子にR3 3Si-基(式中、R3は置換又は非置換の炭素原子数1~6の一価炭化水素基である)を有する化合物を添加して、前記予備処理シリカ粒子の表面に更にR3 3SiO1/2単位(式中、R3は前記の通りである)を導入して表面処理ゾルゲルシリカ粒子を得る工程を含み、かつ、
前記工程(A2)で前記親水性ゾルゲルシリカ粒子の表面に導入する単位と、前記工程(A3)で前記予備処理シリカ粒子の表面に導入する単位はそれぞれ異なることを特徴とする表面処理ゾルゲルシリカ粒子の製造方法。 - 前記工程(A1)を、一般式(i):
Si(OR4)4 (i)
(式中、各R4は同一又は異種の炭素原子数1~6の一価炭化水素基である)
で示される4官能性シラン化合物、その部分加水分解縮合生成物又はこれらの混合物を、塩基性物質の存在下、親水性有機溶媒と水の混合液中で加水分解及び縮合することによって、表面にシラノール基を有し、かつ実質的にSiO2単位からなる親水性ゾルゲルシリカ粒子の混合溶媒分散液を得る工程とし、
前記工程(A2)を、得られた前記親水性ゾルゲルシリカ粒子の混合溶媒分散液に、一般式(ii):
R1R2 2SiNHSiR1R2 2 (ii)
(式中、R1及びR2は前記の通りである)
で示されるシラザン化合物、ヘキサエチルジシラザン、一般式(iii-1):
R1R2 2SiX (iii-1)
(式中、R1及びR2は前記の通りであり、XはOH基又は加水分解性基である)
で示される1官能性シラン化合物、一般式(iii-2):
(C2H5)3SiX (iii-2)
(式中、Xは前記の通りである)
で示される1官能性シラン化合物、又はこれらの混合物を、前記親水性ゾルゲルシリカ粒子中のSiO2単位1モルあたり0.001~1モルを添加して、前記親水性ゾルゲルシリカ粒子の表面に(C2H5)3SiO1/2単位又はR1R2 2SiO1/2単位(R1及びR2は前記の通りである)を導入して予備処理シリカ粒子の混合溶媒分散液を得る工程とし、
前記工程(A3)を、得られた前記予備処理シリカ粒子の混合溶媒分散液に、一般式(iv):
R3 3SiNHSiR3 3 (iv)
(式中、R3は前記の通りである)
で示されるシラザン化合物、一般式(v):
R3 3SiX (v)
(式中、R3及びXは前記の通りである)
で示される1官能性シラン化合物、又はこれらの混合物を、前記予備処理シリカ粒子中のSiO2単位1モルあたり5~50モルを添加して、前記予備処理シリカ粒子の表面にR3 3SiO1/2単位(R3は前記の通りである)を導入して表面処理ゾルゲルシリカ粒子を得る工程とする
ことを特徴とする請求項1に記載の表面処理ゾルゲルシリカ粒子の製造方法。 - 前記R1を炭素原子数6~8のアルキル基、フェニル基、又はビニル基とし、前記R2をメチル基、エチル基、プロピル基又はイソプロピル基とし、前記R3をメチル基又はエチル基とすることを特徴とする請求項1又は請求項2に記載の表面処理ゾルゲルシリカ粒子の製造方法。
- 表面にR1R2 2SiO1/2単位(式中、R1は炭素原子数6~8のアルキル基もしくはアリール基、又はビニル基であり、R2は同一又は異種の炭素原子数1~4のアルキル基である)及びR3 3SiO1/2単位(式中、R3は同一又は異種の置換又は非置換の炭素原子数1~6の1価炭化水素基である)を有するものである表面処理ゾルゲルシリカ粒子であって、
動的光散乱法におけるメジアン径が5nm~99nmであり、
平均円形度が0.8~1.0であり、
屈折率が1.38~1.42であり、
真密度が1.7g/cm3以上1.9g/cm3未満であり、
水蒸気吸着比表面積/窒素吸着比表面積で表される比が0.4~1.9であり、
メタノール疎水化度が67%以上75%以下
のものであることを特徴とする表面処理ゾルゲルシリカ粒子。 - 前記R1が炭素原子数6~8のアルキル基、フェニル基、又はビニル基であり、前記R2がメチル基、エチル基、プロピル基又はイソプロピル基であり、前記R3がメチル基又はエチル基であることを特徴とする請求項4に記載の表面処理ゾルゲルシリカ粒子。
- 請求項4又は請求項5に記載の表面処理ゾルゲルシリカ粒子を含有するものであることを特徴とする静電荷像現像用トナー外添剤。
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JP2014114175A (ja) * | 2012-12-06 | 2014-06-26 | Shin Etsu Chem Co Ltd | 表面疎水化球状シリカ微粒子、その製造方法及びそれを用いた静電荷像現像用トナー外添剤 |
JP2015059054A (ja) * | 2013-09-18 | 2015-03-30 | 信越化学工業株式会社 | 表面有機樹脂被覆疎水性球状シリカ微粒子、その製造方法及びそれを用いた静電荷像現像用トナー外添剤 |
JP2020033224A (ja) * | 2018-08-29 | 2020-03-05 | 信越化学工業株式会社 | 正帯電型疎水性球状シリカ粒子、その製造方法及びそれを用いた正帯電トナー組成物 |
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WO2023145780A1 (ja) * | 2022-01-28 | 2023-08-03 | 日産化学株式会社 | 低誘電正接シリカゾル及び低誘電正接シリカゾルの製造方法 |
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