JP5655800B2 - Method for producing associated silica - Google Patents
Method for producing associated silica Download PDFInfo
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- JP5655800B2 JP5655800B2 JP2012028211A JP2012028211A JP5655800B2 JP 5655800 B2 JP5655800 B2 JP 5655800B2 JP 2012028211 A JP2012028211 A JP 2012028211A JP 2012028211 A JP2012028211 A JP 2012028211A JP 5655800 B2 JP5655800 B2 JP 5655800B2
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- fine particles
- silica fine
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- hydrophobic
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 311
- 239000000377 silicon dioxide Substances 0.000 title claims description 153
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000010419 fine particle Substances 0.000 claims description 129
- 230000002209 hydrophobic effect Effects 0.000 claims description 72
- 239000002245 particle Substances 0.000 claims description 58
- 239000011164 primary particle Substances 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 239000007859 condensation product Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 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 class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 description 34
- 239000000654 additive Substances 0.000 description 21
- 238000005259 measurement Methods 0.000 description 18
- 230000000996 additive effect Effects 0.000 description 17
- 238000000691 measurement method Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 108091008695 photoreceptors Proteins 0.000 description 10
- -1 silane compound Chemical class 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- 241000519995 Stachys sylvatica Species 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000012669 compression test Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 3
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 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
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000013112 stability test 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
- 238000012546 transfer Methods 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241001248531 Euchloe <genus> Species 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- APDDLLVYBXGBRF-UHFFFAOYSA-N [diethyl-(triethylsilylamino)silyl]ethane Chemical compound CC[Si](CC)(CC)N[Si](CC)(CC)CC APDDLLVYBXGBRF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000012730 carminic acid Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006482 condensation reaction Methods 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
- 238000004200 deflagration Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical class [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001575 sodium mineral Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-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
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- Developing Agents For Electrophotography (AREA)
Description
本発明は、会合シリカ微粒子、特には高分散性、低凝集性を有する疎水性の会合シリカ微粒子の製造方法に関する。
The present invention relates to a method for producing associated silica fine particles, particularly hydrophobic associative silica fine particles having high dispersibility and low aggregation .
電子写真法等で使用する乾式現像剤は、結着樹脂中に着色剤を分散したトナーそのものを用いる一成分現像剤と、そのトナーにキャリアを混合した二成分現像剤とに大別できる。これらの現像剤を用いてコピー操作を行う場合、プロセス適合性を有するためには、現像剤が流動性、耐ケーキング性、定着性、帯電性、クリーニング性等に優れていることが必要である。特に、流動性、耐ケーキング性、定着性、クリーニング性を高めるために、外添剤として無機微粒子をトナーに添加することがしばしば行われている。 Dry developers used in electrophotography and the like can be roughly classified into a one-component developer using a toner itself in which a colorant is dispersed in a binder resin and a two-component developer in which a carrier is mixed with the toner. When performing a copying operation using these developers, in order to have process compatibility, the developer needs to be excellent in fluidity, caking resistance, fixing properties, charging properties, cleaning properties, and the like. . In particular, in order to improve fluidity, anti-caking property, fixing property and cleaning property, inorganic fine particles are often added to the toner as an external additive.
トナー表面に混合機を用いて外添剤とトナーを混合させた場合に、これらの凝集体を解きほぐしながらトナー表面に付着させることが必要であり、その際にトナー表面に付着せず遊離した状態のまま存在したり、あるいはある程度付着しているが現像器内のストレス、摺擦等によりトナー表面より脱離し遊離状態となる場合もある。これらの遊離外添剤は、感光体表面にトナーが現像される際にトナーと共に感光体に移行し、転写後も感光体表面にとどまり、クリーニングされずに感光体表面に付着することがしばしば認められる。 When an external additive and toner are mixed on the toner surface using a mixer, it is necessary to unravel these aggregates and attach them to the toner surface. In some cases, the toner remains present or adheres to some extent, but may be detached from the toner surface due to stress, rubbing, or the like in the developing device. It is often recognized that these free external additives migrate to the photoreceptor together with the toner when the toner is developed on the photoreceptor surface, remain on the photoreceptor surface after transfer, and adhere to the photoreceptor surface without being cleaned. It is done.
これらの遊離外添剤が感光体表面に蓄積されると、コピー上の画質欠陥の原因（フィルミング、その他）となったり、感光体表面にキズをつけることがしばしば見られ、感光体の寿命を短くする原因となっている。また、現像時に現像機からこれら遊離外添剤がこぼれ落ちて複写機内を汚染するという問題もある。あるいは、現像剤中のキャリア表面に付着し、キャリアとトナー間での電荷授受を阻害し、結果としてトナーの帯電を低下させる一要因となることもある。 When these free external additives accumulate on the surface of the photoconductor, they often cause image quality defects on the copy (filming, etc.) or scratch the photoconductor surface. Is a cause of shortening. Another problem is that these free external additives spill from the developing machine during development and contaminate the copying machine. Alternatively, it may adhere to the surface of the carrier in the developer, impeding charge transfer between the carrier and the toner, resulting in a factor that lowers the charge of the toner.
無機系の外添剤としてヒュームドシリカの使用が報告されている（例えば、特許文献１：特開２００２−１１６５７５号公報参照）。しかし、ヒュームドシリカは、その複雑な粒子構造からトナーの流動性の付与効果において不十分であるという問題があった。また、球状溶融シリカをトナー用外添剤として使用することも報告されている（例えば、特許文献２：特開２００２−１５４８２０号公報参照）。しかし、この場合も、球状であるがためにトナー樹脂粒子の表面への付着力が乏しく、シリカ微粒子が脱落したトナー粒子表面がコピー機の感光体表面と接触し、トナーが所定の用紙に転写されず、感光体表面に残存し易い等の問題を有している。 The use of fumed silica as an inorganic external additive has been reported (for example, see Patent Document 1: Japanese Patent Application Laid-Open No. 2002-116575). However, fumed silica has a problem that its fluidity imparting effect is insufficient due to its complicated particle structure. It has also been reported that spherical fused silica is used as an external additive for toner (see, for example, JP-A-2002-154820). However, in this case as well, the adhesion to the surface of the toner resin particles is poor due to the spherical shape, and the surface of the toner particles from which the silica fine particles have dropped contacts the photoconductor surface of the copying machine, so that the toner is transferred to a predetermined paper. However, there is a problem that it tends to remain on the surface of the photoreceptor.
本発明は、上記事情に鑑みなされたもので、会合シリカ微粒子、特には高分散性、低凝集性を有する疎水性の会合シリカ微粒子の製造方法を提供することを目的とする。
更に、トナーの流動性は保ちながら、トナーからの脱落が少ない会合シリカ微粒子からなる静電荷像現像用トナー外添剤を提供することを他の目的とする。
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing associated silica fine particles, in particular, hydrophobic associative silica fine particles having high dispersibility and low aggregation.
It is another object of the present invention to provide a toner external additive for developing an electrostatic charge image, which is composed of associated silica fine particles which are less likely to fall out of the toner while maintaining the fluidity of the toner.
本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、下記製造方法によって得られた会合シリカが静電荷像現像用トナーの外添剤として非常に有効であることを知見した。 As a result of intensive studies to achieve the above object, the present inventors have found that the associated silica obtained by the following production method is very effective as an external additive for toner for developing electrostatic images. .
即ち、本発明は、上記の課題を解決する手段として、第一に、
下記一般式（１）：
Ｓｉ（ＯＲ1）4 （１）
（式中、Ｒ1は同一又は異なり、炭素原子数１〜６のアルキル基である。）
で示されるテトラアルコキシシラン及びその部分加水分解縮合生成物からなる群から選ばれる少なくとも１種の化合物を加水分解及び縮合することによって得られたＳｉＯ2単位からなる親水性シリカ微粒子の表面に、Ｒ4ＳｉＯ3/2単位（式中、Ｒ4は置換又は非置換の炭素原子数１〜２０の１価炭化水素基である。）を導入し、更にＲ6 3ＳｉＯ1/2単位（式中、Ｒ6は同一又は異なり、置換又は非置換の炭素原子数１〜２０の１価炭化水素基である。）を導入する疎水化処理により得られた疎水性球状シリカ微粒子であって、炭素含有量が２〜５質量％であり、アルコキシ基含有量が０．３〜１０質量％であり、粒子径が０．０１〜２００ｎｍである疎水性球状シリカ微粒子を、加湿雰囲気下、温度を１００〜５００℃で反応させることを特徴とする平均粒子径が５〜５００ｎｍの範囲にある１次粒子が２個以上会合した会合シリカの製造方法を提供する。
That is, as a means for solving the problems described above,
The following general formula (1):
Si (OR 1 ) 4 (1)
(In the formula, R 1 is the same or different and is an alkyl group having 1 to 6 carbon atoms.)
On the surface of hydrophilic silica fine particles comprising SiO 2 units obtained by hydrolyzing and condensing at least one compound selected from the group consisting of tetraalkoxysilanes and partial hydrolysis-condensation products thereof 4 SiO 3/2 unit (wherein R 4 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms), and further R 6 3 SiO 1/2 unit (wherein , R 6 are the same or different and are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms.) Hydrophobic spherical silica fine particles obtained by hydrophobizing treatment to introduce carbon Hydrophobic spherical silica fine particles having an amount of 2 to 5% by mass, an alkoxy group content of 0.3 to 10% by mass, and a particle size of 0.01 to 200 nm are heated in a humidified atmosphere at a temperature of 100 to 100%. Special reaction at 500 ℃ A method for producing associated silica in which two or more primary particles having an average particle diameter of 5 to 500 nm are associated.
本発明は、第二に、
（Ａ）下記一般式（１）：
Ｓｉ（ＯＲ1）4 （１）
（式中、Ｒ1は同一又は異なり、炭素原子数１〜６のアルキル基である。）
で示されるテトラアルコキシシラン及びその部分加水分解縮合生成物からなる群から選ばれる少なくとも１種の化合物を、塩基性物質の存在下で親水性有機溶媒と水との混合媒体中で加水分解、縮合して、親水性シリカ微粒子を生成させ、親水性シリカ微粒子混合媒体分散液を得る工程と、
（Ｂ）前記親水性シリカ微粒子混合媒体分散液中の親水性シリカ微粒子の表面にＲ4ＳｉＯ3/2単位（式中、Ｒ4は置換又は非置換の炭素原子数１〜２０の１価炭化水素基である。）を導入し、第一次疎水性球状シリカ微粒子を得る工程と、
（Ｃ）得られた第一次疎水性球状シリカ微粒子の表面にＲ6 3ＳｉＯ1/2単位（式中、Ｒ6は同一又は異なり、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。）を導入して第二次疎水性シリカ微粒子を得る工程と、
（Ｄ）得られた第二次疎水性球状シリカ微粒子を加湿雰囲気下、温度を１００〜５００℃で反応させることにより上記会合シリカを製造する方法を提供する。
The present invention secondly,
(A) The following general formula (1):
Si (OR 1 ) 4 (1)
(In the formula, R 1 is the same or different and is an alkyl group having 1 to 6 carbon atoms.)
Hydrolysis and condensation of at least one compound selected from the group consisting of tetraalkoxysilanes and partial hydrolysis-condensation products thereof in a mixed medium of a hydrophilic organic solvent and water in the presence of a basic substance And producing hydrophilic silica fine particles to obtain a hydrophilic silica fine particle mixed medium dispersion,
(B) R 4 SiO 3/2 units on the surface of the hydrophilic silica fine particles in the hydrophilic silica fine particle mixed medium dispersion (wherein R 4 is a substituted or unsubstituted monovalent carbon atom having 1 to 20 carbon atoms) A hydrogen group) to obtain primary hydrophobic spherical silica fine particles,
(C) R 6 3 SiO 1/2 unit (wherein R 6 is the same or different and is a substituted or unsubstituted monovalent valence of 1 to 6 carbon atoms) on the surface of the obtained primary hydrophobic spherical silica fine particles. A hydrocarbon group) to obtain secondary hydrophobic silica fine particles,
(D) A method for producing the associated silica by reacting the obtained secondary hydrophobic spherical silica fine particles in a humidified atmosphere at a temperature of 100 to 500 ° C. is provided.
本発明は、第三に、
上記疎水性球状シリカ微粒子を、槽内に入れて搬送しつつ乾燥する乾燥機に投入し、加熱搬送しながらかつ向流側から加熱蒸気を加えながら、温度を１００〜５００℃で反応させることを特徴とする上記会合シリカの製造方法を提供する。
この場合、上記乾燥機が、撹拌用ブレード付きフィーダー型、スクリューフィーダー型、ロータリーキルン型、又はスパイラルリフタ型であることが好ましく、特に撹拌用ブレード付きフィーダー型であることが好ましい。
Third, the present invention
The hydrophobic spherical silica fine particles are put into a dryer which is dried while being transported in a tank, and the reaction is performed at a temperature of 100 to 500 ° C. while heating and transporting and adding heated steam from the countercurrent side. Provided is a method for producing the associated silica.
In this case, the dryer is preferably a feeder type with a stirring blade, a screw feeder type, a rotary kiln type, or a spiral lifter type, and particularly preferably a feeder type with a stirring blade.
更に、本発明は、前記方法で得られた疎水性会合シリカ微粒子からなる静電荷像現像用トナー外添剤を提供する。 Furthermore, the present invention provides a toner external additive for developing an electrostatic charge image comprising the hydrophobic associated silica fine particles obtained by the above method.
本発明の製造方法により得られた疎水化した会合シリカ微粒子は、トナー外添剤として有用であり、トナーの流動性を改良することができ、更に、また粒子が会合した形の異形粒子であるため、トナー表面より脱離し遊離することが少なくなり、コピー上の画質欠陥の原因（フィルミング、その他）となることがない。このトナー外添剤を用いることで、電子写真法、静電記録法等における静電荷像の現像に応用することにより、高画質化が期待できる。 The hydrophobized associative silica fine particles obtained by the production method of the present invention are useful as an external toner additive, can improve the fluidity of the toner, and are irregularly shaped particles in which the particles are associated. Therefore, it is less likely to be detached and released from the toner surface, and it does not cause image quality defects on the copy (filming, etc.). By using this toner external additive, high image quality can be expected by applying it to the development of electrostatic images in electrophotography, electrostatic recording, and the like.
以下、本発明について詳細に説明する。
合成シリカ微粒子は、その製法によって、シラン化合物を燃焼させて得られる燃焼法シリカ（即ち、ヒュームドシリカ）、金属珪素粉を爆発的に燃焼させて得られる爆燃法シリカ、珪酸ナトリウムと鉱酸との中和反応によって得られる湿式シリカ（このうちアルカリ条件で合成したものを沈降法シリカ、酸性条件で合成したものをゲル法シリカという）、ヒドロカルビルオキシシランの加水分解によって得られるゾルゲル法シリカ（いわゆるＳｔｏｅｂｅｒ法）に大別される。本発明は、このうち、ゾルゲル法シリカに関するものであり、ゾルゲル法を改良した会合型シリカである。
Hereinafter, the present invention will be described in detail.
Synthetic silica fine particles are produced by combustion method silica obtained by burning a silane compound (that is, fumed silica), deflagration silica obtained by explosively burning metal silicon powder, sodium silicate and mineral acid. Wet silica obtained by the neutralization reaction of the above (the one synthesized under alkaline conditions is precipitated silica, the one synthesized under acidic conditions is gel silica), the sol-gel silica obtained by hydrolysis of hydrocarbyloxysilane (so-called (Stober method). Among these, the present invention relates to a sol-gel method silica, and is an associative silica obtained by improving the sol-gel method.
＜会合シリカ微粒子の特徴＞
まず、本発明の会合シリカ微粒子の特徴について、詳細に説明する。
本発明における会合シリカ微粒子とは、１次粒子が集合して球状となったり、又は凝集して塊状となった通常の形態の粒子ではなく、２個以上の１次粒子が会合して鎖状、繊維状、その他、異形の形態にある粒子のことをいう。
この会合シリカ微粒子における１次粒子の会合態様として、図１に示したように、１次粒子が２個会合したもの、３個以上鎖状に会合したもの、３個が３点で会合したもの、４個が平面的にあるいはテトラポット型に会合したもの、同様に５個以上の粒子が会合したもの、などの他、更にこれら会合シリカ粒子群同士が結合した会合シリカ微粒子も挙げることができる。
<Characteristics of associated silica fine particles>
First, the characteristics of the associated silica fine particles of the present invention will be described in detail.
The associated silica fine particles in the present invention are not particles in a normal form in which primary particles are aggregated into a spherical shape or aggregated into a lump, but two or more primary particles are associated to form a chain. , Refers to particles in the form of fibers and other irregular shapes.
As the mode of association of primary particles in the associated silica fine particles, as shown in FIG. 1, two primary particles are associated, three or more are associated in a chain, and three are associated at three points. In addition to those in which four particles are associated planarly or in a tetrapot type, and in which five or more particles are similarly associated, associated silica fine particles in which these associated silica particle groups are bonded to each other can also be exemplified. .
上記会合シリカ微粒子を構成する１次粒子は２個以上、好ましくは２〜２０個、特に好ましくは２〜６個、互いに会合している。会合シリカ微粒子を構成する１次粒子は必ずしも球状である必要はなく、卵状、サイコロ状、棒状であってもよいが、外添剤用途を考えると１次粒子は球状であることが好ましい。また、１次粒子の粒子径は互いに異なっていてもよく、更に会合部分の大きさは１次粒子の粒子径と同程度が好ましい。
上記１次粒子の平均粒子径は０．０１〜２００ｎｍ、好ましくは０．１〜１５０ｎｍの範囲にある。平均粒子径が０．０１ｎｍ未満の場合は、１次粒子が凝集して得られる粒子群が塊状になる傾向があり、現像剤の流動性、耐ケーキング性、定着性等が不十分なものとなり、平均粒子径が２００ｎｍを超えると、粒子が大きすぎて、感光体の変質や削れ、上記微粒子のトナーへの付着性の低下等の不都合を生じる場合がある。
Two or more, preferably 2 to 20, and particularly preferably 2 to 6, primary particles constituting the associated silica fine particles are associated with each other. The primary particles constituting the associated silica fine particles do not necessarily have to be spherical, and may be oval, dice, or rod-shaped, but the primary particles are preferably spherical in consideration of the use of external additives. Moreover, the particle diameters of the primary particles may be different from each other, and the size of the association part is preferably about the same as the particle diameter of the primary particles.
The average particle diameter of the primary particles is 0.01 to 200 nm, preferably 0.1 to 150 nm. When the average particle size is less than 0.01 nm, the particle group obtained by agglomeration of primary particles tends to be agglomerated and the developer fluidity, caking resistance, fixing property, etc. are insufficient. If the average particle diameter exceeds 200 nm, the particles may be too large, resulting in inconveniences such as alteration or scraping of the photoreceptor and a decrease in adhesion of the fine particles to the toner.
また、会合シリカの平均粒子径は５〜５００ｎｍであり、より好ましくは５０〜４００ｎｍである。 The average particle size of the associated silica is 5 to 500 nm, more preferably 50 to 400 nm.
会合シリカ微粒子を構成する１次粒子の割合は、会合シリカ微粒子の透過型電子顕微鏡写真を撮影し、任意エリア中の全粒子について、会合している１次粒子の総数と１次粒子のみからなる粒子の数を夫々求め、下記計算式で求めることができる。
［（会合している１次粒子の総数）／（会合している１次粒子の総数＋１次粒子のみの数）］×１００＝１次粒子の割合（％）
粒子数の計測は、１次粒子の総数が約３００個となるようなエリアについて測定するのがよい。
なお、ここで「粒子径」とは体積基準メジアン径を意味する。
The ratio of the primary particles constituting the associated silica fine particles is composed of the total number of primary particles associated with each other and only the primary particles for all particles in an arbitrary area obtained by taking a transmission electron micrograph of the associated silica fine particles. The number of particles can be obtained, and can be obtained by the following formula.
[(Total number of associated primary particles) / (Total number of associated primary particles + 1 Number of only primary particles)] × 100 = Ratio of primary particles (%)
The number of particles is preferably measured in an area where the total number of primary particles is about 300.
Here, “particle diameter” means a volume-based median diameter.
＜会合シリカ微粒子の製造方法＞
次に、本発明の会合シリカ微粒子の製造方法について詳細に説明する。該会合シリカ微粒子は、下記一般式（１）：
Ｓｉ（ＯＲ1）4 （１）
（式中、Ｒ1は同一又は異なり、炭素原子数１〜６のアルキル基である。）
で示されるテトラアルコキシシラン及びその部分加水分解縮合生成物からなる群から選ばれる少なくとも１種の化合物を加水分解及び縮合することによって得られたＳｉＯ2単位からなる親水性シリカ微粒子の表面にＲ4ＳｉＯ3/2単位（式中、Ｒ4は置換又は非置換の炭素原子数１〜２０の１価炭化水素基である。）を導入し、更にＲ6 3ＳｉＯ1/2単位（式中、Ｒ6は同一又は異なり、置換又は非置換の炭素原子数１〜２０の１価炭化水素基である。）を導入する疎水化処理により得られた疎水性球状シリカ微粒子であって、炭素含有量が２〜５質量％であり、アルコキシ基含有量が０．３〜１０質量％であり、粒子径が０．０１〜２００ｎｍである疎水性球状シリカ微粒子を、加湿雰囲気下、温度を１００〜５００℃で反応させることにより平均粒子径が５〜５００ｎｍの範囲にある１次粒子が２個以上会合した会合シリカが得られる。
<Method for producing associated silica fine particles>
Next, the method for producing associated silica fine particles of the present invention will be described in detail. The associated silica fine particles have the following general formula (1):
Si (OR 1 ) 4 (1)
(In the formula, R 1 is the same or different and is an alkyl group having 1 to 6 carbon atoms.)
R 4 on the surface of hydrophilic silica fine particles composed of SiO 2 units obtained by hydrolysis and condensation of at least one compound selected from the group consisting of tetraalkoxysilanes and partial hydrolysis-condensation products thereof. An SiO 3/2 unit (wherein R 4 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms) is further introduced, and an R 6 3 SiO 1/2 unit (wherein R 6 is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.) Hydrophobic spherical silica fine particles obtained by hydrophobizing treatment to introduce a carbon content Is 5 to 5% by mass, the alkoxy group content is 0.3 to 10% by mass, and the hydrophobic spherical silica fine particles having a particle size of 0.01 to 200 nm are heated at a temperature of 100 to 500 in a humidified atmosphere. By reacting at ℃ An associated silica in which two or more primary particles having an average particle diameter in the range of 5 to 500 nm are associated is obtained.
この場合、より好ましくは、
（Ａ）下記一般式（１）：
Ｓｉ（ＯＲ1）4 （１）
（式中、Ｒ1は同一又は異なり、炭素原子数１〜６のアルキル基である。）
で示されるテトラアルコキシシラン及びその部分加水分解縮合生成物からなる群から選ばれる少なくとも１種の化合物を、塩基性物質の存在下で親水性有機溶媒と水との混合媒体中で加水分解、縮合して、親水性シリカ微粒子を生成させ、親水性シリカ微粒子混合媒体分散液を得る工程と、
（Ｂ）前記親水性シリカ微粒子混合媒体分散液中の親水性シリカ微粒子の表面にＲ4ＳｉＯ3/2単位（式中、Ｒ4は置換又は非置換の炭素原子数１〜２０の１価炭化水素基である。）を導入し、第一次疎水性球状シリカ微粒子を得る工程と、
（Ｃ）得られた第一次疎水性球状シリカ微粒子の表面にＲ6 3ＳｉＯ1/2単位（式中、Ｒ6は同一又は異なり、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。）を導入して第二次疎水性シリカ微粒子を得る工程と、
（Ｄ）得られた第二次疎水性球状シリカ微粒子を加湿雰囲気下、温度を１００〜５００℃で反応させることにより上記会合シリカを製造することができる。以下に詳細説明する。
In this case, more preferably,
(A) The following general formula (1):
Si (OR 1 ) 4 (1)
(In the formula, R 1 is the same or different and is an alkyl group having 1 to 6 carbon atoms.)
Hydrolysis and condensation of at least one compound selected from the group consisting of tetraalkoxysilanes and partial hydrolysis-condensation products thereof in a mixed medium of a hydrophilic organic solvent and water in the presence of a basic substance And producing hydrophilic silica fine particles to obtain a hydrophilic silica fine particle mixed medium dispersion,
(B) R 4 SiO 3/2 units on the surface of the hydrophilic silica fine particles in the hydrophilic silica fine particle mixed medium dispersion (wherein R 4 is a substituted or unsubstituted monovalent carbon atom having 1 to 20 carbon atoms) A hydrogen group) to obtain primary hydrophobic spherical silica fine particles,
(C) R 6 3 SiO 1/2 unit (wherein R 6 is the same or different and is a substituted or unsubstituted monovalent valence of 1 to 6 carbon atoms) on the surface of the obtained primary hydrophobic spherical silica fine particles. A hydrocarbon group) to obtain secondary hydrophobic silica fine particles,
(D) The associated silica can be produced by reacting the obtained secondary hydrophobic spherical silica fine particles at a temperature of 100 to 500 ° C. in a humidified atmosphere. This will be described in detail below.
−親水性シリカ微粒子の合成−
まず親水性シリカ微粒子混合媒体分散液を作製する（Ａ）工程について説明する。
一般式（１）：
Ｓｉ（ＯＲ1）4 （１）
（式中、Ｒ1は同一又は異なり、炭素原子数１〜６のアルキル基である。）
で示されるテトラアルコキシシラン及び／又はその部分加水分解縮合生成物を加水分解及び縮合させ親水性シリカ微粒子を生成させる。
-Synthesis of hydrophilic silica fine particles-
First, the step (A) for producing a hydrophilic silica fine particle mixed medium dispersion will be described.
General formula (1):
Si (OR 1 ) 4 (1)
(In the formula, R 1 is the same or different and is an alkyl group having 1 to 6 carbon atoms.)
Hydroxyl silica fine particles are produced by hydrolyzing and condensing the tetraalkoxysilane and / or its partial hydrolysis-condensation product represented by formula (1).
上記一般式（１）中、Ｒ1は、好ましくは炭素原子数１〜６、より好ましくは１〜４、更に好ましくは１〜２のアルキル基である。Ｒ1としては、例えば、メチル基、エチル基、プロピル基、ブチル基等、好ましくは、メチル基、エチル基、プロピル基、ブチル基、特に好ましくは、メチル基、エチル基が挙げられる。 In the general formula (1), R 1 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 2 carbon atoms. Examples of R 1 include a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a methyl group, an ethyl group, a propyl group, and a butyl group, and particularly preferably a methyl group and an ethyl group.
上記一般式（１）で示される４官能性シラン化合物としては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のテトラアルコキシシラン等が挙げられ、好ましくは、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、特に好ましくは、テトラメトキシシラン、テトラエトキシシランが挙げられる。また、一般式（１）で示される４官能性シラン化合物の部分加水分解縮合生成物としては、例えば、メチルシリケート、エチルシリケート等が挙げられる。 Examples of the tetrafunctional silane compound represented by the general formula (1) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and preferably tetramethoxysilane. , Tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, particularly preferably tetramethoxysilane and tetraethoxysilane. Examples of the partial hydrolysis-condensation product of the tetrafunctional silane compound represented by the general formula (1) include methyl silicate and ethyl silicate.
前記親水性有機溶媒としては、一般式（１）で示される４官能性シラン化合物と、この部分加水分解縮合生成物と、水とを溶解するものであれば特に制限されず、例えば、アルコール類、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、酢酸セロソルブ等のセロソルブ類、アセトン、メチルエチルケトン等のケトン類、ジオキサン、テトラヒドロフラン等のエーテル類等、好ましくは、アルコール類、セロソルブ類、特に好ましくはアルコール類が挙げられる。アルコール類としては、一般式（２）：
Ｒ3ＯＨ （２）
（式中、Ｒ3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。
The hydrophilic organic solvent is not particularly limited as long as it dissolves the tetrafunctional silane compound represented by the general formula (1), the partial hydrolysis-condensation product, and water. For example, alcohols 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, preferably alcohols and cellosolves, particularly preferably alcohols . As alcohols, general formula (2):
R 3 OH (2)
(In the formula, R 3 is a monovalent hydrocarbon group having 1 to 6 carbon atoms.)
The alcohol shown by is mentioned.
上記一般式（２）中、Ｒ3は、好ましくは炭素原子数１〜４、特に好ましくは１〜２の１価炭化水素基である。Ｒ3で表される１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基等のアルキル基など、好ましくはメチル基、エチル基、プロピル基、イソプロピル基、より好ましくはメチル基、エチル基が挙げられる。一般式（２）で示されるアルコールとしては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等、好ましくは、メタノール、エタノールが挙げられる。アルコールの炭素原子数が増えると、生成する会合シリカ微粒子の粒子径が大きくなる。従って、目的とする会合シリカ微粒子の粒子径によりアルコールの種類を選択することが望ましい。 In the general formula (2), R 3 is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms. Examples of the monovalent hydrocarbon group represented by R 3 include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, More preferably, a methyl group and an ethyl group are mentioned. Examples of the alcohol represented by the general formula (2) include methanol, ethanol, propanol, isopropanol, butanol and the like, preferably methanol and ethanol. As the number of carbon atoms in the alcohol increases, the particle size of the associated silica fine particles to be generated increases. Therefore, it is desirable to select the type of alcohol according to the particle size of the target associated silica fine particles.
また、上記塩基性物質としてはアンモニア、及びジメチルアミン、ジエチルアミン等のジ低級アルキルアミン、好ましくは、アンモニア及びジエチルアミン、特に好ましくはアンモニアが挙げられる。これらの塩基性物質は、所要量を水に溶解した後、得られた水溶液（塩基性）を前記親水性有機溶媒と混合すればよい。 Examples of the basic substance include ammonia and di-lower alkylamines such as dimethylamine and diethylamine, preferably ammonia and diethylamine, and particularly preferably ammonia. These basic substances may be dissolved in water in a required amount, and the obtained aqueous solution (basic) may be mixed with the hydrophilic organic solvent.
このとき使用される水の量は、上記一般式（１）で表されるテトラアルコキシシラン及び／又はその部分加水分解縮合生成物のアルコキシ基の合計１モルに対して０．５〜５モルであることが好ましく、０．６〜２モルであることがより好ましく、０．７〜１モルであることが特に好ましい。水に対する親水性有機溶媒の比率は、質量比で０．５〜１０であることが好ましく、１〜５であることがより好ましく、１．５〜２であることが特に好ましい。塩基性物質の量は、上記一般式（１）で表されるテトラアルコキシシラン及び／又はその部分加水分解縮合生成物のアルコキシ基の合計１モルに対して０．０１〜２モルであることが好ましく、０．５〜１．５モルであることがより好ましく、１．０〜１．２モルであることが特に好ましい。 The amount of water used at this time is 0.5 to 5 mol with respect to a total of 1 mol of the tetraalkoxysilane represented by the general formula (1) and / or the alkoxy group of the partially hydrolyzed condensation product. Preferably, it is 0.6 to 2 mol, more preferably 0.7 to 1 mol. The ratio of the hydrophilic organic solvent to water is preferably 0.5 to 10 by mass ratio, more preferably 1 to 5, and particularly preferably 1.5 to 2. The amount of the basic substance is 0.01 to 2 mol with respect to a total of 1 mol of the tetraalkoxysilane represented by the general formula (1) and / or the alkoxy group of the partially hydrolyzed condensation product thereof. Preferably, it is 0.5 to 1.5 mol, more preferably 1.0 to 1.2 mol.
上記一般式（１）で表されるテトラアルコキシシラン及び／又はその部分加水分解縮合生成物の加水分解及び縮合は、周知の方法、即ち、塩基性物質を含む親水性有機溶媒と水との混合物中に、上記一般式（１）で表されるテトラアルコキシシラン及び／又はその部分加水分解縮合生成物を添加することにより行われる。 Hydrolysis and condensation of the tetraalkoxysilane represented by the general formula (1) and / or a partial hydrolysis-condensation product thereof is a well-known method, that is, a mixture of a hydrophilic organic solvent containing a basic substance and water. It is carried out by adding a tetraalkoxysilane represented by the general formula (1) and / or a partial hydrolysis-condensation product thereof.
−第一次疎水性球状シリカ微粒子の合成−
次に第一次疎水性球状シリカ微粒子を作製する（Ｂ）工程について説明する。
第一次疎水性球状シリカ微粒子の製造は、上記の本質的にＳｉＯ2単位からなる親水性シリカ微粒子の表面にＲ4ＳｉＯ3/2単位を導入する。
-Synthesis of primary hydrophobic spherical silica particles-
Next, the step (B) for producing the primary hydrophobic spherical silica fine particles will be described.
In the production of the primary hydrophobic spherical silica fine particles, R 4 SiO 3/2 units are introduced on the surface of the hydrophilic silica fine particles consisting essentially of the SiO 2 units.
上記Ｒ4ＳｉＯ3/2単位を導入するためには親水性球状シリカ微粒子分散液に一般式（３）：
Ｒ4Ｓｉ（ＯＲ5）3 （３）
（但し、Ｒ4は置換又は非置換の炭素原子数１〜２０の１価炭化水素基、Ｒ5は同一又は異種の炭素原子数１〜６の１価炭化水素基を示す。）
で示される３官能性シラン化合物及びその部分加水分解縮合物から選択される１種又は２種以上の化合物を添加し処理する。
In order to introduce the R 4 SiO 3/2 unit, the general formula (3):
R 4 Si (OR 5 ) 3 (3)
(However, R 4 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 5 represents the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms.)
One or two or more compounds selected from trifunctional silane compounds represented by the formula (1) and partial hydrolysis condensates thereof are added and treated.
この場合、Ｒ4としては、アルキル基、アリール基、アラルキル基等が挙げられるが、より好ましくは炭素原子数１〜１２、特に１〜８のアルキル基が挙げられ、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基等が挙げられる。また、上記置換１価炭化水素基としては、上記した基の水素原子の１個又はそれ以上をハロゲン原子で置換した基等が挙げられる。
上記Ｒ5としては、アルキル基、アラルキル基、フェニル基等が挙げられる。
In this case, examples of R 4 include an alkyl group, an aryl group, an aralkyl group, and the like, more preferably an alkyl group having 1 to 12 carbon atoms, particularly 1 to 8 carbon atoms, a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group and the like. Examples of the substituted monovalent hydrocarbon group include groups obtained by substituting one or more hydrogen atoms of the above groups with halogen atoms.
Examples of R 5 include an alkyl group, an aralkyl group, and a phenyl group.
一般式（３）で示される３官能性シラン化合物の具体例としては、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、イソプロピルトリメトキシシラン、イソプロピルトリエトキシシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、ヘキシルトリメトキシシラン等のトリアルコキシシランが挙げられ、また、これらの部分加水分解縮合物を用いてもよい。 Specific examples of the trifunctional silane compound represented by the general formula (3) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltrimethoxysilane. Examples include trialkoxysilanes such as ethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, and hexyltrimethoxysilane, and these partially hydrolyzed condensates may also be used. .
一般式（３）で示される３官能性シラン化合物の添加量は、処理される親水性シリカ微粒子が含有するＳｉＯ2単位１モル当たり１〜０．００１モル、好ましくは０．１〜０．０１モル用いるのがよい。 The addition amount of the trifunctional silane compound represented by the general formula (3) is 1 to 0.001 mol, preferably 0.1 to 0.01, per 1 mol of SiO 2 unit contained in the hydrophilic silica fine particles to be treated. It is better to use a mole.
また、上記３官能性シラン化合物又はその（部分）加水分解縮合物を添加、処理する場合の処理条件は、反応温度は、１０〜７０℃が好ましく、より好ましくは２０〜５０℃であり、反応時間は、通常１０分〜１０時間、特には３０分〜５時間である。 Moreover, as for the process conditions in the case of adding and processing the said trifunctional silane compound or its (partial) hydrolysis-condensation product, 10-70 degreeC of reaction temperature is preferable, More preferably, it is 20-50 degreeC, The time is usually 10 minutes to 10 hours, particularly 30 minutes to 5 hours.
なお、Ｒ4ＳｉＯ3/2単位の導入量は、処理される親水性シリカ微粒子が含有するＳｉＯ2単位１モル当たり０．０００１〜１質量％であることが好ましく、より好ましくは０．００１〜０．１質量％である。 The amount of R 4 SiO 3/2 units introduced is preferably 0.0001 to 1% by mass, more preferably 0.001 to 1 mass% per mole of SiO 2 units contained in the hydrophilic silica fine particles to be treated. 0.1% by mass.
−第二次疎水性球状シリカ微粒子の合成−
更に第二次疎水性球状シリカ微粒子を作製する（Ｃ）工程について説明する。
第二次疎水性球状シリカ微粒子の製造は、更にＲ6 3ＳｉＯ1/2単位を導入するもので、上記第一次疎水性球状シリカ微粒子に、引き続き下記一般式（４）：
Ｒ6 3ＳｉＮＨＳｉＲ6 3 （４）
（式中、Ｒ6は同一又は異なり、置換又は非置換の炭素原子数１〜２０の１価炭化水素基である。）
で表されるシラザン化合物、又は下記一般式（５）：
Ｒ6 3ＳｉＸ （５）
（式中、Ｒ6は上記と同じであり、ＸはＯＨ基又は加水分解性基である。）
で表される１官能性シラン化合物、あるいはこれらの組み合わせを添加し、上記第一次疎水性球状ゾルゲルシリカ微粒子表面に残存する反応性基をトリオルガノシリル化し疎水化する。
-Synthesis of secondary hydrophobic spherical silica particles-
Further, the step (C) for producing secondary hydrophobic spherical silica fine particles will be described.
The production of the secondary hydrophobic spherical silica fine particles further involves introducing R 6 3 SiO 1/2 units, and the following general formula (4):
R 6 3 SiNHSiR 6 3 (4)
(In the formula, R 6 is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.)
Or a silazane compound represented by the following general formula (5):
R 6 3 SiX (5)
(In the formula, R 6 is the same as above, and X is an OH group or a hydrolyzable group.)
And a reactive group remaining on the surface of the primary hydrophobic spherical sol-gel silica fine particles is triorganosilylated to be hydrophobized.
上記一般式（４）及び（５）中、Ｒ6は、好ましくは炭素原子数１〜４、特に好ましくは１〜２の１価炭化水素基である。Ｒ6で表される１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基等のアルキル基など、好ましくは、メチル基、エチル基、プロピル基、特に好ましくは、メチル基、エチル基が挙げられる。また、これらの１価炭化水素基の水素原子の一部又は全部が、フッ素原子、塩素原子、臭素原子等のハロゲン原子、好ましくは、フッ素原子で置換されていてもよい。 In the general formulas (4) and (5), R 6 is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms. The monovalent hydrocarbon group represented by R 6 is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, preferably a methyl group, an ethyl group, or a propyl group. Includes a methyl group and an ethyl group. Further, some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom, preferably fluorine atom.
Ｘで表される加水分解性基としては、例えば、塩素原子、アルコキシ基、アミノ基、アシルオキシ基等、好ましくは、アルコキシ基、アミノ基、特に好ましくは、アルコキシ基が挙げられる。 Examples of the hydrolyzable group represented by X include a chlorine atom, an alkoxy group, an amino group, and an acyloxy group, preferably an alkoxy group and an amino group, and particularly preferably an alkoxy group.
上記一般式（４）で表されるシラザン化合物としては、例えば、ヘキサメチルジシラザン、ヘキサエチルジシラザン等、好ましくはヘキサメチルジシラザンが挙げられる。上記一般式（５）で表される１官能性シラン化合物としては、例えば、トリメチルシラノール、トリエチルシラノール等のモノシラノール化合物、トリメチルクロロシラン、トリエチルクロロシラン等のモノクロロシラン、トリメチルメトキシシラン、トリメチルエトキシシラン等のモノアルコキシシラン、トリメチルシリルジメチルアミン、トリメチルシリルジエチルアミン等のモノアミノシラン、トリメチルアセトキシシラン等のモノアシルオキシシラン、好ましくは、トリメチルシラノール、トリメチルメトキシシラン、トリメチルシリルジエチルアミン、特に好ましくは、トリメチルシラノール、トリメチルメトキシシランが挙げられる。 Examples of the silazane compound represented by the general formula (4) include hexamethyldisilazane and hexaethyldisilazane, preferably hexamethyldisilazane. Examples of the monofunctional silane compound represented by the general formula (5) include monosilanol compounds such as trimethylsilanol and triethylsilanol, monochlorosilanes such as trimethylchlorosilane and triethylchlorosilane, trimethylmethoxysilane, and trimethylethoxysilane. Monoalkoxysilane, trimethylsilyldimethylamine, monoaminosilane such as trimethylsilyldiethylamine, monoacyloxysilane such as trimethylacetoxysilane, preferably trimethylsilanol, trimethylmethoxysilane, trimethylsilyldiethylamine, particularly preferably trimethylsilanol, trimethylmethoxysilane .
これらの使用量は、使用した親水性シリカ微粒子のＳｉＯ2単位１モルに対して０．０５〜０．５モルである。 The amount of these used is 0.05-0.5 mol with respect to 1 mol of SiO 2 units of the used hydrophilic silica fine particles.
上記式（４）のシラザン化合物及び／又は式（５）の１官能性シラン化合物を用いて疎水化処理する場合の処理条件は、反応温度は１０〜８０℃であることが好ましく、より好ましくは２０〜７０℃であり、反応時間は、通常３０分〜２４時間、特には１〜１２時間である。 As for the treatment conditions when hydrophobizing using the silazane compound of the above formula (4) and / or the monofunctional silane compound of the formula (5), the reaction temperature is preferably 10 to 80 ° C., more preferably It is 20-70 degreeC, and reaction time is 30 minutes-24 hours normally, Especially it is 1 to 12 hours.
こうして得られた疎水性球状シリカ微粒子を、常法の乾燥方法によって疎水性球状シリカ微粒子粉体とする。 The hydrophobic spherical silica fine particles thus obtained are made into hydrophobic spherical silica fine particle powders by a conventional drying method.
得られた疎水性球状シリカ微粒子粉体は、炭素含有量が２〜５質量％であり、アルコキシ基含有量が０．３〜１０質量％であり、粒子径が０．０１〜２００ｎｍである疎水性球状シリカ微粒子が好ましい。 The obtained hydrophobic spherical silica fine particle powder has a carbon content of 2 to 5% by mass, an alkoxy group content of 0.3 to 10% by mass, and a particle size of 0.01 to 200 nm. Spherical silica fine particles are preferred.
この時、特にアルコキシ基含有量が、０．３〜１０質量％、好ましくは１．０〜６質量％である。この量が０．３質量％より少ないと会合するシリカの割合が低くなり、１０質量％よりも多いと凝集物が増加する場合がある。 At this time, especially alkoxy group content is 0.3-10 mass%, Preferably it is 1.0-6 mass%. When this amount is less than 0.3% by mass, the proportion of silica to be associated becomes low, and when it is more than 10% by mass, aggregates may increase.
−会合シリカ微粒子の合成−
上記（Ｃ）工程で得られた疎水性球状シリカ微粒子粉体を用いて会合シリカを作製する（Ｄ）工程について説明する。
疎水性球状シリカ微粒子粉体を加湿雰囲気下で温度を１００〜５００℃で反応させることにより、疎水性球状シリカ微粒子同士を会合させ、会合シリカ微粒子を作製する。この場合、微粒子間でアルコキシ基の縮合反応が生じると考えられる。
-Synthesis of associated silica fine particles-
The step (D) for producing the associated silica using the hydrophobic spherical silica fine particle powder obtained in the step (C) will be described.
By reacting the hydrophobic spherical silica fine particle powder in a humidified atmosphere at a temperature of 100 to 500 ° C., the hydrophobic spherical silica fine particles are associated with each other to produce associated silica fine particles. In this case, it is considered that a condensation reaction of alkoxy groups occurs between the fine particles.
この時、単に加湿雰囲気下で温度をかけることによりシリカ粒子同士が会合はするが、より会合を促進させるために、シリカ粒子を槽内に入れて搬送させつつ、乾燥できるような乾燥機を用いることが特に好ましい。
このような乾燥機としては、撹拌用ブレード付きフィーダー型、スクリューフィーダー型、ロータリーキルン型、スパイラルリフタ型であることが好ましい。
この場合、加熱搬送しながらかつ向流側から加熱蒸気を加えながら、撹拌混合し、１００〜５００℃に加熱することが好ましい。
そのような乾燥機は、撹拌用ブレード付きフィーダー型のものが、会合シリカを製造するには最も好ましい。
At this time, silica particles are associated with each other simply by applying a temperature in a humidified atmosphere, but in order to further promote the association, a dryer that can be dried while being carried in a tank is used. It is particularly preferred.
Such a dryer is preferably a feeder type with a stirring blade, a screw feeder type, a rotary kiln type, or a spiral lifter type.
In this case, it is preferable to stir and mix and heat to 100 to 500 ° C. while heating and conveying and adding heated steam from the countercurrent side.
Such a dryer is most preferably a feeder type with a stirring blade for producing associated silica.
この時の加熱温度は１００〜５００℃、特に２００〜４００℃が好ましい。この温度が１００℃未満であると会合比率が上がらず、この温度が５００℃を超えると凝集物が増加することがある。 The heating temperature at this time is preferably 100 to 500 ° C, particularly 200 to 400 ° C. If this temperature is less than 100 ° C, the association ratio does not increase, and if this temperature exceeds 500 ° C, aggregates may increase.
また、蒸気量は、特に制限されないが、０．５〜５０ｋｇ／ｈが好ましく、より好ましくは５〜３０ｋｇ／ｈであり、加熱時間は、通常１０分〜１０時間、特には３０分〜５時間である。 The amount of steam is not particularly limited, but is preferably 0.5 to 50 kg / h, more preferably 5 to 30 kg / h, and the heating time is usually 10 minutes to 10 hours, particularly 30 minutes to 5 hours. It is.
＜疎水性会合シリカ微粒子からなるトナー外添剤＞
本発明の疎水性会合シリカ微粒子は、トナー外添剤等として有用である。該会合微粒子からなるトナー外添剤のトナーに対する配合量は、トナー１００質量部に対して、通常０．０１〜２０質量部であり、好ましくは０．１〜５質量部、特に好ましくは１〜２質量部である。この配合量が少なすぎると、トナーへの付着量が少なく十分な流動性が得られず、多すぎるとトナーの帯電性に悪影響を及ぼす。
<Toner external additive comprising hydrophobic associative silica fine particles>
The hydrophobic associative silica fine particles of the present invention are useful as an external toner additive. The amount of the toner external additive composed of the associated fine particles is usually 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 1 to 1 part by weight with respect to 100 parts by weight of the toner. 2 parts by mass. If the blending amount is too small, the adhesion amount to the toner is small and sufficient fluidity cannot be obtained, and if it is too large, the chargeability of the toner is adversely affected.
該会合微粒子のトナー粒子表面への付着状態は、単に機械的に付着していても、ゆるく固着されていてもよい。また、この付着した微粒子は、トナー粒子の表面全体を覆っていても、一部だけを覆っていてもよい。更に、該微粒子は、その一部が凝集体を形成してトナー粒子の表面を覆っていてもよいが、単層粒子の状態で覆っていることが好ましい。 The associating state of the associated fine particles on the toner particle surface may be merely mechanically adhered or loosely fixed. The adhered fine particles may cover the entire surface of the toner particles or only a part thereof. Further, the fine particles may partially form aggregates and cover the surface of the toner particles, but are preferably covered in the form of single layer particles.
本発明の会合微粒子を適用可能なトナー粒子としては、結着樹脂と着色剤とを主成分として含有する公知のトナー粒子等が挙げられ、必要に応じて、更に帯電制御剤等が添加されていてもよい。 Examples of the toner particles to which the associated fine particles of the present invention can be applied include known toner particles containing a binder resin and a colorant as main components, and a charge control agent or the like is further added as necessary. May be.
本発明の会合微粒子からなるトナー外添剤を添加されたトナーは、例えば、電子写真法、静電記録法等により、静電荷像を現像するために使用される静電荷像現像用等に使用される。前記トナーは、一成分現像剤として使用することができるが、それをキャリアと混合し、二成分現像剤として使用することもできる。二成分現像剤として使用する場合には、上記トナー外添剤を予めトナー粒子に添加せず、トナーとキャリアとの混合時に添加してトナーの表面被覆を行ってもよい。該キャリアとしては、公知のもの、例えば、フェライト、鉄粉等、又は、それらの表面に樹脂コーティングされたもの等が使用できる。 The toner to which the toner external additive composed of the associated fine particles of the present invention is added is used for developing an electrostatic image used for developing an electrostatic image by, for example, electrophotography, electrostatic recording method, etc. Is done. The toner can be used as a one-component developer, but it can also be used as a two-component developer by mixing it with a carrier. When used as a two-component developer, the toner external coating may not be added to the toner particles in advance, but may be added when the toner and the carrier are mixed to cover the surface of the toner. As the carrier, known ones, for example, ferrite, iron powder, etc., or those coated on the surface with resin can be used.
更に、本発明者らは、本発明に係る疎水性会合シリカ微粒子からなるトナー外添剤は、所望の特性に加えて、粒子が会合した形の異形粒子であるため、トナー表面より脱離し遊離することが少なくなり、コピー上の画質欠陥の原因（フィルミング、その他）となることがなく、高画質化が可能であることを見出したものである。 Furthermore, the present inventors have found that the toner external additive comprising the hydrophobic associative silica fine particles according to the present invention is an irregularly shaped particle in which the particles are associated in addition to the desired characteristics, so that it is detached from the toner surface and released. It has been found that image quality can be improved without causing image quality defects on copying (filming, etc.).
以下、実施例及び比較例を用いて本発明を具体的に説明する。なお、下記の実施例は、本発明を何ら制限するものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The following examples do not limit the present invention.
［実施例１］
［疎水性会合シリカ微粒子の合成］
撹拌機と、滴下ロートと、温度計とを備えた３リットルのガラス製反応器にメタノール８５７ｇと、水７４ｇと、２５質量％アンモニア水５１．１ｇとを入れて混合した。この溶液を３０℃となるように調整し、撹拌しながらテトラメトキシシラン８００ｇ（５．２６モル）及び３．５質量％アンモニア水２８７ｇを同時に添加し始め、両方を４時間で滴下した。その後３０℃を保ちながら、１時間撹拌した。そこにメチルトリメトキシシラン７．２ｇ（０．０５３モル）を０．５時間かけて滴下し、５０℃で１時間撹拌を行い、親水性球状微粒子シリカを得た。その後一旦室温まで冷却し、ヘキサメチルジシラザン１６９ｇ（１．０５モル）を０．５時間かけて滴下した後、この分散液を６７℃に加熱し、８時間反応させた。次いで、この分散液中の溶媒を８０℃、減圧下（６，６５０Ｐａ）で留去することにより、疎水性球状シリカ微粒子３１５ｇを疎水性球状シリカ微粒子粉体として得た。
この疎水性球状シリカ微粒子粉体の炭素含有量は３．６質量％であり、アルコキシ基含有量が３．２質量％であり、平均粒子径は８０ｎｍである球状シリカあった。
[Example 1]
[Synthesis of hydrophobic-associated silica fine particles]
In a 3 liter glass reactor equipped with a stirrer, a dropping funnel, and a thermometer, 857 g of methanol, 74 g of water, and 51.1 g of 25% by mass ammonia water were mixed. This solution was adjusted to 30 ° C., and 800 g (5.26 mol) of tetramethoxysilane and 287 g of 3.5% by mass ammonia water were simultaneously added while stirring, and both were added dropwise over 4 hours. Thereafter, the mixture was stirred for 1 hour while maintaining 30 ° C. Thereto, 7.2 g (0.053 mol) of methyltrimethoxysilane was added dropwise over 0.5 hours, followed by stirring at 50 ° C. for 1 hour to obtain hydrophilic spherical fine particle silica. Thereafter, the mixture was once cooled to room temperature and 169 g (1.05 mol) of hexamethyldisilazane was added dropwise over 0.5 hours, and then this dispersion was heated to 67 ° C. and reacted for 8 hours. Next, the solvent in the dispersion was distilled off at 80 ° C. under reduced pressure (6,650 Pa) to obtain 315 g of hydrophobic spherical silica fine particles as hydrophobic spherical silica fine particles.
The hydrophobic spherical silica fine particle powder had a carbon content of 3.6% by mass, an alkoxy group content of 3.2% by mass and an average particle size of 80 nm.
この疎水性球状シリカ微粒子粉体２００ｇを撹拌用ブレード付きフィーダー型乾燥機に添加し、向流側からスチームを流しながら、温度を２００℃に保ち、滞留時間を２時間で反応を行い、疎水性会合シリカ微粒子粉体１を１９４ｇ得た。 200 g of this hydrophobic spherical silica fine particle powder is added to a feeder-type dryer with a stirring blade, and the reaction is carried out with a residence time of 2 hours while maintaining the temperature at 200 ° C. while flowing steam from the countercurrent side. 194 g of associative silica fine particle powder 1 was obtained.
得られた疎水性会合シリカ微粒子１について、下記の測定方法に従って、それぞれの測定を行った。結果を表１に示す。上記会合前の疎水性球状シリカ粒子の粒子径は下記測定方法１、会合されていることは、測定方法２および３、アルコキシ基含有量は下記測定方法６、炭素含有量は下記測定方法７で測定を行った。 Each of the obtained hydrophobic associative silica fine particles 1 was measured according to the following measurement method. The results are shown in Table 1. The particle diameter of the hydrophobic spherical silica particles before the association is the following measurement method 1, the association is the measurement methods 2 and 3, the alkoxy group content is the following measurement method 6, and the carbon content is the following measurement method 7. Measurements were made.
・測定方法１：疎水性球状シリカ微粒子粉体及び疎水性会合シリカ微粒子の粒子径測定
メタノールにシリカ微粒子を０．５質量％となるように添加し、１０分間超音波にかけることにより、該微粒子を分散させた。このように処理した微粒子の粒度分布を、レーザー回折散乱式粒度分布測定装置（堀場製作所製、商品名：ＬＡ９１０）により測定し、その体積基準メジアン径を粒子径とした。なお、メジアン径とは粒子径分布を累積分布として表したときの累積５０％に相当する粒子径である。
Measurement method 1: Particle size measurement of hydrophobic spherical silica fine particle powder and hydrophobic associative silica fine particles Silica fine particles are added to methanol so as to be 0.5% by mass, and subjected to ultrasonic waves for 10 minutes. Was dispersed. The particle size distribution of the fine particles treated in this way was measured with a laser diffraction / scattering particle size distribution analyzer (trade name: LA910, manufactured by Horiba, Ltd.), and the volume-based median diameter was defined as the particle size. The median diameter is a particle diameter corresponding to 50% cumulative when the particle size distribution is expressed as a cumulative distribution.
・測定方法２：疎水性球状シリカ微粒子の形状測定
電子顕微鏡（日立製作所製、商品名：Ｓ−４７００型、倍率：１０万倍）によって観察を行い、形状を確認した。
Measurement method 2: Shape measurement of hydrophobic spherical silica fine particles The shape was confirmed by observation with an electron microscope (manufactured by Hitachi, trade name: S-4700 type, magnification: 100,000 times).
・測定方法３：会合シリカ微粒子を構成する１次粒子の割合測定
会合シリカ微粒子を構成する１次粒子の割合は、会合シリカ微粒子の透過型電子顕微鏡（日立製作所製、商品名：ＨＦ−３３００）にて写真を撮影し、任意エリア中の全粒子について、会合している１次粒子の総数と１次粒子のみからなる粒子の数を夫々求め、下記計算式で求めることができる。
［（会合している１次粒子の総数）／（会合している１次粒子の総数＋１次粒子のみの数）］×１００＝１次粒子の割合（％）
粒子数の計測は、１次粒子の総数が約３００個となるようなエリアについて測定した。
Measurement method 3: Measurement of the proportion of primary particles constituting the associated silica fine particles The proportion of the primary particles constituting the associated silica fine particles is determined by the transmission electron microscope of the associated silica fine particles (trade name: HF-3300, manufactured by Hitachi, Ltd.). The total number of associated primary particles and the number of particles composed only of primary particles are obtained for all particles in an arbitrary area, respectively, and can be obtained by the following calculation formula.
[(Total number of associated primary particles) / (Total number of associated primary particles + 1 Number of only primary particles)] × 100 = Ratio of primary particles (%)
The number of particles was measured in an area where the total number of primary particles was about 300.
・測定方法４：会合粒子の１次粒子結合数
会合シリカ微粒子を構成する１次粒子の結合数は、会合シリカ微粒子の透過型電子顕微鏡（日立製作所製、商品名：ＨＦ−３３００）にて写真を撮影し、任意エリア中の会合粒子について、会合している１次粒子の総数と会合粒子の数を夫々求め、下記計算式で求めることができる。
（１次粒子の総数）／（会合粒子の総数）＝１次粒子の結合数
粒子数の計測は、１次粒子の総数が約３００個となるようなエリアについて測定した。
Measurement method 4: number of primary particles bonded to associated particles The number of bonds of primary particles constituting the associated silica fine particles is photographed with a transmission electron microscope (trade name: HF-3300, manufactured by Hitachi, Ltd.) of the associated silica fine particles. , The total number of associated primary particles and the number of associated particles are determined for the associated particles in an arbitrary area, respectively, and can be calculated by the following calculation formula.
(Total number of primary particles) / (Total number of associated particles) = Number of bonded primary particles The number of particles was measured in an area where the total number of primary particles was about 300.
・測定方法５：疎水性シリカ微粒子のアルコキシ基含有量
シリカ微粒子５ｇに１Ｎ水酸化カリウム−イソプロピルアルコール溶液１０ｇを添加し、７０℃で１時間加熱しシリカの分解を行い、その後、液体分を蒸留して取る。この留分をガスクロマトグラフ分析し含有されるメタノール量を定量することで、シリカ微粒子に含有されるアルコキシ基量を定量する。
Measurement method 5: Alkoxy group content of hydrophobic silica fine particles 10 g of 1N potassium hydroxide-isopropyl alcohol solution is added to 5 g of silica fine particles, heated at 70 ° C. for 1 hour to decompose the silica, and then the liquid is distilled. Take it. The fraction of the alkoxy group contained in the silica fine particles is quantified by gas chromatographic analysis of this fraction and quantifying the amount of methanol contained.
・測定方法６：疎水性シリカ微粒子の炭素含有量
堀場製作所製ＥＭＩＡ−１１０型機を使用し、シリカ微粒子をボードに０．１ｇ採取し、燃焼炉にそのボードを送って１，２００℃で燃焼させる。その時の二酸化炭素量により炭素量を換算した。
Measurement method 6: Carbon content of hydrophobic silica fine particles Using an EMIA-110 type machine manufactured by HORIBA, Ltd., 0.1 g of silica fine particles was sampled on a board, sent to a combustion furnace, and burned at 1,200 ° C. Let The amount of carbon was converted by the amount of carbon dioxide at that time.
［外添剤混合トナーの作製］
ガラス転移温度Ｔg６０℃、軟化点１１０℃であるポリエステル樹脂９６質量部と、着色剤（住友カラー（株）製、商品名：カーミン６ＢＣ）４質量部とを、溶融混練、粉砕及び分級することにより、平均粒子径７μｍのトナーを得た。このトナー４０ｇに上記疎水性会合疎水性シリカ微粒子１ｇをサンプルミルにより混合し、外添剤混合トナーとした。これを用いて、下記の測定方法４に従って、トナー流動性を測定した。なお、得られた結果を表２に示す。
[Preparation of external additive mixed toner]
96 parts by mass of a polyester resin having a glass transition temperature T g of 60 ° C. and a softening point of 110 ° C. and 4 parts by mass of a colorant (manufactured by Sumitomo Color Co., Ltd., trade name: Carmine 6BC) are melt-kneaded, pulverized and classified. As a result, a toner having an average particle diameter of 7 μm was obtained. 40 g of this toner was mixed with 1 g of the hydrophobic associative hydrophobic silica fine particles by a sample mill to obtain an external additive mixed toner. Using this, toner fluidity was measured according to the following measurement method 4. The results obtained are shown in Table 2.
・測定方法７：トナー流動性の測定
トナーの流動性は、粉体流動性分析装置ＦＴ−４（シスメックス（株）製）を用いて測定した。この装置の測定原理を説明する。垂直に置かれた筒状容器に粉体を充填し、該粉体中を垂直な軸棒の先端に設けられた二枚の回転翼（ブレード）を回転させながら一定の距離（高さＨ１からＨ２まで）下降させる。このときに粉体から受ける力をトルク成分と荷重成分とに分けて測定することにより、ブレードがＨ１からＨ２まで下降するのに伴うそれぞれの仕事量（エネルギー）を求め、次いで両者のトータルエネルギー量を求める。こうして測定されたトータルエネルギー量が小さいほど粉体の流動性が良好であることを意味するので、粉体流動性の指標として使用する。
Measurement method 7: Measurement of toner fluidity The toner fluidity was measured using a powder fluidity analyzer FT-4 (manufactured by Sysmex Corporation). The measurement principle of this apparatus will be described. A cylindrical container placed vertically is filled with powder, and while rotating two rotating blades (blades) provided at the tip of a vertical shaft rod in the powder, a certain distance (from height H1) Down to H2. The force received from the powder at this time is measured separately for the torque component and the load component, so that each work (energy) associated with the blade descending from H1 to H2 is obtained, and then the total energy amount of both Ask for. The smaller the total energy measured in this way, the better the fluidity of the powder, so it is used as an index of powder fluidity.
また、以下のように、安定性試験、流速試験、通気試験、及び圧縮試験を行った。 In addition, a stability test, a flow rate test, an aeration test, and a compression test were performed as follows.
容器：
安定性、流速及び通気の試験では、容積１２０ｍｌ、内径８０ｍｍ、長さ６０ｍｍのガラス製円筒型容器を使用した。圧縮試験では容積２５ｍｌ、内径２５ｍｍ、長さ５２．５ｍｍのガラス製円筒型容器を使用した。容器の下部から空気を導入することができるように構成されている。
container:
In the stability, flow rate and ventilation tests, a glass cylindrical container having a volume of 120 ml, an inner diameter of 80 mm, and a length of 60 mm was used. In the compression test, a glass cylindrical container having a volume of 25 ml, an inner diameter of 25 mm, and a length of 52.5 mm was used. It is comprised so that air can be introduce | transduced from the lower part of a container.
ブレード：
円筒型容器内の中央に鉛直に装入されるステンレス製の軸棒の先端に水平に対向する形で二枚取り付けられている。ブレードは、容積１２０ｍｌの容器の場合は直径４８ｍｍのものを使用し、容積２５ｍｌの容器の場合には直径２３．５ｍｌのものを使用する。
blade:
Two stainless steel shaft rods are vertically mounted in the center of the cylindrical container so as to be horizontally opposed to each other. A blade with a diameter of 48 mm is used for a container with a volume of 120 ml, and a blade with a diameter of 23.5 ml is used for a container with a volume of 25 ml.
Ｈ１からＨ２までの長さ：容積１２０ｍｌの容器の場合は５０ｍｍであり、容積２５ｍｌの容器の場合には４７．５ｍｍである。 Length from H1 to H2: 50 mm for a container with a volume of 120 ml and 47.5 mm for a container with a volume of 25 ml.
安定性試験：
上記のようにして、測定容器に充填した粉体を静置した状態から流動させた場合の粉体流動特性をみる。ブレード先端の回転速度を１００ｍｍ／ｓｅｃの条件とし、トータルエネルギー量を７回連続して測定する。７回目のトータルエネルギー量（最も安定した状態であるので基本流動性エネルギーと称される）を表２に示した。小さいほど安定性が高い。
Stability test:
As described above, the powder flow characteristics when the powder filled in the measurement container is caused to flow from a stationary state are observed. The total energy amount is measured seven times continuously under the condition that the rotational speed of the blade tip is 100 mm / sec. Table 2 shows the total amount of energy for the seventh time (referred to as basic fluidity energy because it is the most stable state). The smaller the value, the higher the stability.
流速試験：
流速の変化に対する粉体流動特性をみる。ブレード先端の回転速度を１０ｍｍ／ｓｅｃで測定した際のトータルエネルギー量を表２に示した。小さいほど流動性が高い。
Flow rate test:
The powder flow characteristics with respect to the change of flow velocity are observed. Table 2 shows the total energy amount when the rotational speed of the blade tip was measured at 10 mm / sec. The smaller the value, the higher the fluidity.
通気試験：
通気量に応じた粉体流動特性をみる。ブレード先端の回転速度を１００ｍｍ／ｓｅｃとし、容器下部から導入する空気の通気量を０ｍｍ／ｓｅｃから０．１ｍｍ／ｓｅｃずつ増加させ０．５ｍｍ／ｓｅｃまでの６段階で別々に順序に測定し、最小の通気量（０ｍｍ／ｓｅｃ）及び最大の通気量（０．５ｍｍ／ｓｅｃ）でのトータルエネルギー量を表２に示した。小さいほど空気が関与する状態での粉体流動性が高い。
Ventilation test:
Check the powder flow characteristics according to the air flow rate. The rotational speed of the blade tip is set to 100 mm / sec, the air flow rate introduced from the lower part of the container is increased in increments of 0 mm / sec by 0.1 mm / sec and measured separately in six steps from 0.5 mm / sec, Table 2 shows the total energy amount at the minimum air flow rate (0 mm / sec) and the maximum air flow rate (0.5 mm / sec). The smaller the value, the higher the powder fluidity when air is involved.
圧縮試験：
圧縮に対する粉体流動特性をみるものである。粉体にピストンを介して加重を加えて１０Ｎにて加圧して圧縮した後、ブレード先端の回転速度を１００ｍｍ／ｓｅｃとして測定しトータルエネルギー量を求めた。結果を表２に示した。小さいほど粉体が圧縮を受けた場合の粉体流動性が高い。
Compression test:
The powder flow characteristics with respect to compression are observed. After applying a weight to the powder through a piston and compressing it by applying pressure at 10 N, the rotational speed of the blade tip was measured at 100 mm / sec to obtain the total energy amount. The results are shown in Table 2. The smaller the powder, the higher the powder fluidity when the powder is compressed.
［現像剤の調製］
上で調製した外添剤混合トナー５質量部と、平均粒子径８５μｍのフェライトコアにパーフルオロアルキルアクリレート樹脂及びアクリル樹脂をポリブレンドしたポリマーでコーティングしたキャリア９５質量部とを混合して、現像剤を調製した。この現像剤を用いて、下記の測定方法８及び９に従って、トナー帯電量及び感光体へのトナー付着について測定した。なお、得られた結果を表２に示す。
[Developer preparation]
5 parts by weight of the external additive mixed toner prepared above and 95 parts by weight of a carrier coated with a polymer obtained by polyblending a perfluoroalkyl acrylate resin and an acrylic resin on a ferrite core having an average particle diameter of 85 μm are mixed together to prepare a developer. Was prepared. Using this developer, the toner charge amount and toner adhesion to the photoreceptor were measured according to the following measurement methods 8 and 9. The results obtained are shown in Table 2.
・測定方法８：トナー帯電量の測定
上記現像剤を高温高湿（３０℃、９０％ＲＨ）又は低温低湿（１０℃、１５％ＲＨ）の条件下に１日放置した後、振とう機により３０秒間混合して、摩擦帯電を行った。それぞれの試料の帯電量を、同一条件下で、ブローオフ粉体帯電量測定装置（東芝ケミカル（株）製、商品名：ＴＢ−２００型）を用いて測定した。上記２つの条件におけるトナー帯電量の差を求めることにより、該トナーの環境依存性について評価した。
Measurement method 8: Measurement of toner charge amount The developer is left for one day under conditions of high temperature and high humidity (30 ° C., 90% RH) or low temperature and low humidity (10 ° C., 15% RH), and then shaken. The mixture was mixed for 30 seconds to perform tribocharging. The charge amount of each sample was measured using a blow-off powder charge amount measuring device (trade name: TB-200, manufactured by Toshiba Chemical Corporation) under the same conditions. By determining the difference in toner charge amount under the above two conditions, the environmental dependency of the toner was evaluated.
・測定方法９：感光体へのトナー付着測定
上記現像剤を有機感光体が備えられた二成分改造現像機に入れ、３０，０００枚のプリントテストを行った。該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。白抜けの程度を次の基準で評価した。
白抜け１０個以上／ｃｍ2：多い
白抜け１〜９個／ｃｍ2：少ない
白抜け０個／ｃｍ2：なし
Measurement Method 9: Measurement of Toner Adhesion on Photoreceptor The above developer was placed in a two-component modified developer equipped with an organic photoreceptor, and a 30,000 print test was performed. The adhesion of toner to the photoreceptor can be detected as white spots in all solid images. The degree of white spots was evaluated according to the following criteria.
White spots more than 10 / cm 2: many white spots 1 to 9 / cm 2: little white spots 0 / cm 2: None
・測定方法１０：クリーニング性
クリーニング性評価については、実機評価終了後、潜像担持体上表面の傷や残留トナーの固着発生状況と出力画像への影響を目視で評価した。
◎ ： 未発生
○ ： 傷がわずかに認められるが、画像への影響はない
△ ： 残留トナーや傷が認められるが、画像への影響は少ない
× ： 残留トナーがかなり多く、縦スジ状の画像欠陥が発生
××： 残留トナーが固着して、画像欠陥も多数発生
Measurement method 10: Cleaning property With regard to the cleaning property evaluation, after completion of the actual machine evaluation, scratches on the surface of the latent image bearing member and the occurrence of sticking of residual toner and the influence on the output image were visually evaluated.
◎: Not generated ○: Scratches are slightly observed but there is no effect on the image △: Residual toner and scratches are observed, but there is little effect on the images Defects occur XX: Residual toner adheres and many image defects occur
［実施例２］
実施例１において、撹拌用ブレード付きフィーダー型乾燥機での条件を４００℃とした以外は同様にして、疎水性会合シリカ微粒子１９１ｇを乾燥粉体として得た。この疎水性会合シリカ微粒子２を用いて実施例１と同様に測定した。この結果を表１及び表２に示す。
[Example 2]
In Example 1, 191 g of hydrophobic associative silica fine particles were obtained as a dry powder in the same manner except that the conditions in a feeder dryer with a stirring blade were set to 400 ° C. Measurement was performed in the same manner as in Example 1 using the hydrophobic-associated silica fine particles 2. The results are shown in Tables 1 and 2.
［実施例３］
実施例１において、撹拌用ブレード付きフィーダー型乾燥機での条件を滞留時間４時間とした以外は同様にして、疎水性会合シリカ微粒子１９２ｇを乾燥粉体として得た。この疎水性会合シリカ微粒子３を用いて実施例１と同様に測定した。この結果を表１及び表２に示す。
[Example 3]
In Example 1, 192 g of hydrophobic associative silica fine particles were obtained as a dry powder in the same manner except that the conditions in a feeder dryer with a stirring blade were set to a residence time of 4 hours. Measurement was performed in the same manner as in Example 1 using the hydrophobic-associated silica fine particles 3. The results are shown in Tables 1 and 2.
［実施例４］
実施例１において、撹拌用ブレード付きフィーダー型乾燥機での条件を５００℃で滞留時間を４時間とした以外は同様にして、疎水性会合シリカ微粒子１９２ｇを乾燥粉体として得た。この疎水性会合シリカ微粒子４を用いて実施例１と同様に測定した。この結果を表１及び表２に示す。
[Example 4]
In Example 1, 192 g of hydrophobic associative silica fine particles were obtained as a dry powder in the same manner except that the conditions in a feeder dryer equipped with a stirring blade were 500 ° C. and the residence time was 4 hours. Measurement was performed in the same manner as in Example 1 using the hydrophobic-associated silica fine particles 4. The results are shown in Tables 1 and 2.
［実施例５］
実施例１において、スクリューフィーダー型乾燥機での条件を４００℃で滞留時間を２時間とした以外は同様にして、疎水性会合シリカ微粒子１９２ｇを乾燥粉体として得た。この疎水性会合シリカ微粒子５を用いて実施例１と同様に測定した。この結果を表１及び表２に示す。
[Example 5]
In Example 1, 192 g of hydrophobic associative silica fine particles were obtained as a dry powder in the same manner except that the conditions in a screw feeder type dryer were 400 ° C. and the residence time was 2 hours. Measurement was performed in the same manner as in Example 1 using the hydrophobic-associated silica fine particles 5. The results are shown in Tables 1 and 2.
［実施例６］
実施例１において、ロータリーキルン型乾燥機での条件を４００℃で滞留時間を２時間とした以外は同様にして、疎水性会合シリカ微粒子１９２ｇを乾燥粉体として得た。この疎水性会合シリカ微粒子６を用いて実施例１と同様に測定した。この結果を表１及び表２に示す。
[Example 6]
In Example 1, 192 g of hydrophobic associative silica fine particles were obtained as a dry powder in the same manner except that the conditions in the rotary kiln dryer were 400 ° C. and the residence time was 2 hours. Measurement was performed in the same manner as in Example 1 using the hydrophobic-associated silica fine particles 6. The results are shown in Tables 1 and 2.
［実施例７］
実施例１において、スパイラルリフタ型乾燥機での条件を４００℃で滞留時間を２時間とした以外は同様にして、疎水性会合シリカ微粒子１９２ｇを乾燥粉体として得た。この疎水性会合シリカ微粒子７を用いて実施例１と同様に測定した。この結果を表１及び表２に示す。
[Example 7]
In Example 1, 192 g of hydrophobic associated silica fine particles were obtained as a dry powder in the same manner except that the conditions in the spiral lifter dryer were 400 ° C. and the residence time was 2 hours. Measurement was performed in the same manner as in Example 1 using the hydrophobic-associated silica fine particles 7. The results are shown in Tables 1 and 2.
［比較例１］
実施例１において、撹拌用ブレード付きフィーダー型乾燥機での条件を向流側からのスチームを流さずに行った以外は同様にして疎水性シリカ微粒子１９６ｇを乾燥粉体として得た。この疎水性シリカ微粒子を用いて実施例１と同様に測定した。この結果を表１及び表２に示す。
[Comparative Example 1]
196 g of hydrophobic silica fine particles were obtained as a dry powder in the same manner as in Example 1 except that the conditions in the feeder dryer with a stirring blade were changed without flowing steam from the countercurrent side. Measurement was performed in the same manner as in Example 1 using the hydrophobic silica fine particles. The results are shown in Tables 1 and 2.
［比較例２］
実施例１において、撹拌用ブレード付きフィーダー型乾燥機での条件を６００℃とした以外は同様にして、疎水性会合シリカ微粒子１８９ｇを乾燥粉体として得た。この疎水性シリカ微粒子を用いて実施例１と同様に測定した。この結果を表１及び表２に示す。
[Comparative Example 2]
In Example 1, 189 g of hydrophobic associative silica fine particles were obtained as a dry powder in the same manner except that the conditions in a feeder dryer equipped with a stirring blade were 600 ° C. Measurement was performed in the same manner as in Example 1 using the hydrophobic silica fine particles. The results are shown in Tables 1 and 2.
［比較例３］
実施例１において、撹拌用ブレード付きフィーダー型乾燥機での条件を８０℃とした以外は同様にして、疎水性会合シリカ微粒子１９５ｇを乾燥粉体として得た。この疎水性シリカ微粒子を用いて実施例１と同様に測定した。この結果を表１及び表２に示す。
[Comparative Example 3]
In Example 1, 195 g of hydrophobic associative silica fine particles were obtained as a dry powder in the same manner except that the conditions in a feeder dryer with a stirring blade were set to 80 ° C. Measurement was performed in the same manner as in Example 1 using the hydrophobic silica fine particles. The results are shown in Tables 1 and 2.
（１）７回目
（２）ブレードスピード １０ｍｍ／ｓ
（３）通気量 ０ｍｍ／ｓ
（４）通気量 ０．５ｍｍ／ｓ
（５）加圧 １０Ｎ
(1) 7th time (2) Blade speed 10mm / s
(3) Aeration rate 0mm / s
(4) Aeration rate 0.5mm / s
(5) Pressure 10N
Claims (5)
Ｓｉ（ＯＲ1）4 （１）
（式中、Ｒ1は同一又は異なり、炭素原子数１〜６のアルキル基である。）
で示されるテトラアルコキシシラン及びその部分加水分解縮合生成物からなる群から選ばれる少なくとも１種の化合物を加水分解及び縮合することによって得られたＳｉＯ2単位からなる親水性シリカの表面に、Ｒ4ＳｉＯ3/2単位（式中、Ｒ4は置換又は非置換の炭素原子数１〜２０の１価炭化水素基である。）を導入し、更にＲ6 3ＳｉＯ1/2単位（式中、Ｒ6は同一又は異なり、置換又は非置換の炭素原子数１〜２０の１価炭化水素基である。）を導入する疎水化処理により得られた疎水性球状シリカ微粒子であって、炭素含有量が２〜５質量％であり、アルコキシ基含有量が０．３〜１０質量％であり、１次粒子の平均粒子径が０．０１〜２００ｎｍである疎水性球状シリカ微粒子を、加湿雰囲気下、温度を１００〜５００℃で反応させることを特徴とする平均粒子径が５〜５００ｎｍの範囲にある１次粒子が２個以上会合した会合シリカの製造方法。 The following general formula (1):
Si (OR 1 ) 4 (1)
(In the formula, R 1 is the same or different and is an alkyl group having 1 to 6 carbon atoms.)
On the surface of hydrophilic silica composed of SiO 2 units obtained by hydrolyzing and condensing at least one compound selected from the group consisting of tetraalkoxysilanes and partial hydrolysis-condensation products thereof, represented by R 4 An SiO 3/2 unit (wherein R 4 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms) is further introduced, and an R 6 3 SiO 1/2 unit (wherein R 6 is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.) Hydrophobic spherical silica fine particles obtained by hydrophobizing treatment to introduce a carbon content Is 2 to 5% by mass, the alkoxy group content is 0.3 to 10% by mass, and the primary spherical particles have an average particle diameter of 0.01 to 200 nm. The reaction is performed at a temperature of 100 to 500 ° C. A method for producing associated silica in which two or more primary particles having an average particle diameter in the range of 5 to 500 nm are associated.
Ｓｉ（ＯＲ1）4 （１）
（式中、Ｒ1は同一又は異なり、炭素原子数１〜６のアルキル基である。）
で示されるテトラアルコキシシラン及びその部分加水分解縮合生成物からなる群から選ばれる少なくとも１種の化合物を、塩基性物質の存在下で親水性有機溶媒と水との混合媒体中で加水分解、縮合して、親水性シリカを生成させ、親水性シリカ微粒子混合媒体分散液を得る工程と、
（Ｂ）前記親水性シリカ混合媒体分散液中の親水性シリカ微粒子の表面にＲ4ＳｉＯ3/2単位（式中、Ｒ4は置換又は非置換の炭素原子数１〜２０の１価炭化水素基である。）を導入し、第一次疎水性球状シリカ微粒子を得る工程と、
（Ｃ）得られた第一次疎水性球状シリカ微粒子の表面にＲ6 3ＳｉＯ1/2単位（式中、Ｒ6は同一又は異なり、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。）を導入して第二次疎水性シリカ微粒子を得る工程と、
（Ｄ）得られた第二次疎水性球状シリカ微粒子を加湿雰囲気下、温度を１００〜５００℃で反応させることを特徴とする請求項１記載の会合シリカの製造方法。 (A) The following general formula (1):
Si (OR 1 ) 4 (1)
(In the formula, R 1 is the same or different and is an alkyl group having 1 to 6 carbon atoms.)
Hydrolysis and condensation of at least one compound selected from the group consisting of tetraalkoxysilanes and partial hydrolysis-condensation products thereof in a mixed medium of a hydrophilic organic solvent and water in the presence of a basic substance And producing hydrophilic silica to obtain a hydrophilic silica fine particle mixed medium dispersion,
(B) R 4 SiO 3/2 units on the surface of the hydrophilic silica fine particles in the hydrophilic silica mixed medium dispersion (wherein R 4 is a substituted or unsubstituted monovalent hydrocarbon having 1 to 20 carbon atoms) A step of obtaining primary hydrophobic spherical silica fine particles,
(C) R 6 3 SiO 1/2 unit (wherein R 6 is the same or different and is a substituted or unsubstituted monovalent valence of 1 to 6 carbon atoms) on the surface of the obtained primary hydrophobic spherical silica fine particles. A hydrocarbon group) to obtain secondary hydrophobic silica fine particles,
(D) The method for producing associated silica according to claim 1, wherein the obtained secondary hydrophobic spherical silica fine particles are reacted at a temperature of 100 to 500 ° C. in a humidified atmosphere.
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