JP2019109297A - Toner external additive for electrostatic latent image development - Google Patents
Toner external additive for electrostatic latent image development Download PDFInfo
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- JP2019109297A JP2019109297A JP2017240715A JP2017240715A JP2019109297A JP 2019109297 A JP2019109297 A JP 2019109297A JP 2017240715 A JP2017240715 A JP 2017240715A JP 2017240715 A JP2017240715 A JP 2017240715A JP 2019109297 A JP2019109297 A JP 2019109297A
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- latent image
- electrostatic latent
- external additive
- image development
- toner external
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- 239000000654 additive Substances 0.000 title claims abstract description 100
- 230000000996 additive effect Effects 0.000 title claims abstract description 91
- 238000011161 development Methods 0.000 title claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 124
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 51
- 239000000194 fatty acid Substances 0.000 claims abstract description 51
- 229930195729 fatty acid Natural products 0.000 claims abstract description 51
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 22
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 235000021357 Behenic acid Nutrition 0.000 claims description 3
- 229940116226 behenic acid Drugs 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 33
- 239000002245 particle Substances 0.000 abstract description 19
- 230000008859 change Effects 0.000 abstract description 11
- 238000013019 agitation Methods 0.000 abstract description 2
- 230000018109 developmental process Effects 0.000 description 63
- 238000000034 method Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 23
- 230000007613 environmental effect Effects 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000035882 stress Effects 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 fatty acid salt Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 101150096839 Fcmr gene Proteins 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
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- 150000004679 hydroxides Chemical class 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- AGDANEVFLMAYGL-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCC(O)=O AGDANEVFLMAYGL-UHFFFAOYSA-N 0.000 description 1
- WLGSIWNFEGRXDF-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O WLGSIWNFEGRXDF-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- KYYWBEYKBLQSFW-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCC(O)=O KYYWBEYKBLQSFW-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- NHXTZGXYQYMODD-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCC(O)=O NHXTZGXYQYMODD-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
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- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- NNNVXFKZMRGJPM-KHPPLWFESA-N sapienic acid Chemical compound CCCCCCCCC\C=C/CCCCC(O)=O NNNVXFKZMRGJPM-KHPPLWFESA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- CBYCSRICVDBHMZ-UHFFFAOYSA-N tetracosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCCCC(O)=O CBYCSRICVDBHMZ-UHFFFAOYSA-N 0.000 description 1
- ZTUXEFFFLOVXQE-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCC(O)=O ZTUXEFFFLOVXQE-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QPQANCNBWQXGTQ-UHFFFAOYSA-N trihydroxy(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](O)(O)O QPQANCNBWQXGTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Developing Agents For Electrophotography (AREA)
Abstract
Description
本発明は、複写機やプリンターなどの電子写真機器に用いられるトナー外添剤に係り、さらに詳しくは、体積抵抗率が低く、ストレスや温湿度が変化する環境の下においても安定した帯電性能を発現する静電潜像現像用トナー外添剤に関するものである。 The present invention relates to a toner external additive used in electrophotographic devices such as copying machines and printers, and more specifically, it has low volume resistivity and stable charging performance even in an environment where stress, temperature and humidity change. The present invention relates to a toner external additive for developing an electrostatic latent image which develops.
近年、複写機やプリンターなどの電子写真機器において、静電画像の高精細化、高画質化への要求が高まっている。これらを実現するために、温湿度などの環境変化に対応できる帯電性能や流動性が必要になることから、トナーに対して帯電性能や流動性を付与し、さらにクリーニング性を向上させる目的で、シリカや酸化チタンなどの無機微粒子を外添することが行われている。 In recent years, in electrophotographic devices such as copying machines and printers, there has been an increasing demand for higher definition and higher image quality of electrostatic images. In order to realize these, it is necessary to have charging performance and fluidity that can cope with environmental changes such as temperature and humidity. Therefore, for the purpose of imparting charging performance and fluidity to the toner and further improving the cleaning performance, Inorganic fine particles such as silica and titanium oxide are externally added.
しかしながら、一般的に、シリカは流動性が優れているものの、帯電性能の環境安定性が十分でないという問題があり、酸化チタンは帯電性能の環境安定性に優れているものの、流動性が充分ではなく、また高価であるという問題がある。 However, although silica generally has excellent fluidity, it has a problem that the environmental stability of the charging performance is not sufficient. Titanium oxide has excellent environmental stability of the charging performance but has sufficient fluidity. There is also the problem of being expensive and expensive.
ここで、シリカを使用する際の問題点となる帯電性能の環境安定性の低さは、特許文献１の［０００５］にも記載されている通り、シリカの持つ高い体積抵抗率に起因するものである。そして、この物性によってトナーが帯電する際に帯電量が過度に高くなる、いわゆるチャージアップ現象が生じ、現像を繰り返した際に画質が低下するという問題が生じる。また、このチャージアップ現象は低温、低湿度の環境下において顕著なものとなる。 Here, the low environmental stability of the charging performance, which becomes a problem when using silica, is caused by the high volume resistivity of silica as described in [0005] of Patent Document 1 It is. This physical property causes a so-called charge-up phenomenon in which the charge amount becomes excessively high when the toner is charged, and there is a problem that the image quality is deteriorated when the development is repeated. Also, this charge-up phenomenon is remarkable in a low temperature and low humidity environment.
従って、シリカの体積抵抗を低減することが出来れば、シリカの持つ流動性の高さを生かしつつ、帯電性能の環境安定性に優れる、理想的なトナー外添剤を作製することができることになる。 Therefore, if the volume resistance of silica can be reduced, it is possible to produce an ideal toner external additive that is excellent in the environmental stability of the charging performance while making use of the high fluidity of the silica. .
ここで、特許文献２では、シリカ粒子の表面に特殊な方法（超臨界二酸化炭素中）で脂肪酸金属塩を直接、被覆したトナー外添剤が開示されているが、超臨界条件を実現する必要があるため設備が大掛かりになってしまうという問題がある。 Here, Patent Document 2 discloses a toner external additive in which a fatty acid metal salt is directly coated on the surface of silica particles by a special method (in supercritical carbon dioxide), but it is necessary to realize supercritical conditions. There is a problem that the equipment becomes large because of
今回、本願発明者らは鋭意検討を行った結果、シリカ粒子の表面を金属元素の酸化物、水酸化物、またはこれらの混合物で被覆し、被覆した金属元素の酸化物、水酸化物、またはこれらの混合物をさらに脂肪酸で被覆する構造とすることによって、シリカ粒子が本来有する流動性を発現させつつ、体積抵抗率が低く、各種の安定性（耐ストレス性、環境安定性）に優れたトナー外添剤を得ることができるという知見を得るに至った。また、係るトナー外添剤を、超臨界装置などを用いることなく、簡単な設備、製造方法によって得ることができるという知見を得るに至った。 Here, as a result of intensive investigations by the present inventors, the surface of the silica particle is coated with an oxide, hydroxide or a mixture of metal elements, and the oxide, hydroxide or metal of a metal element coated By forming a mixture of these mixtures with a fatty acid in addition, a toner having low volume resistivity and excellent in various kinds of stability (stress resistance, environmental stability) while exhibiting fluidity originally possessed by silica particles We came to the knowledge that external additives can be obtained. In addition, it has been found that such a toner external additive can be obtained by a simple equipment and a manufacturing method without using a supercritical device or the like.
本発明は上記のような背景のもと、従来のトナー外添剤が有する問題点に鑑みてなされたものであって、体積抵抗率が低く、流動性に優れ、且つストレスや温湿度が変化する環境の下においても安定した帯電性能を発現することができる静電潜像現像用トナー外添剤の提供を目的とするものである。 The present invention was made in view of the problems of the conventional toner external additives under the above background, and has low volume resistivity, excellent fluidity, and changes in stress, temperature and humidity. It is an object of the present invention to provide a toner external additive for electrostatic latent image development which can exhibit stable charging performance even under the above circumstances.
上記目的を達成するために、本発明の請求項１に係る静電潜像現像用トナー外添剤は、シリカ粒子の表面の少なくとも一部を、金属元素の酸化物、水酸化物、またはこれらの混合物で被覆し、金属元素の酸化物、水酸化物、またはこれらの混合物の少なくとも一部を、さらに脂肪酸で被覆している構造となっていることを特徴とする。 In order to achieve the above object, the toner external additive for electrostatic latent image development according to claim 1 of the present invention comprises an oxide of a metal element, a hydroxide, or at least a part of a surface of a silica particle. And at least a part of the oxide of the metal element, the hydroxide, or the mixture thereof is further coated with a fatty acid.
本発明の請求項２に係る静電潜像現像用トナー外添剤は、前記金属元素の酸化物、水酸化物、またはこれらの混合物の被覆量が、前記シリカ粒子に対して酸化物換算で１〜４０質量％であることを特徴とする。 In the toner external additive for electrostatic latent image development according to claim 2 of the present invention, the coating amount of the oxide of the metal element, the hydroxide thereof, or the mixture thereof is in terms of oxide with respect to the silica particles. It is characterized by being 1-40 mass%.
本発明の請求項３に係る静電潜像現像用トナー外添剤は、前記金属元素がアルミニウム、亜鉛、マグネシウム、バリウムから選択される少なくとも一種であることを特徴とする。 The toner external additive for electrostatic latent image development according to claim 3 of the present invention is characterized in that the metal element is at least one selected from aluminum, zinc, magnesium and barium.
本発明の請求項４に係る静電潜像現像用トナー外添剤は、前記脂肪酸の被覆量が、前記シリカ粒子に対して１〜４０質量％であることを特徴とする。 The toner external additive for electrostatic latent image development according to claim 4 of the present invention is characterized in that the coated amount of the fatty acid is 1 to 40% by mass with respect to the silica particle.
本発明の請求項５に係る静電潜像現像用トナー外添剤は、前記脂肪酸が、総炭素数８〜２６のものであることを特徴とする。 The external additive for toner for electrostatic latent image development according to claim 5 of the present invention is characterized in that the fatty acid has 8 to 26 carbon atoms in total.
本発明の請求項６に係る静電潜像現像用トナー外添剤は、前記脂肪酸が、ステアリン酸、オレイン酸、イソステアリン酸、ラウリン酸、ベヘン酸から選択される少なくとも一種であることを特徴とする。 The toner external additive for electrostatic latent image development according to claim 6 of the present invention is characterized in that the fatty acid is at least one selected from stearic acid, oleic acid, isostearic acid, lauric acid and behenic acid. Do.
本発明の請求項７に係る静電潜像現像用トナー外添剤は、前記シリカ粒子が、１０〜４００ｍ２／ｇのＢＥＴ比表面積を持つものであることを特徴とする。 The toner external additive for electrostatic latent image development according to claim 7 of the present invention is characterized in that the silica particles have a BET specific surface area of 10 to 400 m 2 / g.
本発明の請求項８に係る静電潜像現像用トナー外添剤は、疎水化度が５０％以上であることを特徴とする。 The electrostatic latent image developing toner external additive according to claim 8 of the present invention is characterized in that the degree of hydrophobicity is 50% or more.
本発明の請求項９に係る静電潜像現像用トナー外添剤は、体積抵抗率が１．０×１０１１Ω・ｃｍ以下であることを特徴とする。 The toner external additive for electrostatic latent image development according to claim 9 of the present invention is characterized by having a volume resistivity of 1.0 × 10 11 Ω · cm or less.
本発明の請求項１０に係る静電潜像現像用トナーは、本発明の静電潜像現像用トナー外添剤を含有することを特徴とする。 The toner for electrostatic latent image development according to claim 10 of the present invention is characterized by containing the external additive for toner for electrostatic latent image development according to the present invention.
以下にそれぞれの構成要件について説明する。 The respective configuration requirements are described below.
（シリカ粒子）
本発明の静電潜像現像用トナー外添剤は、基材としてシリカ粒子を用いることを必須とする。本発明は、基材としてシリカ粒子を使用することによって、シリカが有する高い流動性を活かすことができるのである。なお、本発明に用いられるシリカ粒子は、製造される際の方法に限定されることはなく、液相法や気相法など各種の方法によって作製したものを用いることができる。
(Silica particles)
The toner external additive for electrostatic latent image development of the present invention essentially uses silica particles as a substrate. The present invention can take advantage of the high flowability of silica by using silica particles as a substrate. In addition, the silica particle used for this invention is not limited to the method at the time of manufacturing, What was produced by various methods, such as a liquid phase method and a gaseous-phase method, can be used.
本発明に用いるシリカ粒子の比表面積は特に限定されないが、静電画像の高精細化、高画質化の点から、ＢＥＴ比表面積が１０〜４００ｍ２／ｇであることが好ましく、３０〜３５０ｍ２／ｇであることがより好ましく、５０〜３００ｍ２／ｇであることがさらに好ましい。なお、本発明におけるＢＥＴ比表面積は、気体吸着法に基づいて窒素ガスの吸着量を検出することにより算出するものである。 Although the specific surface area of the silica particles used in the present invention is not particularly limited, high definition of the electrostatic image, from the viewpoint of high image quality, it is preferable that a BET specific surface area of 10~400m 2 / g, 30~350m 2 It is more preferable that it is / g, and it is further more preferable that it is 50-300 m < 2 > / g. The BET specific surface area in the present invention is calculated by detecting the amount of adsorption of nitrogen gas based on the gas adsorption method.
（金属元素の酸化物、水酸化物、またはこれらの混合物）
本発明の静電潜像現像用トナー外添剤は、基材としてシリカ粒子の表面の少なくとも一部を金属元素の酸化物、水酸化物、またはこれらの混合物で被覆することが必要である。このように本発明は、シリカ粒子の表面をまず金属元素の酸化物、水酸化物、またはこれらの混合物で被覆することによって、シリカの体積抵抗を低減させることができるのである。また、金属元素の酸化物、水酸化物、またはこれらの混合物がバインダーとしての役目を果たし、シリカ粒子に脂肪酸を被覆することができるのである。さらに、脂肪酸の被覆を超臨界装置などの大掛かりな設備を用いることなく、簡単な設備、製造方法で行うことができるのである。
(Oxides, hydroxides, or a mixture of these)
The toner external additive for electrostatic latent image development of the present invention is required to cover at least a part of the surface of the silica particle as a substrate with an oxide of metal element, a hydroxide, or a mixture thereof. Thus, according to the present invention, the volume resistance of silica can be reduced by first coating the surface of the silica particles with an oxide of metal element, a hydroxide, or a mixture thereof. In addition, an oxide of metal element, a hydroxide, or a mixture of these functions as a binder, and silica particles can be coated with a fatty acid. Furthermore, fatty acid coating can be performed with simple equipment and manufacturing method without using extensive equipment such as supercritical equipment.
本発明に用いる金属元素の酸化物、水酸化物、またはこれらの混合物の種類は特に限定されることなく、アルミニウム、亜鉛、カルシウム、マグネシウム、ストロンチウム、バリウム、チタン、ジルコニウム、スズ、鉄、銅など、各種の金属元素の酸化物、水酸化物、またはこれらの混合物で被覆することができる。そしてこれらの中でも、シリカ粒子が持つ高い体積抵抗を低減することができると共に、得られるトナー外添剤の特性（疎水性、体積抵抗率など）をさらに向上させることができることから、アルミニウム、亜鉛、マグネシウム、バリウムの酸化物、水酸化物、またはこれらの混合物で被覆することが好ましい。 The types of oxides, hydroxides or mixtures thereof of metal elements used in the present invention are not particularly limited, and aluminum, zinc, calcium, magnesium, strontium, barium, titanium, zirconium, tin, iron, copper, etc. And oxides of various metal elements, hydroxides, or a mixture thereof. Among these, aluminum, zinc, and the like can be further improved because the high volume resistance of the silica particles can be reduced and the characteristics (hydrophobicity, volume resistivity, etc.) of the resultant toner external additive can be further improved. It is preferable to coat with magnesium, an oxide of barium, a hydroxide or a mixture thereof.
金属元素の酸化物、水酸化物、またはこれらの混合物の被覆量については、シリカ粒子の体積抵抗を十分に低減させるために一定量以上の被覆量が必要である。
なお、本発明の静電潜像現像用トナー外添剤における金属元素については、製造時の条件（特に、後記する製造方法においてはｐＨや加温時の温度など）によって、シリカ粒子の表面に形成される形態も酸化物や水酸化物やこれらの混合物など様々なものとなる。
従って、金属元素の酸化物、水酸化物、またはこれらの混合物の被覆量については、酸化物換算によって決定することが好ましく、具体的には、シリカ粒子の質量を基準にして酸化物換算で１〜４０質量％とすることが好ましく、その中でも５〜２５質量％とすることがより好ましい。
金属元素の酸化物、水酸化物、またはこれらの混合物の被覆量が酸化物換算で１質量％よりも少ない場合には、基材の表面を十分に被覆することができず、シリカ粒子が持つ高い体積抵抗を低減する効果が不十分となる恐れがある。一方、４０質量％よりも多い場合には、シリカ粒子が有する高い流動性という利点が損なわれる恐れがある。
With respect to the coating amount of the oxide of the metal element, the hydroxide, or a mixture thereof, the coating amount of a certain amount or more is necessary to sufficiently reduce the volume resistance of the silica particles.
The metal element in the toner external additive for electrostatic latent image development of the present invention is applied to the surface of the silica particles under the conditions at the time of production (in particular, pH and heating temperature in the production method described later). The form to be formed is also various, such as oxides, hydroxides, and mixtures thereof.
Therefore, the coverage of the oxide of the metal element, the hydroxide, or a mixture thereof is preferably determined in terms of the oxide, specifically, 1 based on the mass of the silica particles in terms of the oxide. It is preferable to set it as -40 mass%, and it is more preferable to set it as 5-25 mass% also in it.
When the coverage of the oxide of the metal element, the hydroxide, or a mixture thereof is less than 1% by mass in terms of oxide, the surface of the substrate can not be sufficiently covered, and the silica particles have The effect of reducing high volume resistance may be insufficient. On the other hand, if it is more than 40% by mass, the advantage of the high fluidity of the silica particles may be lost.
なお、詳細については後記するが、シリカ粒子に金属元素の酸化物、水酸化物、またはこれらの混合物を被覆する方法としては、まず被覆したい金属元素の水溶性塩を用意し、係る水溶性塩の水溶液をシリカ粒子に添加した後、水酸化ナトリウム水溶液などのアルカリ物質を加えて金属元素の水溶性塩の加水分解を起こさせることによって、金属元素を酸化物、水酸化物、またはこれらの混合物としてシリカ粒子に被覆する方法などを挙げることができる。
このような金属元素の水溶性塩としては、上記した金属元素の塩化物、臭化物、硫酸塩、硝酸塩、酢酸塩、炭酸塩、炭酸水素塩などを挙げることができる。
In addition, although mentioned later about details, as a method of covering the oxide of a metal element, a hydroxide, or these mixtures on a silica particle, the water-soluble salt of the metal element to be coated is first prepared, and the water-soluble salt concerned. An aqueous solution of the above is added to the silica particles, and then an alkaline substance such as an aqueous sodium hydroxide solution is added to cause hydrolysis of the water-soluble salt of the metallic element, whereby the metallic element is an oxide, hydroxide or a mixture thereof And the method of coating on silica particles.
Examples of such water-soluble salts of metal elements include chlorides, bromides, sulfates, nitrates, acetates, carbonates and hydrogencarbonates of the above-mentioned metal elements.
（脂肪酸）
本発明の静電潜像現像用トナー外添剤は、トナー外添剤の表面の少なくとも一部に脂肪酸が形成されていることを必要とするものである。このように本発明は、シリカ粒子の表面を金属元素の酸化物、水酸化物、またはこれらの混合物で被覆し、被覆した金属元素の酸化物、水酸化物、またはこれらの混合物をさらに脂肪酸で被覆する構成にすることによって、流動性に優れ、体積抵抗率が低く、疎水性が高く、さらに各種の安定性（耐ストレス性、環境安定性）に優れたトナー外添剤を得ることができるのである。
(fatty acid)
The toner external additive for electrostatic latent image development of the present invention requires that a fatty acid be formed on at least a part of the surface of the toner external additive. Thus, according to the present invention, the surface of the silica particles is coated with an oxide, hydroxide or mixture of metal elements, and the oxide, hydroxide or mixture of metal elements coated further with fatty acid By using the coating configuration, it is possible to obtain a toner external additive that is excellent in fluidity, low in volume resistivity, high in hydrophobicity, and further excellent in various kinds of stability (stress resistance, environmental stability). It is
ここで、本発明で用いられる脂肪酸としては、総炭素数が８〜２６の化合物を用いるのが好ましい。なお、炭化水素基は不飽和結合を有していてもよく、直鎖状または分岐状のいずれであってもよい。
このような脂肪酸の例としては、カプリル酸（オクタン酸）、ラウリン酸（ドデカン酸）、ミリスチン酸（テトラデカン酸）、パルミチン酸（ヘキサデカン酸）、ステアリン酸（オクタデカン酸）、アラキジン酸（エイコサン酸）、ベヘン酸（ドコサン酸）、リグノセリン酸（テトラコサン酸）、ミリストレイン酸、サピエン酸、オレイン酸、エルカ酸、イソステアリン酸などが挙げられる。そして、これらの中でも疎水性付与効果に優れるという点から、炭素数が１０以上である化合物を使用することが好ましく、具体的にはラウリン酸、ステアリン酸、オレイン酸、イソステアリン酸、ベヘン酸で被覆することが好ましい。
Here, as the fatty acid used in the present invention, it is preferable to use a compound having 8 to 26 carbon atoms in total. The hydrocarbon group may have an unsaturated bond, and may be linear or branched.
Examples of such fatty acids are caprylic acid (octanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid) And behenic acid (docosanoic acid), lignoceric acid (tetracosanoic acid), myristoleic acid, sapienic acid, oleic acid, erucic acid, isostearic acid and the like. And among these, it is preferable to use a compound having a carbon number of 10 or more from the viewpoint of being excellent in hydrophobicity imparting effect, and specifically coated with lauric acid, stearic acid, oleic acid, isostearic acid and behenic acid It is preferable to do.
脂肪酸の被覆量については、十分な疎水性および各種の安定性（耐ストレス性、環境安定性）を発現させるために一定量以上の被覆量が必要であり、具体的には、シリカ粒子の質量を基準にして１〜４０質量％とすることが好ましく、５〜２５質量％とすることがより好ましい。
脂肪酸の被覆量が１質量％よりも少ない場合には、基材の表面を十分に被覆することができず、十分な疎水性や各種の安定性（耐ストレス性、環境安定性）が得られない恐れがある。一方、４０質量％よりも多い場合には、得られるトナー外添剤の凝集力が強くなりすぎ、流動性が悪化する恐れがある。
With regard to the coating amount of fatty acid, a coating amount of a certain amount or more is necessary to develop sufficient hydrophobicity and various stability (stress resistance, environmental stability), and specifically, the mass of silica particles It is preferable to set it as 1-40 mass% on the basis of, and it is more preferable to set it as 5-25 mass%.
When the amount of fatty acid coating is less than 1% by mass, the surface of the substrate can not be sufficiently coated, and sufficient hydrophobicity and various types of stability (stress resistance, environmental stability) can be obtained. There is no fear. On the other hand, if it is more than 40% by mass, the cohesion of the obtained toner external additive may be too strong, and the fluidity may be deteriorated.
なお、詳細については後記するが、シリカ粒子に脂肪酸を被覆する方法（金属元素の酸化物、水酸化物、またはこれらの混合物の表面に脂肪酸を被覆する方法）としては、まず被覆したい脂肪酸の塩を用意し、係る脂肪酸塩の水溶液をシリカ粒子に添加した後、水酸化ナトリウム水溶液などのアルカリ物質を加えて脂肪酸塩の加水分解を起こさせることによって、脂肪酸として被覆する方法などを挙げることができる。
このような脂肪酸塩としては、上記した脂肪酸のナトリウム塩、カルシウム塩、カリウム塩、アルミニウム塩、バリウム塩、マグネシウム塩、アンモニウム塩などの各種の脂肪酸塩を挙げることができる。そしてその中でも、取り扱いが容易である点から脂肪酸のナトリウム塩を用いることが好ましい。
Although details will be described later, as a method of coating a fatty acid on a silica particle (a method of coating a fatty acid on the surface of an oxide of a metal element, a hydroxide, or a mixture thereof), salts of fatty acid to be coated first The aqueous solution of the fatty acid salt is added to the silica particles, and then an alkaline substance such as an aqueous sodium hydroxide solution is added to cause hydrolysis of the fatty acid salt, thereby forming a coating as a fatty acid. .
Examples of such fatty acid salts include various fatty acid salts such as sodium salts, calcium salts, potassium salts, aluminum salts, barium salts, magnesium salts and ammonium salts of the above-mentioned fatty acids. Among them, it is preferable to use a sodium salt of fatty acid from the viewpoint of easy handling.
（被覆形態）
本発明の静電潜像現像用トナー外添剤は、シリカ粒子の表面の少なくとも一部が金属元素の酸化物、水酸化物、またはこれらの混合物で被覆され、係る金属元素の酸化物、水酸化物、またはこれらの混合物の少なくとも一部がさらに脂肪酸で被覆された構造となっていることを特徴とするものであるが、その被覆形態としては各種の形態を取ることができる。具体的には、以下のような形態を取ることができる。
（１）シリカ粒子の表面の全てが金属元素の酸化物、水酸化物、またはこれらの混合物による第一層によって被覆され、さらに係る第一層の表面の全てが脂肪酸によって被覆されている形態（図１（ａ））。
（２）シリカ粒子の表面の一部が金属元素の酸化物、水酸化物、またはこれらの混合物によって被覆され、さらに係る金属元素の酸化物、水酸化物、またはこれらの混合物の表面の全てが脂肪酸によって被覆されている形態（シリカ粒子の表面に図１（ｂ）が多数存在している形態）。
（３）シリカ粒子の表面の一部が金属元素の酸化物、水酸化物、またはこれらの混合物によって被覆され、さらに係る金属元素の酸化物、水酸化物、またはこれらの混合物の表面の一部が脂肪酸によって被覆されている形態（シリカ粒子の表面に図１（ｃ）が多数存在している形態）。
（４）シリカ粒子の表面の一部が金属元素の酸化物、水酸化物、またはこれらの混合物によって被覆され、さらに係る金属元素の酸化物、水酸化物、またはこれらの混合物の表面の全てが脂肪酸によって被覆され、かつ脂肪酸が金属元素の酸化物、水酸化物、またはこれらの混合物をはみ出してシリカ粒子の表面に物理吸着などによって存在している形態（シリカ粒子の表面に図１（ｄ）が多数存在している形態）。
（５）（２）〜（４）の形態が、シリカ粒子の表面に混在している形態（図１（ｅ））。
(Coating form)
In the toner external additive for electrostatic latent image development of the present invention, at least a part of the surface of the silica particle is coated with an oxide of metal element, a hydroxide, or a mixture thereof, and an oxide of metal element, water It is characterized in that at least a part of the oxide or a mixture thereof is further coated with a fatty acid, and the form of the coating may be various forms. Specifically, the following forms can be taken.
(1) A form in which all of the surface of the silica particle is covered with the first layer with an oxide of metal element, a hydroxide, or a mixture thereof, and further all the surface of the first layer is covered with fatty acid ( Fig. 1 (a).
(2) A part of the surface of the silica particle is covered with the oxide, hydroxide or mixture of metal elements, and further, the surface of the oxide, hydroxide or mixture of such metal elements is all A form coated with a fatty acid (a form in which a large number of FIG. 1 (b) are present on the surface of silica particles).
(3) A part of the surface of the silica particle is covered with an oxide, a hydroxide or a mixture of metal elements, and a part of the surface of an oxide, a hydroxide or a mixture of such metal elements Is coated with a fatty acid (a form in which a large number of FIG. 1 (c) are present on the surface of silica particles).
(4) A part of the surface of the silica particle is covered with the oxide, hydroxide or mixture of metal elements, and further, the surface of the oxide, hydroxide or mixture of such metal elements is all A form coated with a fatty acid and in which the fatty acid is present on the surface of the silica particle by physical adsorption or the like by protruding the oxide, hydroxide or mixture of metal elements (FIG. 1 (d) on the surface of the silica particle) There are many forms of
(5) A form in which the forms of (2) to (4) are mixed on the surface of the silica particle (FIG. 1 (e)).
（体積抵抗率）
本発明の静電潜像現像用トナー外添剤は、上記構成を有することによってシリカ粒子が本来有する流動性を発現させつつ高い体積抵抗の発現を抑制することができ、その結果トナーに添加（外添）した場合におけるトナーのチャージアップ現象を効果的に抑制することが可能となる。具体的には、本発明の静電潜像現像用トナー外添剤は１．０×１０１１Ω・ｃｍ以下の体積抵抗率を示すもの（半導電性の特性を示すもの）であり、その中でも金属元素の酸化物、水酸化物、またはこれらの混合物、および脂肪酸の被覆形態がより良好な場合には５．０×１０１０Ω・ｃｍ以下の体積抵抗率を示すものとなる。
(Volume resistivity)
The toner external additive for electrostatic latent image development of the present invention can suppress the development of high volume resistance while exhibiting the fluidity originally possessed by the silica particles by having the above constitution, and as a result, it is added to the toner ( It becomes possible to effectively suppress the toner charge-up phenomenon when externally added. Specifically, the toner external additive for electrostatic latent image development of the present invention is one which exhibits a volume resistivity of 1.0 × 10 11 Ω · cm or less (which exhibits semiconductive properties), Above all, when the coating form of the oxide of the metal element, the hydroxide, or the mixture thereof and the fatty acid is better, the volume resistivity is 5.0 × 10 10 Ω · cm or less.
（耐ストレス性：経時安定性）
また、本発明の静電潜像現像用トナー外添剤は、上記構成を有することによって、トナーに外添して使用される際（摩擦や攪拌などによる物理的なストレスを受ける際）にも安定した帯電性能を発現するものとなる。具体的には、下記計算式で求められる経時変動値の絶対値が２０以下を示すものとなる。なお、計算式中の帯電量（ＮＮ：２分）および帯電量（ＮＮ：３０分）は、以下の方法にて測定したブローオフ帯電量である。
計算式：経時変動値（μＣ／ｇ）＝帯電量（ＮＮ：２分）−帯電量（ＮＮ：３０分）
（１）温度２０℃、湿度５０％の条件（ＮＮ：標準温度（Normal）・標準湿度（Normal）の意である）で２４時間暴露したトナー外添剤０．４ｇをフェライト９６ｇに混合する。
（２）（１）の混合物０．０５ｇを窒素ブロー圧：０．５ｋｇ/ｃｍ２、ブロー時間：２０秒の条件でブローオフ粉体帯電量測定装置ＴＢ−２００（東芝ケミカル社製）にて測定する。このとき、（１）にて２分間混合後の混合物の測定値を帯電量（ＮＮ：２分）とし、３０分間混合後の混合物の測定値を帯電量（ＮＮ：３０分）とする。
(Stress resistance: stability over time)
In addition, the toner external additive for electrostatic latent image development of the present invention has the above-mentioned constitution, and is used even when it is used by being externally added to the toner (when physical stress due to friction, stirring, etc. is received) It will exhibit stable charging performance. Specifically, the absolute value of the time-dependent fluctuation value determined by the following formula shows 20 or less. The charge amount (NN: 2 minutes) and the charge amount (NN: 30 minutes) in the formula are blow-off charge amounts measured by the following method.
Calculation formula: Aging fluctuation value (μC / g) = charge amount (NN: 2 minutes) -charge amount (NN: 30 minutes)
(1) 0.4 g of the toner external additive exposed for 24 hours at a temperature of 20 ° C. and a humidity of 50% (NN: meaning normal temperature and normal humidity) is mixed with 96 g of ferrite.
(2) Measure 0.05 g of the mixture of (1) with a blow-off powder charge amount measuring apparatus TB-200 (manufactured by Toshiba Chemical Co., Ltd.) under the conditions of nitrogen blow pressure: 0.5 kg / cm 2 and blow time: 20 seconds. Do. At this time, the measured value of the mixture after mixing for 2 minutes in (1) is taken as the charge amount (NN: 2 minutes), and the measured value of the mixture after mixed for 30 minutes is taken as the charge amount (NN: 30 minutes).
（環境安定性）
さらに、本発明の静電潜像現像用トナー外添剤は、上記構成を有することによって、温湿度が変化する環境下において使用される際にも安定した帯電性能を発現するものとなる。具体的には、下記計算式で求められる環境変動値の絶対値が１０以下を示すものとなる。なお、計算式中の帯電量（ＬＬ）および帯電量（ＨＨ）は、以下の方法にて測定したブローオフ帯電量である。
計算式：環境変動値（μＣ／ｇ）＝帯電量（ＬＬ）−帯電量（ＨＨ）
（１）温度１０℃、湿度２０％の条件（ＬＬ：低温（Low）・低湿度（Low）の意である）で２４時間暴露したトナー外添剤０．４ｇをフェライト９６ｇに１５分間混合する。
（２）温度３０℃、湿度８０％の条件（ＨＨ：高温（High）・高湿度（High）の意である）で２４時間暴露したトナー外添剤０．４ｇをフェライト９６ｇに１５分間混合する。
（３）（１）の混合物（ＬＬ）０．０５ｇと、（２）の混合物（ＨＨ）０．０５ｇをそれぞれ窒素ブロー圧：０．５ｋｇ/ｃｍ２、ブロー時間：２０秒の条件でブローオフ粉体帯電量測定装置ＴＢ−２００（東芝ケミカル社製）にて測定する。
(Environmental stability)
Furthermore, the toner external additive for electrostatic latent image development of the present invention exhibits stable charging performance even when used under the environment where temperature and humidity change by having the above-mentioned constitution. Specifically, the absolute value of the environmental fluctuation value determined by the following equation shows 10 or less. The charge amount (LL) and the charge amount (HH) in the formula are blow-off charge amounts measured by the following method.
Calculation formula: Environmental fluctuation value (μC / g) = charge amount (LL) -charge amount (HH)
(1) 0.4 g of toner external additive which has been exposed for 24 hours at a temperature of 10 ° C. and a humidity of 20% (LL: meaning low temperature and low humidity) is mixed with 96 g of ferrite for 15 minutes .
(2) 0.4 g of toner external additive exposed for 24 hours under the conditions of temperature 30 ° C. and humidity 80% (HH: high temperature / high humidity) is mixed with 96 g of ferrite for 15 minutes .
(3) 0.05 g of the mixture (LL) of (1) and 0.05 g of the mixture (HH) of (2) respectively under nitrogen blow pressure: 0.5 kg / cm 2 and blow time: 20 seconds It measures by body charge amount measuring apparatus TB-200 (made by Toshiba Chemical Co., Ltd.).
なお、本発明においては、必要に応じて、シランカップリング剤、シリコーンオイル、シラザン、トリメチルシロキシケイ酸といった有機ケイ素化合物や、チタネート系カップリング剤などでさらに被覆を行うこともできる。 In the present invention, if necessary, the coating may be further coated with an organosilicon compound such as a silane coupling agent, silicone oil, silazane or trimethylsiloxysilicic acid, or a titanate coupling agent.
（静電潜像現像用トナー外添剤の製造方法）
本発明の静電潜像現像用トナー外添剤の製造方法としては、シリカ粒子の表面の少なくとも一部を金属元素の酸化物、水酸化物、またはこれらの混合物で被覆する工程と、被覆した金属元素の酸化物、水酸化物、またはこれらの混合物の少なくとも一部をさらに脂肪酸で被覆する工程を備えるものとなる。具体的な被覆処理の方法に関しては公知の方法を用いることができるが、例えば以下のような方法を挙げることができる。
まず、シリカ粒子を水中に分散させ、金属元素の水溶性塩または金属元素の水溶性塩の水溶液を添加した後、酸または塩基を用いてｐＨが４〜９になるように調整し、一定時間熟成させる。このようにすることで、金属元素の水溶性塩の加水分解が起こり、シリカ粒子の表面の少なくとも一部が金属元素の酸化物、水酸化物、またはこれらの混合物で被覆されることになる。
次に、上記熟成後のスラリーに脂肪酸塩または脂肪酸塩の水溶液を添加し、その後酸または塩基を用いてｐＨが４〜９になるように中和し、一定時間熟成させる。このようにすることで、脂肪酸塩の加水分解が起こり、金属元素の酸化物、水酸化物、またはこれらの混合物の表面の少なくとも一部が脂肪酸で被覆されることになる。
最後に、得られたスラリーをろ過、洗浄、乾燥し、得られた乾燥物を粉砕することによって本発明の静電潜像現像用トナー外添剤を得ることができる。
(Method for producing toner external additive for developing electrostatic latent image)
In the method of producing the toner external additive for electrostatic latent image development of the present invention, the step of coating at least a part of the surface of the silica particles with an oxide of metal element, a hydroxide or a mixture thereof, The method further comprises the step of further covering at least a part of the oxide of the metal element, the hydroxide, or the mixture thereof with a fatty acid. Although a well-known method can be used regarding the method of a specific coating process, For example, the following methods can be mentioned.
First, silica particles are dispersed in water, a water-soluble salt of a metal element or an aqueous solution of a water-soluble salt of a metal element is added, and then the pH is adjusted to 4 to 9 using an acid or a base. Mature. By doing so, hydrolysis of the water-soluble salt of the metal element occurs, and at least a part of the surface of the silica particle is coated with the oxide, hydroxide or a mixture of these metal elements.
Next, a fatty acid salt or an aqueous solution of a fatty acid salt is added to the above-aged slurry, and then neutralized with an acid or a base so that the pH is 4 to 9 and aged for a certain time. In this way, hydrolysis of the fatty acid salt occurs, and at least a part of the surface of the oxide, hydroxide or mixture of metal elements is covered with fatty acid.
Finally, the obtained slurry is filtered, washed and dried, and the obtained dried product is pulverized to obtain the external additive for toner for electrostatic latent image development of the present invention.
なお、脂肪酸による被覆処理が良好に行われているかどうかは、疎水化度によって確認することができる。具体的には、以下の方法で疎水化度の測定を行った場合、本発明の静電潜像現像用トナー外添剤は５０％以上の疎水化度を示すものとなる。
（１）２５０ｍｌのビーカーに純水７０ｍｌを入れ、トナー外添剤０．０３ｇを水面上に浮かべる。
（２）３００ｒｐｍの回転数で攪拌しながら、メタノールを２．６ｍｌ／ｍｉｎの速度で滴下する。
（３）粉体濡れ性試験機ＷＥＴ−１００Ｐ（レスカ社製）にてメタノール滴下開始直後からの分散液の透過率を測定し、透過率が最小となった時点の分散液中のメタノール濃度を疎水化度とする。
In addition, it can be confirmed by the degree of hydrophobization whether the coating process by a fatty acid is performed favorably. Specifically, when the degree of hydrophobicity is measured by the following method, the toner external additive for electrostatic latent image development of the present invention exhibits a degree of hydrophobicity of 50% or more.
(1) Put 70 ml of pure water in a 250 ml beaker, and float 0.03 g of toner external additive on the water surface.
(2) While stirring at a rotational speed of 300 rpm, methanol is dropped at a speed of 2.6 ml / min.
(3) The permeability of the dispersion immediately after the start of methanol dropping was measured with a powder wettability tester WET-100P (manufactured by Lesca), and the methanol concentration in the dispersion when the permeability was minimized was measured. Degree of hydrophobicity.
本発明の静電潜像現像用トナー外添剤によれば、基材であるシリカ粒子の表面の少なくとも一部が、金属元素の酸化物、水酸化物、またはこれらの混合物および脂肪酸で被覆されているので、流動性に優れ、体積抵抗率が低く、疎水性が高い静電潜像現像用トナー外添剤とすることができる。また、使用時（トナーへの外添時）において、摩擦や攪拌などによる物理的なストレスを受けた場合や、温湿度が変化する環境の下においても安定した帯電性能を発現させることができる。 According to the toner external additive for electrostatic latent image development of the present invention, at least a portion of the surface of the silica particles as the substrate is coated with an oxide of metal element, a hydroxide, or a mixture thereof and a fatty acid Thus, the toner external additive for developing an electrostatic latent image can be made excellent in fluidity, low in volume resistivity and high in hydrophobicity. Further, in use (at the time of external addition to toner), stable charging performance can be exhibited even under physical stress due to friction or stirring, or under an environment where temperature and humidity change.
本発明の請求項２、３に係る静電潜像現像用トナー外添剤によれば、シリカ粒子を被覆する金属元素の酸化物、水酸化物、またはこれらの混合物の被覆量や金属元素の種類を特定の量、種類とすることによって、より優れた体積抵抗率の低減効果を発現させることができる。また、脂肪酸の被覆を強固なものとすることができることから、静電潜像現像用トナー外添剤としての特性についてもより優れたものとすることができる。 According to the toner external additive for electrostatic latent image development of claims 2 and 3 of the present invention, the amount of the metal element coated with the oxide, hydroxide or mixture of these metal elements covering the silica particles By setting the type to a specific amount and type, it is possible to exhibit a more excellent reduction effect of volume resistivity. Further, since the fatty acid coating can be made strong, the characteristics as a toner external additive for electrostatic latent image development can be made more excellent.
本発明の請求項４から６のいずれかに係る静電潜像現像用トナー外添剤によれば、脂肪酸の種類や被覆量を特定の量、種類とすることによって、より高い疎水性を発現させることができ、帯電性能（耐ストレス性、環境安定性）により優れた静電潜像現像用トナー外添剤とすることができる。 According to the toner external additive for electrostatic latent image development according to any one of claims 4 to 6 of the present invention, higher hydrophobicity is exhibited by setting the type and the coating amount of fatty acid to a specific amount and type The toner external additive for electrostatic latent image development can be made excellent by the charging performance (stress resistance, environmental stability).
本発明の請求項７に係る静電潜像現像用トナー外添剤によれば、基材として使用されるシリカ粒子に特定の範囲のＢＥＴ比表面積のシリカ粒子を用いているので、静電画像の高精細化、高画質化を実現することができる。 According to the toner external additive for electrostatic latent image development according to claim 7 of the present invention, since the silica particles having a BET specific surface area within a specific range are used as the silica particles used as the base material, electrostatic image High definition and high image quality can be realized.
本発明の請求項１０に係る静電潜像現像用トナーによれば、本発明の静電潜像現像用トナー外添剤を含有しているので、摩擦や攪拌などによる物理的なストレスを受けた場合や温湿度が変化する環境の下においても安定して高精細かつ高画質の静電画像を得ることができる。 According to the electrostatic latent image developing toner according to claim 10 of the present invention, the toner external additive for electrostatic latent image development according to the present invention is contained, so that physical stress due to friction, stirring, etc. is received. It is possible to stably obtain high-resolution and high-quality electrostatic images even in an environment where temperature and humidity change.
次に、実施例と比較例とを対比させて、本発明の静電潜像現像用トナー外添剤および静電潜像現像用トナー外添剤の製造方法を説明する。なお、以下に述べる実施例は本発明を具体化した一例に過ぎず、本発明の技術的範囲を限定するものではない。 Next, the method for producing the toner external additive for electrostatic latent image development of the present invention and the toner external additive for electrostatic latent image development of the present invention will be described in comparison with Examples and Comparative Examples. The embodiments described below are merely examples embodying the present invention, and do not limit the technical scope of the present invention.
（実施例１）
まず、液相法で製造されたシリカ粒子（東ソーシリカ製 ニップシールＳＰ−２００ ＢＥＴ比表面積２００ｍ２／ｇ)１００ｇを２Ｌの水に分散し、８５℃に加温した。
次に、シリカ粒子に対してＡｌ２Ｏ３換算で１０質量％となる量の塩化アルミニウム水溶液を添加し、水酸化ナトリウム水溶液でｐＨ５．５に調整した後、３０分間攪拌しながら保持することによって塩化アルミニウムを加水分解させ、シリカ粒子の表面に水酸化アルミニウムを被覆した。
次に、シリカ粒子に対してステアリン酸換算で１０質量％となる量のステアリン酸ナトリウムを添加し、水酸化ナトリウム水溶液でｐＨ７．０に調整し、１時間攪拌しながら保持することによってステアリン酸ナトリウムを加水分解させ、水酸化アルミニウムの表面にステアリン酸を被覆したシリカのスラリーを得た。
次に、得られたスラリーをろ過してケーキを得た。
次に、得られたケーキを再度２Ｌの水に分散し、８０℃に加温し、塩酸でｐＨ５．０に調整し、１時間攪拌しながら保持した後、ろ過するとともにろ材上の残渣を水洗することによって洗浄ケーキを得た。
最後に、この洗浄ケーキを１２０℃で乾燥した後、メディア式微粉砕機で粉砕することによって、実施例１の静電潜像現像用トナー外添剤を作製した。
Example 1
First, 100 g of silica particles (manufactured by Toso Silica Nip Seal SP-200, BET specific surface area 200 m 2 / g) manufactured by a liquid phase method was dispersed in 2 L of water and heated to 85 ° C.
Next, an aqueous solution of aluminum chloride is added to the silica particles in an amount of 10% by mass in terms of Al 2 O 3 , adjusted to pH 5.5 with an aqueous solution of sodium hydroxide, and maintained while stirring for 30 minutes. The aluminum chloride was hydrolyzed to coat the surface of the silica particles with aluminum hydroxide.
Next, sodium stearate is added to the silica particles in an amount of 10% by mass in terms of stearic acid, adjusted to pH 7.0 with an aqueous solution of sodium hydroxide, and held while stirring for 1 hour. Were hydrolyzed to obtain a slurry of silica coated with stearic acid on the surface of aluminum hydroxide.
Next, the obtained slurry was filtered to obtain a cake.
Next, the obtained cake is dispersed again in 2 L of water, heated to 80 ° C., adjusted to pH 5.0 with hydrochloric acid, held with stirring for 1 hour, then filtered and, at the same time, the residue on the filter is washed with water I got a wash cake by doing.
Finally, the washed cake was dried at 120 ° C., and then ground with a media type pulverizer to prepare a toner external additive for electrostatic latent image development of Example 1.
（実施例２）
シリカ粒子を気相法で製造されたもの（トクヤマ製 レオロシールＱＳ−１０２ ＢＥＴ比表面積２００ｍ２／ｇ）に変更した他は実施例１と同様にして、実施例２の静電潜像現像用トナー外添剤を作製した。
(Example 2)
Toner for developing an electrostatic latent image of Example 2 in the same manner as Example 1 except that the silica particles were changed to those manufactured by a vapor phase method (Reosil QS-102, BET specific surface area: 200 m 2 / g, manufactured by Tokuyama) An external additive was prepared.
（実施例３）
塩化アルミニウム水溶液の添加量をシリカ粒子に対してＡｌ２Ｏ３換算で５質量％となる量に、ステアリン酸ナトリウムの添加量をシリカ粒子に対してステアリン酸換算で５質量％となる量に変更した他は実施例１と同様にして、実施例３の静電潜像現像用トナー外添剤を作製した。
(Example 3)
Change the addition amount of aluminum chloride aqueous solution to an amount of 5% by mass in terms of Al 2 O 3 with respect to silica particles, and change the addition amount of sodium stearate to 5% by mass in terms of stearic acid with respect to silica particles The toner external additive for electrostatic latent image development of Example 3 was produced in the same manner as in Example 1 except for the above.
（実施例４）
塩化アルミニウム水溶液の添加量をシリカ粒子に対してＡｌ２Ｏ３換算で２５質量％となる量に、ステアリン酸ナトリウムの添加量をシリカ粒子に対してステアリン酸換算で２５質量％となる量に変更した他は実施例１と同様にして、実施例４の静電潜像現像用トナー外添剤を作製した。
(Example 4)
Change the addition amount of aluminum chloride aqueous solution to an amount of 25% by mass in terms of Al 2 O 3 with respect to silica particles, and change the addition amount of sodium stearate to an amount of 25% by mass with respect to silica particles The toner external additive for electrostatic latent image development of Example 4 was produced in the same manner as in Example 1 except for the above.
（実施例５）
ステアリン酸ナトリウムをラウリン酸ナトリウムに変更し、その添加量をシリカ粒子に対してラウリン酸換算で１０質量％となる量にした他は実施例１と同様にして、実施例５の静電潜像現像用トナー外添剤を作製した。
(Example 5)
The electrostatic latent image of Example 5 was carried out in the same manner as Example 1, except that sodium stearate was changed to sodium laurate and the addition amount was made to be 10% by mass in terms of lauric acid based on silica particles. A toner external additive for development was prepared.
（実施例６）
まず、液相法で製造されたシリカ粒子（東ソーシリカ製 ニップシールＳＰ−２００ ＢＥＴ比表面積２００ｍ２／ｇ)１００ｇを２Ｌの水に分散し、８５℃に加温した。
次に、シリカ粒子に対してＺｎＯ換算で１０質量％となる量の塩化亜鉛水溶液を添加し、水酸化ナトリウム水溶液でｐＨ８．０に調整した後、３０分間攪拌しながら保持することによって塩化亜鉛を加水分解させ、シリカ粒子の表面に酸化亜鉛（ＺｎＯ）を被覆した。
次に、シリカ粒子に対してステアリン酸換算で１０質量％となる量のステアリン酸ナトリウムを添加し、水酸化ナトリウム水溶液でｐＨ８．０に調整し、１時間攪拌しながら保持することによってステアリン酸ナトリウムを加水分解させ、酸化亜鉛の表面にステアリン酸を被覆したシリカのスラリーを得た。
次に、得られたスラリーをろ過してケーキを得た。
次に、得られたケーキを再度２Ｌの水に分散し、８０℃に加温し、１時間攪拌しながら保持した後、ろ過するとともにろ材上の残渣を水洗することによって洗浄ケーキを得た。
最後に、この洗浄ケーキを８０℃で乾燥した後、メディア式微粉砕機で粉砕することで、実施例６の静電潜像現像用トナー外添剤を作製した。
(Example 6)
First, 100 g of silica particles (manufactured by Toso Silica Nip Seal SP-200, BET specific surface area 200 m 2 / g) manufactured by a liquid phase method was dispersed in 2 L of water and heated to 85 ° C.
Next, an aqueous solution of zinc chloride is added to the silica particles in an amount of 10% by mass in terms of ZnO, adjusted to pH 8.0 with an aqueous solution of sodium hydroxide and zinc chloride is maintained by stirring for 30 minutes. It was hydrolyzed, and zinc oxide (ZnO) was coated on the surface of the silica particles.
Next, sodium stearate is added to the silica particles in an amount of 10% by mass in terms of stearic acid, adjusted to pH 8.0 with an aqueous solution of sodium hydroxide, and held while stirring for 1 hour. Were hydrolyzed to obtain a slurry of silica coated with stearic acid on the surface of zinc oxide.
Next, the obtained slurry was filtered to obtain a cake.
Next, the obtained cake was dispersed again in 2 L of water, heated to 80 ° C., and kept stirring for 1 hour, and then filtered, and the residue on the filter medium was washed with water to obtain a washed cake.
Finally, the washed cake was dried at 80 ° C., and then ground with a media type pulverizer to prepare a toner external additive for electrostatic latent image development of Example 6.
（比較例１）
まず、液相法で製造されたシリカ粒子（東ソーシリカ製 ニップシールＳＰ−２００ ＢＥＴ比表面積２００ｍ２／ｇ)１００ｇを２Ｌの水に分散し、８５℃に加温した。
次に、シリカ粒子に対してＡｌ２Ｏ３換算で１０質量％となる量の塩化アルミニウム水溶液を添加し、水酸化ナトリウム水溶液でｐＨ５．５に調整した後、３０分間攪拌しながら保持した後、ろ過するとともにろ材上の残渣を水洗することによって洗浄ケーキを得た。
次に、この洗浄ケーキを１２０℃で乾燥した後、メディア式微粉砕機で粉砕した。
最後に、得られた粉体５５ｇを小型ミキサーへ投入し、デシルトリメトキシシラン７．５ｇを添加して１５分混合した後、１２０℃で再乾燥することによって、比較例１の静電潜像現像用トナー外添剤を作製した。
(Comparative example 1)
First, 100 g of silica particles (manufactured by Toso Silica Nip Seal SP-200, BET specific surface area 200 m 2 / g) manufactured by a liquid phase method was dispersed in 2 L of water and heated to 85 ° C.
Next, an aqueous solution of aluminum chloride is added to the silica particles in an amount of 10% by mass in terms of Al 2 O 3 , adjusted to pH 5.5 with an aqueous solution of sodium hydroxide, and maintained while stirring for 30 minutes, A filter cake was obtained by filtering and washing the residue on the filter with water.
Next, the washed cake was dried at 120 ° C. and then crushed using a media mill.
Finally, 55 g of the obtained powder is charged into a small mixer, 7.5 g of decyltrimethoxysilane is added, mixed for 15 minutes, and then redried at 120 ° C., to obtain an electrostatic latent image of Comparative Example 1 A toner external additive for development was prepared.
（比較例２）
デシルトリメトキシシランをジメチルポリシロキサンに、再乾燥時の温度を２００℃に変更した他は比較例１と同様にして、比較例２の静電潜像現像用トナー外添剤を作製した。
(Comparative example 2)
A toner external additive for electrostatic latent image development of Comparative Example 2 was produced in the same manner as in Comparative Example 1 except that decyltrimethoxysilane was changed to dimethylpolysiloxane and the temperature at redrying was changed to 200 ° C.
（比較例３）
ヘキサメチルジシラザンで表面処理された気相法シリカ粒子（日本アエロジル製 Ｒ８２００）を比較例３の静電潜像現像用トナー外添剤とした。
(Comparative example 3)
The fumed silica particles (R8200, manufactured by Nippon Aerosil) surface-treated with hexamethyldisilazane were used as the toner external additive for electrostatic latent image development of Comparative Example 3.
（比較例４）
塩化アルミニウム水溶液の添加（ｐＨ５．５への調整および３０分間の攪拌保持を含む）を行わなかった他は実施例１と同様にして、比較例４の静電潜像現像用トナー外添剤を作製した。
(Comparative example 4)
A toner external additive for electrostatic latent image development of Comparative Example 4 was prepared in the same manner as in Example 1 except that the addition of the aqueous aluminum chloride solution (including the adjustment to pH 5.5 and the stirring for 30 minutes) was not performed. Made.
（比較例５）
まず、トルエン３００ｇにステアリン酸アルミニウム１５ｇを添加して溶解させ、そこに液相法で製造されたシリカ粒子（東ソーシリカ製 ニップシールＳＰ−２００ ＢＥＴ比表面積２００ｍ２／ｇ)１００ｇを添加して１０分間撹拌した。
次に、この混合物を真空加熱式ニーダーに移し、加熱しながら減圧することによってトルエンを留去したあと、１２０℃で２時間保持することによってキュアリング（熟成）を行った。
最後に、得られた粉体をメディア式微粉砕機で粉砕することによって、比較例５の静電潜像現像用トナー外添剤を作製した。
(Comparative example 5)
First, 15 g of aluminum stearate is added to 300 g of toluene and dissolved, and 100 g of silica particles (made by Toso Silica Nip Seal SP-200 BET specific surface area of 200 m 2 / g) manufactured by a liquid phase method is added thereto for 10 minutes It stirred.
Next, this mixture was transferred to a vacuum heating type kneader, and after removing toluene by heating under reduced pressure, curing (aging) was performed by holding at 120 ° C. for 2 hours.
Finally, the powder obtained was pulverized with a media type pulverizer to prepare a toner external additive for electrostatic latent image development of Comparative Example 5.
実施例１〜６および比較例１〜５の構成を表１に示す。 The configurations of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 1.
（各特性の測定）
次に、実施例１〜６および比較例１〜５の各静電潜像現像用トナー外添剤の特性について測定を行った。なお、各特性の測定方法は下記に示す通りである。
(Measurement of each characteristic)
Next, the characteristics of the toner external additives for developing electrostatic latent images of Examples 1 to 6 and Comparative Examples 1 to 5 were measured. In addition, the measuring method of each characteristic is as showing below.
（体積抵抗率の測定）
粉体抵抗測定システム（粉体抵抗測定ユニットＭＣＰ−ＰＤ５１、高抵抗率計ＭＣＰ−ＨＴ４５０：三菱化学アナリテック社製）を使用して下記の条件で測定した。なお、静電潜像現像用トナー外添剤は、２０℃／５０％の温湿度環境下に２４時間暴露した物を使用した。
サンプル：２．０ｇ
印加電圧：１０Ｖ〜１０００Ｖ（印加電圧については、各静電潜像現像用トナー外添剤の体積抵抗率に合わせて設定した。）
加重：２０ｋＮ
測定時間：１０秒
測定レンジ：オートレンジ
(Measurement of volume resistivity)
It measured on condition of the following using powder resistance measurement system (powder resistance measurement unit MCP-PD51, high resistivity meter MCP-HT450: made by Mitsubishi Chemical Analytech Co., Ltd.). In addition, the toner external additive for electrostatic latent image development used what was exposed to the temperature and humidity environment of 20 degreeC / 50% for 24 hours.
Sample: 2.0 g
Applied voltage: 10 V to 1000 V (The applied voltage was set in accordance with the volume resistivity of each toner external additive for electrostatic latent image development.)
Weight: 20kN
Measurement time: 10 seconds Measurement range: Auto range
（疎水化度の測定）
粉体濡れ性試験機ＷＥＴ−１００Ｐ（レスカ社製）を使用して下記の方法で測定した。
（１）２５０ｍｌのトールビーカーに純水７０ｍｌを入れ、静電潜像現像用トナー外添剤０．０３ｇを水面上に浮かべた。
（２）スターラーにより３００ｒｐｍで攪拌しながら、定量ポンプでメタノールを２．６ｍｌ／ｍｉｎで滴下した。
（３）滴下直後からこの分散液の透過率を測定し、透過率が最小となった時点のメタノール濃度を疎水化度とした。
(Measurement of hydrophobicity)
It measured by the following method using powder wettability tester WET-100P (made by a Lesca company).
(1) 70 ml of pure water was placed in a 250 ml tall beaker, and 0.03 g of a toner external additive for electrostatic latent image development was floated on the water surface.
(2) While stirring at 300 rpm by a stirrer, methanol was dropped at a metering pump at 2.6 ml / min.
(3) The permeability of this dispersion was measured immediately after dropping, and the methanol concentration at the time when the permeability became the minimum was taken as the degree of hydrophobicity.
（比表面積の測定）
比表面積測定装置Ｍａｃｓｏｒｂ（登録商標） ＨＭ−Ｍｏｄｅｌ−１２１０（マウンテック製）を使用して、窒素ガスの吸着量を検出することによって、実施例および比較例の静電潜像現像用トナー外添剤のＢＥＴ比表面積を測定した。
(Measurement of specific surface area)
Toner external additive for electrostatic latent image development of Examples and Comparative Examples by detecting the adsorption amount of nitrogen gas using a specific surface area measurement device Macsorb (registered trademark) HM-Model-1210 (manufactured by MUNTECH) BET specific surface area was measured.
（ブローオフ帯電量の測定：耐ストレス性および環境安定性の評価）
ブローオフ粉体帯電量測定装置ＴＢ−２００（東芝ケミカル社製）を使用して下記の方法で測定した。なお、静電潜像現像用トナー外添剤は、３水準の温湿度環境下（ＬＬ：１０℃／２０％、ＮＮ：２０℃／５０％、ＨＨ：３０℃／８０％）に２４時間暴露した物を使用した。
（１）各静電潜像現像用トナー外添剤０．４ｇとフェライト９６ｇをポリプロピレン製の容器に量り取り、２軸のローター上で１００ｒｐｍの速度で回転して混合した。このときの混合時間は、ＬＬ品とＨＨ品については１５分間（１水準）、ＮＮ品については２分間および３０分間（２水準）とした。
（２）その後、上記混合物０．０５ｇを５００メッシュの金網上に量り取り、窒素ブロー圧：０．５ｋｇ/ｃｍ２、ブロー時間：２０秒の条件でブローオフ帯電量を測定した。
(Measurement of blow-off charge: Evaluation of stress resistance and environmental stability)
It measured by the following method using blow-off powder charge amount measuring apparatus TB-200 (made by Toshiba Chemical Co., Ltd.). The toner external additives for electrostatic latent image development are exposed for 24 hours under three temperature and humidity environments (LL: 10 ° C / 20%, NN: 20 ° C / 50%, HH: 30 ° C / 80%) We used what we did.
(1) 0.4 g of each toner external additive for electrostatic latent image development and 96 g of ferrite were weighed in a container made of polypropylene and mixed by rotating at a speed of 100 rpm on a biaxial rotor. The mixing time at this time was 15 minutes (1 level) for the LL and HH products, and 2 minutes and 30 minutes (2 levels) for the NN product.
(2) Thereafter, 0.05 g of the above mixture was weighed on a 500 mesh wire mesh, and the blow-off charge amount was measured under the conditions of nitrogen blow pressure: 0.5 kg / cm 2 and blow time: 20 seconds.
帯電性能の耐ストレス性（経時安定性）の評価として、測定した帯電量から下記計算式を用いて経時変動値を求めた。
計算式：経時変動値（μＣ／ｇ）＝帯電量（ＮＮ：２分）−帯電量（ＮＮ：３０分）
As the evaluation of the stress resistance (the stability over time) of the charging performance, the fluctuation over time was determined from the measured charge amount using the following formula.
Calculation formula: Aging fluctuation value (μC / g) = charge amount (NN: 2 minutes) -charge amount (NN: 30 minutes)
帯電性能の環境安定性の評価として、測定した帯電量から下記計算式を用いて環境変動値を求めた。
計算式：環境変動値（μＣ／ｇ）＝帯電量（ＬＬ）−帯電量（ＨＨ）
As an evaluation of the environmental stability of the charging performance, the environmental fluctuation value was determined from the measured charge amount using the following formula.
Calculation formula: Environmental fluctuation value (μC / g) = charge amount (LL) -charge amount (HH)
（嵩の測定）
なお、トナー外添剤の流動性は嵩が高いほど良好であることから、トナー外添剤の嵩（見かけ比容）についても測定を行った。具体的には、ＪＩＳ Ｋ５１０１−１２−１：２００４に基づき、トナー外添剤の嵩（見かけ比容）を測定した。
(Measurement of bulk)
In addition, since the fluidity of the toner external additive is better as the bulk is higher, the volume (apparent specific volume) of the toner external additive was also measured. Specifically, the bulk (apparent specific volume) of the toner external additive was measured based on JIS K5101-12-1: 2004.
実施例１〜６および比較例１〜５の測定結果を表２に示す。 The measurement results of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 2.
表２で示すとおり、実施例１〜６の静電潜像現像用トナー外添剤は、いずれも体積抵抗率が１．０×１０１１Ω・ｃｍ以下の半導電性の特性を発現するとともに、５０％以上の疎水化度を発現するものであった。また、実施例１〜６の静電潜像現像用トナー外添剤は、経時変動値の絶対値についてもいずれも２０以下と低く帯電性能の経時安定性に優れていることが分かった。さらに、環境変動値の絶対値についてもいずれも１０以下と低く帯電性能の環境安定性にも優れていることが分かった。 As shown in Table 2, the toner external additives for electrostatic latent image development of Examples 1 to 6 all exhibit a semiconductive characteristic having a volume resistivity of 1.0 × 10 11 Ω · cm or less. And 50% or more of hydrophobicity. Further, it was found that the toner external additive for electrostatic latent image development in Examples 1 to 6 was as low as 20 or less in all of the absolute values of the time-dependent fluctuation value, and was excellent in the time-lapse stability of the charging performance. Furthermore, it was found that the absolute value of the environmental fluctuation value was as low as 10 or less, and the environmental stability of the charging performance was also excellent.
一方、比較例１〜３の静電潜像現像用トナー外添剤は、体積抵抗率がいずれも１．０×１０１１Ω・ｃｍより高い（悪い）結果となったことから、使用時（トナーに外添した際）にはチャージアップ現象が発生することが予想される。また、比較例１〜３の静電潜像現像用トナー外添剤は、経時変動値の絶対値がいずれも２０を超える高い値となり、帯電性能が経時で低下してしまうことが分かった。さらに、環境変動値の絶対値についてもいずれも１０を超える高い値となり、帯電性能の環境安定性も悪い結果となった。
次に、比較例４の静電潜像現像用トナー外添剤については、疎水化度が０％となった。これは、脂肪酸がほとんど被覆されておらずシリカが剥き出しの状態になっていることを示すものである、従って、シリカ粒子の表面を金属元素の酸化物、水酸化物、またはこれらの混合物で被覆しない場合には、脂肪酸で被覆するのが困難であることが分かった。
次に、比較例５の静電潜像現像用トナー外添剤については、疎水化度が５０％を下回るとともに、環境変動値の絶対値が１０を超える高い値となり、帯電性能の環境安定性が悪い結果となった。
On the other hand, since the toner external additives for electrostatic latent image development of Comparative Examples 1 to 3 all had a volume resistivity higher than 1.0 × 10 11 Ω · cm (bad), they were used at the time of use ( It is expected that a charge up phenomenon will occur when externally added to toner. The toner external additives for electrostatic latent image development of Comparative Examples 1 to 3 were found to have high absolute values of over time all over 20, and the charging performance was degraded over time. Furthermore, the absolute value of the environmental fluctuation value is also a high value over 10, and the environmental stability of the charging performance is also bad.
Next, regarding the external additive for developing electrostatic latent image of Comparative Example 4, the degree of hydrophobicity was 0%. This indicates that the fatty acid is barely coated and the silica is in an exposed state, therefore, the surface of the silica particle is coated with an oxide, hydroxide or a mixture of metal elements. If not, it was found to be difficult to coat with fatty acid.
Next, regarding the toner external additive for electrostatic latent image development of Comparative Example 5, the degree of hydrophobicity falls below 50%, and the absolute value of the environmental fluctuation value becomes a high value exceeding 10, and the environmental stability of the charging performance It resulted in bad results.
なお、各実施例および各比較例の静電潜像現像用トナー外添剤について、帯電量（ＮＮ：２分）と帯電量（ＮＮ：３０分）の変化傾向を比較すると、実施例では帯電量の絶対値が変化しないか僅かな変動傾向を示す程度であるが、比較例では帯電量の絶対量が大きく変動する傾向を示すものとなった。このような挙動の違いを示す理由として、実施例（本発明）の静電潜像現像用トナー外添剤については、表面が脂肪酸で被覆されていることによって滑り性が向上し、使用する際に受ける摩擦や攪拌などの物理ストレスが軽減されていることと、体積抵抗率が十分に低減されていることから、静電潜像現像用トナー外添剤の帯電（チャージアップ）が抑制されていることが考えられる。
一方、比較例の静電潜像現像用トナー外添剤については、脂肪酸で被覆されていないことから滑り性が悪く、使用する際に受ける摩擦や攪拌などの物理ストレスが軽減されず、また体積抵抗率が十分に低減されていないことから、静電潜像現像用トナー外添剤の帯電（チャージアップ）が進行してしまうことが考えられる。
In the toner external additives for electrostatic latent image development of each of the examples and the comparative examples, when the change tendency of the charge amount (NN: 2 minutes) and the charge amount (NN: 30 minutes) is compared, Although the absolute value of the amount did not change or showed a slight fluctuation tendency, in the comparative example, the absolute amount of the charge amount showed a large fluctuation tendency. As a reason for showing such a difference in behavior, the external additive for developing a toner for electrostatic latent image of the example (the present invention) is improved in slipperiness by covering the surface with a fatty acid, and it is used Since the physical stress such as friction and agitation received is reduced and the volume resistivity is sufficiently reduced, the charge (charge up) of the toner external additive for electrostatic latent image development is suppressed. Can be considered.
On the other hand, the toner external additive for electrostatic latent image development of the comparative example has poor slipperiness because it is not coated with a fatty acid, and physical stress such as friction and stirring received at the time of use is not reduced. Since the resistivity is not sufficiently reduced, it is conceivable that the charging (charge up) of the external toner for electrostatic latent image development proceeds.
本発明の静電潜像現像用トナー外添剤および静電潜像現像用トナー外添剤の製造方法は、複写機やプリンターなどの電子写真機器に用いられるトナー外添剤に用いることができる。 The toner external additive for electrostatic latent image development and the toner external additive for electrostatic latent image development of the present invention can be used for a toner external additive used for electrophotographic apparatus such as a copier and a printer. .
１ 静電潜像現像用トナー外添剤
２ シリカ粒子
３ 金属元素の酸化物、水酸化物、またはこれらの混合物
４ 脂肪酸
1 electrostatic latent image developing toner external additive 2 silica particles 3 oxide of metal element, hydroxide, or mixture thereof 4 fatty acid
Claims (10)
前記金属元素の酸化物、水酸化物、またはこれらの混合物の少なくとも一部を、さらに脂肪酸で被覆している構造となっていることを特徴とする静電潜像現像用トナー外添剤。
Coating at least a part of the surface of the silica particles with an oxide, hydroxide or mixture of metal elements;
A toner external additive for electrostatic latent image development characterized in that at least a part of the oxide, hydroxide or mixture of the metal elements is further coated with a fatty acid.
前記シリカ粒子に対して酸化物換算で１〜４０質量％であることを特徴とする請求項１に記載の静電潜像現像用トナー外添剤。
The coverage of the oxide, hydroxide or mixture of the above metal elements is
The toner external additive for electrostatic latent image development according to claim 1, wherein the amount is 1 to 40% by mass in terms of oxide with respect to the silica particles.
アルミニウム、亜鉛、マグネシウム、バリウムから選択される少なくとも一種であることを特徴とする請求項１または請求項２に記載の静電潜像現像用トナー外添剤。
The metal element is
3. The toner external additive for electrostatic latent image development according to claim 1, which is at least one selected from aluminum, zinc, magnesium and barium.
前記シリカ粒子に対して１〜４０質量％であることを特徴とする請求項１から請求項３のいずれか一項に記載の静電潜像現像用トナー外添剤。
The coated amount of the fatty acid is
The toner external additive for electrostatic latent image development according to any one of claims 1 to 3, wherein the amount is 1 to 40% by mass with respect to the silica particles.
総炭素数８〜２６のものであることを特徴とする請求項１から請求項４のいずれか一項に記載の静電潜像現像用トナー外添剤。
The fatty acid is
The toner external additive for electrostatic latent image development according to any one of claims 1 to 4, which has a total carbon number of 8 to 26.
ステアリン酸、オレイン酸、イソステアリン酸、ラウリン酸、ベヘン酸から選択される少なくとも一種であることを特徴とする請求項１から請求項５のいずれか一項に記載の静電潜像現像用トナー外添剤。
The fatty acid is
The toner for developing an electrostatic latent image according to any one of claims 1 to 5, which is at least one selected from stearic acid, oleic acid, isostearic acid, lauric acid and behenic acid. Additives.
１０〜４００ｍ２／ｇのＢＥＴ比表面積を持つものであることを特徴とする請求項１から請求項６のいずれか一項に記載の静電潜像現像用トナー外添剤。
The silica particles are
The toner external additive for electrostatic latent image development according to any one of claims 1 to 6, which has a BET specific surface area of 10 to 400 m 2 / g.
５０％以上であることを特徴とする請求項１から請求項７のいずれか一項に記載の静電潜像現像用トナー外添剤。
The degree of hydrophobicity is
The toner external additive for electrostatic latent image development according to any one of claims 1 to 7, which is 50% or more.
１．０×１０１１Ω・ｃｍ以下であることを特徴とする請求項１から請求項８のいずれか一項に記載の静電潜像現像用トナー外添剤。
The volume resistivity is
The toner external additive for electrostatic latent image development according to any one of claims 1 to 8, wherein the external additive is 1.0 × 10 11 Ω · cm or less.
An electrostatic latent image developing toner comprising the external additive for electrostatic latent image development according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021128218A (en) * | 2020-02-12 | 2021-09-02 | 株式会社リコー | Toner, toner storage unit, developer, image forming apparatus, and image forming method |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001296688A (en) * | 2000-02-08 | 2001-10-26 | Sakata Corp | Single-component developer and method for printing using the same |
| JP2002148848A (en) * | 2000-11-09 | 2002-05-22 | Konica Corp | Electrostatic charge image developing toner, electrostatic charge image developer, method for developing, method and device for image forming |
| JP2004093735A (en) * | 2002-08-30 | 2004-03-25 | Seiko Epson Corp | Toner and image forming apparatus using the same |
| JP2004109632A (en) * | 2002-09-19 | 2004-04-08 | Fuji Xerox Co Ltd | Electrostatic charge image dry type toner composition, developer for developing electrostatic latent image and image forming method |
| JP2004155648A (en) * | 2002-10-15 | 2004-06-03 | Tokuyama Corp | Surface-treated silica particle and its use |
| JP2005128128A (en) * | 2003-10-22 | 2005-05-19 | Konica Minolta Business Technologies Inc | Electrostatic charge image developing toner |
| JP2005292592A (en) * | 2004-04-01 | 2005-10-20 | Tokuyama Corp | Surface-treated silica |
| JP2006250990A (en) * | 2005-03-08 | 2006-09-21 | Konica Minolta Business Technologies Inc | Electrostatic charge image developing toner |
| JP2007041049A (en) * | 2005-07-29 | 2007-02-15 | Kyocera Mita Corp | Developer for image forming apparatus and image forming apparatus using the developer |
| JP2007114292A (en) * | 2005-10-18 | 2007-05-10 | Fuji Xerox Co Ltd | External additive for toner, electrophotographic toner, and electrophotographic developer |
| JP2009062274A (en) * | 2008-12-10 | 2009-03-26 | Tokuyama Corp | Method for producing surface-treated silica |
| JP2012123196A (en) * | 2010-12-08 | 2012-06-28 | Canon Inc | Toner |
| JP2014134594A (en) * | 2013-01-08 | 2014-07-24 | Fuji Xerox Co Ltd | Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method |
| JP2014234326A (en) * | 2013-06-03 | 2014-12-15 | 富士ゼロックス株式会社 | Silica composite particle and method for producing the same |
| JP2015001536A (en) * | 2013-06-13 | 2015-01-05 | 富士ゼロックス株式会社 | Non-magnetic one-component toner, electrostatic charge image developer, process cartridge, image forming method, and image forming apparatus |
| JP2017003659A (en) * | 2015-06-05 | 2017-01-05 | 京セラドキュメントソリューションズ株式会社 | Multi-color toner, image formation device, and image formation method |
| JP2017116570A (en) * | 2015-12-21 | 2017-06-29 | キヤノン株式会社 | Toner and manufacturing method of toner |
-
2017
- 2017-12-15 JP JP2017240715A patent/JP6849581B2/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001296688A (en) * | 2000-02-08 | 2001-10-26 | Sakata Corp | Single-component developer and method for printing using the same |
| JP2002148848A (en) * | 2000-11-09 | 2002-05-22 | Konica Corp | Electrostatic charge image developing toner, electrostatic charge image developer, method for developing, method and device for image forming |
| JP2004093735A (en) * | 2002-08-30 | 2004-03-25 | Seiko Epson Corp | Toner and image forming apparatus using the same |
| JP2004109632A (en) * | 2002-09-19 | 2004-04-08 | Fuji Xerox Co Ltd | Electrostatic charge image dry type toner composition, developer for developing electrostatic latent image and image forming method |
| JP2004155648A (en) * | 2002-10-15 | 2004-06-03 | Tokuyama Corp | Surface-treated silica particle and its use |
| JP2005128128A (en) * | 2003-10-22 | 2005-05-19 | Konica Minolta Business Technologies Inc | Electrostatic charge image developing toner |
| JP2005292592A (en) * | 2004-04-01 | 2005-10-20 | Tokuyama Corp | Surface-treated silica |
| JP2006250990A (en) * | 2005-03-08 | 2006-09-21 | Konica Minolta Business Technologies Inc | Electrostatic charge image developing toner |
| JP2007041049A (en) * | 2005-07-29 | 2007-02-15 | Kyocera Mita Corp | Developer for image forming apparatus and image forming apparatus using the developer |
| JP2007114292A (en) * | 2005-10-18 | 2007-05-10 | Fuji Xerox Co Ltd | External additive for toner, electrophotographic toner, and electrophotographic developer |
| JP2009062274A (en) * | 2008-12-10 | 2009-03-26 | Tokuyama Corp | Method for producing surface-treated silica |
| JP2012123196A (en) * | 2010-12-08 | 2012-06-28 | Canon Inc | Toner |
| JP2014134594A (en) * | 2013-01-08 | 2014-07-24 | Fuji Xerox Co Ltd | Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method |
| JP2014234326A (en) * | 2013-06-03 | 2014-12-15 | 富士ゼロックス株式会社 | Silica composite particle and method for producing the same |
| JP2015001536A (en) * | 2013-06-13 | 2015-01-05 | 富士ゼロックス株式会社 | Non-magnetic one-component toner, electrostatic charge image developer, process cartridge, image forming method, and image forming apparatus |
| JP2017003659A (en) * | 2015-06-05 | 2017-01-05 | 京セラドキュメントソリューションズ株式会社 | Multi-color toner, image formation device, and image formation method |
| JP2017116570A (en) * | 2015-12-21 | 2017-06-29 | キヤノン株式会社 | Toner and manufacturing method of toner |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021128218A (en) * | 2020-02-12 | 2021-09-02 | 株式会社リコー | Toner, toner storage unit, developer, image forming apparatus, and image forming method |
| JP7447525B2 (en) | 2020-02-12 | 2024-03-12 | 株式会社リコー | Toner, toner storage unit, developer, image forming device, and image forming method |
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