JPH02208661A - Electrostatic charge image developing toner - Google Patents
Electrostatic charge image developing tonerInfo
- Publication number
- JPH02208661A JPH02208661A JP1029151A JP2915189A JPH02208661A JP H02208661 A JPH02208661 A JP H02208661A JP 1029151 A JP1029151 A JP 1029151A JP 2915189 A JP2915189 A JP 2915189A JP H02208661 A JPH02208661 A JP H02208661A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- particles
- resin
- base particles
- specific surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 claims abstract description 140
- 239000011347 resin Substances 0.000 claims abstract description 67
- 229920005989 resin Polymers 0.000 claims abstract description 67
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 229920005992 thermoplastic resin Polymers 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 7
- 239000010419 fine particle Substances 0.000 description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 20
- 238000012546 transfer Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 238000007600 charging Methods 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000012217 deletion Methods 0.000 description 2
- 230000037430 deletion Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005792 styrene-acrylic resin Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- 150000001408 amides Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000008164 mustard oil Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は電子写真法に用いられる静電像現像トナーに関
し、更に詳しくは低温定着性、耐ブロッキング性および
耐久性等に優れた静Ｔｉ像現像トナーに関する。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to an electrostatic image developing toner used in electrophotography, and more specifically to an electrostatic Ti image that has excellent low-temperature fixability, blocking resistance, durability, etc. Regarding developing toner.
［従来技術］
電子写真法においては、通常、感光体に帯電、露光によ
り静電！像を形成し、この静電潜像をトナーによって現
像し、得られたトナー像を転写紙などに転写し定着して
可視画像を形成する。[Prior art] In electrophotography, a photoreceptor is normally charged and exposed to light, which causes static electricity! An image is formed, this electrostatic latent image is developed with toner, and the resulting toner image is transferred to a transfer paper or the like and fixed to form a visible image.
このように可視画像を得るためにはトナー像を定着する
ことが必要であり、従来から熱効率が高くて高速定着が
可能な熱ローラ定着方式が広く採用されている。このよ
うな熱ローラ定着方式においては、熱ローラの表面温度
を１６０〜２００℃に設定したものが一般的であるが、
最近においては、（イ）感光体の熱劣化を防止すること
、（ロ）定着器を作動せしめてから熱Ｏ−ラが定着可能
な温度にまで上昇するのに要するウオームアツプタイム
を短くすること、（ハ）転写紙へ熱が吸収されることに
よる熱Ｏ−ラの温度低下を小さくして多数回に亘る連続
コピーを可能にすること、（ニ）転写紙のカール現象の
発生による搬送系統の故障を防ぐことなどの要請から、
熱ローラの温度をより低くした状態で定着処理を可能に
することが強く要求されている。従ってトナーにおいて
も低温で良好に定着し得るものであることが必要とされ
る。In order to obtain a visible image as described above, it is necessary to fix the toner image, and conventionally, a heat roller fixing method that has high thermal efficiency and can perform high-speed fixing has been widely adopted. In such a heat roller fixing method, the surface temperature of the heat roller is generally set at 160 to 200°C.
Recently, efforts have been made to (a) prevent thermal deterioration of the photoconductor, and (b) shorten the warm-up time required for the heat roller to rise to a temperature that allows fixing after the fixing device is activated. , (c) Enable continuous copying many times by reducing the temperature drop of the heat roller due to heat absorption into the transfer paper, and (d) Conveyance system due to the occurrence of the curling phenomenon of the transfer paper. Due to requests such as preventing breakdown of
There is a strong demand to be able to perform the fixing process while keeping the temperature of the heat roller lower. Therefore, the toner is also required to be able to be fixed well at low temperatures.
低温での定着を可能とするためには、トナー用バインダ
ー樹脂の軟化点を低くする必要があるが、その場合ブロ
ッキング現象、フィルミング現象、キャリアへのトナー
スペント、流動性・摩擦帯電性の低下等により良好な現
像性・クリーニング性・画質を長期にわたって維持する
ことができなかった。In order to enable fixing at low temperatures, it is necessary to lower the softening point of the toner binder resin, but in this case, blocking phenomenon, filming phenomenon, toner spending on the carrier, and decrease in fluidity and triboelectric charging properties occur. Due to such factors, it was not possible to maintain good developability, cleanability, and image quality over a long period of time.
一方、こうしたフィルミング現象、ブロッキング現象を
防止し、クリーニング性、流動性、＊ｉ帯電性を改善す
るために、次のような有機微粒子を含有する技術が提案
されている。例えば特開昭６０−１８６８５１号及び同
６０−１８６８５２号では、トナー粒子よりも平均粒径
の小さいアクリル系、若しくはアクリル−スチレン系の
重合性微粉末を含有したトナーについての提案がなされ
ているが、トナーと重合性微粉末が単に混合されるのみ
であるため、当該重合性微粉末がトナー粒子より遊離し
やすく、十分な耐フィルミング性、耐ブロッキング性を
得ることができない。もし、十分な耐フィルミング性、
耐ブロッキング性を確保するために微粉末を多聞に添加
した場合、流動性の低下を招き、また耐久性についても
低下してしまう。On the other hand, in order to prevent such filming and blocking phenomena and to improve cleaning properties, fluidity, and charging properties, the following technology containing organic fine particles has been proposed. For example, JP-A-60-186851 and JP-A-60-186852 propose a toner containing acrylic or acrylic-styrene polymerizable fine powder with a smaller average particle size than the toner particles. Since the toner and the polymerizable fine powder are simply mixed, the polymerizable fine powder is easily separated from the toner particles, making it impossible to obtain sufficient filming resistance and blocking resistance. If there is sufficient filming resistance,
If a large amount of fine powder is added to ensure blocking resistance, fluidity will be reduced and durability will also be reduced.
そこで、特開昭６３−１３１１４９号では、熱定着性母
体粒子の表面に、該熱定着性母体粒子の軟化点よりも高
い軟化点をもち、しかも平均粒径が０．１以上かつ該熱
定着性母体粒子の平均粒径の１７４以下である有機微粒
子を埋設被覆したトナーについて開示している。しかし
、この技術ではどの程度まで有機微粒子を母体粒子に埋
設するかという点については十分な検討がなされておら
ず、未だ満足できる現像剤は得られていない。すなわち
、有機微粒子の埋設深さが小さくなると、該有機微粒子
は母体粒子より遊離しやすくなり、１１！ｌだ有機微粒
子がキャリアや現像スリーブあるいは帯電、転写、分離
極のコロナワイヤに付着し、その結実現像剤の耐久性が
低下したり、濃度ムラや転写分離不良などの問題が発生
する。また、逆に有機微粒子の埋設深さが大きくなり、
有機微粒子が母体粒子に埋めこまれた状態になると、耐
フィルミング性や耐ブロッキング性が低下するという欠
点がある。Therefore, in JP-A No. 63-131149, the surface of the heat-fixable base particles has a softening point higher than that of the heat-fixable base particles, and an average particle diameter of 0.1 or more, and This patent discloses a toner in which organic fine particles having an average particle size of 174 or less of the average particle size of the base particles are embedded and coated. However, with this technique, sufficient consideration has not been made as to the extent to which organic fine particles are embedded in base particles, and a satisfactory developer has not yet been obtained. That is, when the buried depth of the organic fine particles becomes smaller, the organic fine particles become more easily released than the base particles, and 11! The organic fine particles adhere to the carrier, the developing sleeve, or the corona wire of the charging, transfer, and separation electrodes, reducing the durability of the formed image agent and causing problems such as density unevenness and poor transfer separation. On the other hand, the buried depth of organic particles increases,
When the organic fine particles are embedded in the base particles, there is a drawback that the filming resistance and blocking resistance are reduced.
［発明が解決しようとする課題］
このような低温定着性、耐ブロッキング性、耐フィルミ
ング性及び流動性のすべてに優れ、濃度ムラや転写分離
不良等を生じず、しかも高耐久性を有するトナーを得る
ことは非常に難しく、長期間にわたる数多くの研究にも
かかわらず満足のいくものは得られなかった。[Problems to be Solved by the Invention] A toner that has excellent low-temperature fixing properties, anti-blocking properties, anti-filming properties, and fluidity, does not cause density unevenness or poor transfer separation, and has high durability. It is very difficult to obtain, and despite many long-term studies, no satisfactory results have been obtained.
そこで、本発明の目的は耐ブロッキング性、耐フィルミ
ング性、クリーニング性、摩擦帯電性、流動性、低温定
着性及び耐久性に優れ、濃度ムラや転写分離不良を生じ
ない高品質のコピー画像を長期にわたって維持できるよ
うな静電像現像トナーを提供することにある。Therefore, the purpose of the present invention is to provide high-quality copy images that are excellent in blocking resistance, filming resistance, cleaning properties, triboelectric charging properties, fluidity, low-temperature fixing properties, and durability, and that do not cause density unevenness or transfer separation defects. An object of the present invention is to provide an electrostatic image developing toner that can be maintained for a long period of time.
［課題を解決するための手段１
本発明の上記目的は、軟化点１２０℃以下の熱可塑性樹
脂をバインダーとする母体粒子に樹脂微粒子を機械的衝
撃力により固着被覆させた静電像用像トナーにおいて、
該トナーの比表面積をＡｆ／ｇ１該母体粒子の比表面積
をＳｔ’／（ｌとすると、０．３＜Ａ−８＜ ０．１
・・・（１）が成り立つことを特徴とする静電
像現像トナーによって達成される。[Means for Solving the Problems 1] The above-mentioned object of the present invention is to provide an image toner for electrostatic images in which fine resin particles are fixedly coated by mechanical impact force on base particles containing a thermoplastic resin having a softening point of 120° C. or less as a binder. In,
If the specific surface area of the toner is Af/g1 and the specific surface area of the base particle is St'/(l, then 0.3<A-8<0.1
...This is achieved by an electrostatic image developing toner characterized by satisfying (1).
［作用１
本発明の要件を備えたトナーは、母体粒子用バインダー
の軟化点が１２０℃以下と低いために、得られるトナー
においては十分な低温定着性が発揮される。[Effect 1] In a toner that meets the requirements of the present invention, the softening point of the binder for base particles is as low as 120° C. or lower, so that the resulting toner exhibits sufficient low-temperature fixability.
さらに本発明では母体粒子表面に樹脂微粒子を機械的Ｗ
ｌａ力により、前記（１）式で示された関係を満足する
ような状態で固着被覆されているので、母体粒子の軟質
な特性の発現が抑止されて、耐ブロッキング性、耐フィ
ルミング性及び流動性が改善され、クリーニング不良、
画像流れ等の画像不良の発生を防止し、安定した現像性
を得ることができると同時に、樹脂微粒子の遊離による
様々な欠点を解決することができる。Furthermore, in the present invention, fine resin particles are applied to the surface of the base particles by mechanical W.
Due to the la force, the coating is fixed and coated in a state that satisfies the relationship shown in equation (1) above, so the expression of soft characteristics of the base particles is suppressed, and blocking resistance, filming resistance, and Fluidity is improved, cleaning defects are improved,
It is possible to prevent image defects such as image deletion and obtain stable developability, and at the same time, it is possible to solve various drawbacks caused by the release of fine resin particles.
［置体的構成］ 以下に本発明の詳細な説明する。[Body composition] The present invention will be explained in detail below.
本発明の静電像現像トナーは、軟化点が１２０℃以下の
熱可塑性樹脂をバインダーとする母体粒子に樹脂微粒子
を機械的衝撃力により固着被覆したものであり、該トナ
ーの比表面積をＡｆ／Ｑ、該母体粒子の比表面積をＢｆ
ｌｏとすると、−〇、３＜Ａ−８＜ ０．１の関係が成
り立つ、Ａ−８≧ ０．１の場合には、樹脂微粒子の固
着化が十分に進行していないため、母体粒子から遊離し
やすく、遊離した樹脂微粒子がキャリアや現像スリーブ
、帯電、転写、分離極のコロナワイヤに付着して、現像
剤の耐久性が低下したり、画像濃度ムラや転写分離不良
などの問題が発生する。The electrostatic image developing toner of the present invention is made by coating base particles of a thermoplastic resin having a softening point of 120° C. or less as a binder with fine resin particles fixedly coated by mechanical impact force, and the specific surface area of the toner is Af/ Q, the specific surface area of the base particle is Bf
If lo is -〇, 3<A-8<0.1 holds true. If A-8≧0.1, the solidification of the resin fine particles has not progressed sufficiently, so that the resin particles are separated from the base particles. It is easily released, and the released resin particles adhere to the carrier, developing sleeve, charging, transfer, and corona wire of the separation electrode, reducing the durability of the developer and causing problems such as uneven image density and poor transfer separation. do.
また、Ａ−Ｂ≦−０，３の関係にある時は樹脂微粒子の
固着化が進行しすぎているために、母体粒子の軟質な特
性が発現するようになり、耐フィルミング性や耐ブロッ
キング性等に悪影響を及ぼす。In addition, when the relationship of A-B≦-0,3 exists, the fixation of the resin fine particles has progressed too much, and the soft characteristics of the base particles are expressed, resulting in film- ing resistance and blocking resistance. It has a negative impact on sexuality, etc.
ここで言う軟化点とは、ｈ化成フローテスター（島津製
作所製）を用いて、１Ｃ−３の試料を昇温速度６℃／分
で加熱しながらプランジャーにより２０ ｋｇ／ ｃｍ
２の荷重を与え、直径１膳−１長さ１１ｍのノズルを押
し出すようにし、これにより当該フローテスターのプラ
ンジャー降下１−温度曲線（軟化流動曲線）を描き、そ
のＳ字曲線の高さをｈとするときｈ／２に対応する温度
を軟化点としたものである。The softening point referred to here is 20 kg/cm using a plunger while heating a 1C-3 sample at a heating rate of 6°C/min using an h chemical flow tester (manufactured by Shimadzu Corporation).
Apply a load of 2 and extrude a nozzle with a diameter of 1 and a length of 11 m, thereby drawing a plunger drop 1 - temperature curve (softening flow curve) of the flow tester, and calculate the height of the S-shaped curve. When h is the temperature corresponding to h/2, the softening point is defined as the temperature corresponding to h/2.
また、ここで言う比表面積とは、窒素吸着によるＢＥＴ
比表面積のことであり、測定は「フローソーブＩ［２３
００Ｊ （島津製作所製）を用いて測定した。In addition, the specific surface area mentioned here refers to BET due to nitrogen adsorption.
It refers to the specific surface area, and is measured using “Flowsorb I [23
00J (manufactured by Shimadzu Corporation).
母体粒子のバインダー樹脂としては、軟化点が１２０℃
以下であればよい。具体的には、例えばスチレン系樹脂
、アクリル系樹脂、スチレン−アクリル系樹脂、ポリエ
ステル樹脂、エポキシ樹脂等を挙げることができる。The softening point of the binder resin for the base particles is 120°C.
The following is sufficient. Specifically, examples include styrene resins, acrylic resins, styrene-acrylic resins, polyester resins, and epoxy resins.
好ましいバインダー樹脂は、結晶性重合体と、この結晶
性重合体と結合を形成する官能基を有する非品性ビニル
重合体とが化学的に結合してなるブロック共重合体もし
くはグラフト共重合体である。A preferred binder resin is a block copolymer or a graft copolymer formed by chemically bonding a crystalline polymer and a non-grade vinyl polymer having a functional group that forms a bond with the crystalline polymer. be.
母体粒子のバインダー樹脂の軟化点が１２０℃をこえる
と低温での定着性が低下する。When the softening point of the binder resin of the base particles exceeds 120° C., the fixability at low temperatures decreases.
前記の如きバインダーからなる母体粒子の表面に固着さ
せる樹脂微粒子は、例えばビニル系重合体もしくは共重
合体、ポリエステル樹脂、フッ素樹脂などであるが、特
にスチレン系樹脂、アクリル系樹脂、スチレン−アクリ
ル系樹脂が好ましい。The fine resin particles fixed to the surface of the base particles made of the binder as described above are, for example, vinyl polymers or copolymers, polyester resins, fluororesins, etc., but especially styrene resins, acrylic resins, styrene-acrylic resins, etc. Resins are preferred.
樹脂微粒子のガラス転移点Ｔｏは良好な耐ブロッキング
性を確保するため５５℃以上が好ましい。The glass transition point To of the resin particles is preferably 55° C. or higher to ensure good blocking resistance.
また、樹脂微粒子の軟化点は、優れた低温定着性を得る
ため、また容易に前記（１）式で示される関係を満足す
るような固着状態を得るために１００〜２００℃が好ま
しい。さらに樹脂微粒子の平均粒径は、母体粒子との付
着力を強めるために、０．０２〜０．６μ園であること
が好ましい。Further, the softening point of the fine resin particles is preferably 100 to 200° C. in order to obtain excellent low-temperature fixability and to easily obtain a fixed state that satisfies the relationship expressed by the above formula (1). Further, the average particle diameter of the fine resin particles is preferably 0.02 to 0.6 μm in order to strengthen the adhesion to the base particles.
本発明におけるガラス転移点Ｔ９は示差走査熱ａｌｌ定
法（ＤＳＣ）に従い、例えばｒｏｓｃ−２０」 （セイ
コー電子工業社顎）によって測定でき、具体的には、試
料的１０−ｇを一定の昇温速度（１０℃／１ｎ）で加熱
し、ベースラインと吸熱ピークの傾線との交点よりガラ
ス転移点を得る。The glass transition point T9 in the present invention can be measured according to differential scanning calorimetry (DSC), for example, using ROSC-20'' (manufactured by Seiko Electronics Co., Ltd.). (10°C/1n) and obtain the glass transition point from the intersection of the baseline and the slope of the endothermic peak.
本発明において、母体粒子の表面に樹脂微粒子が固着さ
れた状態は、透過電子顕微鏡または通常の電子顕微鏡に
よりトナー粒子の表面を観察することにより容易に確認
することができる。In the present invention, the state in which the fine resin particles are fixed to the surface of the base particles can be easily confirmed by observing the surface of the toner particles using a transmission electron microscope or an ordinary electron microscope.
このような状態を得るためには、母体粒子と樹脂微粒子
とが共に存在する系において、母体粒子が粉砕されない
大きさの衝撃力、例えば粉砕時に通常必要とされる力の
１７５〜１／１０の大きさの衝撃力を作用させればよい
。In order to obtain such a state, in a system where base particles and fine resin particles coexist, an impact force of a magnitude that does not crush the base particles, for example, 175 to 1/10 of the force normally required for crushing, is required. It is sufficient to apply an impact force of the same magnitude.
母体粒子のバインダー樹脂と共に用いられるその他のト
ナー成分としては、着色剤、荷電制御剤、ワックス、無
機微粒子、滑剤等積々の添加剤があり、必要に応じて用
いることができる。Other toner components used together with the binder resin of the base particles include a variety of additives such as colorants, charge control agents, waxes, inorganic fine particles, and lubricants, which can be used as necessary.
着色剤としては、例えばカーボンブラック、りＯムイエ
０−、デュポンオイルレッド、キノリンイエロー、フタ
ロシアニンブル−、マラカイトグリーンオフサレート、
その他を用いることができる。Examples of the coloring agent include carbon black, RiOmuie 0-, DuPont oil red, quinoline yellow, phthalocyanine blue, malachite green offsalate,
Others can be used.
荷電制御剤としては、例えばニグロシン系染料、含金属
アゾ染料、金Ｊｌ銘体等を挙げることができる。Examples of the charge control agent include nigrosine dyes, metal-containing azo dyes, and gold JI nameplates.
トナーの溶融時の粘弾性を一層好適なものとするため、
あるいは定着性をさらに向上させるために、ワックスを
バインダー樹脂と共に混練して使用することが好ましい
。具体的には、固型のパラフィン、ポリエチレンもしく
はポリプロピレン等の低分子量ポリオレフィン、脂肪酸
エステル、高級アルコール、アミド系ワックス等を用い
ることができる。In order to further improve the viscoelasticity of the toner when it is melted,
Alternatively, in order to further improve fixing properties, it is preferable to knead wax with a binder resin. Specifically, solid paraffin, low molecular weight polyolefin such as polyethylene or polypropylene, fatty acid ester, higher alcohol, amide wax, etc. can be used.
また本発明の静電像現像トナーには、例えばシリカ、ア
ルミナ、チタニア、チタン酸バリウム、チタン酸マグネ
シウム、チタン酸カルシウム、チタン酸ストロンチウム
、酸化亜鉛、酸化セリウム、三酸化アンチモン、酸化ジ
ルコニウム、炭化ケイ素、窒化ケイ素等の無機微粒子を
外部添加剤として混合することができる。特にシリカ微
粒子を用いることが好ましい。更にトナーを正に帯電さ
せるためにはアミン変性シリコン化合物で表面処理され
たシリカ微粒子が好ましい。また上記無線微粒子の添加
混合割合は、トナー全体の０．０１〜５重量％が好まし
く、特に０．０５〜２１量％が好ましい。Further, the electrostatic image developing toner of the present invention includes, for example, silica, alumina, titania, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, cerium oxide, antimony trioxide, zirconium oxide, silicon carbide. , inorganic fine particles such as silicon nitride can be mixed as an external additive. In particular, it is preferable to use silica fine particles. Furthermore, in order to positively charge the toner, silica fine particles whose surface is treated with an amine-modified silicon compound are preferable. The addition and mixing ratio of the wireless fine particles is preferably 0.01 to 5% by weight, particularly preferably 0.05 to 21% by weight, based on the total toner.
また滑剤として、例えばステアリン酸亜鉛、ステアリン
酸アルミニウム、ステアリン酸リチウム、ステアリン酸
、硬化とマシ油、その他を外部添加することができる。Further, as a lubricant, for example, zinc stearate, aluminum stearate, lithium stearate, stearic acid, hardened mustard oil, and others can be externally added.
これらの滑剤の添加混合割合は、トナー全体の例えば０
．０１〜２重量％が好ましい。The addition and mixing ratio of these lubricants is, for example, 0 for the entire toner.
．． 01-2% by weight is preferred.
本発明の静電像現像トナーは、キャリアと混合して二成
分系現像剤として用いてもよいし、キャリアと混合ぜず
に磁性トナーもしくは非磁性トナーのみからなる一成分
系現像剤として用いてもよい。The electrostatic image developing toner of the present invention may be mixed with a carrier and used as a two-component developer, or it may be used as a one-component developer consisting only of magnetic toner or non-magnetic toner without being mixed with a carrier. Good too.
キャリアとしては、従来公知のものを用いることができ
るが、トナー粒子を正に帯電させるために、鉄、ニッケ
ル、コバルト等の強磁性金底、これらの金属を含む合金
、フェライト、マグネタイト等の強磁性金属の化合物の
粒子に、フッ化ビニリデン−四フッ化エチレン共重合体
、テトラフルオロエチレン、２．２．２−トリフルオロ
エチルメタクリレート、ペンタフルオｏ−ｎ−プロピル
メタクリレート等のフッ素樹脂、あるいはシリコーン樹
脂を被覆したものが好ましい。As the carrier, conventionally known carriers can be used, but in order to positively charge the toner particles, ferromagnetic metals such as iron, nickel, and cobalt, alloys containing these metals, ferrite, magnetite, and other strong carriers are used. A fluororesin such as vinylidene fluoride-tetrafluoroethylene copolymer, tetrafluoroethylene, 2.2.2-trifluoroethyl methacrylate, pentafluoro-on-propyl methacrylate, or silicone resin is added to the particles of the magnetic metal compound. Preferably, it is coated with.
キャリアの平均粒径は２０〜２００μｍが好ましく、特
に３０〜１５０μ−が好ましい。The average particle diameter of the carrier is preferably 20 to 200 μm, particularly preferably 30 to 150 μm.
本発明の静電像現像トナーの好適な製造方法の一例を挙
げると、まずバインダー樹脂の材料樹脂を粉砕し分級し
て、トナーとして望ましい粒径の母体粒子を得る。この
母体粒子中には、既述のようなトナーｈＪＩ％分を含有
させておくことができる。To give an example of a preferred method for manufacturing the electrostatic image developing toner of the present invention, first, the material resin of the binder resin is crushed and classified to obtain base particles having a desired particle size for the toner. The base particles may contain toner hJI% as described above.
そして母体粒子に、粉砕し分級して望ましい粒径となっ
ている樹脂微粒子を加えて例えばＶ型混合機により撹拌
を行い、これにより母体粒子の表面に静電的に樹脂微粒
子を付着させ、次いでこれを・衝撃式微粉砕機に投入し
て衝撃を加える。このように処理することによって、母
体粒子の表面に樹脂微粒子を固着させることができる。Then, fine resin particles that have been crushed and classified to a desired particle size are added to the base particles, and the mixture is stirred using, for example, a V-type mixer, so that the fine resin particles are electrostatically attached to the surface of the base particles, and then This is placed in an impact-type pulverizer and subjected to impact. By treating in this way, the resin fine particles can be fixed to the surface of the base particles.
その後キャリアと混合して二成分現像剤を得ることがで
きる。Thereafter, it can be mixed with a carrier to obtain a two-component developer.
なお、母体粒子中に、者色剤、定着性向上剤、その他の
特性改良剤などのトナー成分を分散含有させる場合には
、予めエクストルーダー等によりそれらを均一に混合さ
せた後、粉砕分級して所望の粒子径の粉体とすればよい
。また、無機微粒子等の外部添加剤は、樹脂微粒子を固
着させた後に、添加混合する。In addition, when toner components such as a colorant, a fixability improver, and other property improvers are dispersed and contained in the base particles, they are mixed uniformly in advance using an extruder, etc., and then pulverized and classified. The powder may have a desired particle size. Further, external additives such as inorganic fine particles are added and mixed after the resin fine particles are fixed.
［実施例Ｊ
以下、本発明の実施例を具体的に説明するが、本発明が
これらの実施例に限定されるものではない。[Example J Examples of the present invention will be specifically described below, but the present invention is not limited to these Examples.
〈母体粒子用バインダー〉
（１）母体粒子用バインダー１（本発明用）スチレン−
ｎブチルアクリレート共重合体（軟化点Ｔｓｐ−１１５
℃）
（２）母体粒子用バインダー２（本発明用）スチレン／
ｎ−ブチルアクリレート／メチルメタクリレート重合体
とポリへキサメチレンセバケートとのグラフト共重合体
（軟化点Ｔｓｐ−１１０℃）
（３）母体粒子用バインダー３（比較用）スチレン／ｎ
−ブチルアクリレート／メチルメタクリレート共重合体
（軟化点ＴＳＤ−１３０℃）
く母体粒子の製造〉
（１）母体粒子１（本発明用）
母体粒子用バインダー１ １００重量部カーボ
ンブラック「モーガルＬ」
（キャボット社製＞ １０重量部パラフ
ィンワックス「サゾールワックスＨ１Ｊ（サゾールマー
ケッティング社製） ３重山部アルキレンビス脂肪酸ア
ミド［ヘキストワックスＣＪ （ヘキスト社製）
３重量部以上の組成物を混合し、加熱ロールによ
り溶融混練し、冷却した後、粗粉砕し、風力分級機によ
り分級して、平均粒径１１μｍの母体粒子１を得た。こ
の母体粒子１の比表面積は１．３０ｍ’１０であった。<Binder for base particles> (1) Binder 1 for base particles (for the present invention) Styrene-
n-butyl acrylate copolymer (softening point Tsp-115
℃) (2) Binder 2 for base particles (for the present invention) styrene/
Graft copolymer of n-butyl acrylate/methyl methacrylate polymer and polyhexamethylene sebacate (softening point Tsp - 110°C) (3) Binder 3 for base particles (for comparison) Styrene/n
-Butyl acrylate/methyl methacrylate copolymer (softening point TSD - 130°C) Production of base particles> (1) Base particles 1 (for the present invention) Binder for base particles 1 100 parts by weight Carbon black "Mogul L" (Cabot > 10 parts by weight Paraffin wax “Sasol Wax H1J (manufactured by Sasol Marketing Company) Triple Yamabe alkylene bis fatty acid amide [Hoechst Wax CJ (manufactured by Hoechst Company)
3 parts by weight or more of the composition were mixed, melt-kneaded using heating rolls, cooled, coarsely pulverized, and classified using an air classifier to obtain base particles 1 having an average particle size of 11 μm. The specific surface area of this base particle 1 was 1.30 m'10.
（２）母体粒子２（本発明用）
上記母体粒子１の製造において、母体粒子用バインダー
１の代わりに母体粒子用バインダー２を用いた他は同様
にして母体粒子２を得た。この母体粒子２の比表面積は
１．２７ ｆ ／Ｑであった。(2) Base particles 2 (for the present invention) Base particles 2 were obtained in the same manner as in the production of base particles 1, except that binder 2 for base particles was used instead of binder 1 for base particles. The specific surface area of this base particle 2 was 1.27 f /Q.
（３）母体粒子３（本発明用）
母体粒子用バインダー２ ６０ｉｌ量部マグネ
タイトｒＢＬ−１００Ｊ
（チタン工業社製）３５重患部
低分子量ポリプロピレン［６６ＱＰＪ
（三洋化成社製） ３重量部拘置制御
剤［ボントロンＥ−８２Ｊ
（オリエント化学社製） ２重Ｅｔ ＮＳ以
上の組成物を混合し、加熱ロールにより溶融混練し、冷
却した後、粗粉砕し、風力分級機により分級して、平均
粒径１１μｍの母体粒子３を得た。この母体粒子３の比
表面積は１．０６ｆ１０であった。(3) Base particle 3 (for the present invention) Base particle binder 2 60 il parts Magnetite rBL-100J (manufactured by Titanium Kogyo Co., Ltd.) 35 heavily affected areas Low molecular weight polypropylene [66QPJ (manufactured by Sanyo Chemical Co., Ltd.) 3 parts by weight Detention control agent [ Bontron E-82J (manufactured by Orient Chemical Co., Ltd.) A composition of double Et NS or higher was mixed, melted and kneaded with a heating roll, cooled, coarsely ground, and classified with an air classifier to obtain a powder with an average particle size of 11 μm. Base particles 3 were obtained. The specific surface area of this base particle 3 was 1.06f10.
（４）母体粒子４（比較用）
上記母体粒子１の製造において、母体粒子用バインダー
１の代わりに母体粒子用バインダー３を用いた他は同様
にして母体粒子４を得た。この母体粒子４の比表面積は
１．２９ｒ／ｃｌであった。(4) Base particles 4 (for comparison) Base particles 4 were obtained in the same manner as in the production of base particles 1, except that binder 3 for base particles was used instead of binder 1 for base particles. The specific surface area of this base particle 4 was 1.29 r/cl.
く樹脂微粒子の製造〉
（１）樹脂微粒子１
過硫酸カリウムとチオ硫酸ナトリウムを開始剤として用
い、スチレン７５１５１部、メチルメタクリレート５重
１部、ｎ−ブチルアクリレート２０重量部を重合させて
平均粒径０．４μ−の樹脂微粒子１を得た。Production of fine resin particles> (1) Fine resin particles 1 Using potassium persulfate and sodium thiosulfate as initiators, 75,151 parts of styrene, 1 part of 5-weight methyl methacrylate, and 20 parts by weight of n-butyl acrylate were polymerized to obtain an average particle size. Resin fine particles 1 of 0.4 μm were obtained.
（ガラス転移点ＴＣＩ−６８℃、軟化点Ｔｓｐ−１４０
℃）（２）樹脂微粒子２
樹脂微粒子１と同組成で平均粒径０，０６μｌの樹脂微
粒子２を得た。(Glass transition point TCI -68℃, softening point Tsp -140
(°C) (2) Resin Fine Particles 2 Resin fine particles 2 having the same composition as resin fine particles 1 and an average particle size of 0.06 μl were obtained.
（ガラス転移点Ｔｏ−ａｓ℃、軟化点Ｔｓｐ −１３０
℃）（３）樹脂微粒子３
過硫酸アンモニウムを開始剤として用い、メチルメタク
リレート５０重量部、ｎ−ブチルアクリレート２０重鐙
部、スチレン３０重量部を重合させて平均粒径０．０６
μ鳳の樹脂微粒子３を得た。(Glass transition point To-as°C, softening point Tsp -130
°C) (3) Resin fine particles 3 Using ammonium persulfate as an initiator, 50 parts by weight of methyl methacrylate, 20 parts by weight of n-butyl acrylate, and 30 parts by weight of styrene were polymerized to obtain an average particle size of 0.06.
Resin fine particles 3 of μ-ho were obtained.
（ガラス転移点Ｔｇ−６７℃、軟化点Ｔｓｐ−１６０℃
）（４）樹脂微粒子４
過硫酸アンモニウムを開始剤として用い、メチルメタク
リレート７５重量部、ｎ−ブチルアクリレート２５重層
部を重合させて平均粒径０．４μ諺の樹脂微粒子４を得
た。(Glass transition point Tg - 67℃, softening point Tsp - 160℃
) (4) Fine resin particles 4 Using ammonium persulfate as an initiator, 75 parts by weight of methyl methacrylate and 25 parts by weight of n-butyl acrylate were polymerized to obtain fine resin particles 4 having an average particle size of 0.4 μm.
（ガラス転移点ＴＱ−Ｔｏ℃、軟化点Ｔｓｐ−２１９℃
）くトナーの製造〉
（１）トナー１
当該母体粒子１の９５重量部に、樹脂微粒子１の５重量
部を添加し、これを■型混合機により十分に撹拌混合し
て、樹脂微粒子を母体粒子に静電的に付着させた。次い
で、これらを［奈良ハイブリダイゼーションシステムＮ
Ｈ８−ＩＪ （奈良機械製作所製）に移し、衝撃羽根
の回転数を６００゜ｒｐｍとして５分間にわたり処理し
、もって母体粒子の表面に樹脂微粒子を固着させた。尚
、この時の比表面積は１．２１１／ｌ）であった。(Glass transition point TQ-To℃, softening point Tsp-219℃
) Production of toner> (1) Toner 1 5 parts by weight of resin fine particles 1 were added to 95 parts by weight of the base particles 1, and the mixture was thoroughly stirred and mixed using a ■ type mixer to form the resin fine particles into the matrix. Electrostatically attached to particles. Next, these were subjected to [Nara Hybridization System N]
It was transferred to H8-IJ (manufactured by Nara Kikai Seisakusho) and treated for 5 minutes with the impact blade rotation speed at 600° rpm, thereby fixing the resin fine particles to the surface of the base particles. The specific surface area at this time was 1.211/l).
さらに、前記樹脂微粒子を固着させた母体粒子１００重
ｌ１８１Ｓに対して、表面をポリシロキサンアンモニウ
ム塩で処理したシリカ微粒子を０．８重量部、ステアリ
ン酸亜鉛を０．２重量部添加し、Ｖ型混合機により混合
して、本発明用トナー１を得た。Furthermore, 0.8 parts by weight of silica particles whose surface was treated with polysiloxane ammonium salt and 0.2 parts by weight of zinc stearate were added to 100 parts by weight of the base particles 1181S to which the resin particles were fixed, and V-shaped The mixture was mixed using a mixer to obtain Toner 1 for the present invention.
ここに得られたトナーは、電子顕微鏡による表面観察お
よび透過電子顕微鏡による観察により、母体粒子の表面
に静電的に付着していた樹脂微粒子が、母体粒子の表面
に強固に固着された状態となっていることが認められた
。Surface observation using an electron microscope and transmission electron microscope revealed that the resin fine particles electrostatically attached to the surface of the base particles were firmly fixed to the surface of the base particles. It was recognized that this was the case.
（２）トナー２
母体粒子１の９８重量部に、樹脂微粒子２の２１量部を
添加し、これを■型混合機により十分に撹拌混合して、
樹脂微粒子を母体粒子に静電的に付着させた。さらに、
衝撃羽根の回転数６００゜ｒｐｍを５００Ｏｒｐｍに代
えた以外はトナー１の製造と同様にして母体粒子の表面
に樹脂微粒子を固着させた。尚、この時比表面積は１．
１８ｆ１０であった９次にトナー１の製造と同様にシリ
カ微粒子とステアリン酸亜鉛を添加混合処理して、本発
明用トナー２を得た。(2) Toner 2 21 parts by weight of resin fine particles 2 were added to 98 parts by weight of base particles 1, and the mixture was thoroughly stirred and mixed using a ■ type mixer.
Resin fine particles were electrostatically attached to base particles. moreover,
Fine resin particles were adhered to the surface of the base particles in the same manner as in the production of Toner 1, except that the rotation speed of the impact blade was changed from 600 rpm to 500 rpm. In addition, the specific surface area at this time is 1.
Next, in the same manner as in the production of Toner 1, fine silica particles and zinc stearate were added and mixed to obtain Toner 2 for use in the present invention.
（３）トナー３
母体粒子２を用いた他はトナー１の製造と同様にして樹
脂微粒子１を固着させた。樹脂微粒子を固着させた母体
粒子の比表面積は１．１７１ ／Ｑであった。さらにト
ナー１の製造と同様にしてシリカ微粒子とステアリン酸
亜鉛を添加混合処理して、本発明用トナー３を得た。(3) Toner 3 Resin fine particles 1 were fixed in the same manner as toner 1 except that base particles 2 were used. The specific surface area of the base particles to which the fine resin particles were fixed was 1.171/Q. Further, in the same manner as in the production of Toner 1, fine silica particles and zinc stearate were added and mixed to obtain Toner 3 for the present invention.
（４）トナー４
母体粒子２を用いた他はトナー２の製造と同様にして樹
脂微粒子２を固着させた。樹脂微粒子を固着させた母体
粒子の比表面積は１．１５ｍ’／（ｌであった。さらに
トナー１の製造と同様にしてシリカ微粒子とステアリン
酸亜鉛を添加混合処理して、本発明用トナー４を得た。(4) Toner 4 Resin fine particles 2 were fixed in the same manner as toner 2 except that base particles 2 were used. The specific surface area of the base particles to which fine resin particles were fixed was 1.15 m'/(l.Furthermore, fine silica particles and zinc stearate were added and mixed in the same manner as in the production of Toner 1 to obtain Toner 4 for the present invention. I got it.
（５）トナー５
母体粒子２の９６重量部に、樹脂微粒子２の４１ｆｆｉ
部を添加し、これを■型混合機により十分に撹拌混合し
て、樹脂微粒子を母体粒子に静電的に付着させた。さら
に衝撃羽根の回転数６０００ｒｐｍを５ｏｏｏｒｐ−に
代えた以外はトナー１の製造と同様にして母体粒子の表
面に樹脂微粒子を固着させた。(5) Toner 5 41ffi of resin fine particles 2 is added to 96 parts by weight of base particles 2.
The mixture was thoroughly stirred and mixed using a type 2 mixer to electrostatically adhere the resin fine particles to the base particles. Further, fine resin particles were adhered to the surface of the base particles in the same manner as in the production of Toner 1 except that the rotation speed of the impact blade was changed from 6000 rpm to 500 rpm.
尚、この時の比表面積は１．３６ｍ’／（ｌであった。The specific surface area at this time was 1.36 m'/(l).
次にトナー１の製造と同様にシリカ微粒子とステアリン
酸亜鉛を添加混合処理して、本発明用トナー５を得た。Next, in the same manner as in the production of Toner 1, fine silica particles and zinc stearate were added and mixed to obtain Toner 5 for the present invention.
（６）トナー６
母体粒子１の代わりに母体粒子３、樹脂微粒子２の代わ
りに樹脂微粒子３を用いた他はトナー２の製造と同様に
して樹脂微粒子３を固着させた。(6) Toner 6 Resin fine particles 3 were fixed in the same manner as in the production of toner 2, except that base particles 3 were used instead of base particles 1 and resin fine particles 3 were used instead of resin fine particles 2.
この時の比表面積は０．７７ｆ１０であった。さらに前
記樹脂微粒子を固着させた母体粒子１００重船部に対し
て、シリカ微粒子［アエロジルＲ−８１２Ｊ（日本アエ
ロジル社製）０．６重量部を添加し、Ｖ型混合機により
混合して本発明用トナー６を得た。The specific surface area at this time was 0.77f10. Furthermore, 0.6 parts by weight of silica fine particles [Aerosil R-812J (manufactured by Nippon Aerosil Co., Ltd.)] were added to 100 parts by weight of the base particles to which the resin fine particles were fixed, and the mixture was mixed in a V-type mixer. Toner 6 was obtained.
（１）比較トナー１
トナー２の製造において、「奈良パイプリダイゼーショ
ンシステムＮＨ８−ＩＪを用いず、ヘンシェルミキサー
により母体粒子１と樹脂微粒子２と撹拌混合した。この
トナー粒子の比表面積はｔ、６２ｆ／Ｕであった。その
後、トナー２の製造と同様にシリカ微粒子とステアリン
酸亜鉛を添加混合処理して、比較トナー１を得た。(1) Comparative Toner 1 In manufacturing Toner 2, base particles 1 and resin particles 2 were stirred and mixed using a Henschel mixer without using the Nara Pipe Redization System NH8-IJ.The specific surface area of this toner particle was t, 62f. /U. Thereafter, silica fine particles and zinc stearate were added and mixed in the same manner as in the production of Toner 2 to obtain Comparative Toner 1.
（２）比較トナー２
母体粒子２の９０重量部に、樹脂微粒子４の１０重量部
を添加し、これをＶ型混合機により十分に撹拌混合して
、樹脂微粒子を母体粒子に静電的に付着させた。さらに
トナー１の！ｙＪ造と同様にして母体粒子の表面に樹脂
微粒子を固着させた。(2) Comparative toner 2 10 parts by weight of resin fine particles 4 were added to 90 parts by weight of base particles 2, and the mixture was sufficiently stirred and mixed using a V-type mixer to electrostatically transfer the resin fine particles to the base particles. Attached. Plus toner 1! Resin fine particles were fixed to the surface of the base particles in the same manner as in yJ construction.
この時の比表面積は１．３７ ｆ ／Ｑであった。次に
トナー１の製造と同様にシリカ微粒子とステアリン酸亜
鉛を添加混合処理して比較トナー２を得た。The specific surface area at this time was 1.37 f /Q. Next, in the same manner as in the production of Toner 1, fine silica particles and zinc stearate were added and mixed to obtain Comparative Toner 2.
（３）比較トナー３
トナー６の製造において、樹脂微粒子３の代わりに樹脂
微粒子２を用い、［奈良ハイブリダイゼーションシステ
ムＮＨ３−１Ｊの衝撃羽根の回転数を７００Ｏｒｐｍと
した他はｌ・ナー６の製造と同様にして樹脂微粉子２を
固着させた。このトナー粒子の比表面積は０．７６ｖ”
／（Ｊであった。その後、トナー６の製造と同様にシリ
カ微粒子を添加混合処理して比較トナー３を得た。(3) Comparative Toner 3 In manufacturing Toner 6, Resin Fine Particles 2 was used instead of Resin Fine Particles 3, and the number of revolutions of the impact blade of Nara Hybridization System NH3-1J was 700 Orpm. Fine resin powder 2 was fixed in the same manner as above. The specific surface area of this toner particle is 0.76v"
/(J. Thereafter, silica fine particles were added and mixed in the same manner as in the production of Toner 6 to obtain Comparative Toner 3.
（４）比較トナー４
母体粒子１の代わりに母体粒子４を用いた他はトナー１
の製造と同様にして樹脂微粒子１を母体粒子４に固着さ
せた。この時の比表面積は１．２５ｆ／Ｑであった。さ
らにトナー１の製造と同様にシリカ微粒子とステアリン
酸亜鉛を添加混合処理して比較トナー４を得た。(4) Comparative toner 4 Toner 1 except that base particle 4 was used instead of base particle 1
Resin fine particles 1 were fixed to base particles 4 in the same manner as in the production of. The specific surface area at this time was 1.25f/Q. Further, in the same manner as in the production of Toner 1, fine silica particles and zinc stearate were added and mixed to obtain Comparative Toner 4.
く現像剤の調製〉
トナー１〜５及び比較トナー１．２．４はそれぞれ、銅
−亜鉛系フェライトよりなる磁性体粒子（日本鉄粉工業
社製）に２．２．２−トリフルオロエチルメタクリレ−
Ｉ〜を被覆した平均粒径８０μ−のキャリアと混合して
、トナー濃度５重量％の２成分系現像剤を調製した。Preparation of Developer> Toners 1 to 5 and Comparative Toner 1.2.4 were each made by adding 2.2.2-trifluoroethyl methacrylate to magnetic particles made of copper-zinc ferrite (manufactured by Nippon Tetsuko Kogyo Co., Ltd.). Ray
A two-component developer having a toner concentration of 5% by weight was prepared by mixing with a carrier having an average particle size of 80 μm coated with I~.
く耐久性の評価〉
キャリアと混合して２成分系現像剤としたトナー１〜５
及び比較トナー１．２．４については、定着熱０−ラの
設定温度を１４０℃に設定した電子写真複写ＩＩ ｒＵ
−Ｂｉｘ １５５０ ＭＲＪ （コニカ社製）を用いて
、ａ温高湿環境下−（温度３３℃、相対湿度８０％）に
おいて、１０万回にわたる実写テストを行ない（第１表
、実施例１〜５．比較例１゜２．４）、トナーの帯１１
ｍの推移、及び得られた画像を目視で観察することによ
り耐久性を評価した。トナーの帯電量については、３５
０メツシユのステンレス網を通してブローオフ法により
測定した（ブロー圧力０．２ｋｇ／ ｃｍ２ 、ブロー
時間５５ｅｃ）。Evaluation of durability> Toners 1 to 5 mixed with carrier to form two-component developer
And for comparison toner 1.2.4, electrophotographic copying II rU with fixing heat 0-ra setting temperature set at 140°C
- Using Bix 1550 MRJ (manufactured by Konica), a live-action test was conducted 100,000 times in a high-temperature and high-humidity environment (temperature 33°C, relative humidity 80%) (Table 1, Examples 1 to 5). .Comparative Example 1゜2.4), Toner band 11
Durability was evaluated by visually observing the change in m and the obtained image. Regarding the amount of charge of toner, 35
Measurement was performed by the blow-off method through a stainless steel mesh of 0 mesh (blow pressure 0.2 kg/cm2, blow time 55 ec).
また、トナーと比較トナー３については、定着熱ローラ
の設定温度を１６０℃に設定した電子写真複写機［Ｎ
Ｐ −７５５０４（キャノン社製）を用いて、同様に高
′ＩＡ高湿環境下（温度３３℃、相対湿度８０％）にお
いて１０万回にわたる実写テストを行ない（第１表、実
施例６．比較例３）、画像濃度、及び得られた画像を目
視でｉ察することにより耐久性を評価した。In addition, regarding toner and comparison toner 3, an electrophotographic copying machine [N
Using P-75504 (manufactured by Canon), we conducted a 100,000-shot test in a high IA high humidity environment (temperature 33°C, relative humidity 80%) (Table 1, Example 6. Comparison). Example 3), image density, and durability were evaluated by visually observing the obtained images.
以上の結果より、次の事が明らかとなった。From the above results, the following became clear.
〈実施例１〜４〉
１０万回コピー後のトナー帯電量は初期とほとんど変わ
らず、クリーニング不良や画像流れ、カブリのない良好
な画質が維持された。また現像部やクリーニング部での
トナーブロッキングもなく、定着性も良好であった。さ
らにドラムあるいは現像スリーブへのフィルミングも全
く認められず、またトナーや樹脂微粒子の飛散による機
内汚染、帯電ムラ、転写分離不良等も発生しなかった。Examples 1 to 4 The toner charge amount after 100,000 copies was almost the same as the initial value, and good image quality was maintained without poor cleaning, image deletion, or fog. Furthermore, there was no toner blocking in the developing section or cleaning section, and the fixing properties were also good. Furthermore, no filming was observed on the drum or developing sleeve, and no internal contamination due to scattering of toner or resin particles, uneven charging, or poor transfer separation occurred.
〈実施例５〉
１０万回コピー後の画像濃度は初期とほとんど変わらず
良好で、クリーニング不良やカブリのない良好な画質が
維持された。また現像部やクリーニング部でのトナーブ
ロッキングもなく定着性も良好であった。さらにドラム
あるいは現像スリーブへのフィルミングも全く認められ
ず、またトナーや樹脂微粒子の飛散による機内汚染、帯
電ムラ、転写分離不良等も発生しなかった。<Example 5> The image density after 100,000 copies was almost the same as the initial value, and good image quality was maintained without poor cleaning or fogging. Furthermore, there was no toner blocking in the developing section or cleaning section, and the fixing performance was also good. Furthermore, no filming was observed on the drum or developing sleeve, and no internal contamination due to scattering of toner or resin particles, uneven charging, or poor transfer separation occurred.
く比較例１〉
１０万回コピー後の帯電量は＋４μＣ／Ｑと初期に比べ
大幅に低下しており、そのため３０００回以降カブリが
著しく、トナー飛散による機内汚染が激しかった。また
樹脂微粒子の帯電、転写、分離極への付着が非常に多く
、帯電ムラ、転写分離不良などが多発した。Comparative Example 1 The amount of charge after 100,000 copies was +4 μC/Q, which was significantly lower than the initial value, and as a result, after 3,000 copies, fogging was significant and the inside of the machine was seriously contaminated due to toner scattering. Further, there was a great deal of charging, transfer, and adhesion of resin particles to the separation electrodes, resulting in frequent occurrences of uneven charging, poor transfer separation, and the like.
く比較例２〉
１０万回コピー後の帯電−は＋７μＣ／Ｑと初期に比べ
大幅に低下しており、そのため１万回以降カブリが著し
く、トナー飛散による機内汚染も激しかった。また樹脂
微粒子の帯電、転写、分離極への付着が非常に多く、帯
電ムラ、転写分離不良などが多発した。また、定着ロー
ラの汚れがひどく、巻き付きなどが発生した。Comparative Example 2> After 100,000 copies, the charge was +7 μC/Q, which was significantly lower than the initial value, and as a result, after 10,000 copies, fogging was significant and the inside of the machine was seriously contaminated due to toner scattering. Further, there was a great deal of charging, transfer, and adhesion of resin particles to the separation electrodes, resulting in frequent occurrences of uneven charging, poor transfer separation, and the like. In addition, the fixing roller was heavily soiled and curling occurred.
く比較例３〉
４０００回以降、現鍮器内でトナーがブロッキングし、
現像剤搬送不良により画像ヌケなどの画像不良や、画像
上にトナーの凝集物が多数見られた。Comparative Example 3> After 4000 times, toner blocks in the current brass container,
Due to poor developer transport, image defects such as missing images and many aggregates of toner were observed on the images.
また、１０万回コピー侵の画像濃度は０．７５と初期に
対し大幅に低下し、また、ドラムにはトナーフィルミン
グが認められ、画像はカブリが顕著で不鮮明であった。Further, the image density after 100,000 copies was 0.75, which was significantly lower than the initial value, toner filming was observed on the drum, and the image was unclear with significant fogging.
〈比較例４〉
初期から定着性が悪く、容易に転写材より定着トナーが
剥離した。また顕著なアンダーオフセットが発生した。<Comparative Example 4> Fixing performance was poor from the beginning, and the fixed toner was easily peeled off from the transfer material. Also, a noticeable under-offset occurred.
［発明の効果］
以上詳細に説明したように、本発明の静電像現像トナー
により、耐ブロッキング性、耐フィルミング性、クリー
ニング性、摩擦帯電性、流動性、低温定着性、離型性及
び耐久性に優れ、帯電ムラや転写分離不良を生じない高
品質のコピー画像を長期にわたって得ることができた。[Effects of the Invention] As explained in detail above, the electrostatic image developing toner of the present invention has excellent blocking resistance, filming resistance, cleaning property, triboelectric charging property, fluidity, low temperature fixing property, mold releasability and It was possible to obtain high-quality copy images over a long period of time with excellent durability and without uneven charging or poor transfer separation.
Claims (1)
母体粒子に樹脂微粒子を機械的衝撃力により固着被覆さ
せた静電像現像トナーにおいて、該トナーの比表面積を
Ａｍ＾２／ｇ該母体粒子の比表面積をＢｍ＾２／ｇとす
ると、 −０．３＜Ａ−Ｂ＜０．１ が成り立つことを特徴とする静電像現像トナー。[Claims] An electrostatic image developing toner in which fine resin particles are fixedly coated on base particles using a thermoplastic resin having a softening point of 120° C. or less as a binder by mechanical impact force, and the specific surface area of the toner is Am^2. /g An electrostatic image developing toner characterized in that -0.3<A-B<0.1 holds true when the specific surface area of the base particles is Bm^2/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1029151A JP2838410B2 (en) | 1989-02-08 | 1989-02-08 | Electrostatic image developing toner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1029151A JP2838410B2 (en) | 1989-02-08 | 1989-02-08 | Electrostatic image developing toner |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02208661A true JPH02208661A (en) | 1990-08-20 |
| JP2838410B2 JP2838410B2 (en) | 1998-12-16 |
Family
ID=12268256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1029151A Expired - Lifetime JP2838410B2 (en) | 1989-02-08 | 1989-02-08 | Electrostatic image developing toner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2838410B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7709174B2 (en) | 2005-12-15 | 2010-05-04 | Ricoh Company Limited | Toner, method of preparing the toner, and developer, image forming method, image forming apparatus, and process cartridge using the toner |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5760689B2 (en) | 2010-05-24 | 2015-08-12 | 株式会社リコー | Toner for developing electrostatic image, image forming apparatus, and process cartridge |
| JP5888030B2 (en) | 2011-03-17 | 2016-03-16 | 株式会社リコー | Toner, developer, image forming apparatus, and process cartridge |
| JP6011776B2 (en) | 2011-04-26 | 2016-10-19 | 株式会社リコー | Toner, image forming apparatus, and process cartridge |
| RU2555182C2 (en) | 2011-04-26 | 2015-07-10 | Рикох Компани, Лтд. | Toner developing electrostatic image, image forming device, image forming method and process cartridge |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS632075A (en) * | 1986-01-13 | 1988-01-07 | Konica Corp | Toner for developing electrostatic image having improved characteristic |
| JPS6349766A (en) * | 1986-08-20 | 1988-03-02 | Toyo Ink Mfg Co Ltd | Insulating magnetic toner |
| JPS63131149A (en) * | 1986-11-20 | 1988-06-03 | Ricoh Co Ltd | Toner for developing electrostatic latent image |
| JPS63311264A (en) * | 1987-06-12 | 1988-12-20 | Toyo Ink Mfg Co Ltd | Low-temperature fixable toner for electrophotography |
-
1989
- 1989-02-08 JP JP1029151A patent/JP2838410B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS632075A (en) * | 1986-01-13 | 1988-01-07 | Konica Corp | Toner for developing electrostatic image having improved characteristic |
| JPS6349766A (en) * | 1986-08-20 | 1988-03-02 | Toyo Ink Mfg Co Ltd | Insulating magnetic toner |
| JPS63131149A (en) * | 1986-11-20 | 1988-06-03 | Ricoh Co Ltd | Toner for developing electrostatic latent image |
| JPS63311264A (en) * | 1987-06-12 | 1988-12-20 | Toyo Ink Mfg Co Ltd | Low-temperature fixable toner for electrophotography |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7709174B2 (en) | 2005-12-15 | 2010-05-04 | Ricoh Company Limited | Toner, method of preparing the toner, and developer, image forming method, image forming apparatus, and process cartridge using the toner |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2838410B2 (en) | 1998-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4882258A (en) | Toner for development of electrostatic image and electrostatic latent image developer | |
| JP2004347654A (en) | Electrostatic latent image developer and image forming method | |
| JPH0734125B2 (en) | Toner composition for use in developing electrostatic charge patterns | |
| JP2872352B2 (en) | Positively chargeable toner | |
| JPH0450859A (en) | Electrostatic image developing toner | |
| JP3389779B2 (en) | Electrostatic latent image developing carrier, electrostatic latent image developer, image forming method and image forming apparatus | |
| JPH02208661A (en) | Electrostatic charge image developing toner | |
| JPH025070A (en) | Toner for developing electrostatic charge image | |
| JPH1039534A (en) | Nonmagnetic one-component toner | |
| JPH04188154A (en) | Electrostatic image developing toner | |
| JPH06342224A (en) | Toner particles | |
| JP2769626B2 (en) | Image forming method | |
| JPH10293413A (en) | Electrostatic latent image developing toner | |
| JPS6396663A (en) | Electrostatic charge image developing toner | |
| JPH0812446B2 (en) | Toner for electrostatic latent image development | |
| JPH04188155A (en) | Electrostatic image developing toner | |
| JP2826739B2 (en) | Image forming method | |
| JPH09106104A (en) | Toner composition | |
| JPH0833681B2 (en) | Toner composition | |
| JP2839926B2 (en) | toner | |
| JP3333976B2 (en) | Image forming method | |
| JP4038160B2 (en) | Method for producing toner for developing electrostatic image | |
| JP3034759B2 (en) | Electrophotographic developer | |
| JPH11258846A (en) | Electrostatic charge image developing toner and method for measuring circularity of toner | |
| JP2002049183A (en) | Electrifying member for development of electrostatic latent image, developer for electrostatic latent image and method for image formation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081016 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081016 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091016 Year of fee payment: 11 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091016 Year of fee payment: 11 |