JPH1095855A - Production of surface-treating resin powder - Google Patents
Production of surface-treating resin powderInfo
- Publication number
- JPH1095855A JPH1095855A JP26914196A JP26914196A JPH1095855A JP H1095855 A JPH1095855 A JP H1095855A JP 26914196 A JP26914196 A JP 26914196A JP 26914196 A JP26914196 A JP 26914196A JP H1095855 A JPH1095855 A JP H1095855A
- Authority
- JP
- Japan
- Prior art keywords
- resin powder
- toner
- treating agent
- spherical
- mixer
- 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.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 87
- 229920005989 resin Polymers 0.000 title claims abstract description 72
- 239000011347 resin Substances 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 230000002093 peripheral effect Effects 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000011164 primary particle Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 abstract description 21
- 238000001694 spray drying Methods 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract 1
- 239000012756 surface treatment agent Substances 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 239000008119 colloidal silica Substances 0.000 description 23
- 230000002209 hydrophobic effect Effects 0.000 description 23
- 238000011109 contamination Methods 0.000 description 16
- 238000012546 transfer Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 108091008695 photoreceptors Proteins 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 241000519995 Stachys sylvatica Species 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- -1 polypropylene Polymers 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000004760 silicates Chemical class 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
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本願発明は、高速回転する球状ミ
キサ−を使用して、樹脂粉体に表面処理剤が均一に付着
処理された表面処理樹脂粉体の製造方法に関するもので
る。詳しくは電子写真用トナ−製造の際に、最適な製造
方法を提供するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a surface-treated resin powder in which a surface treating agent is uniformly attached to a resin powder by using a high-speed rotating spherical mixer. More specifically, the present invention provides an optimum manufacturing method when manufacturing an electrophotographic toner.
【０００２】[0002]
【従来の技術】従来より、粒径が1〜100μｍ程度の樹脂
粉体の表面に微粒子状の表面処理剤を付着処理する方法
としては、湿式処理法と乾式処理法が行われている。湿
式処理法では、表面処理剤を分散した溶液中に樹脂粉体
を投入して付着した後に、溶剤を除去し乾燥する方法が
行われている。乾式処理法では、攪拌混合器を使用して
樹脂粉体と表面処理剤を攪拌することで樹脂粉体に表面
処理剤を付着することが行われている。特に樹脂粉体表
面に表面処理剤を付着する技術は、近年、電子写真機器
の各種用途への開発と多機能化に伴い高品質化された微
粉末化電子写真用トナ−の製造の際に、上記の製造法に
よる各種方法が検討されている。2. Description of the Related Art Conventionally, a wet treatment method and a dry treatment method have been used as a method for attaching a fine particle surface treating agent to the surface of a resin powder having a particle size of about 1 to 100 μm. In the wet treatment method, a method is employed in which a resin powder is put into a solution in which a surface treating agent is dispersed, adhered thereto, and then the solvent is removed and dried. In the dry processing method, the surface treatment agent is adhered to the resin powder by stirring the resin powder and the surface treatment agent using a stirring mixer. In particular, the technology of attaching a surface treating agent to the surface of a resin powder has recently been used in the production of fine powdered electrophotographic toners of high quality due to the development and various functions of electrophotographic devices. Various methods based on the above-mentioned production methods have been studied.
【０００３】一般に電子写真用トナ−（以後トナ−と省
略する）は、熱可塑性樹脂中に電荷制御剤、オフセット
防止剤、着色剤等を配合してなる樹脂粉体である未処理
トナ−表面を疎水化された微粉末化表面処理剤によって
処理されており、この処理状態によってトナ−の性能が
大きく左右されるものである。特に、未処理トナ−と表
面処理剤の混合の際、攪拌混合処理が不十分で得られた
トナ−の粒子個々の表面処理状態が異なり、表面処理剤
によって表面全体が処理されたトナ−粒子と一部分が処
理されたトナ−粒子が混在したようなトナ−系では、粒
子個々の摩擦帯電量が不均一になってしまうために、複
写時にカブリと称する画像汚れが発生したり、画像形成
に寄与しないで回収されるトナ−量が増大してしまう欠
点がある。Generally, an electrophotographic toner (hereinafter referred to as toner) is an untreated toner surface which is a resin powder obtained by blending a charge control agent, an anti-offset agent, a coloring agent, etc. in a thermoplastic resin. Is treated with a hydrophobized fine powder surface treating agent, and the performance of the toner is greatly affected by the treatment state. In particular, when the untreated toner and the surface treatment agent are mixed, the toner particles whose entire surface is treated with the surface treatment agent are different due to insufficient stirring and mixing of the toner particles. In a toner system in which toner particles partially treated are mixed, the frictional charge amount of each particle becomes non-uniform, so that image fouling called fog occurs at the time of copying, There is a disadvantage that the amount of toner collected without contributing increases.
【０００４】そして、この環境下では得られたトナ−粒
子個々の疎水性も異なってしまうために環境安定性が悪
く、画像は複写時の環境の影響を受け易くなってしまう
欠点がある。このようにトナ−は、その表面に付着した
表面処理剤の付着状態によってトナ−自体の性能が大き
く左右される。一方、トナ−系中に存在する遊離した表
面処理剤は、トナ−の流動特性に関係するためにトナ−
系には必要であるが、その量は他の特性に影響するため
に適性量がある。例えば、付着状態の弱い表面処理剤が
多いトナ−では、使用時に表面処理剤がトナ−から遊離
し易く、これが原因でトナ−系における遊離した表面処
理剤量が適性量を越えてしまい様々な問題がしばしば発
生している。[0004] Under this environment, the obtained toner particles also have different hydrophobicities, so that environmental stability is poor, and the image is disadvantageously susceptible to the environment during copying. As described above, the performance of the toner itself is greatly affected by the state of the surface treatment agent attached to the surface of the toner. On the other hand, the free surface treatment agent present in the toner system is related to the flow characteristics of the toner, so that the toner is not used.
Although necessary for the system, the amount is adequate to affect other properties. For example, in a toner having a large amount of a surface treatment agent having a weakly adhered state, the surface treatment agent is easily released from the toner at the time of use. Problems often arise.
【０００５】即ち、遊離した表面処理剤が感光体に固着
すると感光体上に良質な潜像が形成されないために、画
質が低下したり、回収トナ−が増大するといった現象が
発生する。また、遊離した表面処理剤が浮遊しチャ−ジ
ャ−装置を汚染すると、感光体上に良質な潜像が形成さ
れなくなったり、紙へのトナ−の転写が十分に行われな
いようになり、画質は低下し回収トナ−が増大するとい
った同様の現象が発生する。また、遊離した表面処理剤
は、トナ−系中に均一に混合添加されない場合には系全
体の中で流動性のバラツキが発生し、複写時のトナ−補
給の程度が変化してしまうために画像濃度が一定しない
といった問題が発生する。That is, if the released surface treatment agent adheres to the photoreceptor, a high-quality latent image is not formed on the photoreceptor, so that the image quality deteriorates and the collected toner increases. Also, if the released surface treatment agent floats and contaminates the charger, a high-quality latent image cannot be formed on the photoreceptor or toner cannot be sufficiently transferred to paper. Similar phenomena occur such that the image quality decreases and the collection toner increases. Also, if the released surface treatment agent is not uniformly mixed and added into the toner system, the fluidity of the system will vary, and the degree of toner replenishment during copying will change. There is a problem that the image density is not constant.
【０００６】また、表面処理剤の大きな凝集体がトナ−
系中に存在すると、それが感光体上に移行して感光体の
傷の発生原因になったり、紙に転写された場合には画質
が低下してしまう。更に、近年商品化が盛んなトナ−と
キヤリア−からなる２成分タイプトナ−では、その表面
に角のないトナ−が流動性及びスペントトナ−の発生に
関して有利である。これらの様々な問題点は、全てトナ
−表面の状態に関わっており、その表面状態は、樹脂粉
体と表面処理剤の混合方法に大きく左右されているので
ある。このため、樹脂粉体（未処理トナ−）の表面を表
面処理剤で処理して得られる微粉末化された電子写真用
トナ−は、その特性を発揮するために流動性・摩擦帯電
性・環境安定性等を調整し疎水化された表面処理剤で処
理製造される必要がある。そして、該トナ−を製造する
ために、従来より湿式法と乾式法が採用されている。Further, large aggregates of the surface treating agent are
If it is present in the system, it migrates onto the photoreceptor and causes damage to the photoreceptor, or if it is transferred to paper, the image quality deteriorates. Further, in a two-component type toner composed of a toner and a carrier, which has been widely commercialized in recent years, a toner having no corner on its surface is advantageous in terms of fluidity and generation of spent toner. These various problems all relate to the state of the toner surface, and the surface state largely depends on the method of mixing the resin powder and the surface treating agent. For this reason, a finely powdered electrophotographic toner obtained by treating the surface of a resin powder (untreated toner) with a surface treatment agent has a fluidity, a triboelectric chargeability, It is necessary to adjust the environmental stability and the like, and to process and manufacture with a hydrophobic surface treatment agent. In order to manufacture the toner, a wet method and a dry method have been conventionally used.
【０００７】しかし、湿式法では、製造過程で使用した
溶液がトナ−系中に残留し易く、これにより摩擦帯電特
性が不良となったり、使用時に残留溶液に起因する臭気
の問題が発生するために残留溶液を完全に乾燥除去する
必要がある。このため、溶液中からのトナ−の製造操作
は、非常に煩雑となり作業性を著しく低下する原因とな
っている。このような湿式処理法を欠点を解消する製法
として、溶剤を使用せずに気相中で攪拌混合処理する乾
式処理法が挙げられる。例えば、樹脂粉体と表面処理剤
をジエツトミルや高速ミキサ−中に投入後、攪拌混合して
処理する方法等がある。しかし、乾式処理法では、ジエツ
トミルを使用する場合には、ジエツトエア−の発生にエネ
ルギ−コストが多く掛かったり、ジエツトエア−の温度を
自在にコントロ−ルすることが難しいといった欠点があ
る。However, in the wet method, the solution used in the production process tends to remain in the toner system, which causes a problem of triboelectric charging and a problem of odor caused by the residual solution during use. It is necessary to completely remove the residual solution by drying. For this reason, the operation of producing the toner from the solution is extremely complicated and causes a significant reduction in workability. As a method for eliminating such disadvantages by such a wet treatment method, there is a dry treatment method in which a stirring and mixing treatment is performed in a gas phase without using a solvent. For example, there is a method in which a resin powder and a surface treating agent are charged into a jet mill or a high-speed mixer, and then stirred and mixed for treatment. However, in the dry processing method, when a jet mill is used, there are disadvantages in that the generation of jet air requires a large energy cost and it is difficult to control the temperature of the jet air freely.
【０００８】しかも、トナ−のように粒子径が慎重に制
御される物質では、ジエツトミルを使用した場合、ジエツト
エア−の速度が大きいと樹脂粉体が粉砕され、制御され
た粒度分布が変化してしまう恐れがあり好ましくない。
また、その形状が円筒状混合機であるヘンシエルミキサ
−やハイスピ−ドミキサ−の使用では、混合攪拌するた
めの回転羽の周速度が、他のミキサ−に比べ比較的速い
ことからトナ−製造の際に好んで使用されている。しか
し、ヘンシエルミキサ−やハイスピ−ドミキサ−では、
攪拌容器の形態が底が平面の円筒形容器であるために試
料が容器の底に滞留するのみならず、円筒壁面にも付着
し易い欠点がある。従って、ヘンシエルミキサ−やハイ
スピ−ドミキサ−の容器内では、試料の十分な攪拌が行
われ難く均一な混合物の製造が期待できず、樹脂粉末表
面に表面処理剤により均一に処理されたトナ−を得るこ
とことが困難である。In addition, in the case of a substance whose particle diameter is carefully controlled, such as toner, when a jet mill is used, if the jet air speed is high, the resin powder is pulverized and the controlled particle size distribution changes. It is not preferable because there is a possibility that it may occur.
In addition, in the case of using a Hensiel mixer or a high-speed mixer whose shape is a cylindrical mixer, the peripheral speed of the rotating blades for mixing and stirring is relatively high as compared with other mixers, so that the toner is manufactured. It is used favorably at the time. However, in Hensiel mixers and high-speed mixers,
Since the shape of the stirring vessel is a cylindrical vessel having a flat bottom, not only does the sample stay at the bottom of the vessel, but there is a drawback that the sample easily adheres to the cylindrical wall surface. Therefore, in a container of a Hensiel mixer or a high-speed mixer, it is difficult to sufficiently agitate the sample, and a uniform mixture cannot be expected. Therefore, the toner uniformly treated with the surface treating agent on the surface of the resin powder is not expected. Is difficult to obtain.
【０００９】また、ヘンシエルミキサ−やハイスピ−ド
ミキサ−では、攪拌混合するための回転羽の周速度が最
大でも40m／secであるために、これらの装置を使用して
樹脂粉体に微粉体を均一に付着したり、樹脂粉体表面を
短時間で平滑にすることは難しく、このためには処理に
長時間が必要である。 この様に、攪拌混合処理が不十
分でありトナ−の粒子個々の表面処理状態にバラツキを
生じ、樹脂粉末の表面全体が処理されたトナ−粒子と一
部分が処理されたトナ−粒子の混合物となり、粒子個々
の摩擦帯電量が不均一になってしまうために複写時にカ
ブリと称する画像汚れが発生したり、画像形成に寄与し
ないで回収されるトナ−量が増大してしまう欠点があ
る。In a Hensiel mixer or a high-speed mixer, the peripheral speed of a rotary blade for stirring and mixing is at most 40 m / sec. It is difficult to uniformly adhere the resin and smooth the surface of the resin powder in a short time, which requires a long processing time. As described above, the stirring and mixing treatment is insufficient, and the surface treatment state of the individual toner particles varies, resulting in a mixture of the treated toner particles on the entire surface of the resin powder and the partially treated toner particles. In addition, since the frictional charge amount of each particle becomes non-uniform, image fouling called fog occurs at the time of copying, and the amount of toner collected without contributing to image formation increases.
【００１０】[0010]
【本発明が解決しようとする課題】そこで本願発明者ら
は、樹脂粉体に表面処理剤を付着処理する際に、攪拌効
率が良好であり、混合及び微粉体凝集物の解砕も可能な
装置を使用することにより、攪拌混合によって樹脂粉体
の表面を平滑化するとともに、該樹脂粉体表面に表面処
理剤を均一状態に付着処理することが容易な表面処理樹
脂粉体の製造方法を検討したのである。Accordingly, the present inventors have found that when applying a surface treating agent to a resin powder, the stirring efficiency is good, and it is possible to mix and disintegrate fine powder aggregates. By using the apparatus, a method for producing a surface-treated resin powder which can smoothen the surface of the resin powder by stirring and mixing and easily apply a surface treatment agent to the surface of the resin powder in a uniform state. We considered.
【００１１】[0011]
【課題を解決するための手段】すなわち本発明は、樹脂
粉体と表面処理剤を、球状容器内底面に沿って回転する
下段回転羽と容器中央部に周速度40ｍ／sec以上で回転
する上段回転羽を設けた球状ミキサ−を使用して、攪拌
混合し得られる表面処理樹脂粉体の製造方法を確立した
のである。一般にトナ−（電子写真用トナ−）は、熱可
塑性樹脂中に電荷制御剤、オフセット防止剤、着色剤等
を配合してなる樹脂粉体（未処理トナ−）表面に疎水化
された微粉末化表面処理剤によって処理製造されるもの
であるが、この処理状態によってトナ−の性能が大きく
左右されるものである。しかし、本発明の製造方法によ
るトナ−の製造では、表面の均一処理が可能であるばか
りか、球状ミキサ−の周速度を大きくすることにより表
面処理剤の一部を樹脂粉体中に埋没した状態にすること
も可能である。That is, according to the present invention, a resin powder and a surface treating agent are provided by rotating a lower rotating blade rotating along the inner bottom surface of a spherical container and an upper rotating blade rotating at a peripheral speed of 40 m / sec or more at the center of the container. A method for producing a surface-treated resin powder obtained by stirring and mixing was established using a spherical mixer provided with rotating blades. Generally, toner (toner for electrophotography) is a fine powder obtained by blending a charge control agent, an anti-offset agent, a colorant, etc. in a thermoplastic resin, and a fine hydrophobic powder on the surface of an untreated toner. The surface treatment agent is manufactured by using a chemical surface treatment agent, and the performance of the toner greatly depends on the processing state. However, in the production of toner by the production method of the present invention, not only can the surface be uniformly treated, but also a part of the surface treatment agent is buried in the resin powder by increasing the peripheral speed of the spherical mixer. It is also possible to make it a state.
【００１２】従って、本発明の製造法により得られたト
ナ−は、表面処理剤が遊離し難く、従来のトナ−の一般
的な欠点を解消したのである。本発明で使用する球状ミ
キサ−の容器内面の構造としては、眞球のみならず、ほ
ぼ球状のもの、例えば卵型や断面が楕円状の球状容器等
が挙げられる。また、容器内で回転する攪拌羽は、容器
底面に沿って回転する下段回転羽と、中央部で回転する
速度の高い上段回転羽の少なくとも２種の回転羽が必要
である。その代表例としてTherefore, in the toner obtained by the production method of the present invention, the surface treatment agent is hardly released, and the general disadvantages of the conventional toner have been solved. As the structure of the inner surface of the container of the spherical mixer used in the present invention, not only a true sphere but also a substantially spherical one, for example, a spherical container having an oval or elliptical cross section can be mentioned. Further, the stirring blade rotating in the container needs at least two kinds of rotating blades, a lower rotating blade rotating along the bottom surface of the container and an upper rotating blade rotating at a high speed in the central portion. As a typical example
【図１】で示す球状ミキサ−により説明すると、球状ミ
キサ−は、試料の投入口(1)及び取出口(2)を有し、内部
が球状であり、球状容器底面に沿って下段回転羽(3)と
中央部で回転する上段回転羽(4)を有する。容器内の底
面中央部分に存在する試料は、下段回転羽(3)の回転力
で強く攪拌され、容器底部から周辺部分へと、そして下
方から上方へと壁面に沿って押し上げられる。容器壁面
に沿って押し上げられた試料は容器内が球状のために、
中央部で回転する上段回転羽(4)上に落ち、強烈に攪拌
混合される。The spherical mixer shown in FIG. 1 will be described. The spherical mixer has a sample inlet (1) and a sample outlet (2), is internally spherical, and has lower rotating blades along the spherical container bottom surface. (3) and an upper rotary wing (4) rotating at the center. The sample existing at the center of the bottom surface in the container is strongly stirred by the rotational force of the lower rotating blade (3), and is pushed up along the wall surface from the container bottom to the peripheral portion and from below to above. The sample pushed up along the container wall is spherical because the inside of the container is spherical.
It falls on the upper rotating blade (4) rotating at the center and is vigorously stirred and mixed.
【００１３】この際に、球状ミキサ−の回転羽の周速度
を大きくすると、従来の円筒形容器の混合機、例えばヘ
ンシエルミキサ−に比較して、表面処理剤を粉体表面に
均一に短時間で固着処理できる。即ち、上段回転羽が周
速度40m／sec以上であると、表面処理剤が表面に均一に
固着処理された粉体を得ることができる。特に上段回転
羽の周速度が60〜100m／secであると、短時間で処理が
可能であり、本発明製造方法の特徴を大いに発揮するの
で好ましい。尚、球状ミキサ−の回転羽の周速度を高く
した場合、例えば80m／secでは、球状ミキサ−を冷水な
どによって冷却すると、装置内壁への粉体の付着が減少
し、攪拌効果も向上するので適宜冷却することが好まし
い。また、At this time, when the peripheral speed of the rotating blades of the spherical mixer is increased, the surface treatment agent is uniformly shortened on the powder surface as compared with a conventional mixer of a cylindrical container, for example, a Hensiel mixer. It can be fixed in time. That is, when the upper rotating blade has a peripheral speed of 40 m / sec or more, it is possible to obtain a powder in which the surface treatment agent is uniformly fixed to the surface. In particular, when the peripheral speed of the upper rotary blade is 60 to 100 m / sec, the processing can be performed in a short time, and the characteristics of the production method of the present invention are greatly exhibited, which is preferable. When the peripheral speed of the rotating blades of the spherical mixer is increased, for example, at 80 m / sec, if the spherical mixer is cooled with cold water or the like, the adhesion of powder to the inner wall of the apparatus is reduced, and the stirring effect is also improved. It is preferable to cool appropriately. Also,
【図１】で説明すると、回転羽の駆動軸(5)が上段回転
部分付近から球状容器底面に向かって広がる円錐形の回
転軸を装置すると、球状容器内の底面部分に試料が滞留
せず、効率よく攪拌されるためにために処理が均一に行
われ好ましい。If the driving shaft (5) of the rotating wing is provided with a conical rotating shaft that spreads from the vicinity of the upper rotating part toward the bottom surface of the spherical container, the sample does not stay on the bottom part in the spherical container. For efficient stirring, the treatment is preferably performed uniformly.
【００１４】本発明の製造方法で使用される樹脂粉体
は、平均粒径が3〜30μｍのものであれば、粉砕法、重
合法、噴霧乾燥法、マイクロカプセル法等如何なる方法
で製造されたものであっても使用が容易であり好まし
い。特に、トナ−製造の際に樹脂粉体（未処理トナ−）
の平均粒径が3〜15μｍであると、表面処理樹脂粉体の
製造も容易であり、画像性に優れたトナ−が得られる。
本発明の樹脂粉体の一成分である熱可塑性樹脂として
は、従来より各種のトナ−製造の際に使用されているも
のであれば良く、例えば、スチレン−アクリル酸メチル
共重合体、スチレン−アクリル酸エチル共重合体、スチ
レン−アクリル酸ブチル共重合体、スチレン−アクリル
酸オクチル共重合体、スチレン−メタアクリル酸エチル
共重合体、スチレン−メタアクリル酸ブチル共重合体、
スチレン−ブタジエン共重合体等のスチレン共重合体、
ポリエステル樹脂、エポキシ樹脂、オレフイン系樹脂等
が挙げられる。The resin powder used in the production method of the present invention is produced by any method such as a pulverization method, a polymerization method, a spray drying method, a microcapsule method, as long as the average particle diameter is 3 to 30 μm. Even those which are easy to use are preferable. Particularly, in the case of toner production, resin powder (untreated toner)
When the average particle size is 3 to 15 μm, the production of the surface-treated resin powder is easy, and a toner having excellent image quality can be obtained.
The thermoplastic resin, which is one component of the resin powder of the present invention, may be any of those conventionally used in the production of various toners. For example, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer,
Styrene copolymers such as styrene-butadiene copolymer,
Examples include polyester resin, epoxy resin, and olefin-based resin.
【００１５】本発明の樹脂粉体の一成分である電荷制御
剤としては、アゾ系含金染料、ニグロシン染料、トリフ
エニルメタン系染料、４級アンモニウム塩等従来より使
用されているものであれば何れもよい。本発明の樹脂粉
体の一成分であるオフセット防止剤としては、低分子量
ポリプロピレン、低分子量ポリエチレン等が挙げられ
る。本発明の樹脂粉体の一成分である着色剤としては、
カ−ボンブラック、ベンジジンイエロ−、キナクリド
ン、縮合アゾ系顔料、銅フタロシアニン等従来よりトナ
−製造の際に使用されているものであれば、何れでも良
い。As the charge controlling agent, which is one component of the resin powder of the present invention, any one of conventionally used azo-based dyes, nigrosine dyes, triphenylmethane-based dyes and quaternary ammonium salts can be used. Either is acceptable. Examples of the offset preventing agent, which is one component of the resin powder of the present invention, include low molecular weight polypropylene, low molecular weight polyethylene and the like. As a colorant which is one component of the resin powder of the present invention,
Any of carbon black, benzidine yellow, quinacridone, condensed azo pigments, copper phthalocyanine and the like conventionally used in the production of toner may be used.
【００１６】本発明で表面処理剤として使用される表面
処理剤としては、一次粒子径が2ｎｍ〜2μｍであると本
発明の製造方法が容易となるので好ましい。特に、表面
処理剤一次粒子径が5ｎｍ〜1μｍであると、処理も良好
で画像性にも一層優れたトナ−を得ることができる。ま
た、表面処理剤は一種類に限らす必要に応じて二種類以
上を併用することも可能である。本発明で使用する表面
処理剤としては、疎水性コロイド状シリカ、酸化チタン
系、酸化錫系、酸化アルミニウム系、ステアリン酸塩
類、珪酸塩類、酸化セリユウム、炭化珪素、炭化チタ
ン、チタン酸バリウム、チタン酸ストロンチユウム、ア
クリル酸重合体、アクリル酸エステル重合体、オレフイ
ン重合体、ホルムアルデヒト縮合体等の微粉末が挙げら
れる。以下に実施例及び比較例を述べる。As the surface treating agent used as the surface treating agent in the present invention, it is preferable that the primary particle diameter is 2 nm to 2 μm, since the production method of the present invention becomes easy. In particular, when the primary particle diameter of the surface treatment agent is from 5 nm to 1 μm, a toner which is excellent in treatment and further excellent in image quality can be obtained. The surface treatment agent is not limited to one type, and two or more types can be used in combination as needed. Examples of the surface treatment agent used in the present invention include hydrophobic colloidal silica, titanium oxide, tin oxide, aluminum oxide, stearates, silicates, cerium oxide, silicon carbide, titanium carbide, barium titanate, and titanium. Fine powders such as strontium acid, acrylic acid polymer, acrylic acid ester polymer, olefin polymer, and formaldehyde condensate are exemplified. Examples and comparative examples are described below.
【００１７】[0017]
実施例１ スチレン−アクリル酸エステル共重合体 100重量部 カ−ボンブラック 8重量部 低分子量ポリプロピレン 4重量部 負荷電性抑制剤 1重量部 上記材料をブレンダ−で混合した後、130℃に設定した
２軸押出機により混練し得られる混練物を冷却した後、
ハンマ−ミルにより粗粉砕し、続いてジェット気流を用
いた微粉砕機により微粉砕物を得た。得られた微粉砕粉
中の超微粉を風力分級機で厳密に分級除去して、5〜20
μｍを選択し平均粒径11μｍ黒色の樹脂粉体（未処理ト
ナ−）を得た。該樹脂粉体に表面処理剤として一次粒子
径が約20ｎｍの疎水性コロイド状シリカ1.0％添加し、Example 1 Styrene-acrylate copolymer 100 parts by weight Carbon black 8 parts by weight Low molecular weight polypropylene 4 parts by weight Negative charge inhibitor 1 part by weight The above materials were mixed with a blender and set at 130 ° C. After cooling the kneaded material obtained by kneading with a twin screw extruder,
The resulting mixture was roughly pulverized by a hammer mill, and then finely pulverized by a pulverizer using a jet stream. The ultrafine powder in the obtained finely pulverized powder is strictly classified and removed by an air classifier, and then 5 to 20
μm was selected to obtain a black resin powder (untreated toner) having an average particle size of 11 μm. 1.0% of hydrophobic colloidal silica having a primary particle diameter of about 20 nm is added to the resin powder as a surface treatment agent,
【図１】記載の内容積40リットル球状ミキサ−を冷却しなが
ら周速度70ｍ／secで3分間攪拌混合し、トナ−（電子写
真用トナ−）を得た。FIG. 1 A spherical mixer having an internal volume of 40 liters described was stirred and mixed at a peripheral speed of 70 m / sec for 3 minutes while cooling to obtain a toner (toner for electrophotography).
【００１８】該トナ−の表面を電子顕微鏡で観察したと
ころ、球状ミキサ−による攪拌混合前の樹脂粉体表面に
あった角張った部分が無くなり、表面は丸みがかった状
態に変化していた。また、トナ−系中の疎水性コロイド
状シリカに関しては、一部分が樹脂粉体にくい込んでお
りその表面にしっかりと固着している状態が観察され
た。尚、トナ−系中には、目視確認できるようなシリカ
の大きな凝集体は確認されなかった次に該トナ−を市販
の普通紙複写機に投入し、通常環境で10,000枚の耐久テ
スト及び35℃−80％RHの高温高湿環境で5,000枚の耐久
テストを行い、画像濃度、転写率及び機内の汚染状態に
ついて、下記の条件で測定し、その結果をWhen the surface of the toner was observed with an electron microscope, it was found that there was no angular part on the surface of the resin powder before stirring and mixing by the spherical mixer, and the surface had changed to a rounded state. Further, with respect to the hydrophobic colloidal silica in the toner system, it was observed that a part of the colloidal silica was hardly contained in the resin powder and was firmly fixed to the surface thereof. In the toner system, no large aggregate of silica that could be visually confirmed was confirmed. Then, the toner was put into a commercial plain paper copier, and subjected to a durability test of 10,000 sheets in a normal environment and a 35 Perform a durability test of 5,000 sheets in a high-temperature and high-humidity environment of ℃ -80% RH, and measure the image density, transfer rate, and contamination status in the machine under the following conditions.
【表１】 に記載した。尚、以下の実施例及び比較例についても、
実施例１と同じく通常環境及び高温高湿環境で耐久テス
ト（長期複写性）を行い、下記の条件で測定し、その結
果を[Table 1] It described in. In the following Examples and Comparative Examples,
A durability test (long-term copyability) was performed in a normal environment and in a high-temperature, high-humidity environment as in Example 1, and measured under the following conditions.
【表１】に記載した。The results are shown in Table 1.
【００１９】ａ．画像濃度（I.D.） 反射濃度計により測定した。 ｂ．転写率（％） 実写時に消費された量と回収器に回収された量を測定し
て、下式から算出する。 転写率（％）＝（回収された量÷実写時に消費された
量）×100 ｃ．機内の汚れ 目視により、下記の基準で評価した。 ○……良好、△……機内汚染あり、×……機内汚染及び
感光体に傷発生 実施例１では、A. Image density (ID) Measured with a reflection densitometer. b. Transfer rate (%) Calculate from the following formula by measuring the amount consumed during actual shooting and the amount recovered in the recovery unit. Transfer rate (%) = (recovered amount / amount consumed during actual shooting) × 100 c. In-machine dirt Visual evaluation was made according to the following criteria. …: Good, △: contamination in the machine, ×: contamination in the machine and scratches on the photoreceptor
【表１】に示すごとく画像濃度・転写率は良好で画像カ
ブリや黒ベタ画像中に白点も観察されず機内飛散による
複写機内の汚染も確認されなかった。感光体やチャ−ジ
ャ−装置も確認したところ汚れもなく良好な状態であっ
た。また、高温高湿環境での耐久テストでも、異常は確
認されなかった。As shown in Table 1, the image density and transfer rate were good, no white spots were observed in the image fogging or solid black image, and no contamination in the copying machine due to scattering inside the machine was observed. When the photoreceptor and the charger were also checked, they were in a good condition without any dirt. No abnormality was found in a durability test in a high-temperature and high-humidity environment.
【００２０】実施例２ 実施例１で得られた黒色の樹脂粉体をExample 2 The black resin powder obtained in Example 1 was
【図１】記載の球状ミキサ−を冷却しながら周速度70m
／secで3分間攪拌混合した後、表面処理剤として一次粒
子径が約20ｎｍの疎水性コロイド状シリカを0.8％添加
し、更に周速度70ｍ／secで3分間攪拌混合してトナ−を
得た。該トナ−の表面を電子顕微鏡で観察したところ、
球状ミキサ−による攪拌混合前の樹脂粉体表面にあった
角張った部分が無くなり、表面は丸みを帯びた状態に変
化していた。表面上の疎水性コロイド状シリカは、実施
例１と同様にしっかりと固着している様子が観察され
た。また、トナ−系中に目視により確認されるシリカの
大きな凝集体は確認されなかった。このトナ−を実施例
１と同様に市販の複写機に投入し、通常環境及び高温高
湿環境での耐久テストを行ったが、疎水性コロイド状シ
リカの添加量を0.8％に減量したにもかかわらず、FIG. 1 A peripheral speed of 70 m while cooling the described spherical mixer
/ Sec for 3 minutes, and 0.8% of hydrophobic colloidal silica having a primary particle diameter of about 20 nm was added as a surface treating agent, and further stirred and mixed at a peripheral speed of 70 m / sec for 3 minutes to obtain a toner. . When the surface of the toner was observed with an electron microscope,
The angular portion on the surface of the resin powder before stirring and mixing by the spherical mixer disappeared, and the surface changed to a rounded state. It was observed that the hydrophobic colloidal silica on the surface was firmly fixed as in Example 1. Also, no large aggregates of silica were visually observed in the toner system. This toner was placed in a commercially available copying machine in the same manner as in Example 1, and a durability test was conducted in a normal environment and in a high-temperature, high-humidity environment. regardless of,
【表１】に示すごとく実施例１と同等の良好な結果が得
られた。機械内は汚れもなく良好な状態であった。As shown in Table 1, good results equivalent to Example 1 were obtained. The inside of the machine was in a good condition without contamination.
【００２１】実施例３ スチレン−アクリル酸エステル共重合体 100重量部 カ−ボンブラック 7重量部 低分子量ポリプロピレン 3重量部 負荷電性抑制剤 1重量部 上記材料から実施例１と同様な方法で、5〜20μｍを選
択した平均粒径10μｍの黒色の樹脂粉体を得た。該樹脂
粉体に一次粒子径が約20nmの疎水性コロイド状シリカを
0.8％添加し、Example 3 Styrene-acrylate copolymer 100 parts by weight Carbon black 7 parts by weight Low molecular weight polypropylene 3 parts by weight Negative charge inhibitor 1 part by weight From the above materials, in the same manner as in Example 1, A black resin powder having an average particle size of 10 μm selected from 5 to 20 μm was obtained. A hydrophobic colloidal silica having a primary particle diameter of about 20 nm is added to the resin powder.
0.8% added,
【図１】記載の球状ミキサ−を冷却しながら周速度70m
／secで3分間攪拌混合した後、更に一次粒子径が約0.5
μｍの酸化アルミニウム微粉体を0.2％添加し周速度50m
／secで3分間攪拌混合してトナ−を得た。該トナ−表面
を電子顕微鏡で観察したところ、球状ミキサ−による攪
拌混合前の樹脂粉体表面にあった角張った部分が無くな
り、表面は丸みを帯びた状態に変化していた。FIG. 1 A peripheral speed of 70 m while cooling the described spherical mixer
/ Min for 3 minutes, and then the primary particle size is
0.2% of micron aluminum oxide fine powder is added and peripheral speed is 50m
The mixture was stirred and mixed at a speed of / sec for 3 minutes to obtain a toner. Observation of the toner surface with an electron microscope revealed that there was no angular portion on the surface of the resin powder before stirring and mixing by the spherical mixer, and the surface had changed to a rounded state.
【００２２】また、表面上の疎水性コロイド状シリカ・
酸化アルミニウムからなる表面処理剤はトナ−表面にし
っかり固着していることが観察された。尚、トナ−系中
に目視確認されるような疎水性コロイド状シリカ・酸化
アルミニウムからなる表面処理剤の大きな凝集体は見い
だされなかった。該トナ−を実施例１で使用の異なる市
販の普通紙複写機に投入し、通常環境及び高温高湿環境
での耐久テストを行ったが、Also, hydrophobic colloidal silica on the surface
It was observed that the surface treatment agent composed of aluminum oxide was firmly adhered to the toner surface. Incidentally, no large aggregates of the surface treating agent composed of hydrophobic colloidal silica / aluminum oxide as visually observed in the toner system were found. The toner was put into a commercially available plain paper copier having a different use in Example 1, and a durability test was performed in a normal environment and a high temperature and high humidity environment.
【表１】に示すごとく画像濃度・転写率は良好で、画像
カブリ及び黒ベタ画像中の白点も観察されず機内飛散に
よる複写機内の汚染も確認されなかった。 実施例４ スチレン−アクリル酸エステル共重合体 100重量部 マグネタイト 50重量部 低分子量ポリプロピレン 3重量部 負荷電性抑制剤 1重量部As shown in Table 1, the image density and transfer rate were good, no image fogging and no white spots in the solid black image were observed, and no contamination in the copying machine due to scattering inside the machine was observed. Example 4 Styrene-acrylate copolymer 100 parts by weight Magnetite 50 parts by weight Low molecular weight polypropylene 3 parts by weight Negative charge inhibitor 1 part by weight
【００２３】上記材料から実施例１と同様な方法で、5
〜20μｍを選択した平均粒径11μｍの黒色の樹脂粉体を
得た。該樹脂粉体に表面処理剤として１：１の割合から
なる混合物である一次粒子径が約10nmの疎水性コロイド
状シリカと約1.5μｍの炭化珪素を1.0％添加し、In the same manner as in Example 1, 5
A black resin powder having an average particle size of 11 μm selected from 20 μm was obtained. 1.0% of a hydrophobic colloidal silica having a primary particle size of about 10 nm, which is a mixture having a ratio of 1: 1 as a surface treatment agent, and about 1.5 μm of silicon carbide are added to the resin powder;
【図１】記載の球状ミキサ−を冷却しながら周速度70ｍ
／secで3分間攪拌混合した後、更に一次粒子径が約0.5
μｍの酸化アルミニウム微粉体を0.2％添加し周速度50
ｍ／secで3分間攪拌混合してトナ−を得た。該トナ−の
表面を電子顕微鏡で観察したところ、球状ミキサ−によ
る攪拌混合前の樹脂粉体表面にあった角張った部分が無
くなり、表面は丸みを帯びた状態に変化していた。ま
た、表面上の疎水性コロイド状シリカ・酸化アルミニウ
ムからなる表面処理剤はトナ−表面にしっかり固着して
いることが観察された。尚、トナ−系中に目視確認され
るような疎水性コロイド状シリカ・酸化アルミニウムか
らなる表面処理剤の大きな凝集体は見いだされなかっ
た。FIG. 1 A peripheral speed of 70 m while cooling the described spherical mixer
/ Min for 3 minutes, and then the primary particle size is
0.2% of aluminum oxide fine powder of 0.2 μm and a peripheral speed of 50
The mixture was stirred and mixed at m / sec for 3 minutes to obtain a toner. Observation of the surface of the toner with an electron microscope revealed that there was no angular portion on the surface of the resin powder before stirring and mixing by the spherical mixer, and the surface had changed to a rounded state. It was also observed that the surface treatment agent composed of hydrophobic colloidal silica and aluminum oxide on the surface was firmly adhered to the toner surface. It should be noted that no large aggregates of the surface treating agent composed of hydrophobic colloidal silica and aluminum oxide as visually observed in the toner system were found.
【００２４】該トナ−を実施例１で使用の異なる市販の
普通紙複写機に投入し、通常環境及び高温高湿環境での
耐久テストを行ったが、The toner was placed in a commercially available plain paper copier having a different use in Example 1, and a durability test was conducted in a normal environment and a high temperature and high humidity environment.
【表１】に示すごとく画像濃度・転写率は良好で、画像
カブリ及び黒ベタ画像中の白点も観察されず機内飛散に
よる複写機内の汚染も確認されなかった。 実施例５ ポリエステル 100重量部 マグネタイト 9重量部 低分子量ポリプロピレン 2重量部 負荷電性抑制剤 1重量部 上記材料から実施例１と同様な方法で、5〜20μｍを選
択した平均粒径10μｍが黒色の樹脂粉体を得た。該樹脂
粉体に表面処理剤として一次粒子径が約20ｎｍの疎水性
コロイド状シリカ1.0％と約0.3μｍのポリメチルメタク
リレ−ト微粉体を0.5％添加し、As shown in Table 1, the image density and transfer rate were good, no image fogging and no white spots in the solid black image were observed, and no contamination in the copying machine due to scattering inside the machine was observed. Example 5 100 parts by weight of polyester 9 parts by weight of magnetite 2 parts by weight of low-molecular-weight polypropylene 1 part by weight of a negatively charged inhibitor In the same manner as in Example 1, 5 to 20 μm was selected from the above materials and the average particle diameter was 10 μm. A resin powder was obtained. 1.0% of hydrophobic colloidal silica having a primary particle diameter of about 20 nm and 0.5% of polymethyl methacrylate fine powder of about 0.3 μm are added to the resin powder as a surface treatment agent,
【図１】記載の球状ミキサ−を冷却しながら周速度60ｍ
／secで5分間攪拌混合してトナ−を得た。FIG. 1 A peripheral speed of 60 m while cooling the described spherical mixer
The mixture was stirred and mixed for 5 minutes at a speed / sec to obtain a toner.
【００２５】該トナ−の表面を電子顕微鏡で観察したと
ころ、表面は丸みを帯びた状態に変化していた。また、
表面上の疎水性コロイド状シリカ・ポリメチルメタクリ
レ−トからなる表面処理剤はトナ−表面にしっかり固着
していることが観察された。尚、トナ−系中に目視確認
されるような疎水性コロイド状シリカ・酸化アルミニウ
ムからなる表面処理剤の大きな凝集体は見いだされなか
った。該トナ−を実施例１で使用の異なる市販の普通紙
複写機に投入し、実施例１に記載の通常環境及び高温高
湿環境での耐久テストを行ったが、When the surface of the toner was observed with an electron microscope, it was found that the surface had changed to a rounded state. Also,
It was observed that the surface treatment agent consisting of hydrophobic colloidal silica polymethyl methacrylate on the surface was firmly adhered to the toner surface. Incidentally, no large aggregates of the surface treating agent composed of hydrophobic colloidal silica / aluminum oxide as visually observed in the toner system were found. The toner was put into a commercially available plain paper copier having a different use in Example 1, and a durability test was performed in a normal environment and a high temperature and high humidity environment described in Example 1.
【表１】に示すごとく画像濃度・転写率は良好で、画像
カブリ及び黒ベタ画像中の白点も観察されず機内飛散に
よる複写機内の汚染も確認されなかった。As shown in Table 1, the image density and transfer rate were good, no image fogging and no white spots in the solid black image were observed, and no contamination in the copying machine due to scattering inside the machine was observed.
【００２６】実施例６ 実施例４のスチレン−アクリル酸エステル共重合体をポ
リエステルに変更し、実施例４と同様な方法で、5〜20
μｍを選択した平均粒径11μｍの黒色の樹脂粉体を得
た。得られた黒色の樹脂粉体に表面処理剤として一次粒
子径が約20ｎｍの酸化錫系微粉末を0.5％添加し、Example 6 The styrene-acrylic acid ester copolymer of Example 4 was changed to polyester, and 5 to 20
A black resin powder having an average particle diameter of 11 μm, of which μm was selected, was obtained. 0.5% of tin oxide type fine powder having a primary particle diameter of about 20 nm is added as a surface treatment agent to the obtained black resin powder,
【図１】記載の球状ミキサ−を冷却しながら周速度60ｍ
／secで5分間攪拌混合してトナ−を得た。該トナ−の表
面を電子顕微鏡で観察したところ、球状ミキサ−による
攪拌混合前の樹脂粉体表面にあった角張った部分が無く
なり、表面は丸みを帯びた状態に変化していた。また、
表面上の疎水性コロイド状シリカ・ポリメチルメタクリ
レ−トからなる表面処理剤は樹脂粉体表面にしっかり固
着していることが観察された。尚、トナ−系中に目視確
認されるような表面処理剤の大きな凝集体は見いだされ
なかった。FIG. 1 A peripheral speed of 60 m while cooling the described spherical mixer
The mixture was stirred and mixed for 5 minutes at a speed / sec to obtain a toner. Observation of the surface of the toner with an electron microscope revealed that there was no angular portion on the surface of the resin powder before stirring and mixing by the spherical mixer, and the surface had changed to a rounded state. Also,
It was observed that the surface treating agent composed of hydrophobic colloidal silica / polymethyl methacrylate on the surface was firmly adhered to the resin powder surface. Incidentally, no large aggregate of the surface treatment agent as visually confirmed in the toner system was found.
【００２７】該トナ−を市販の普通紙複写機に投入し、
実施例１に記載の通常環境及び高温高湿環境での耐久テ
ストを行ったが、The toner is put into a commercial plain paper copier,
A durability test was performed in a normal environment and a high-temperature and high-humidity environment described in Example 1.
【表１】に示すごとく画像濃度・転写率は良好で、画像
濃度・転写率は良好で、画像カブリ及び黒ベタ画像中の
白点も観察されず機内飛散による複写機内の汚染も確認
されなかった。 実施例７ ポリエステル 100重量部 マグネタイト 4重量部 上記材料をブレンダ−でよく混合した後、130℃に設定
した２軸押出機にて混練した。得られた混練物を冷却
し、ハンマ−ミルにて粗粉砕した後、ジェット気流を用
いて微粉砕した。得られた微粉砕粉中の超微粉を風力分
級機で厳密に分級除去して、5〜20μｍを選択し平均粒
径10μｍ青色の樹脂粉体を得た。As shown in Table 1, the image density and transfer rate were good, the image density and transfer rate were good, no image fogging and white spots in the solid black image were observed, and no contamination in the copying machine due to scattering inside the machine was confirmed. Was. Example 7 100 parts by weight of polyester 4 parts by weight of magnetite The above materials were mixed well with a blender and kneaded with a twin screw extruder set at 130 ° C. The obtained kneaded material was cooled, coarsely pulverized by a hammer mill, and then finely pulverized using a jet stream. The ultrafine powder in the obtained finely pulverized powder was strictly classified and removed by an air classifier, and 5 to 20 μm was selected to obtain a blue resin powder having an average particle diameter of 10 μm.
【００２８】該樹脂粉体をThe resin powder is
【図１】記載の内容積40リットル球状ミキサ−を冷却しなが
ら周速度80ｍ／secで3分間攪拌混合した後、表面処理剤
として一次粒子径が約20nmの疎水性コロイド状シリカを
0.5％添加し、更に周速度60m／secで2分間攪拌混合しカ
ラ−トナ−を得た。該トナ−の表面を電子顕微鏡で観察
したところ、球状ミキサ−による攪拌混合前の樹脂粉体
表面にあった角張った部分は消滅し、表面は丸みを帯び
た状態に変化していた。また、疎水性コロイド状シリカ
は、樹脂粉体表面にしっかりと固着している状態が観察
された。尚、トナ−系中には、目視確認できるようなシ
リカの大きな凝集体は確認されなかった該トナ−を市販
のカラ−複写機に投入し、通常環境及び高温・高湿環境
での耐久テストを行ったが、[FIG. 1] After stirring and mixing at a peripheral speed of 80 m / sec for 3 minutes while cooling a spherical mixer having an inner volume of 40 liters described above, hydrophobic colloidal silica having a primary particle diameter of about 20 nm is used as a surface treatment agent.
0.5% was added, and the mixture was further stirred and mixed at a peripheral speed of 60 m / sec for 2 minutes to obtain a color toner. Observation of the surface of the toner with an electron microscope revealed that the angular portion on the surface of the resin powder before stirring and mixing by the spherical mixer had disappeared, and the surface had changed to a rounded state. Further, a state was observed in which the hydrophobic colloidal silica was firmly fixed to the surface of the resin powder. In the toner system, large aggregates of silica that could be visually confirmed were not confirmed. The toner was put into a commercially available color copier, and subjected to a durability test in a normal environment and in a high temperature and high humidity environment. Went,
【表１】に示すごとく濃度の高い鮮明なシアン画像が得
られ、カブリ増加等画像品質の低下もなく機内飛散によ
る複写機内の汚染等も確認されなかった。また、感光体
やチャ−ジャ−装置を確認したところ汚れもなく良好な
状態であった。As shown in Table 1, a clear cyan image having a high density was obtained, and there was no decrease in image quality such as an increase in fog, and no contamination in the copying machine due to scattering inside the machine was observed. In addition, when the photoreceptor and the charger were confirmed, they were in a good condition without contamination.
【００２９】比較例１ 実施例１で使用の球状ミキサ−を内容積40リットルヘンシェ
ルミキサ−に変更して周速度を70m／secに変更する以外
は、実施例１と同様な操作を行った。得られたトナ−の
表面を電子顕微鏡で観察したところ、表面の凹凸状態は
角ばった部分が多く観察された。また、疎水性コロイド
状シリカは樹脂粉体表面に固着した状態が見あたらず、
トナ−系中に疎水性コロイド状シリカの凝集体が観察さ
れた。該トナ−を実施例１で用いた普通紙複写機に投入
し、通常環境での耐久テストを行ったところ、Comparative Example 1 The same operation as in Example 1 was performed, except that the spherical mixer used in Example 1 was changed to a 40-liter Henschel mixer having an inner volume of 70 m / sec and the peripheral speed was changed to 70 m / sec. Observation of the surface of the obtained toner with an electron microscope revealed that many irregularities on the surface were square. In addition, hydrophobic colloidal silica was not found to be fixed on the surface of the resin powder,
Agglomerates of hydrophobic colloidal silica were observed in the toner system. The toner was put into the plain paper copying machine used in Example 1 and subjected to a durability test in a normal environment.
【表１】に示すように転写率が減少し、画像性において
はカブリの発生や黒ベタ中に白点が観察され実用上許容
できない様な画像が得られた。また、複写機内を点検し
たところ、機内飛散による機内汚染が確認された。更
に、高温高湿環境では、転写率は更に低下しカブリの発
生や機内汚染もさらに悪化した。As shown in Table 1, the transfer rate was reduced, and in terms of image quality, fog occurred and white spots were observed in solid black, and an image which was not practically acceptable was obtained. When the inside of the copying machine was inspected, contamination inside the machine due to scattering inside the machine was confirmed. Further, in a high-temperature and high-humidity environment, the transfer rate was further reduced, and the occurrence of fog and contamination in the apparatus were further worsened.
【００３０】比較例２ 実施例４において使用の球状ミキサ−を内容積40リットルヘ
ンシェルミキサ−に変更して周速度を30ｍ／secに変更
する以外は、実施例４と同様な操作を行った。得られた
トナ−の表面を電子顕微鏡で観察したところ、表面の凹
凸状態は角ばった部分が多く観察された。また、表面処
理剤である疎水性コロイド状シリカ及び炭化珪素がトナ
−表面に固着した状態が見あたらず、トナ−系中に該表
面処理剤の凝集体が観察された。該トナ−を実施例４で
用いた複写機に投入し、通常環境では、Comparative Example 2 The same operation as in Example 4 was carried out except that the spherical mixer used in Example 4 was changed to a 40-liter Henschel mixer having an inner volume of 30 m / sec and the peripheral speed was changed to 30 m / sec. Observation of the surface of the obtained toner with an electron microscope revealed that many irregularities on the surface were square. Further, no state was observed in which hydrophobic colloidal silica and silicon carbide as surface treatment agents were fixed to the toner surface, and aggregates of the surface treatment agent were observed in the toner system. The toner was put into the copying machine used in Example 4, and in a normal environment,
【表１】に示すように転写率が低く、画像性においても
カブリや文字まわりのチリ更に黒ベタ中に白点が観察さ
れ実用上許容できない様な画像が得られた。また、複写
機内を汚れ状態は実施例４に比較し著しく汚染され、感
光体表面にも顕著に傷が確認された。更に、高温高湿環
境では、転写率は更に低下しカブリの発生や機内汚染も
さらに悪化した。As shown in Table 1, the transfer rate was low, and in terms of image quality, fog and dust around characters and white spots in black solid were observed, and an image which was not practically acceptable was obtained. Further, the inside of the copying machine was significantly contaminated as compared with Example 4, and the surface of the photoreceptor was also markedly scratched. Further, in a high-temperature and high-humidity environment, the transfer rate was further reduced, and the occurrence of fog and contamination in the apparatus were further worsened.
【００３１】比較例３ 実施例６で使用の球状ミキサ−を内容積40リットルヘンシェ
ルミキサ−にかえ周速度を30ｍ／secに変更する以外
は、実施例６と同様の操作を行った。得られた樹脂粉体
の表面を電子顕微鏡で観察したところ、表面の凹凸状態
は角ばった部分が多く観察された。また、表面処理剤で
ある疎水性コロイド状シリカ及び酸化錫微粉末がトナ−
の表面に固着した状態が見あたらず、トナ−系中に該表
面処理剤の凝集体が観察された。該トナ−を実施例６で
用いた市販の複写機に投入し、通常環境での耐久テスト
では、Comparative Example 3 The same operation as in Example 6 was performed except that the spherical mixer used in Example 6 was changed to a 40-liter Henschel mixer having an inner volume of 40 m / sec and the peripheral speed was changed to 30 m / sec. Observation of the surface of the obtained resin powder with an electron microscope revealed that many irregularities on the surface were square. Further, hydrophobic colloidal silica and fine powder of tin oxide, which are surface treatment agents, are used as toners.
No fixation to the surface was observed, and aggregates of the surface treating agent were observed in the toner system. The toner was put into the commercial copying machine used in Example 6, and a durability test was performed in a normal environment.
【表１】に示すように転写率が低く、画像性においても
カブリや文字まわりのチリ、更に、黒ベタ中に白点が観
察され実用上許容できない様な画像が得られた。また、
複写機内を汚れ状態は実施例６に比較し著しく汚染さ
れ、感光体表面にも顕著に傷が確認された。更に、高温
高湿環境テストでは、転写率は更に低下しカブリの発生
や機内汚染もさらに悪化した。As shown in Table 1, the transfer rate was low, and in terms of image quality, fog, dust around characters, and white spots were observed in solid black, and an image which was not practically acceptable was obtained. Also,
The inside of the copying machine was significantly contaminated compared to Example 6, and the surface of the photoreceptor was markedly damaged. Further, in the high-temperature and high-humidity environment test, the transfer rate was further reduced, and the occurrence of fog and contamination in the machine were further deteriorated.
【００３２】比較例４ 実施例７で使用の球状ミキサ−を内容積40リットルヘンシェ
ルミキサ−にかえ周速度を30ｍ／secに変更する以外
は、実施例７と同様の操作を行った。。得られたトナ−
の表面を電子顕微鏡で観察したところ、表面の凹凸状態
は角ばった部分が多く観察された。また、表面処理剤で
ある疎水性コロイド状シリカが樹脂トナ−表面に固着し
た状態が見あたらず、トナ−系中に該表面処理剤の凝集
体が観察された。該トナ−を実施例７で用いた市販のカ
ラ−複写機に投入し、通常環境での耐久テストでは、Comparative Example 4 The same operation as in Example 7 was performed except that the spherical mixer used in Example 7 was replaced with a 40-liter Henschel mixer having an inner volume of 40 m / sec and the peripheral speed was changed to 30 m / sec. . Obtained toner
As a result of observing the surface of the sample with an electron microscope, many irregularities were observed on the surface. Further, no state was observed in which the hydrophobic colloidal silica as the surface treating agent was fixed to the resin toner surface, and aggregates of the surface treating agent were observed in the toner system. The toner was put into the commercially available color copier used in Example 7, and the durability test in a normal environment showed that
【表１】に示すように画像濃度が不均一でカブリが多く
細線再現性の低い実用上許容できない画像が得られた。
また、複写機内の汚れ状態は実施例７に比較し著しく汚
染され、感光体表面にも顕著に傷が確認された。更に、
高温高湿環境でのテストでは、画像性や感光体表面上の
傷の発生状態は常温環境時に比べ更に悪化した。As shown in Table 1, an image having a non-uniform image density, a lot of fog, and a low reproducibility of fine lines, which was not practically acceptable, was obtained.
Further, the dirt condition in the copying machine was significantly contaminated compared to Example 7, and the surface of the photoreceptor was also markedly scratched. Furthermore,
In the test in a high-temperature and high-humidity environment, the image quality and the state of occurrence of scratches on the surface of the photoreceptor were further deteriorated as compared with those in a normal temperature environment.
【００３３】[0033]
【発明の効果】本発明の製造方法では、球状ミキサ−を
使用することで、従来法と比較して、核となる樹脂粉末
に表面処理剤が容易に均一付着（固着）することが可能
となったのである。特に、本発明による製造法は、電子
写真用トナ−製造の際に樹脂粉体である未処理トナ−へ
表面処理剤を均一化した状態で付着（固着）が容易であ
り、得られたトナ−を複写機に使用すると、画像性、機
内汚れ、転写率、長期複写性及び環境性等に優れた効果
を発揮するトナ−を提供するものである。According to the production method of the present invention, the use of the spherical mixer makes it possible to easily and uniformly adhere (fix) the surface treating agent to the core resin powder as compared with the conventional method. It has become. In particular, according to the production method of the present invention, the surface treatment agent is easily adhered (fixed) to an untreated toner which is a resin powder in the state of producing the toner for electrophotography in a uniform state, and the obtained toner is obtained. When-is used in a copying machine, the present invention provides a toner exhibiting excellent effects such as image quality, in-machine contamination, transfer rate, long-term copying property and environmental friendliness.
【００３４】[0034]
【図１】本発明で用いる球状ミキサ−本体の構成例を示
す部分断面図である。FIG. 1 is a partial sectional view showing a configuration example of a spherical mixer main body used in the present invention.
１．試料の投入口 ２．試料の取出口 ３．下段の回転羽 ４．上段の回転羽 ５．回転羽の駆動軸 1. 1. Sample inlet 2. Sample outlet Lower rotating wings 4. 4. Upper rotating wings Rotary wing drive shaft
Claims (4)
面に沿って回転する下段回転羽と容器中央部に周速度40
ｍ／sec以上で回転する上段回転羽を設けた球状ミキサ
−を使用して、攪拌混合し得られる表面処理樹脂粉体の
製造方法。A resin powder and a surface treating agent are supplied to a lower rotating blade rotating along the inner bottom surface of a spherical container and a peripheral speed of 40 to a central portion of the container.
A method for producing a surface-treated resin powder obtained by stirring and mixing using a spherical mixer provided with an upper rotary blade rotating at m / sec or more.
μｍ〜30μｍである表面処理樹脂粉体の製造方法。2. The resin powder according to claim 1, which has an average particle size of 3
A method for producing a surface-treated resin powder having a size of from 30 μm to 30 μm.
が、2ｎｍ〜2μｍである表面処理樹脂粉体の製造方法。3. A method for producing a surface-treated resin powder according to claim 1, wherein the surface-treating agent has a primary particle diameter of 2 nm to 2 μm.
表面処理樹脂粉体が電子写真用トナ−であることを特徴
とする表面処理樹脂粉体の製造方法。4. A method for producing a surface-treated resin powder, wherein the surface-treated resin powder according to claim 1, 2 or 3 is an electrophotographic toner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26914196A JPH1095855A (en) | 1996-09-20 | 1996-09-20 | Production of surface-treating resin powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26914196A JPH1095855A (en) | 1996-09-20 | 1996-09-20 | Production of surface-treating resin powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1095855A true JPH1095855A (en) | 1998-04-14 |
Family
ID=17468265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26914196A Pending JPH1095855A (en) | 1996-09-20 | 1996-09-20 | Production of surface-treating resin powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1095855A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002351141A (en) * | 2001-03-22 | 2002-12-04 | Ricoh Co Ltd | Method of manufacturing electrophotographic toner and developing method |
| JP2003015357A (en) * | 2001-07-02 | 2003-01-17 | Ricoh Co Ltd | Manufacturing method of electrophotographic toner |
| JP2003098741A (en) * | 2001-09-21 | 2003-04-04 | Ricoh Co Ltd | Electrophotographic toner |
| US7011921B2 (en) | 2002-08-12 | 2006-03-14 | Ricoh Company, Ltd. | Method and apparatus for producing toner for electrophotography |
| JP2007084709A (en) * | 2005-09-22 | 2007-04-05 | Tokyo Printing Ink Mfg Co Ltd | Powder coating and method for producing the same |
| JP2008006391A (en) * | 2006-06-30 | 2008-01-17 | Tokyo Printing Ink Mfg Co Ltd | Method of regenerating powder coating |
| US8703378B2 (en) | 2010-09-16 | 2014-04-22 | Ricoh Company, Ltd. | Method of manufacturing toner and toner manufactured by the method |
| JP2014202965A (en) * | 2013-04-05 | 2014-10-27 | キヤノン株式会社 | Toner processing device |
-
1996
- 1996-09-20 JP JP26914196A patent/JPH1095855A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002351141A (en) * | 2001-03-22 | 2002-12-04 | Ricoh Co Ltd | Method of manufacturing electrophotographic toner and developing method |
| JP2003015357A (en) * | 2001-07-02 | 2003-01-17 | Ricoh Co Ltd | Manufacturing method of electrophotographic toner |
| JP2003098741A (en) * | 2001-09-21 | 2003-04-04 | Ricoh Co Ltd | Electrophotographic toner |
| US7011921B2 (en) | 2002-08-12 | 2006-03-14 | Ricoh Company, Ltd. | Method and apparatus for producing toner for electrophotography |
| JP2007084709A (en) * | 2005-09-22 | 2007-04-05 | Tokyo Printing Ink Mfg Co Ltd | Powder coating and method for producing the same |
| JP2008006391A (en) * | 2006-06-30 | 2008-01-17 | Tokyo Printing Ink Mfg Co Ltd | Method of regenerating powder coating |
| US8703378B2 (en) | 2010-09-16 | 2014-04-22 | Ricoh Company, Ltd. | Method of manufacturing toner and toner manufactured by the method |
| JP2014202965A (en) * | 2013-04-05 | 2014-10-27 | キヤノン株式会社 | Toner processing device |
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