JPH0346670A - Carrier for developer - Google Patents
Carrier for developerInfo
- Publication number
- JPH0346670A JPH0346670A JP1183151A JP18315189A JPH0346670A JP H0346670 A JPH0346670 A JP H0346670A JP 1183151 A JP1183151 A JP 1183151A JP 18315189 A JP18315189 A JP 18315189A JP H0346670 A JPH0346670 A JP H0346670A
- Authority
- JP
- Japan
- Prior art keywords
- group
- carrier
- silicone oil
- developer
- resin
- 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
- 229920002545 silicone oil Polymers 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 6
- 238000000576 coating method Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
- 239000011247 coating layer Substances 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims 4
- 239000000126 substance Substances 0.000 claims 2
- 239000000969 carrier Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000011162 core material Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- -1 for example Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001282736 Oriens Species 0.000 description 1
- 101000579646 Penaeus vannamei Penaeidin-1 Proteins 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 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 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000012050 conventional carrier Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 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
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin 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
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc 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等に使用する現像剤用キャリアに関
し、より詳細には流動性と耐久性が著しく向上した現像
剤用キャリアに関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a developer carrier used in electrophotography, and more particularly to a developer carrier with significantly improved fluidity and durability.
（従来技術）
二成分現像剤を用いる電子写真法は、結着樹脂中に着色
剤が分散された着色樹脂粒子であるトナーと鉄粉やフェ
ライト等からなる磁性キャリアとを混合し、この二成分
現像剤を内部に磁石を備えた現像スリーブ上に供給して
、この組成物からなる磁気ブラシを形成させ、静電潜像
を有する光導電性物質から成る感光層にこの磁気ブラシ
を摺擦せしめることにより、トナー像を感光層上に形成
させる。トナーは磁性キャリアとの摩擦によって所望の
摩擦電荷を所得し、磁気ブラシ上のトナーが感光層上の
静電潜像へ静電気力等によって移行して付着し静電潜像
の現像が行われる。そして、現像によって得られた感光
層上のトナー像は転写紙等の転写材上に転写され、熱ま
たは圧力によって転写材」二に定着されて画像形成がな
されるものである。(Prior art) Electrophotography using a two-component developer mixes toner, which is colored resin particles in which a colorant is dispersed in a binder resin, and a magnetic carrier made of iron powder, ferrite, etc. A magnetic brush made of this composition is formed by supplying a developer onto a developing sleeve having a magnet therein, and the magnetic brush is rubbed against a photosensitive layer made of a photoconductive material having an electrostatic latent image. As a result, a toner image is formed on the photosensitive layer. The toner acquires a desired triboelectric charge by friction with the magnetic carrier, and the toner on the magnetic brush moves and adheres to the electrostatic latent image on the photosensitive layer by electrostatic force, and the electrostatic latent image is developed. The toner image on the photosensitive layer obtained by development is transferred onto a transfer material such as transfer paper, and is fixed to the transfer material by heat or pressure to form an image.
そして、上記の画像形成によって現像装置内のトナーは
消費されていくために、画像形成を繰り返し行うために
は、消費に見合った量の新たなトナーが装置内に供給さ
れ、磁性ギヤリアとの摩擦攪拌によって速やかに帯電す
ることが必要となる。Since the toner in the developing device is consumed by the image formation described above, in order to repeatedly form images, new toner is supplied into the device in an amount commensurate with the consumption, and friction with the magnetic gear It is necessary to charge the material quickly by stirring.
しかしながら、磁性キャリアは現像作業の繰り返しとと
もに表面にトナー膜を形成するスペント化を発生したり
、吸湿性を示すために良好な帯電量９卸が行えなくなっ
たりする。そこで、このような欠点を解決するために、
従来より樹脂やシリコンオイルによって磁性キャリアを
被覆し、スペント化と耐湿度性の付与をおこなっている
。この被覆層を有するキャリアは上記の欠点をある程度
改善し、電気抵抗が調整できるというメリットもあって
多く使用されるようになってきており、近年においては
、樹脂被覆層にシリコーンオイルを含有させたキャリア
も種々提案されている。However, as the magnetic carrier is repeatedly subjected to development operations, it may become spent to form a toner film on its surface, or it may become hygroscopic, making it impossible to achieve a good charge amount. Therefore, in order to solve these shortcomings,
Traditionally, magnetic carriers have been coated with resin or silicone oil to make them spent and provide moisture resistance. Carriers with this coating layer have improved the above drawbacks to some extent and have the advantage of being able to adjust electrical resistance, so they have come to be widely used.In recent years, carriers containing silicone oil in the resin coating layer Various carriers have also been proposed.
（発明が解決しようとする問題点）
近年において、複写機等の画像形成装置は高速化が進み
、毎分５０〜７０枚（Ａ４判）のスピードで画像形成が
行われたり、また、複写機の使用頻度も年々多くなって
きており、現像剤の攪拌もより高速且つ頻繁に行われる
ようになってきているため、現像剤、特にキャリアの耐
久性の向上が大きな技術的課題となっている。(Problems to be Solved by the Invention) In recent years, image forming devices such as copying machines have become faster, and images are formed at a speed of 50 to 70 sheets per minute (A4 size). The frequency of use of the developer is increasing year by year, and the agitation of the developer is also becoming faster and more frequent, so improving the durability of the developer, especially the carrier, has become a major technical issue. .
そして、上記従来の被覆層にシリコーンオイルを有する
キャリアは未被覆のキャリアに比べて、耐湿度性やスペ
ント化の防止においである程度の成果をあげることがで
きている。しかしながら、高速攪拌を行ったり、長期の
連続攪拌を行うような過酷な条件下で複写作業を行うと
、シリコーンオイルとキャリアコア材、或いはシリコー
ンオイルと被覆樹脂との固定化が充分に行えないためか
、被覆層の表面状態を粗悪なものとし、その粘着性のた
めに現像剤の流動性を低下させて、帯電の立ち上がりが
不十分であったり、帯電量の変動がおこって、画像カブ
リや画像濃度の低下を引き起こすことがある。そして、
このことは複写作業の継続とともに一層激しく起こるよ
うになる。The above-mentioned conventional carrier having silicone oil in its coating layer has been able to achieve certain results in terms of moisture resistance and prevention of spent, compared to uncoated carriers. However, when copying work is performed under harsh conditions such as high-speed stirring or continuous stirring for a long period of time, the silicone oil and carrier core material or silicone oil and coating resin cannot be sufficiently immobilized. Or, the surface condition of the coating layer may be poor, and its tackiness may reduce the fluidity of the developer, resulting in insufficient charge build-up or fluctuations in the amount of charge, resulting in image fogging or May cause a decrease in image density. and,
This problem becomes more severe as the copying process continues.
本発明は」二記点に鑑みてなされたものであり、その目
的は、シリコーンオイルのキャリアへの固定化を充分に
おこない、スペント化の防止と耐湿度性に優れ、且つ、
流動性と安定した摩擦帯電性を長期にわたって維持でき
る耐久性の向上した現像剤用キャリアを提供することに
ある。The present invention has been made in view of two points, and its purpose is to sufficiently fix silicone oil to a carrier, prevent it from becoming spent, and have excellent moisture resistance.
It is an object of the present invention to provide a developer carrier with improved durability that can maintain fluidity and stable triboelectric charging properties over a long period of time.
（問題点を解決するための手段及び作用）本発明によれ
ば、下記一般式のシリコーンオイルを含有してなる被覆
層が形成されていることを特徴とする現像剤用キャリア
が提供される。(Means and effects for solving the problems) According to the present invention, there is provided a developer carrier characterized in that a coating layer containing a silicone oil of the following general formula is formed.
更に、
本発明によれば被覆樹脂層に少なくとも下記一般式のシ
リコーンオイルが含有されていることを特徴とする現像
剤用キャリアが提供される。Further, according to the present invention, there is provided a developer carrier characterized in that the coating resin layer contains at least a silicone oil of the following general formula.
本発明は、
被覆層に含有させるシリコーンオイ
ルとして、上記の一般式で表される末端反応性シリコー
ンオイルを含有させることを特徴とするものである。The present invention is characterized in that the coating layer contains a terminal-reactive silicone oil represented by the above general formula as the silicone oil.
つまり、シリコーンオイル中に存在する水酸基がキャリ
ア表面或いは被覆樹脂中の水酸基と反応して固定化反応
が起こり、シリコーンオイルのキャリア表面での固定化
が良好となって、スペント化の防止、耐環境性はもとよ
り、流動性、帯電安定性が長期にわたって良好に維持で
き、耐久性が著しく向上する。In other words, the hydroxyl groups present in the silicone oil react with the hydroxyl groups on the carrier surface or coating resin to cause a fixation reaction, which improves the fixation of the silicone oil on the carrier surface, prevents spent from forming, and improves environmental resistance. Not only the properties but also the fluidity and charging stability can be maintained well over a long period of time, and the durability is significantly improved.
本発明の現像剤用キャリアは電気抵抗の調整、耐久性の
点で被覆樹脂中に上記一般式のシリコーンオイルを含有
させて生成することが好ましいが、シリコーンオイルを
単独でキャリアコア材に被覆しても優れた効果を得るこ
とができる。The developer carrier of the present invention is preferably produced by containing silicone oil of the above general formula in the coating resin in terms of electrical resistance adjustment and durability. You can get excellent results even if you use it.
本発明に使用するシリコーンオイルはジメチルポリシロ
キサンに一級のアルコール性○Ｈ５を導入した構造を有
するもので、具体例としては、信越シリコーン社製、Ｘ
−２２−１６０ＡＳ、、Ｘ２２−１６０Ｂ、χ−２１−
１６０Ｃ，東芝シリコーン社製、ＸＦ４２−２２０ （
何れも商品名）として人手することができる。The silicone oil used in the present invention has a structure in which primary alcoholic ○H5 is introduced into dimethylpolysiloxane.
-22-160AS,,X22-160B,χ-21-
160C, manufactured by Toshiba Silicone Co., Ltd., XF42-220 (
Both products can be manufactured by hand (product name).
これらシリコーンオイルの使用割合としては、後述する
キャリアコア材に対して０．００００１乃至１０重量％
、好ましくは０．０００１乃至５重量％使用する。また
、被覆樹脂とともに使用する場合は被覆樹脂に対して０
．０１重量％以上、特に０．１重量％以上を使用すると
よい。上記範囲を越えて多く使用しすぎると、被覆表面
が不均一になって耐久性、流動性に影響を与える。また
、上記範囲よりも使用量が少なくなると、本発明のシリ
コンオイルによる効果が発揮されず耐環境性、スペント
化の防止、耐久性の向上が期待できなくなる。 本発明
に使用されるキャリアコア拐としては、この分野で使用
されるそれ自体公知の電子写真用現像剤用キャリアコア
材が使用でき、例えば、酸化鉄、還元鉄、銅、フェライ
ト、ニッケル、コバルト等やこれら亜鉛、アルごニウム
等との合金等が挙げられるが、電気抵抗の環境及び経時
変化が小さく、柔らかい穂の形成できるフェライト系粒
子が好ましく、例えば、Ｚｎ系フェライト、Ｎｉ系フェ
ライ１〜、Ｃｕ系フェライト、Ｍｎ系フェライト、Ｎｉ
−Ｚｎ系フェライ１−１−１Ｍｎ−系フェライ１〜、Ｃ
ｕ −Ｍ ｇ系フェライト、ＭｎＺｎ系フェライト、Ｍ
ｎ−Ｃｕ−Ｚｎ系フェライト等が挙げられる。特に、Ｍ
ｎ−Ｃｕ−Ｚｎ系フェライトが好ましい。これらコア祠
の粒径は１０乃至２００μｍ、好ましくは３０乃至１５
０μｍのものが使用され、飽和磁化は３５乃至７０ｅｍ
ｕ／ｇ特に４０乃至６５ ｅｍｕ／ｇのものが好ましく
使用される。The proportion of these silicone oils used is 0.00001 to 10% by weight based on the carrier core material described below.
, preferably 0.0001 to 5% by weight. Also, when used with a coating resin, the coating resin should be 0%
．． It is preferable to use 0.01% by weight or more, especially 0.1% by weight or more. If it is used in an amount exceeding the above range, the coated surface will become non-uniform and the durability and fluidity will be affected. Furthermore, if the amount used is less than the above range, the effects of the silicone oil of the present invention will not be exhibited, and improvements in environmental resistance, prevention of spent, and durability cannot be expected. As the carrier core material used in the present invention, carrier core materials for electrophotographic developers known per se used in this field can be used, such as iron oxide, reduced iron, copper, ferrite, nickel, cobalt. etc., and alloys of these with zinc, argonium, etc., but ferrite-based particles that have small environmental and aging changes in electrical resistance and can form soft spikes are preferred, such as Zn-based ferrite, Ni-based ferrite 1- , Cu-based ferrite, Mn-based ferrite, Ni
-Zn-based ferrite 1-1-1Mn-based ferrite 1~, C
u -M g-based ferrite, MnZn-based ferrite, M
Examples include n-Cu-Zn ferrite. In particular, M
Preferred is n-Cu-Zn ferrite. The grain size of these core grains is 10 to 200 μm, preferably 30 to 15 μm.
0 μm is used, and the saturation magnetization is 35 to 70 em.
U/g, especially 40 to 65 emu/g is preferably used.
また、本発明においてシリコーンオイルとともに使用す
る被覆樹脂としては、それ自体公知のキャリア用被覆樹
脂が用いられ、例えば、アクリル樹脂、スチレン樹脂、
ポリエステル樹脂、エポキシ樹脂、シリコーン樹脂、ウ
レタン樹脂、ポリアセクール樹脂、ポリアミド樹脂、ボ
リカーボ不一１・樹脂、フェノール樹脂、酢酸ビニル樹
脂、セルロース樹脂、ポリオレフィン樹脂、フッソ樹脂
、アくノ樹脂等の一種または二種以上が混合して用いら
れる。Furthermore, as the coating resin used together with the silicone oil in the present invention, known carrier coating resins are used, such as acrylic resin, styrene resin,
One or two of polyester resins, epoxy resins, silicone resins, urethane resins, polyacecool resins, polyamide resins, polycarbonate resins, phenol resins, vinyl acetate resins, cellulose resins, polyolefin resins, fluorocarbon resins, acrylic resins, etc. A mixture of more than one species is used.
本発明のキャリアの製造方法としては、キャリアコア材
に単独でシリコーンオイルを被着さセてもよいが、溶剤
で希釈して用いてもよく、このような溶剤としては、ト
ルエン、キシレン等の芳香族炭化水素類や、トリククロ
ロエチレン、パークロロエチレン等のハロゲン化炭化水
素類や、アセトンやメチルエチルケトン等のアセトン類
や、テトラヒドロフラン等の環状エーテル類、メタノー
ル、エタノール、イソプロピルアルコール等のアルコー
ル類等が使用でき、この濃度はシリコーンオイルの濃度
が０．１乃至８０重量％であることが好ましい。また、
被覆樹脂とともに用いる場合は、被覆樹脂とシリコーン
オイルとを上記の適当な溶剤に溶解して用いるとよい。In the method for producing the carrier of the present invention, silicone oil may be applied alone to the carrier core material, but it may also be diluted with a solvent. Examples of such a solvent include toluene, xylene, etc. Aromatic hydrocarbons, halogenated hydrocarbons such as trichloroethylene and perchlorethylene, acetones such as acetone and methyl ethyl ketone, cyclic ethers such as tetrahydrofuran, alcohols such as methanol, ethanol, isopropyl alcohol, etc. The silicone oil concentration is preferably 0.1 to 80% by weight. Also,
When used together with a coating resin, the coating resin and silicone oil may be dissolved in the above-mentioned appropriate solvent.
この場合、樹脂溶液は樹脂分が０．０５乃至５０重量％
、好ましくは０．１乃至４０重量％程度の濃度にすると
よい
そして、被覆に用いる処理機としては、それ自体公知の
混合機例えば、ヘンシェルミキサー（＝０
井三池製作所製）、Ｖ型ブレンダー（不二パウダル社製
）、ナウターミキサ−（細用ミクロン社製）等を挙げら
れることができ、他の方法としては、得られた溶液を、
浸漬法、スプレー法、流動床法等の方法によってキャリ
アコア材表面に塗布し、その後、加熱、乾燥して溶剤を
揮発させるか、溶剤の揮発後に更に加熱処理を行って硬
化することもできる。In this case, the resin solution has a resin content of 0.05 to 50% by weight.
, preferably at a concentration of about 0.1 to 40% by weight. Processing machines used for coating include a mixer known per se, such as a Henschel mixer (=0, manufactured by Imiike Seisakusho), a V-type blender (non-woven), etc. (manufactured by Nipaudal Co., Ltd.), Nauta mixer (manufactured by Hoyoi Micron Co., Ltd.), etc.;
It can also be applied to the surface of the carrier core material by a method such as a dipping method, a spray method, or a fluidized bed method, and then heated and dried to volatilize the solvent, or it can be further hardened by further heat treatment after the solvent has volatilized.
また、加熱、乾燥工程においては、溶剤の種類、量など
により異なるが、加熱温度が３０乃至１５０°Ｃの範囲
が適当である。加熱、乾燥後の硬化反応においては、一
般に８０乃至６００ ’Ｃ１特に１００乃至４００°Ｃ
の温度で行うのがよい。また、発明のキャリアには、被
覆層中に他の添加剤を含有させることもでき、例えば、
シリカ、アルミナ、カーボンブラック、脂肪酸金属塩、
等をあげることができる。
このようにして得られた本発明のキャリアは電
気抵抗が１０’乃至１０１４Ω・ｃｍｒｎ、特に１０’
乃至１０１４Ω・ｃｍの範囲に調整することが好ましく
、使用するキャリアコア材自体の電気抵抗、被覆層の厚
み、添加剤の種類と量を種々変更して調整することがで
きる。In addition, in the heating and drying steps, it is appropriate that the heating temperature be in the range of 30 to 150°C, although it varies depending on the type and amount of the solvent. In the curing reaction after heating and drying, the temperature is generally 80 to 600°C, especially 100 to 400°C.
It is best to do this at a temperature of In addition, the carrier of the invention can also contain other additives in the coating layer, for example,
Silica, alumina, carbon black, fatty acid metal salts,
etc. can be given.
The carrier of the present invention thus obtained has an electrical resistance of 10' to 1014 Ωcmrn, particularly 10'
It is preferable to adjust to a range of 1014 Ω·cm to 10 14 Ω·cm, and it can be adjusted by variously changing the electrical resistance of the carrier core material used, the thickness of the coating layer, and the type and amount of additives.
本発明のキャリアは、それ自体公知の絶縁性の定着用樹
脂中にそれ自体公知の着色剤等の添加剤が分散した粒径
が５乃至２５μｍの樹脂粒子である１〜ナーと混合して
現像剤とする。本発明のキャリアとトナーの混合割合と
しては、９８：２乃至９０：１０の範囲に調整するのが
よい。また、この時シリカ、アルミナ、酸化スズ、酸化
ストロンチウム、各種樹脂粉等のこの分野で使用される
外部添加剤を同時に混合して現像剤に調整することもで
きる。The carrier of the present invention is developed by mixing it with 1 to 1 to 1 toner, which are resin particles having a particle size of 5 to 25 μm, in which additives such as colorants, which are known per se, are dispersed in an insulating fixing resin, which is known per se. as a drug. The mixing ratio of the carrier and toner of the present invention is preferably adjusted to a range of 98:2 to 90:10. Further, at this time, external additives used in this field such as silica, alumina, tin oxide, strontium oxide, various resin powders, etc. can be mixed at the same time to prepare the developer.
以下、本発明を実施例にもとづいて説明する。The present invention will be explained below based on examples.
（実施例１）
王土ｌヱ
信越シリコーン社製シリコーンオイル、Ｘ−２２−１６
０Ａ（商品名）１０重量部をトルエン２００重量部で希
釈したものを用い、キャリアコア祠として平均粒径が１
００μｍのフェライトキャ１
リア粒子１０００重量部を使用して、流動床コーティン
グ装置を用いて被覆処理を行った。次いで、温度５０’
Ｃで乾燥して溶剤を除去した後、更に、２００°Ｃで加
熱処理を行って、硬化反応を進行させた。このようにし
て得られたキャリアの電気抵抗は１．２Ｘ１０”Ω・ｃ
ｍであった。(Example 1) Silicone oil, X-22-16, manufactured by Shinetsu Silicone Co., Ltd.
Using 10 parts by weight of 0A (trade name) diluted with 200 parts by weight toluene, the average particle size was 1 as a carrier core.
A coating treatment was carried out using a fluidized bed coating apparatus using 1000 parts by weight of 00 μm ferrite carrier particles. Then the temperature is 50'
After drying at C to remove the solvent, heat treatment was further performed at 200 C to advance the curing reaction. The electrical resistance of the carrier thus obtained was 1.2×10”Ω・c
It was m.
上士二
スヂレンーアクリル共重合体 １００重量部カーボン
ブラック １０重量部（ＭＡ−１００、
三菱化成社製）
電荷制御剤 １．５垂量部（ボント
ロン５−３２、オリエンｌ−化学社製）低分子量ポリプ
ロピレン ３重量部（ビスコール５５０Ｐ、
三洋化戒社製）上記処方からなる混合物をヘンシェルミ
キサーで前混合した後、二軸押し出し機で熔融混練した
後放冷した。この混練品をカッティングミルで粗粉砕し
たものを越音波式ジェントξルで微粉砕してアルピネ分
級機で粒径５μｍ以下をカットして、５〜２０μｍの範
囲で平均粒径が１１μｍのトナ３
ｔ
−を得た。Kamishinisujirene-acrylic copolymer 100 parts by weight Carbon black 10 parts by weight (MA-100,
(manufactured by Mitsubishi Kasei Corporation) Charge control agent 1.5 parts by weight (Bontron 5-32, manufactured by Orien L-Chemical Co., Ltd.) Low molecular weight polypropylene 3 parts by weight (Viscol 550P,
A mixture consisting of the above formulation (manufactured by Sanyo Kakaisha) was premixed using a Henschel mixer, then melt-kneaded using a twin-screw extruder, and then allowed to cool. This kneaded product was roughly pulverized with a cutting mill, finely pulverized with a sonic generator, and then cut with an Alpine classifier to particles with a particle size of 5 μm or less. t- was obtained.
上記キャリアとトナーを混合してｌ・ナー濃度３゜５％
の現像剤に調整し、電子写真複写機ＤＣ−５５８５（Ａ
４版５５枚／分、三田工業社製商品名）改造機で１００
０００枚の耐刷試験を行ったところ、初期〔画像濃度（
１，Ｄ）： １．３３、カブリ濃度（Ｆ、Ｄ）０．００
３、スペント量（％）：０〕 １０００００枚目Ｃ１，
ｌ）： １．３５、Ｆ、Ｄ：０．００２、スペン１へ量
（％）０゜０６〕で長期にわたって良好な画像が得られ
た。Mix the above carrier and toner to obtain a l-toner concentration of 3.5%.
The developer was adjusted to
4th edition 55 sheets/min, Sanda Kogyo Co., Ltd. product name) 100 sheets with modified machine
When we conducted a printing durability test of 000 sheets, we found that the initial [image density (
1, D): 1.33, fog density (F, D) 0.00
3. Spent amount (%): 0] 100,000th sheet C1,
1): 1.35, F, D: 0.002, amount (%) of pen 1: 0.06], good images were obtained over a long period of time.
また、高温・高湿（３５’Ｃ１８５％ＲＨ）下において
も上記画像特性とほぼ同様の良好画像が１０００００枚
を通して得られた。Further, even under high temperature and high humidity (35'C, 185% RH), good images with almost the same image characteristics as described above were obtained through 100,000 sheets.
（実施例２）
被覆樹脂としてのシリコーン樹脂９．９重量部、信越シ
リコーン社製シリコーンオイル、Ｘ−２２１６０Ａ（商
品名）０．１重量部をトルエン２００重量部で希釈した
ものを用い、キャリアコア材として平均粒径が１００μ
ｍのフェライトキャリア粒子１０００重量部を使用して
、流動床コー４
ティング装置を用いて被覆処理を行った。次いで、温度
５０°Ｃで乾燥して溶剤を除去した後、更に、２００
’Ｃで加熱処理を行って、硬化反応を進行させた。この
ようにして得られたキャリアの電気抵抗は１．５Ｘ１０
Ｉ０Ω・ｃｍであった。(Example 2) Using 9.9 parts by weight of silicone resin as a coating resin and 0.1 parts by weight of silicone oil manufactured by Shin-Etsu Silicone Co., Ltd., X-22160A (trade name) diluted with 200 parts by weight of toluene, a carrier core was prepared. As a material, the average particle size is 100μ
The coating treatment was carried out using a fluidized bed coating apparatus using 1000 parts by weight of ferrite carrier particles of 1.0 m. Next, after drying at a temperature of 50°C to remove the solvent,
A heat treatment was performed at 'C to advance the curing reaction. The electrical resistance of the carrier obtained in this way is 1.5X10
It was I0Ω·cm.
上記キャリアと実施例１と同様の１〜ナーを用いて］・
ナー濃度３．５％の現像剤に調整し、同様にして１００
０００枚の耐刷試験を行ったところ、初期〔画像濃度（
１，Ｄ）： ］、４３、カブリ濃度（Ｆ、Ｄ）Ｏ、スペ
ント蚤（％）：０：ｌ ｔｏ。Using the above carrier and the same materials 1 to 1 as in Example 1]
Adjust the developer concentration to 3.5%, and apply 100% in the same manner.
When we conducted a printing durability test of 000 sheets, we found that the initial [image density (
1, D): ], 43, Fog density (F, D) O, Spent flea (%): 0:l to.
０００枚目［１，Ｄ：１．４３、Ｆ、Ｄ：０．００１、
スペン１〜量（％）０．０９）で長期にわたって良好な
画像が得られた。また、高温・高湿（３５°Ｃ１８５％
ＲＨ）下においても上記画像特性とほぼ同様の良好画像
か１０００００枚を通して得られた。000th sheet [1, D: 1.43, F, D: 0.001,
Good images were obtained over a long period of time with a pen of 1 to 0.09 (%). In addition, high temperature and high humidity (35°C 185%)
RH), good images with almost the same image characteristics as above were obtained through 100,000 sheets.
（比較例１）
被覆樹脂としてのシリコーン樹脂１０重量部、をトルエ
ン２００置部部で希釈したものを用い、キャリアコア材
として平均粒径が１００μｍのフエクイ１−キャリア粒
子１０００重量部を使用して、流動床コーティング装置
を用いて被覆処理を行った。次いで、温度５０’Ｃで乾
燥して溶剤を除去した後、更に、２００ ’Ｃで加熱処
理を行って、硬化反応を進行させた。このようにして得
られたキャリアの電気抵抗は１．５Ｘ１０”Ω・ｃｍで
あった。(Comparative Example 1) 10 parts by weight of silicone resin diluted with 200 parts of toluene was used as the coating resin, and 1000 parts by weight of Huequi 1 carrier particles with an average particle size of 100 μm were used as the carrier core material. The coating process was carried out using a fluidized bed coating device. Next, after drying at a temperature of 50'C to remove the solvent, a heat treatment was further performed at 200'C to advance the curing reaction. The electrical resistance of the carrier thus obtained was 1.5×10”Ω·cm.
」二記キャリアと実施例１と同様のトナーを用いてトナ
ー濃度３．５％の現像剤に調整し、同様にして１０００
００枚の耐刷試験を行ったところ、初期〔画像濃度（１
，Ｄ）：ｌ、４３、カブリ濃度（Ｆ、Ｄ）０．００１、
スペント量（％）二〇）１０００００枚目［：１．Ｄ：
１．５０、Ｆ。A developer with a toner concentration of 3.5% was prepared using the carrier mentioned above and the same toner as in Example 1.
When we conducted a printing durability test of 00 sheets, we found that the initial [image density (1
, D): l, 43, fog density (F, D) 0.001,
Spent amount (%) 20) 100,000th sheet [:1. D:
1.50, F.
Ｄ：０．００８、スヘン１〜Ｍ（％）０．５０：］で複
写作業の継続とともにカブリが顕著となり、スペントｍ
も増えていった。D: 0.008, Spent 1 to M (%) 0.50:], fogging became noticeable as copying work continued, and spent m
It also increased.
また、高温・高温（３５°Ｃ８８５％ＲＨ）下において
は、−層カブリが発生し、５００００枚を越えた頃から
、画素濃度の異常上昇も認められた。In addition, under high temperature conditions (35 DEG C., 885% RH), negative layer fogging occurred, and an abnormal increase in pixel density was also observed after 50,000 sheets were printed.
（比較例２）
実施例Ｉにおいてシリコーンオイルとして、ジメチルシ
リコーンオイル、ＫＦ−９６（信越シリコーン社製、商
品名）１０重量部を用いた以外は同様にして被覆キャリ
アを作成した。このキャリアの電気抵抗は１．］Ｘｌ０
１０Ω・ｃｍであった。(Comparative Example 2) A coated carrier was prepared in the same manner as in Example I except that 10 parts by weight of dimethyl silicone oil, KF-96 (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) was used as the silicone oil. The electrical resistance of this carrier is 1. ]Xl0
It was 10Ω·cm.
上記キャリアと実施例１と同様のトナーによりトナー濃
度３．５％の現像剤に調整したが、キャリア表面が不均
一なために流動性が極めて悪く、現像剤として使用する
ことができなかった。A developer with a toner concentration of 3.5% was prepared using the above carrier and the same toner as in Example 1, but the carrier surface was uneven and the fluidity was extremely poor, so it could not be used as a developer.
（比校例３）
実施例２においてシリコーンオイルとして、ジメチルシ
リコーンオイル、ＫＦ−９６（信越シリコーン社製、商
品名）を使用した以外は同様にして被覆キャリアを作成
した。キャリアの電気抵抗は１．５Ｘ１０Ｉ０Ω・ｃｍ
であった。(Comparison Example 3) A coated carrier was prepared in the same manner as in Example 2 except that dimethyl silicone oil, KF-96 (manufactured by Shin-Etsu Silicone Co., Ltd., trade name) was used as the silicone oil. The electrical resistance of the carrier is 1.5X10I0Ω・cm
Met.
以下、実施例と同様の耐刷試験を行ったところ、初期〔
画像濃度（Ｉ、Ｄ）＋ １．４３、カブリ濃度（Ｆ、Ｄ
）０．００１、スペント量（％）：０）１０００００枚
目Ｎ、Ｉ）： ］、５０．Ｆ。Hereinafter, when a printing durability test similar to that in the example was conducted, the initial [
Image density (I, D) + 1.43, fog density (F, D)
) 0.001, Spent amount (%): 0) 100,000th sheet N, I): ], 50. F.
７
Ｄ：０．００６、スペンｌ−量（％）０．４６）で複写
作業の継続とともにカブリが顕著となり、スペント量も
増えていった。7 D: 0.006, Spent l-amount (%) 0.46), as the copying work continued, fog became noticeable and the amount spent also increased.
また、高温・高温（３５°Ｃ２８５％ＲＨ）下において
は、−層カブリが発生し、５００００枚を越えた頃から
、画素濃度の異常上昇も認められた。In addition, under high temperature conditions (35 DEG C., 285% RH), negative layer fogging occurred, and an abnormal increase in pixel density was also observed after 50,000 sheets were printed.
（発明の効果）
本発明によれば、シリコーン樹脂とキャリアコア材或い
は被覆樹脂との固定化が良好となり、キャリア表面が均
−且つ滑らかとなって、スペント化の防止、耐環境性、
流動性を著しく向」二さセ、耐刷枚数を飛躍的に向上さ
せることができる。(Effects of the Invention) According to the present invention, the silicone resin and the carrier core material or coating resin are well immobilized, and the carrier surface becomes uniform and smooth, preventing spent from forming and improving environmental resistance.
The fluidity is significantly improved, and the number of sheets printed can be dramatically increased.
Claims (2)
形成されていることを特徴とする現像剤用キャリア。 ▲数式、化学式、表等があります▼ 〔Ｒ＿１はアルキル基（Ｃ：１〜４）、フェニル基、Ｒ
＿２、Ｒ＿３、Ｒ＿４はアルキル基（Ｃ：１〜４）、フ
ェニル基、少なくとも一個の１級のアルコール性ＯＨ基
を含有する有機基を表し、Ｒ＿２、Ｒ＿３、Ｒ＿４のう
ち少なくとも一箇所以上は少なくとも一個の１級のアル
コール性ＯＨ基を含有する有機基であり、ｎとｍは正の
整数を表す。〕(1) A carrier for a developer, characterized in that a coating layer made of silicone oil having the following general formula is formed. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [R_1 is an alkyl group (C: 1-4), phenyl group, R
_2, R_3, and R_4 represent an alkyl group (C: 1 to 4), a phenyl group, and an organic group containing at least one primary alcoholic OH group, and at least one of R_2, R_3, and R_4 is at least It is an organic group containing one primary alcoholic OH group, and n and m represent positive integers. ]
オイルが含有されていることを特徴とする現像剤用キャ
リア。 ▲数式、化学式、表等があります▼ 〔Ｒ＿１はアルキル基（Ｃ：１〜４）、フェニル基、Ｒ
＿２、Ｒ＿３、Ｒ＿４はアルキル基（Ｃ：１〜４）、フ
ェニル基、少なくとも一個の１級のアルコール性ＯＨ基
を含有する有機基を表し、Ｒ＿２、Ｒ＿３、Ｒ＿４のう
ち少なくとも一箇所以上は少なくとも一個の１級のアル
コール性ＯＨ基を含有する有機基であり、ｎとｍは正の
整数を表す。〕(2) A developer carrier characterized in that the coating resin layer contains at least a silicone oil having the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [R_1 is an alkyl group (C: 1-4), phenyl group, R
_2, R_3, and R_4 represent an alkyl group (C: 1 to 4), a phenyl group, and an organic group containing at least one primary alcoholic OH group, and at least one of R_2, R_3, and R_4 is at least It is an organic group containing one primary alcoholic OH group, and n and m represent positive integers. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1183151A JPH0346670A (en) | 1989-07-14 | 1989-07-14 | Carrier for developer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1183151A JPH0346670A (en) | 1989-07-14 | 1989-07-14 | Carrier for developer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0346670A true JPH0346670A (en) | 1991-02-27 |
Family
ID=16130690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1183151A Pending JPH0346670A (en) | 1989-07-14 | 1989-07-14 | Carrier for developer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0346670A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6383639B1 (en) | 1997-05-06 | 2002-05-07 | Fuji Xerox Co., Ltd. | Charging member, electrostatic latent image developer using the same, image forming apparatus and image forming method |
| US10683821B2 (en) | 2017-02-16 | 2020-06-16 | Toyota Jidosha Kabushiki Kaisha | Engine control device |
-
1989
- 1989-07-14 JP JP1183151A patent/JPH0346670A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6383639B1 (en) | 1997-05-06 | 2002-05-07 | Fuji Xerox Co., Ltd. | Charging member, electrostatic latent image developer using the same, image forming apparatus and image forming method |
| US10683821B2 (en) | 2017-02-16 | 2020-06-16 | Toyota Jidosha Kabushiki Kaisha | Engine control device |
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