JP3426941B2 - Positively charged developer - Google Patents
Positively charged developerInfo
- Publication number
- JP3426941B2 JP3426941B2 JP32224697A JP32224697A JP3426941B2 JP 3426941 B2 JP3426941 B2 JP 3426941B2 JP 32224697 A JP32224697 A JP 32224697A JP 32224697 A JP32224697 A JP 32224697A JP 3426941 B2 JP3426941 B2 JP 3426941B2
- Authority
- JP
- Japan
- Prior art keywords
- silica
- och
- positively charged
- polar group
- coupling agent
- 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.)
- Expired - Fee Related
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- Developing Agents For Electrophotography (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は電子写真方式で用い
られる現像剤に関するものであり、特に、正帯電性の現
像剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer used in an electrophotographic system, and more particularly to a positively chargeable developer.
【0002】[0002]
【従来の技術】電子写真現像法においては、静電潜像を
可視化して又は静電潜像を反転現像により可視化して高
品質な画像を得ている。一般にこれらの現像法に適用す
るトナーとしては、バインダーとしての熱可塑性樹脂に
着色剤や帯電制御剤としての染料・顔料や、離型剤とし
てのワックス、磁性材料を混合して混練、粉砕、分級を
行い平均粒径4〜15μmのトナー粒子としたものが用
いられる。そして一般的には、トナーに流動性を付与し
たり、クリーニング性を向上させたりするために、シリ
カや酸化チタン等の無機微粉末が添加される。2. Description of the Related Art In an electrophotographic developing method, a high quality image is obtained by visualizing an electrostatic latent image or visualizing the electrostatic latent image by reversal development. In general, toners used in these developing methods include a thermoplastic resin as a binder, a dye or pigment as a colorant or a charge controlling agent, a wax as a release agent, and a magnetic material, which are kneaded, crushed, and classified. Is used to obtain toner particles having an average particle size of 4 to 15 μm. In general, an inorganic fine powder such as silica or titanium oxide is added in order to impart fluidity to the toner or improve cleaning properties.
【0003】これらの無機微粉末は親水性が高く、その
結果トナーの流動性や帯電立ち上がり性が湿度の影響で
変化する。このような環境条件の影響を防ぐため、これ
らの無機微粉末の表面を疎水化剤で処理したり、極性基
を導入するのが普通である。極性基導入としてアミノシ
ランで処理した金属酸化物を用いた現像剤の一例は、例
えば特開昭52−135739号公報、特開昭56−1
23550号公報に開示されている。この方法による
と、アミノシランのアミノ基により強い正帯電性を示す
現像剤が得られる。[0003] These inorganic fine powders have high hydrophilicity, and as a result, the fluidity and the charge rising property of the toner change due to the influence of humidity. In order to prevent the influence of such environmental conditions, the surface of these inorganic fine powders is usually treated with a hydrophobizing agent or a polar group is introduced. Examples of a developer using a metal oxide treated with aminosilane to introduce a polar group are described in, for example, JP-A-52-135739 and JP-A-56-1.
No. 23550. According to this method, a developer having a stronger positive charge property due to the amino group of the aminosilane can be obtained.
【0004】また、疎水性シリカ微粒子に正帯電制御剤
を吸着または染着させた現像剤の一例は、例えば特開昭
58−215252号公報、特開昭63−73271号
公報、特開昭63−73272号公報に開示されてい
る。この方法によると正帯電制御剤の効果により強い正
帯電性を示す現像剤が得られる。また、負帯電性極性基
と正帯電性極性基の両方の基が表面に結合した無機微粒
子を含有する非磁性1成分現像用トナーの一例は、例え
ば特開平2−66564号公報に開示されている。この
方法によるとトナーの帯電レベルの向上、帯電立ち上が
り性、トナー流動性に優れた現像剤が得られる。Further, examples of a developer in which a positive charge control agent is adsorbed or dyed on hydrophobic silica fine particles are described in, for example, JP-A-58-215252, JP-A-63-73271, and JP-A-63-73271. -73272. According to this method, a developer exhibiting a strong positive charge property can be obtained by the effect of the positive charge control agent. Further, an example of a non-magnetic one-component developing toner containing inorganic fine particles having both a negatively-chargeable polar group and a positively-chargeable polar group bonded to the surface is disclosed in, for example, JP-A-2-66564. I have. According to this method, it is possible to obtain a developer having an improved charge level of the toner, excellent charge rising property, and excellent toner fluidity.
【0005】[0005]
【発明が解決しようとする課題】上記した従来技術は、
次のような問題点を有していた。アミノシランで処理し
た金属酸化物を用いた現像剤では、アミノシランが親水
性であるため、高温高湿環境においてトナー流動性や帯
電の安定性に問題があった。また、疎水性シリカ微粒子
に正帯電制御剤を吸着または染着させた現像剤ではトナ
ー流動性、帯電立ち上がり及び安定性に問題があった。
また、負帯電性極性基と正帯電性極性基の両方の基が表
面に結合した無機微粒子を含有する非磁性1成分現像用
トナーでは、高温高湿環境下における帯電安定性、トナ
ー流動性に問題があった。本発明は、前述の問題点を解
決するためになされたものである。The prior art described above is
It had the following problems. In a developer using a metal oxide treated with aminosilane, since aminosilane is hydrophilic, there is a problem in toner fluidity and charge stability in a high-temperature and high-humidity environment. Further, a developer in which a positive charge control agent is adsorbed or dyed on hydrophobic silica fine particles has problems in toner fluidity, charge rise, and stability.
In addition, a non-magnetic one-component developing toner containing inorganic fine particles having both a negatively-chargeable polar group and a positively-chargeable polar group bonded to the surface has improved charge stability and toner fluidity in a high-temperature and high-humidity environment. There was a problem. The present invention has been made to solve the above problems.
【0006】[0006]
【課題を解決するための手段】前記の問題点を解決する
ために、本発明の正帯電現像剤は、外添用に用いられる
無機微粉末として、正帯電極性基と疎水基を表面に有す
る乾式法により製造されたシリカ微粉末と、正帯電極性
基とフッ素含有負帯電極性基の両極性基を表面に有する
湿式法により製造されたシリカ微粉末とを併用して外添
した点に特徴がある。本発明の正帯電現像剤は、上記の
ような構成をとることにより、正帯電極性基と疎水基を
表面に有する乾式シリカにより帯電立ち上がり性、トナ
ー流動性の環境変化をなくし、且つ、正帯電極性基とフ
ッ素含有負帯電極性基の両極性基を表面に有する湿式シ
リカにより帯電の経時安定性に優れた性能が得られ、飛
躍的に現像剤の長寿命化が達成できる。In order to solve the above-mentioned problems, the positively charged developer of the present invention has a positively charged polar group and a hydrophobic group on the surface as an inorganic fine powder used for external addition. It is characterized in that silica fine powder produced by the dry method and silica fine powder produced by the wet method having both polar groups of a positively charged polar group and a fluorine-containing negatively charged polar group on the surface are externally added in combination. There is. The positively charged developer of the present invention, having the above-described configuration, eliminates environmental changes in charge rising property and toner fluidity by dry silica having a positively charged polar group and a hydrophobic group on the surface, and has a positively charged property. Wet silica having a polar group and a fluorine-containing negatively-charged polar group on its surface provides excellent performance over charge stability over time, and can dramatically increase the life of the developer.
【0007】[0007]
【発明の実施の形態】本発明の正帯電現像剤は、電子写
真方式で用いられる一般的なトナー粒子に、特定の表面
処理が施された湿式シリカと乾式シリカとの2種類の外
添用シリカを混合、外添することにより得られる。本発
明の正帯電現像剤に用いる乾式法により製造されたシリ
カ(ヒュームドシリカ)の正帯電極性基導入は、正帯電
極性基を有するカップリング剤を用いて行うことがで
き、疎水基の導入は一般的な疎水性のアルキルカップリ
ング剤を用いて行うことができる。正帯電性極性基を有
するカップリング剤としては、アミノシランカップリン
グ剤、例えば以下の化1で示す化合物およびそれらの混
合物が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The positively charged developer of the present invention is used for externally adding two types of wet silica and dry silica obtained by applying a specific surface treatment to general toner particles used in an electrophotographic system. It is obtained by mixing and externally adding silica. The introduction of a positively charged polar group of silica (fumed silica) produced by a dry method used for the positively charged developer of the present invention can be performed using a coupling agent having a positively charged polar group, and the introduction of a hydrophobic group can be performed. Can be carried out using a general hydrophobic alkyl coupling agent. Examples of the coupling agent having a positively-chargeable polar group include an aminosilane coupling agent, for example, a compound represented by the following formula 1 and a mixture thereof.
【0008】[0008]
【化1】H2N(CH2)2NH(CH2)3Si(OC
H3)3
H2N(CH2)2NH(CH2)3Si(CH3)(OCH
3)2
H2N(CH2)2NH(CH2)2Si(OCH3)
3
H2N(CH2)2NH(CH2)2NH(CH2)2Si
(OCH3)3
H2N(CH2)3Si(OCH3)3
C6H5NH(CH2)3Si(OCH3)3 Embedded image H 2 N (CH 2 ) 2 NH (CH 2 ) 3 Si (OC
H 3) 3 H 2 N ( CH 2) 2 NH (CH 2) 3 Si (CH 3) (OCH
3 ) 2 H 2 N (CH 2 ) 2 NH (CH 2 ) 2 Si (OCH 3 )
3 H 2 N (CH 2 ) 2 NH (CH 2 ) 2 NH (CH 2 ) 2 Si
(OCH 3 ) 3 H 2 N (CH 2 ) 3 Si (OCH 3 ) 3 C 6 H 5 NH (CH 2 ) 3 Si (OCH 3 ) 3
【0009】アルキルカップリング剤(疎水化剤)とし
ては、例えば、以下の化2のようなシラン系カップリン
グ剤を用いることができる。As the alkyl coupling agent (hydrophobizing agent), for example, a silane coupling agent represented by the following chemical formula 2 can be used.
【化2】CH3Si(OCH3)3 CH3Si(OCH2CH3)3 (CH3)2Si(OCH3)2 CH3(CH2)2Si(OCH3)3 CH3(CH2)5Si(OCH3)3 n−C10H21Si(OCH3)3 C6H5Si(OCH3)3 Embedded image CHThreeSi (OCHThree)Three CHThreeSi (OCHTwoCHThree)Three (CHThree)TwoSi (OCHThree)Two CHThree(CHTwo)TwoSi (OCHThree)Three CHThree(CHTwo)FiveSi (OCHThree)Three n-CTenHtwenty oneSi (OCHThree)Three C6HFiveSi (OCHThree)Three
【0010】また湿式法により製造された湿式シリカ
(コロイダルシリカ)の正帯電極性基および負帯電極性
基の導入は、同様に極性基を有するカップリング剤を用
いて行うことができる。正帯電極性基を有するカップリ
ング剤としては上記のアミノシランカップリング剤を用
いることができ、負帯電極性基をもつカップリング剤と
しては、フッ素系のシランカップリング剤、例えば以下
の化3の化合物およびそれらの混合物が挙げられる。The introduction of the positively charged polar group and the negatively charged polar group of the wet silica (colloidal silica) produced by the wet method can also be carried out by using a coupling agent having a polar group. As the coupling agent having a positively charged polar group, the above-mentioned aminosilane coupling agent can be used, and as the coupling agent having a negatively charged polar group, a fluorine-based silane coupling agent, for example, a compound of the following formula 3 And mixtures thereof.
【0011】[0011]
【化3】CF3(CH2)2Si(OCH3)
3
CF3(CF2)7(CH2)2Si(OCH3)
3
CF3(CH2)2Si(CH3)(OCH3)2
CF3(CF2)3(CH2)2Si(OCH3)
3
CF3(CF2)4(CH2)3Si(OCH3)
3
CF3(CF2)2(CH2)6Si(OCH3)
3
CF3(CF2)6(CH2)2Si(OCH3)
3
CF3(CF2)7(CH2)2Si(CH3)(OCH3)2 Embedded image CF 3 (CH 2 ) 2 Si (OCH 3 )
3 CF 3 (CF 2 ) 7 (CH 2 ) 2 Si (OCH 3 )
3 CF 3 (CH 2) 2 Si (CH 3) (OCH 3) 2 CF 3 (CF 2) 3 (CH 2) 2 Si (OCH 3)
3 CF 3 (CF 2 ) 4 (CH 2 ) 3 Si (OCH 3 )
3 CF 3 (CF 2 ) 2 (CH 2 ) 6 Si (OCH 3 )
3 CF 3 (CF 2 ) 6 (CH 2 ) 2 Si (OCH 3 )
3 CF 3 (CF 2 ) 7 (CH 2 ) 2 Si (CH 3 ) (OCH 3 ) 2
【0012】以上のようなカップリング剤を用いてシリ
カ表面を処理する方法は種々あるが、例えば、次のよう
な方法により実施することができる。まず、カップリン
グ剤をテトラヒドロフラン、トルエン、酢酸エチル、メ
チルエチルケトンあるいはアセトン等の溶剤を用いて混
合希釈し、シリカをブレンダー等で強制的に撹拌しつつ
カップリング剤の希釈液を滴下したり、スプレーしたり
して添加し、充分混合する。次に得られた混合物をバッ
ト等に移してオーブンに入れ加熱し、乾燥させる。その
後再びブレンダーにて撹拌し、充分に解砕する。このよ
うな乾式処理法のほかに、シリカをカップリング剤の有
機溶剤液に浸漬して乾燥させたり、またはシリカを水中
に分散してスラリー状にしたうえでカップリング剤の水
溶液を滴下し、その後シリカを沈降させて加熱乾燥して
解砕する、といった湿式による処理法もある。There are various methods for treating the silica surface with the above-described coupling agent. For example, the method can be carried out by the following method. First, the coupling agent is mixed and diluted with a solvent such as tetrahydrofuran, toluene, ethyl acetate, methyl ethyl ketone, or acetone, and the silica coupling agent is forcibly stirred with a blender or the like, and the coupling agent diluent is dropped or sprayed. Add and mix well. Next, the obtained mixture is transferred to a vat or the like, placed in an oven, heated, and dried. Thereafter, the mixture is again stirred with a blender and sufficiently crushed. In addition to such a dry treatment method, silica is immersed in an organic solvent solution of the coupling agent and dried, or silica is dispersed in water to form a slurry, and then an aqueous solution of the coupling agent is dropped, There is also a wet treatment method in which silica is precipitated, heated, dried and crushed.
【0013】乾式シリカの表面に対する正帯電極性基の
導入量、すなわち乾式シリカに対する処理用カップリン
グ剤の添加量は、シリカに対して3〜25重量%の範囲
が効果的であり、好ましくは5〜20重量%である。ま
た、乾式シリカの表面に対する疎水基の導入量、すなわ
ち乾式シリカに対する処理用カップリング剤の添加量
は、シリカに対して3〜25重量%の範囲が効果的であ
り、好ましくは5〜20重量%である。湿式シリカの表
面に対する正帯電極性基の導入量、すなわち湿式シリカ
に対する処理用カップリング剤の添加量は、シリカに対
して3〜25重量%の範囲が好適であり、好ましくは5
〜20重量%である。また、湿式シリカの表面に対する
フッ素含有負帯電極性基の導入量、すなわち処理用カッ
プリング剤の添加量は1〜25重量%の範囲が効果的で
あり、好ましくは3〜20重量%である。The amount of the positively charged polar group introduced into the surface of the dry silica, that is, the amount of the treatment coupling agent added to the dry silica is in the range of 3 to 25% by weight based on the weight of the silica. -20% by weight. The amount of the hydrophobic group introduced to the surface of the dry silica, that is, the amount of the coupling agent for treatment added to the dry silica is in the range of 3 to 25% by weight based on the silica, and is preferably 5 to 20% by weight. %. The amount of the positively charged polar group introduced into the surface of the wet silica, that is, the amount of the coupling agent for treatment added to the wet silica is preferably in the range of 3 to 25% by weight based on silica, and more preferably 5 to 25% by weight.
-20% by weight. The amount of the fluorine-containing negatively charged polar group introduced to the surface of the wet silica, that is, the amount of the coupling agent for treatment added is effectively in the range of 1 to 25% by weight, preferably 3 to 20% by weight.
【0014】本発明の正帯電現像剤は、トナー粒子に、
上記の如き特定の処理が施された乾式シリカおよび湿式
シリカを混合、外添することにより得られる。本発明の
正帯電現像剤におけるシリカ微粉末の添加量は、トナー
粒子100重量部に対して、乾式シリカ0.1〜1.2
重量部(好ましくは0.2〜1.0重量部)、湿式シリ
カ0.1〜1.2重量部(好ましくは0.2〜1.0重
量部)を外添するのが好適である。また乾式シリカと湿
式シリカとの外添重比率は1/10〜10/1(重量
比)が好適であり、好ましくは3/7〜7/3の範囲が
好ましい。本発明の正帯電現像剤の現像方式は特に問わ
ず、また、一成分現像剤としても二成分現像剤としても
利用できる。さらに、磁性トナー、非磁性トナーのいず
れでもよく、通常のブラックトナーはもちろんのことカ
ラー印刷用のカラートナーとして用いることもできる。[0014] The positively charged developer of the present invention comprises:
It is obtained by mixing and externally adding dry silica and wet silica that have been subjected to the specific treatment as described above. The amount of the silica fine powder added to the positively charged developer of the present invention is 0.1 to 1.2 dry silica based on 100 parts by weight of the toner particles.
It is suitable to externally add 0.1 parts by weight (preferably 0.2 to 1.0 parts by weight) and 0.1 to 1.2 parts by weight (preferably 0.2 to 1.0 parts by weight) of wet silica. The external addition weight ratio between dry silica and wet silica is preferably from 1/10 to 10/1 (weight ratio), and more preferably from 3/7 to 7/3. The developing method of the positively charged developer of the present invention is not particularly limited, and it can be used as a one-component developer or a two-component developer. Further, either a magnetic toner or a non-magnetic toner may be used, and it can be used not only as a normal black toner but also as a color toner for color printing.
【0015】[0015]
【発明の効果】以上の説明から明らかように、本発明に
よれば、上記特定の表面処理を行った乾式シリカと湿式
シリカを併用してトナーの外部添加剤として使用するこ
とにより、得られるトナーの帯電を立ち上がり特性が良
好であり、且つ、耐久性、環境安定性に優れた正帯電特
性を付与することができるので、良好な画像品質を長期
間得る事ができる。As is clear from the above description, according to the present invention, the toner obtained by using the above-mentioned dry silica and wet silica which have been subjected to the specific surface treatment together as an external additive of the toner is used. It has good charge rising characteristics, and can be provided with positive charging characteristics excellent in durability and environmental stability, so that good image quality can be obtained for a long period of time.
【0016】[0016]
【実施例】以下の各外添用シリカを製造した。
シリカa(本発明の乾式シリカ)の製造
ヒュームドシリカ(アエロジル#130;日本アエロジ
ル社製)100gをバイタミックスで撹拌しながら、N
−β−(アミノエチル)−γ−アミノプロピルトリメト
キシシラン5gとプロピルトリメトキシシラン5gをト
ルエン15gに溶解した希釈溶液を徐々に滴下し、滴下
後10分間強く撹拌した。その後150℃の高温槽で加
熱し、解砕を行い、シリカaを得た。EXAMPLES The following silicas for external addition were produced. Production of Silica a (Dry Silica of the Present Invention) While stirring 100 g of fumed silica (Aerosil # 130; manufactured by Nippon Aerosil Co., Ltd.) with Vitamix, N
A diluted solution in which 5 g of -β- (aminoethyl) -γ-aminopropyltrimethoxysilane and 5 g of propyltrimethoxysilane were dissolved in 15 g of toluene was gradually added dropwise, and the mixture was vigorously stirred for 10 minutes after the addition. Thereafter, the mixture was heated in a high-temperature bath at 150 ° C. and crushed to obtain silica a.
【0017】シリカb(本発明の乾式シリカ)の製造
ヒュームドシリカ(アエロジル#130;日本アエロジ
ル社製)100gをバイタミックスで撹拌しながら、γ
−アミノプロピルトリメトキシシラン5gとヘキシルト
リメトキシシラン5gをトルエン15gに溶解した希釈
溶液を徐々に滴下し、滴下後10分間強く撹拌した。そ
の後150℃の高温槽で加熱し、解砕を行い、シリカb
を得た。Production of Silica b (Dry Silica of the Present Invention) While stirring 100 g of fumed silica (Aerosil # 130; manufactured by Nippon Aerosil Co., Ltd.) with Vitamix, γ
A diluted solution of 5 g of aminopropyltrimethoxysilane and 5 g of hexyltrimethoxysilane dissolved in 15 g of toluene was gradually added dropwise, and the mixture was vigorously stirred for 10 minutes after the addition. Thereafter, the mixture is heated in a high-temperature bath at 150 ° C., crushed, and silica b
Got.
【0018】シリカc(本発明の乾式シリカ)の製造
ヒュームドシリカ(アエロジル#130;日本アエロジ
ル社製)100gをバイタミックスで撹拌しながら、N
−フェニル−γ−アミノプロピルトリメトキシシラン5
gとフェニルトリメトキシシラン5gをトルエン15g
に溶解した希釈溶液を徐々に滴下し、滴下後10分間強
く撹拌した。その後150℃の高温槽で加熱し、解砕を
行い、シリカcを得た。Production of Silica c (Dry Silica of the Present Invention) While stirring 100 g of fumed silica (Aerosil # 130; manufactured by Nippon Aerosil Co., Ltd.) with Vitamix, N
-Phenyl-γ-aminopropyltrimethoxysilane 5
g and 5 g of phenyltrimethoxysilane in 15 g of toluene
The diluted solution dissolved in was gradually added dropwise, and the mixture was vigorously stirred for 10 minutes after the addition. Thereafter, the mixture was heated in a high-temperature bath at 150 ° C. and crushed to obtain silica c.
【0019】シリカd(比較例の乾式シリカ)の製造
ヒュームドシリカ(アエロジル#130;日本アエロジ
ル社製)100gをバイタミックスで撹拌しながら、
3,3,3−トリフルオロプロピルトリメトキシシラン
5gとプロピルトリメトキシシラン5gをトルエン15
gに溶解した希釈溶液を徐々に滴下し、滴下後10分間
強く撹拌した。その後150℃の高温槽で加熱し、解砕
を行い、シリカdを得た。Production of Silica d (Dry Silica of Comparative Example) While stirring 100 g of fumed silica (Aerosil # 130; manufactured by Nippon Aerosil Co., Ltd.) with Vitamix,
5 g of 3,3,3-trifluoropropyltrimethoxysilane and 5 g of propyltrimethoxysilane
The diluted solution dissolved in g was gradually added dropwise, and the mixture was vigorously stirred for 10 minutes after the addition. Thereafter, the mixture was heated in a high-temperature bath at 150 ° C. and crushed to obtain silica d.
【0020】シリカe(比較例の乾式シリカ)の製造
ヒュームドシリカ(アエロジル#130;日本アエロジ
ル社製)100gをバイタミックスで撹拌しながら、
3,3,3−トリフルオロプロピルトリメトキシシラン
5gとγ−アミノプロピルトリメトキシシラン5gをト
ルエン15gに溶解した希釈溶液を徐々に滴下し、滴下
後10分間強く撹拌した。その後150℃の高温槽で加
熱し、解砕を行い、シリカeを得た。Production of Silica e (Dry Silica of Comparative Example) While stirring 100 g of fumed silica (Aerosil # 130; manufactured by Nippon Aerosil Co., Ltd.) with Vitamix,
A diluted solution in which 5 g of 3,3,3-trifluoropropyltrimethoxysilane and 5 g of γ-aminopropyltrimethoxysilane were dissolved in 15 g of toluene was gradually added dropwise, and the mixture was vigorously stirred for 10 minutes after the addition. Thereafter, the mixture was heated in a high-temperature bath at 150 ° C. and crushed to obtain silica e.
【0021】シリカf(本発明の湿式シリカ)の製造
トルエン100ml中に3,3,3−トリフルオロプロ
ピルトリメトキシシラン5g及びγ−アミノプロピルト
リメトキシシラン5gを溶解させた後、コロイダルシリ
カ(NipsilE−200;日本シリカ社製)100
gを浸漬させた混合溶液とし、混合溶液を撹拌した後1
20℃で加熱、乾燥を行い、ピンミルを用いて解砕して
シリカfを得た。Preparation of silica f (wet silica of the present invention) After dissolving 5 g of 3,3,3-trifluoropropyltrimethoxysilane and 5 g of γ-aminopropyltrimethoxysilane in 100 ml of toluene, colloidal silica (NipsilE) was dissolved. -200; manufactured by Nippon Silica Co.) 100
g of the mixed solution, and the mixed solution was stirred.
After heating and drying at 20 ° C., the mixture was crushed using a pin mill to obtain silica f.
【0022】シリカg(本発明の湿式シリカ)の製造
トルエン100ml中に4,4,5,5,6,6,7,
7,8,8,8,−ウンデカフルオロオクチルメトキシ
シラン5g及びN−β−(アミエチル)−γ−アミノプ
ロピルトリメトキシシラン5gを溶解させた後、コロイ
ダルシリカ(NipsilE−200;日本シリカ社
製)100gを浸漬させた混合溶液とし、混合溶液を撹
拌した後120℃で加熱、乾燥を行い、ピンミルを用い
て解砕してシリカgを得た。Preparation of silica g (wet silica of the present invention) 4,100,500
After dissolving 5 g of 7,8,8,8, -undecafluorooctylmethoxysilane and 5 g of N-β- (amiethyl) -γ-aminopropyltrimethoxysilane, colloidal silica (NipsilE-200; manufactured by Nippon Silica Co., Ltd.) ) 100 g was immersed in a mixed solution, and the mixed solution was stirred, heated and dried at 120 ° C, and crushed using a pin mill to obtain silica g.
【0023】シリカh(本発明の湿式シリカ)の製造
トルエン100ml中に7,7,8,8,9,9,9,
−ヘプタフルオロノニルトリメトキシラン5g及びN−
フェニル−γ−アミノプロピルトリメトキシシラン5g
を溶解させた後、コロイダルシリカ(NipsilE−
200;日本シリカ社製)100gを浸漬させた混合溶
液とし、混合溶液を撹拌した後120℃で加熱、乾燥を
行い、ピンミルを用いて解砕してシリカhを得た。Preparation of silica h (wet silica of the present invention) 7,7,8,8,9,9,9,9
5 g of heptafluorononyltrimethoxysilane and N-
Phenyl-γ-aminopropyltrimethoxysilane 5 g
Is dissolved, colloidal silica (NipsilE-
200 g (manufactured by Nippon Silica Co., Ltd.) was immersed in the mixed solution. The mixed solution was stirred, heated and dried at 120 ° C., and crushed using a pin mill to obtain silica h.
【0024】シリカi(比較例の湿式シリカ)の製造
トルエン100ml中にN−β−(アミノエチル)−γ
−アミノプロピルトリメトキシシラン5gを溶解させた
後、コロイダルシリカ(NipsilE−200;日本
シリカ社製)100gを浸漬させた混合溶液とし、混合
溶液を撹拌した後120℃で加熱、乾燥を行い、ピンミ
ルを用いて解砕してシリカiを得た。以上シリカa〜i
のシリカ原体とカップリング剤の種類及び量を表1に、
ブローオフ帯電量と疎水化度を表2にまとめた。なお、
対照用として未処理のシリカ原体(ref1,ref
2)を用いた。Preparation of silica i (wet silica of comparative example) N-β- (aminoethyl) -γ
After dissolving 5 g of aminopropyltrimethoxysilane, a mixed solution in which 100 g of colloidal silica (Nipsil E-200; manufactured by Nippon Silica Co., Ltd.) was immersed was heated and dried at 120 ° C. after stirring the mixed solution. And crushed using to obtain silica i. Silica a to i
Table 1 shows the types and amounts of the silica raw material and the coupling agent of
Table 2 shows the blow-off charge amount and the degree of hydrophobicity. In addition,
As a control, an untreated silica bulk material (ref1, ref1)
2) was used.
【0025】[0025]
【表1】 表1:シリカ組成物 シリ シリカ 正 帯 電 性 負 帯 電 性 カ 原 体 カップリング剤 カップリング剤 疎水化剤 a アエロジ H2N(CH2)2NH(CH2)3Si − CH3(CH2)2Si ル#130 (OCH3)3;5wt% (OCH3)3;5wt% b アエロジ H2N(CH2)3Si(OCH3)3 − CH3(CH2)5Si ル#130 ;5wt% (OCH3)3;5wt% c アエロジ C6H5NH(CH2)3Si(OCH3)3 − C6H5Si(OCH3)3 ル#130 ;5wt% ;5wt% d アエロジ − CF3(CH2)2Si(OCH3)3 CH3(CH2)5Si ル#130 ;5wt% (OCH3)3;5wt% e アエロジ H2N(CH2)3Si(OCH3)3 CF3(CH2)2Si(OCH3)3 − ル#130 ;5wt% ;5wt% f NipsilE- H2N(CH2)3Si(OCH3)3 CF3(CH2)2Si(OCH3)3 − 200 ;5wt% ;5wt% g NipsilE- H2N(CH2)2NH(CH2)3Si CF3(CF2)4(CH2)3Si − 200 (OCH3)3;5wt% (OCH3)3;5wt% h NipsilE- C6H5NH(CH2)3Si(OCH3)3 CF3(CF2)2(CH2)6Si − 200 ;5wt% (OCH3)3;5wt% i NipsilE- H2N(CH2)2NH(CH2)3Si − − 200 (OCH3)3;5wt% ref1 アエロジ − − − ル#130 ref2 NipsilE- − − − 200 [Table 1]Table 1: Silica composition Silica Silica Positive band Negative band Mosquito Body Coupling agent Coupling agent Hydrophobizing agent a Aeroji HTwoN (CHTwo)TwoNH (CHTwo)ThreeSi − CHThree(CHTwo)TwoSi # 130 (OCH 3 ) 3 ; 5wt% (OCH 3 ) 3 ; 5wt% b Aerology HTwoN (CHTwo)ThreeSi (OCHThree)Three− CHThree(CHTwo)FiveSi # 130; 5wt% (OCH 3 ) 3 ; 5wt% c Aeroji C6HFiveNH (CHTwo)ThreeSi (OCHThree)Three− C6HFiveSi (OCHThree)Three # 130; 5wt%; 5wt% d Aerogel-CFThree(CHTwo)TwoSi (OCHThree)ThreeCHThree(CHTwo)FiveSi # 130; 5wt% (OCH 3 ) 3 ; 5wt% e Aeroji HTwoN (CHTwo)ThreeSi (OCHThree)ThreeCFThree(CHTwo)TwoSi (OCHThree)Three− # 130; 5wt%; 5wt% f NipsilE- HTwoN (CHTwo)ThreeSi (OCHThree)ThreeCFThree(CHTwo)TwoSi (OCHThree)Three− 200; 5wt%; 5wt% g NipsilE-HTwoN (CHTwo)TwoNH (CHTwo)ThreeSi CFThree(CFTwo)Four(CHTwo)ThreeSi − 200 (OCH 3 ) 3 ; 5wt% (OCH 3 ) 3 ; 5wt% h NipsilE- C6HFiveNH (CHTwo)ThreeSi (OCHThree)ThreeCFThree(CFTwo)Two(CHTwo)6Si − 200; 5wt% (OCH 3 ) 3 ; 5wt% i NipsilE-HTwoN (CHTwo)TwoNH (CHTwo)ThreeSi − − 200 (OCH 3 ) 3 ; 5wt% ref1 Aeroji − − − Le # 130 ref2 NipsilE---- 200
【0026】[0026]
【表2】 [Table 2]
【0027】疎水化度は以下の方法で測定した。200
mlビーカーに純水50mlを入れ、シリカ0.2gを
添加する。ビーカーを撹拌しながらビューレットを用い
て無水硫酸ナトリウムで脱水したメタノールを滴下し、
液面上にシリカの存在が認められなくなった時点を終点
として、滴下したメタノール量から下式の数1により疎
水化度を算出した。The degree of hydrophobicity was measured by the following method. 200
50 ml of pure water is placed in a ml beaker, and 0.2 g of silica is added. While stirring the beaker, methanol dehydrated with anhydrous sodium sulfate was added dropwise using a burette,
The time when the presence of silica was no longer recognized on the liquid surface was defined as the end point, and the degree of hydrophobicity was calculated from the amount of methanol dropped by the following equation (1).
【0028】[0028]
【数1】 疎水化度(%)=(X/(50+X))×100 *式中Xはメタノール滴下量(ml)(Equation 1) Degree of hydrophobicity (%) = (X / (50 + X)) × 100 * In the formula, X is the amount of methanol added (ml)
【0029】 実施例1〜9 スチレン/アクリル樹脂(軟化点:123℃、Tg:65℃) 100重量部 針状マグネタイト 50重量部 電荷制御剤(TP−415;保土ケ谷化学社製) 4重量部 ワックス(ビスコールTS−200;三洋化成工業社製) 2.5重量部[0029] Examples 1 to 9 100 parts by weight of styrene / acrylic resin (softening point: 123 ° C, Tg: 65 ° C) Acicular magnetite 50 parts by weight Charge control agent (TP-415; Hodogaya Chemical Co., Ltd.) 4 parts by weight 2.5 parts by weight of wax (Viscol TS-200; manufactured by Sanyo Chemical Industries, Ltd.)
【0030】以上の組成物を通常知られている方法によ
って混合、混練、粉砕、分級し、平均粒径が10μmで
7〜13μmの範囲に80wt%分布するトナー粒子と
した。前記トナー粒子に対し表3に示す組成でシリカ1
およびシリカ2を添加した後、京セラ製プリンター(F
S−3700)に組み込んで画像出力を行い、初期、3
0万枚印字後、高温高湿環境にて下記に示す項目を評価
し、表4にまとめた。The above composition was mixed, kneaded, pulverized and classified by a generally known method to obtain toner particles having an average particle diameter of 10 μm and a distribution of 80 wt% in the range of 7 to 13 μm. Silica 1 having the composition shown in Table 3 was used for the toner particles.
After adding silica and silica 2, a Kyocera printer (F
S-3700) and output an image.
After printing 100,000 sheets, the following items were evaluated in a high-temperature, high-humidity environment, and the results are summarized in Table 4.
【0031】(1)ソリッド画像濃度(マクベス反射濃
度計で測定)
○:1.3以上
△:1.2以上1.3未満
×:1.2未満
(2)地肌カブリ(目視判断)
○:カブリは良好
△:ややカブリを生じている
×:カブリはひどい
(3)帯電量(ブローオフ帯電量)(1) Solid image density (measured by Macbeth reflection densitometer) ○: 1.3 or more Δ: 1.2 or more and less than 1.3 ×: less than 1.2 (2) Background fog (visual judgment) ○: Good fog: slightly fogged x: severe fog (3) Charge (blow-off charge)
【0032】[0032]
【表3】 [Table 3]
【0033】[0033]
【表4】 表4:評価結果 ソリッド画像濃度 地肌カブリ ブローオフ帯電量(μC/g) 初期 30万 高温 初期 30万 高温 初期 30万 高温 枚後 高湿 枚後 高湿 枚後 高湿 実施例1 ○ ○ ○ ○ ○ ○ 14.8 14.4 14.6 実施例2 ○ ○ ○ ○ ○ ○ 14.6 14.4 14.1 実施例3 ○ ○ ○ ○ ○ ○ 15.3 15.4 15.1 実施例4 ○ ○ ○ ○ ○ ○ 14.1 13.5 14.2 実施例5 ○ ○ ○ ○ ○ ○ 15.6 15.0 15.2 実施例6 ○ ○ ○ ○ ○ ○ 14.1 14.1 14.4 実施例7 ○ ○ ○ ○ ○ ○ 15.3 15.1 15.2 実施例8 ○ ○ ○ ○ ○ ○ 14.8 15.0 14.6 実施例9 ○ ○ ○ ○ ○ ○ 15.3 14.9 14.5 比較例1 ○ × × ○ × × 17.0 11.2 7.8 比較例2 ○ × × ○ × × 15.2 8.4 7.1 比較例3 ○ ○ × ○ ○ × 15.0 14.0 9.3 比較例4 × × × × × × 9.1 3.0 1.1 比較例5 × ○ ○ × ○ ○ 9.1 13.0 12.1 比較例6 × ○ ○ × ○ ○ 8.2 13.6 12.8比較例7 ○ × × ○ △ × 13.9 9.2 6.6 比[Table 4]Table 4: Evaluation results Solid image density Scalp fog Blow-off charge (μC / g) Initial 300,000 high temperature Initial 300,000 high temperature Initial 300,000 high temperature After sheet High humidity After sheet High humidity After sheet High humidity Example 1 ○ ○ ○ ○ ○ ○ 14.8 14.4 14.6 Example 2 ○ ○ ○ ○ ○ ○ 14.6 14.4 14.1 Example 3 ○ ○ ○ ○ ○ ○ 15.3 15.4 15.1 Example 4 ○ ○ ○ ○ ○ ○ 14.1 13.5 14.2 Example 5 ○ ○ ○ ○ ○ ○ 15.6 15.0 15.2 Example 6 ○ ○ ○ ○ ○ ○ 14.1 14.1 14.4 Example 7 ○ ○ ○ ○ ○ ○ 15.3 15.1 15.2 Example 8 ○ ○ ○ ○ ○ ○ 14.8 15.0 14.6 Example 9 ○ ○ ○ ○ ○ ○ 15.3 14.9 14.5 Comparative Example 1 ○ × × ○ × × 17.0 11.2 7.8 Comparative Example 2 ○ × × ○ × × 15.2 8.4 7.1 Comparative Example 3 ○ ○ × ○ ○ × 15.0 14.0 9.3 Comparative Example 4 × × × × × × 9.1 3.0 1.1 Comparative Example 5 × ○ ○ × ○ ○ 9.1 13.0 12.1 Comparative Example 6 × ○ ○ × ○ ○ 8.2 13.6 12.8Comparative Example 7 ○ × × ○ △ × 13.9 9.2 6.6 ratio
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭64−33560(JP,A) 特開 昭63−50862(JP,A) 特開 昭62−227160(JP,A) 特開 昭62−227159(JP,A) 特開 昭59−176753(JP,A) 特開 平7−28278(JP,A) 特開 平2−308174(JP,A) 特開 平2−66564(JP,A) 特開 平2−66558(JP,A) 特開 平1−185657(JP,A) (58)調査した分野(Int.Cl.7,DB名) G03G 9/08 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-64-33560 (JP, A) JP-A-63-50862 (JP, A) JP-A-62-227160 (JP, A) JP-A-62-227160 227159 (JP, A) JP-A-57-176753 (JP, A) JP-A-7-28278 (JP, A) JP-A-2-308174 (JP, A) JP-A-2-66564 (JP, A) JP-A-2-66558 (JP, A) JP-A-1-185657 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) G03G 9/08
Claims (1)
式シリカ微粉末と、正帯電極性基とフッ素含有負帯電極
性基の両極性基を表面に有する湿式シリカ微粉末とを併
用して、トナー粒子に外添したことを特徴とする正帯電
現像剤。1. A dry silica fine powder having a positively charged polar group and a hydrophobic group on its surface, and a wet silica fine powder having on its surface both a positively charged polar group and a fluorine-containing negatively charged polar group on its surface. A positively charged developer externally added to toner particles.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32224697A JP3426941B2 (en) | 1997-11-07 | 1997-11-07 | Positively charged developer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32224697A JP3426941B2 (en) | 1997-11-07 | 1997-11-07 | Positively charged developer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH11143111A JPH11143111A (en) | 1999-05-28 |
JP3426941B2 true JP3426941B2 (en) | 2003-07-14 |
Family
ID=18141543
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP32224697A Expired - Fee Related JP3426941B2 (en) | 1997-11-07 | 1997-11-07 | Positively charged developer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3426941B2 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6203960B1 (en) * | 2000-08-22 | 2001-03-20 | Xerox Corporation | Toner compositions |
JP3956339B2 (en) * | 2001-06-12 | 2007-08-08 | 京セラ株式会社 | Positively charged toner and method for producing the same |
JP3956340B2 (en) * | 2001-06-12 | 2007-08-08 | 京セラ株式会社 | Positively charged toner and method for producing the same |
DE10235225B3 (en) * | 2002-08-01 | 2004-01-22 | Albert-Ludwigs-Universität Freiburg | Process for carrying out chemical reactions involving compounds adsorbed on fluorinated carrier materials via fluorine-fluorine interactions, fluorinated carrier material and the use of the carrier material |
JP4065757B2 (en) * | 2002-10-22 | 2008-03-26 | 株式会社トクヤマ | External toner additive |
JP2007108801A (en) * | 2007-02-01 | 2007-04-26 | Kyocera Corp | Positive charge type toner and method for producing the same |
CN101809507B (en) * | 2007-09-29 | 2012-10-10 | 日本瑞翁株式会社 | Positively chargeable toner for electrostatic charge image development |
JP5289902B2 (en) * | 2008-11-17 | 2013-09-11 | 花王株式会社 | Positively chargeable toner |
JP5407472B2 (en) * | 2009-03-25 | 2014-02-05 | 富士ゼロックス株式会社 | Toner for developing electrostatic image, developer for developing electrostatic image, developer cartridge for developing electrostatic image, process cartridge, and image forming apparatus |
JP5509163B2 (en) | 2011-08-11 | 2014-06-04 | 京セラドキュメントソリューションズ株式会社 | Positively chargeable toner |
JP2013257464A (en) * | 2012-06-13 | 2013-12-26 | Kyocera Document Solutions Inc | Magnetic single component development toner |
JP2018095496A (en) * | 2016-12-12 | 2018-06-21 | 日本アエロジル株式会社 | Inorganic oxide powder with processed surface and method for surface treatment of inorganic oxide powder |
-
1997
- 1997-11-07 JP JP32224697A patent/JP3426941B2/en not_active Expired - Fee Related
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