JP3267087B2 - Hydrophobic metal oxide powder - Google Patents
Hydrophobic metal oxide powderInfo
- Publication number
- JP3267087B2 JP3267087B2 JP02327695A JP2327695A JP3267087B2 JP 3267087 B2 JP3267087 B2 JP 3267087B2 JP 02327695 A JP02327695 A JP 02327695A JP 2327695 A JP2327695 A JP 2327695A JP 3267087 B2 JP3267087 B2 JP 3267087B2
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- group
- oxide powder
- amino
- silane compound
- 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 - Lifetime
Links
Landscapes
- Developing Agents For Electrophotography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、トナー外添剤として用
いられる電荷調整された疎水性金属酸化物粉体に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a charge-controlled hydrophobic metal oxide powder used as an external additive of a toner.
【０００２】[0002]
【従来の技術】複写機、レーザープリンター、普通紙フ
ァクシミリ等の電子写真技術を利用したＯＡ機器は、電
子写真用現像剤により、画像が出現されるが、この電子
写真用現像剤は、主にトナーとキャリアの混合物からな
ると共に、このトナーの流動性改善剤として超微粒子金
属酸化物粉体が広く用いられている。一方この用途にお
いて、粉体は高疎水性であり、また帯電量が良く制御さ
れている必要があり、キャリアである鉄あるいは酸化鉄
に対する摩擦帯電量が重要な性質の一つになっている。
疎水性金属酸化物のキャリアに対する摩擦帯電量は、そ
れに用いられる処理剤の種類によって正または負を示す
が、このうち金属酸化物に正帯電を付与する手段として
アミノ置換シラン化合物を用いることは、キャノン社の
特許出願公報、例えば、特開平５−６６６０１号公報、
特開平５−６６６０３号公報等で公知である。2. Description of the Related Art OA equipment utilizing electrophotographic technology, such as a copier, a laser printer, and a plain paper facsimile, produces an image by an electrophotographic developer. Ultrafine metal oxide powders are widely used as a mixture of a toner and a carrier and as a fluidity improver for the toner. On the other hand, in this application, the powder needs to be highly hydrophobic and the charge amount must be well controlled, and the triboelectric charge amount to iron or iron oxide as a carrier is one of the important properties.
The amount of triboelectric charge on the carrier of the hydrophobic metal oxide indicates positive or negative depending on the type of the treatment agent used, but among these, the use of an amino-substituted silane compound as a means for imparting a positive charge to the metal oxide requires Patent application publications of Canon Inc., for example, JP-A-5-66601,
It is known in JP-A-5-66603 and the like.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前述の
如き公報において用いられるアミノ置換シラン化合物
は、通常アミノ置換シラン化合物のみを用いて処理した
金属酸化物粉体の疎水性は不十分であり、帯電安定性や
耐環境安定性が十分ではないという問題がある。また負
帯電性の制御にアミノ置換シラン化合物を用いる試みは
成されていない。そこで、本発明者等は十分な疎水性と
任意の電荷調整を行うために、鋭意検討を重ねた結果、
窒素原子に直接結合したフェニル基を有するアミノ置換
シラン化合物で金属酸化物粉体を処理することにより、
良好な疎水性を持つばかりでなく負帯電に制御され、か
つ帯電安定性、耐環境安定性に優れた疎水性金属酸化物
粉体を得ることができることを見出した。したがって、
本発明が解決しようとする課題は、負帯電に制御される
と共に良好な疎水性を有し、かつ帯電安定性、耐環境安
定性に優れた疎水性金属酸化物粉体を提供することにあ
る。However, the amino-substituted silane compounds used in the above publications usually have insufficient hydrophobicity of the metal oxide powder treated with only the amino-substituted silane compound, and the chargeability of the metal oxide powder is insufficient. There is a problem that stability and environmental stability are not sufficient. Further, no attempt has been made to use an amino-substituted silane compound for controlling negative chargeability. Therefore, the present inventors have conducted intensive studies in order to perform sufficient hydrophobicity and arbitrary charge adjustment, and as a result,
By treating the metal oxide powder with an amino-substituted silane compound having a phenyl group directly bonded to the nitrogen atom,
It has been found that it is possible to obtain a hydrophobic metal oxide powder having not only good hydrophobicity but also controlled to be negatively charged, and excellent in charge stability and environmental stability. Therefore,
The problem to be solved by the present invention is to provide a hydrophobic metal oxide powder that is controlled to be negatively charged and has good hydrophobicity, and is excellent in charge stability and environmental stability. .
【０００４】[0004]
【課題を解決するための手段】本発明の前記課題を解決
するための手段は、以下の各発明によってそれぞれ達成
される。Means for solving the above-mentioned problems of the present invention are achieved by the following inventions.
【０００５】[0005]
【０００６】（１）アミノ置換シラン化合物で処理され
た金属酸化物であって、該アミノ置換シラン化合物が、
一般式〔Ｉ〕で表される化合物であり、かつ該処理金属
酸化物は負帯電性を有し、透過率法により測定された疎
水率が６０％以上であることを特徴とする疎水性金属酸
化物粉体。(1) A metal oxide treated with an amino-substituted silane compound , wherein the amino-substituted silane compound is
A hydrophobic metal which is a compound represented by the general formula [I], wherein the treated metal oxide has a negative chargeability and a hydrophobicity measured by a transmittance method of 60% or more. Oxide powder.
【０００７】[0007]
【化３】 Embedded image
【０００８】〔式中、Ｒ1 、Ｒ2 、Ｒ3 は水素原子又は
炭素数が１〜３のアルキル基（ただしアルキル基の主鎖
にＶＩＢ族の原子を含んでもよい。）であり、Ｘは炭素
数が１〜３のアルコキシ基であり、Ｙは炭素数が１ある
いは２のアルコキシ基又はフェニル基である。ｎは３〜
４の整数であり、ｍは１〜３の整数である。〕[Wherein R 1 , R 2 and R 3 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (provided that the main chain of the alkyl group may contain a VIB group atom); is an alkoxy group having 1 to 3 carbon atoms, Y is 1 carbon atoms
Or two alkoxy groups or phenyl groups. n is 3 ~
And m is an integer of 1 to 3. ]
【０００９】（３）アミノ置換シラン化合物が一般式
〔ＩＩ〕で表される化合物であることを特徴とする第１
項に記載の疎水性金属酸化物粉体。(3) The first amino acid-substituted silane compound is a compound represented by the general formula [II]:
Item 7. The hydrophobic metal oxide powder according to item 1.
【００１０】[0010]
【化４】 Embedded image
【００１１】〔式中、Ｒ1 、Ｒ2 は水素原子又は炭素数
が１〜３のアルキル基（ただしアルキル基の主鎖にＶＩ
Ｂ族の原子を含んでもよい。）であり、Ｘは炭素数が１
〜３のアルコキシ基であり、Ｙは炭素数が１〜３のアル
コキシ基である。ｎは２〜４の整数であり、ｍは１〜３
の整数である。〕Wherein R 1 and R 2 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (provided that the main chain of the alkyl group is VI
It may contain a group B atom. ), And X has 1 carbon atom.
A to 3 alkoxy groups, Y is 1 to 3 carbon Al
It is a coxy group . n is an integer of 2 to 4, and m is 1 to 3
Is an integer. ]
【００１２】（３）前記第１項又は第２項に記載の疎水
性金属酸化物粉体を用いたことを特徴とする流動性改善
剤。 (3) A fluidity improver using the hydrophobic metal oxide powder according to the above (1) or (2) .
【００１３】以下に本発明を更に詳しく説明すると、本
発明の疎水性金属酸化物粉体は、アミノ置換シラン化合
物で処理されることにより、負帯電性を有すると共に、
透過率法により測定された疎水率が６０％以上のものが
得られる。したがってこれにより負帯電に制御されると
共に良好な疎水性が得られ、かつ帯電安定性、耐環境安
定性に優れた疎水性金属酸化物粉体が得られる。このア
ミノ置換シラン化合物としては、一般式〔Ｉ〕及び一般
式〔ＩＩ〕で示される化合物のとき、優れた前記効果を
奏するものである。The present invention will be described in more detail below. The hydrophobic metal oxide powder of the present invention has a negative charge property by being treated with an amino-substituted silane compound.
Those having a hydrophobicity of 60% or more as measured by the transmittance method are obtained. Therefore, a hydrophobic metal oxide powder which is controlled to be negatively charged, has good hydrophobicity, and is excellent in charge stability and environmental stability can be obtained. This
As the mino-substituted silane compound, the compounds represented by the general formulas [I] and [II] exhibit the excellent effects described above.
【００１４】一般式〔Ｉ〕で示されるアミノ置換シラン
化合物は、置換基として、Ｒ1 、Ｒ2 、Ｒ3 を有し、こ
れらＲ1 、Ｒ2 、Ｒ3 は水素原子又は炭素数が１〜５の
アルキル基で、アルキル基は例えばメチル基、エチル
基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、
ｔ−ブチル基、ペンチル基等であり、またメトキシ基、
エトキシ基でもよく、アルキル基の主鎖に硫黄等のＶＩ
Ｂ族の原子を含んでもよい。Ｘは炭素数が１〜３のアル
コキシ基で、例えばメトキシ基、エトキシ基等であり、
Ｙは炭素数が１〜３のアルキル基又はフェニル基で、ア
ルキル基は例えばメチル基、エチル基等である。ｎは３
〜４の整数であり、ｍは１〜３の整数である。また一般
式〔ＩＩ〕で示されるアミノ置換シラン化合物のＲ1 、
Ｒ2 、Ｘ、Ｙ、ｍ、ｎも一般式〔Ｉ〕で示されるアミノ
置換シラン化合物のＲ1 、Ｒ2 、Ｘ、Ｙ、ｍ、ｎと同義
である。[0014] Amino-substituted silane compound represented by the general formula [I], as the substituent, R 1, has a R 2, R 3, these R 1, R 2, R 3 is a hydrogen atom or a carbon number of 1 Wherein the alkyl group is, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
t-butyl group, pentyl group, etc., and methoxy group,
An ethoxy group may be used, and VI such as sulfur is added to the main chain of the alkyl group.
It may contain a group B atom. X is an alkoxy group having 1 to 3 carbon atoms, such as a methoxy group and an ethoxy group;
Y is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and the alkyl group is, for example, a methyl group, an ethyl group, or the like. n is 3
And m is an integer of 1 to 3. R 1 of the amino-substituted silane compound represented by the general formula [II],
R 2 , X, Y, m and n have the same meanings as R 1 , R 2 , X, Y, m and n of the amino-substituted silane compound represented by the general formula [I].
【００１５】以下に、本発明に用いられるアミノ置換シ
ラン化合物の具体的例を挙げる。The following are specific examples of the amino-substituted silane compound used in the present invention.
【００１６】[0016]
【化５】 Embedded image
【００１７】本発明に用いられる金属酸化物粉体は、ケ
イ素、チタニウムなどの金属の酸化物で、例えばシリカ
やチタニア等が好ましく用いられ、その粒径は用途に適
したものでよく特に比表面積５０ｍ2 ／ｇ以上のものが
好ましい。The metal oxide powder used in the present invention is an oxide of a metal such as silicon or titanium. For example, silica or titania is preferably used. Those having 50 m 2 / g or more are preferred.
【００１８】本発明において、アミノ置換シラン化合物
で処理された金属酸化物粉体の疎水率を実験的に求める
方法としては透過率法があり、以下の手順によって測定
される。アミノ置換シラン化合物で処理された金属酸化
物粉体１．０ｇと蒸留水１００ｍｌを抽出用フラスコに
入れ、１０分間激しく振とう攪拌する。その後１０分間
静置し、フラスコの底から少量の懸濁液を抜き出す。こ
の液の５５０ｎｍの光に対する透過率を、蒸留水の透過
率を１００％として表した値をその金属酸化物粉体の疎
水率とする。このようにして測定された疎水率の値が高
いほど、その金属酸化物粉体の吸湿性は小さく湿度に対
して安定であり、利用価値が高くなる。また本発明で
は、調整された金属酸化物粉体の電荷は鉄に対する摩擦
帯電量として表される。鉄に対する摩擦帯電量の測定方
法は、文献、例えば「色材」（５５、９、６３０−６３
６、１９８２）等によって規定されている。In the present invention, as a method for experimentally determining the hydrophobicity of the metal oxide powder treated with the amino-substituted silane compound, there is a transmittance method, which is measured by the following procedure. 1.0 g of the metal oxide powder treated with the amino-substituted silane compound and 100 ml of distilled water are placed in an extraction flask and shaken vigorously for 10 minutes. Then, let stand for 10 minutes and withdraw a small amount of suspension from the bottom of the flask. The value of the transmittance of this liquid with respect to light of 550 nm assuming that the transmittance of distilled water is 100% is defined as the hydrophobicity of the metal oxide powder. The higher the value of the hydrophobicity measured in this manner, the smaller the hygroscopicity of the metal oxide powder, the more stable it is against humidity, and the higher the utility value. Further, in the present invention, the adjusted charge of the metal oxide powder is represented as a triboelectric charge amount with respect to iron. A method for measuring the triboelectric charge amount with respect to iron is described in a literature, for example, “Coloring Material” (55, 9, 630-63).
6, 1982).
【００１９】本発明に用いられるアミノ置換シラン化合
物の処理量は、粉体表面を均一に被覆できる量であれば
良く特に限定されないが、好ましくは前記化合物の処理
量は、被金属酸化物粉体に対して５重量％〜４０重量％
であり、特に好ましくは１０重量％〜３０重量％であ
る。また、オルガノポリシロキサンと組み合わせて同時
にあるいは順に処理することも可能である。順に処理す
る場合は、アミノ置換シラン化合物およびオルガノポリ
シロキサンのどちらを先に処理しても良い。本発明の疎
水性金属酸化物粉体を形成するための金属酸化物粉体の
処理方法は、該粉体を機械的に十分攪拌しながら、アミ
ノ置換シラン化合物を滴下あるいは噴霧して加える。こ
のときアミノ置換シラン化合物はアルコール、ケトン、
あるいは炭化水素等の溶剤を希釈剤として用いることも
可能である。処理剤を添加後、窒素雰囲気下で１００℃
〜３００℃の範囲の温度で加熱し、反応を完結させると
ともに溶剤を除去する。このようにして本発明では負帯
電性を有する疎水性金属酸化物粉体を提供することがで
き、該粉体とトナーとを混合して電子写真用現像剤を製
造することにより帯電安定性を有すると共に耐環境性、
例えば湿度に対する安定性が極めて良好となる。The treatment amount of the amino-substituted silane compound used in the present invention is not particularly limited as long as it can uniformly coat the surface of the powder. 5% to 40% by weight
And particularly preferably from 10% by weight to 30% by weight. Moreover, it is also possible to treat simultaneously or sequentially in combination with the organopolysiloxane. When the treatment is performed in order, either the amino-substituted silane compound or the organopolysiloxane may be treated first. In the method for treating a metal oxide powder for forming the hydrophobic metal oxide powder of the present invention, the amino-substituted silane compound is added dropwise or sprayed while mechanically sufficiently stirring the powder. At this time, the amino-substituted silane compound is alcohol, ketone,
Alternatively, a solvent such as a hydrocarbon can be used as the diluent. 100 ° C under nitrogen atmosphere after adding treatment agent
Heat at a temperature in the range of ~ 300 ° C to complete the reaction and remove the solvent. As described above, the present invention can provide a hydrophobic metal oxide powder having negative chargeability, and the charge stability can be improved by mixing the powder with a toner to produce an electrophotographic developer. Has environmental resistance,
For example, the stability to humidity becomes extremely good.
【００２０】[0020]
【作用】本発明に用いられるアミノ置換シラン化合物
は、一般式〔Ｉ〕及び一般式〔ＩＩ〕で示される如く、
窒素原子に直接結合したフェニル基を有することによ
り、良好な疎水性が得られると共に負帯電に制御され、
かつ帯電安定性、耐環境安定性に優れた疎水性金属酸化
物粉体を得ることができる。The amino-substituted silane compound used in the present invention is represented by the following general formulas [I] and [II]:
By having a phenyl group directly bonded to the nitrogen atom, good hydrophobicity is obtained and negatively controlled,
In addition, a hydrophobic metal oxide powder having excellent charge stability and environmental stability can be obtained.
【００２１】[0021]
【実施例】以下に、本発明の詳細を実施例で説明する
が、本発明はこれらの例によって限定されるものではな
い。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
【００２２】実施例１〜５ 表１に示される如く加熱乾燥させた金属酸化物粉体２０
ｇをステンレス製の容器に仕込み、窒素雰囲気下攪拌し
ながら浮遊状態にし、表１に記載の処理剤を室温で上記
粉体に噴霧した。噴霧終了後、さらに室温で３０分攪拌
した後、窒素気流下で外部加熱を行い３０分かけて１５
０℃まで昇温し、この温度で１時間処理した後、室温ま
で放冷した。このようにして実施例１〜５、比較例１〜
５により得られた粉体を透過率法により疎水率及び鉄に
対する摩擦帯電量を測定した。得られた結果を表１に示
す。Examples 1 to 5 Metal oxide powder 20 dried by heating as shown in Table 1
g was placed in a stainless steel container and suspended in a nitrogen atmosphere while stirring, and the treating agents shown in Table 1 were sprayed onto the powder at room temperature. After the end of the spraying, the mixture was further stirred at room temperature for 30 minutes, and then externally heated under a nitrogen gas flow for 15 minutes.
The temperature was raised to 0 ° C., and the mixture was treated at this temperature for 1 hour, and then allowed to cool to room temperature. Thus, Examples 1 to 5 and Comparative Examples 1 to
The hydrophobicity and the triboelectric charge on iron of the powder obtained in 5 were measured by a transmittance method. Table 1 shows the obtained results.
【００２３】[0023]
【表１】 [Table 1]
【００２４】表１から明らかなように、本発明に係るア
ミノ置換シラン化合物で処理した金属酸化物粉体は、い
ずれも負の摩擦帯電性に優れると共に疎水性が良好であ
る。これに対して比較例のものは、負に帯電したものは
あるものの疎水性が悪く実用性に乏しいことがわかる。As is evident from Table 1, the metal oxide powders treated with the amino-substituted silane compound according to the present invention are all excellent in negative triboelectric chargeability and good in hydrophobicity. On the other hand, in the case of the comparative example, although it was negatively charged, the hydrophobicity was poor and the practicality was poor.
【発明の効果】本発明は、一般式〔Ｉ〕及び一般式〔Ｉ
Ｉ〕で示される、窒素原子に直接結合したフェニル基を
有するアミノ置換シラン化合物を用いて金属酸化物粉体
を処理したので、良好な疎水性を持つばかりでなく負帯
電に制御された疎水性金属酸化物粉体が得られ、これを
用いて製造した電子写真用現像剤は、帯電安定性、耐環
境安定性に優れたものが得られる。According to the present invention, the compounds represented by the general formula [I] and the general formula [I
Since the metal oxide powder was treated with an amino-substituted silane compound having a phenyl group directly bonded to a nitrogen atom shown in I), not only good hydrophobicity but also hydrophobicity controlled to negative charge was obtained. A metal oxide powder is obtained, and a developer for electrophotography produced using the powder has excellent charge stability and environmental stability.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 桜井 英章 埼玉県大宮市北袋町一丁目297番地 三 菱マテリアル株式会社 中央研究所内 (56)参考文献 特開 平４−34440（ＪＰ，Ａ) 特開 平４−40469（ＪＰ，Ａ) 特開 平４−34439（ＪＰ，Ａ) 特開 平２−66565（ＪＰ，Ａ) 特開 平２−66558（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) G03G 9/08 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideaki Sakurai 1-297 Kitabukuro-cho, Omiya-shi, Saitama Mitsui Materials Co., Ltd. Central Research Laboratory (56) References JP-A-4-34440 (JP, A) JP-A-4-40469 (JP, A) JP-A-4-34439 (JP, A) JP-A-2-66565 (JP, A) JP-A-2-66558 (JP, A) (58) Int.Cl. 7 , DB name) G03G 9/08
Claims (3)
酸化物であって、該アミノ置換シラン化合物が、一般式
〔Ｉ〕で表される化合物であり、かつ該処理金属酸化物
は負帯電性を有し、透過率法により測定された疎水率が
６０％以上であることを特徴とする疎水性金属酸化物粉
体。 【化１】 〔式中、Ｒ1 、Ｒ2 、Ｒ3 は水素原子又は炭素数が１〜
３のアルキル基（ただしアルキル基の主鎖にＶＩＢ族の
原子を含んでもよい。）であり、Ｘは炭素数が１〜３の
アルコキシ基であり、Ｙは炭素数が１あるいは２のアル
コキシ基又はフェニル基である。ｎは３〜４の整数であ
り、ｍは１〜３の整数である。〕1. A metal oxide treated with an amino-substituted silane compound, wherein the amino-substituted silane compound is a compound represented by the general formula [I], and the treated metal oxide has a negative charge property. A hydrophobic metal oxide powder having a hydrophobicity of 60% or more as measured by a transmittance method. Embedded image [Wherein, R 1 , R 2 and R 3 represent a hydrogen atom or a carbon number of 1 to
3 alkyl group (in the main chain of wherein the alkyl group may contain a Group VIB atom.), X is an alkoxy group having 1 to 3 carbon atoms, Y is a carbon number of 1 or 2
It is a oxy group or a phenyl group. n is an integer of 3 to 4, and m is an integer of 1 to 3. ]
で表される化合物であることを特徴とする請求項１に記
載の疎水性金属酸化物粉体。 【化２】 〔式中、Ｒ1 、Ｒ2 は水素原子又は炭素数が１〜３のア
ルキル基（ただしアルキル基の主鎖にＶＩＢ族の原子を
含んでもよい。）であり、Ｘは炭素数が１〜３のアルコ
キシ基であり、Ｙは炭素数が１〜３のアルコキシ基であ
る。ｎは２〜４の整数であり、ｍは１〜３の整数であ
る。〕2. An amino-substituted silane compound represented by the general formula [II]:
The hydrophobic metal oxide powder according to claim 1, which is a compound represented by the following formula: Embedded image [In the formula, R 1 and R 2 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (provided that the main chain of the alkyl group may contain a VIB group atom.), And X has 1 to 3 carbon atoms. And Y is an alkoxy group having 1 to 3 carbon atoms. n is an integer of 2 to 4, and m is an integer of 1 to 3. ]
酸化物粉体を用いたことを特徴とする流動性改善剤。3. A fluidity improver comprising the hydrophobic metal oxide powder according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02327695A JP3267087B2 (en) | 1995-01-19 | 1995-01-19 | Hydrophobic metal oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02327695A JP3267087B2 (en) | 1995-01-19 | 1995-01-19 | Hydrophobic metal oxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08194332A JPH08194332A (en) | 1996-07-30 |
| JP3267087B2 true JP3267087B2 (en) | 2002-03-18 |
Family
ID=12106086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02327695A Expired - Lifetime JP3267087B2 (en) | 1995-01-19 | 1995-01-19 | Hydrophobic metal oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3267087B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI981623A1 (en) * | 1998-07-15 | 2000-01-15 | Great Lakes Chmical Italia S R | SILANS HAVING A PHENYLENDIAMMINE FUNCTION AND THEIR USE AS ANTIOZONATES AND ANTIOXIDANTS FOR NATURAL OR SYNTHETIC RUBBERS |
| CN113252588B (en) * | 2021-05-11 | 2022-08-16 | 西南科技大学 | Organic clay, preparation method thereof, and color development system and method for detecting hydroquinone |
-
1995
- 1995-01-19 JP JP02327695A patent/JP3267087B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08194332A (en) | 1996-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5486420A (en) | Hydrophobic silica powder, manufacturing method thereof and developer for electrophotography | |
| JP4512872B2 (en) | Surface-modified silica fine powder and method for producing the same | |
| EP0799791B1 (en) | Hydrophobic metal oxide powder and use thereof | |
| JPH0528377B2 (en) | ||
| WO2012111452A1 (en) | Surface-modified silica powder and method for producing the same, as well as toner composition for electrophotography | |
| JP3267087B2 (en) | Hydrophobic metal oxide powder | |
| JP3319114B2 (en) | Hydrophobic silica powder, its production method and electrophotographic developer containing it | |
| JPH08319115A (en) | Hydrophobic metal oxide powder and developing agent for electrophotography containing the powder | |
| JPH0545926A (en) | Electrophotographic developer | |
| JP3118921B2 (en) | Charge control agent for toner and toner for developing electrostatic images | |
| JP2964750B2 (en) | Hydrophobic silica | |
| JP2827454B2 (en) | Hydrophobic alumina | |
| JP2946896B2 (en) | Hydrophobic alumina | |
| JP2007055968A5 (en) | ||
| JPH09190014A (en) | Electrostatic charge image developing charge control agent as well as toner and charge imparting material formed by using the same | |
| JP3646440B2 (en) | Charge control agent for developing electrostatic image, toner using the same, and charge imparting material | |
| JP3579527B2 (en) | Charge control agent for developing electrostatic images and toner using the same | |
| JPH0594037A (en) | Electrophotographic developer | |
| JP2005017928A (en) | Electrostatic charge developer | |
| JP3367350B2 (en) | Hydrophobic metal oxide powder and its use | |
| JP3367349B2 (en) | Hydrophobic metal oxide powder and its use | |
| JP2023067180A (en) | Surface-modified inorganic oxide powder modified with nonionic surfactant | |
| EP0582281A1 (en) | Toner compositions for electrostatic developers | |
| JPS63216062A (en) | Electrophotographic toner | |
| JPH09160301A (en) | Charge controlling agent for electrostatic charge image development, and toner and charge imparting member using heat |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20011211 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080111 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090111 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090111 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100111 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100111 Year of fee payment: 8 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100111 Year of fee payment: 8 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110111 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120111 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130111 Year of fee payment: 11 |
|
| EXPY | Cancellation because of completion of term |