JPH08194332A - Hydrophobic metal oxide powder - Google Patents
Hydrophobic metal oxide powderInfo
- Publication number
- JPH08194332A JPH08194332A JP7023276A JP2327695A JPH08194332A JP H08194332 A JPH08194332 A JP H08194332A JP 7023276 A JP7023276 A JP 7023276A JP 2327695 A JP2327695 A JP 2327695A JP H08194332 A JPH08194332 A JP H08194332A
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- oxide powder
- amino
- group
- hydrophobic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Developing Agents For Electrophotography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
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 a toner external additive.
【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 copying machines, laser printers, and plain paper facsimiles, produces an image with a developer for electrophotography, and this developer for electrophotography is mainly used. In addition to a mixture of toner and carrier, ultrafine metal oxide powder is widely used as a fluidity improver for this toner. On the other hand, in this application, the powder is highly hydrophobic and the charge amount needs to be well controlled, and the triboelectric charge amount with respect to the carrier iron or iron oxide is one of the important properties.
The triboelectric charge amount of the hydrophobic metal oxide with respect to the carrier shows positive or negative depending on the type of the treating agent used therein, and of these, the amino-substituted silane compound is used as a means for imparting positive charge to the metal oxide, Canon's patent application publication, for example, JP-A-5-66601,
It is known from Japanese Patent Application Laid-Open No. 5-66603.
【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, in the amino-substituted silane compound used in the above-mentioned publication, the hydrophobicity of the metal oxide powder treated with only the amino-substituted silane compound is usually insufficient, and the charge is 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 the negative charging property. Therefore, the inventors of the present invention have conducted extensive studies to achieve 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 which has not only good hydrophobicity but is controlled to be negatively charged and has excellent charge stability and environmental stability. Therefore,
The problem to be solved by the present invention is to provide a hydrophobic metal oxide powder which is controlled to be negatively charged, 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 problems of the present invention are achieved by the following respective inventions.
【０００５】（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, the treated metal oxide having a negative charging property and having a hydrophobicity measured by a transmittance method of 60% or more. A hydrophobic metal oxide powder characterized by:
【０００６】（２）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ることを特徴とする前記第
１項に記載の疎水性金属酸化物粉体。(2) The hydrophobic metal oxide powder according to item 1, wherein the amino-substituted silane compound is a compound represented by the general formula [I].
【０００７】[0007]
【化３】 Embedded image
【０００８】〔式中、Ｒ1 、Ｒ2 、Ｒ3 は水素原子又は
炭素数が１〜５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
のアルキル基又はフェニル基である。ｎは２〜４の整数
であり、ｍは１〜３の整数である。〕[Wherein R 1 , R 2 and R 3 are hydrogen atoms or an alkyl group having 1 to 5 carbon atoms (provided that the main chain of the alkyl group may contain a VIB group atom), X Is an alkoxy group having 1 to 3 carbon atoms, and Y is 1 to 3 carbon atoms.
Is an alkyl group or a phenyl group. n is an integer of 2 to 4, 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 aspect, wherein the amino-substituted silane compound is a compound represented by the general formula [II]
The hydrophobic metal oxide powder according to the item.
【００１０】[0010]
【化４】 [Chemical 4]
【００１１】〔式中、Ｒ1 、Ｒ2 は水素原子又は炭素数
が１〜５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
キル基又はフェニル基である。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 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (provided that the main chain of the alkyl group is VI.
A group B atom may be included. ), And X has 1 carbon atom
Is an alkoxy group having 3 to 3 carbon atoms, and Y is an alkyl group having 1 to 3 carbon atoms or a phenyl group. n is an integer of 2 to 4, and m is an integer of 1 to 3. ]
【００１２】（４）前記第１項〜第３項のいずれかに記
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。(4) A fluidity improver characterized by using the hydrophobic metal oxide powder according to any one of the above items 1 to 3.
【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。特に一
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 is treated with an amino-substituted silane compound to have negative chargeability and
A resin having a hydrophobicity of 60% or more measured by the transmittance method is obtained. Therefore, this makes it possible to obtain a hydrophobic metal oxide powder which is controlled to be negatively charged, has good hydrophobicity, and has excellent charging stability and environmental stability. In particular, the compounds represented by the general formula [I] and the general formula [II] exhibit the above excellent effects.
【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２
〜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。The amino-substituted silane compound represented by the general formula [I] has R 1 , R 2 and R 3 as substituents, and these R 1 , R 2 and R 3 have a hydrogen atom or a carbon number of 1 And 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., methoxy group,
It may be an ethoxy group, and the main chain of the alkyl group contains VI such as sulfur.
A group B atom may be included. X is an alkoxy group having 1 to 3 carbon atoms, such as a methoxy group or 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 or an ethyl group. n is 2
Is an integer of 4 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 are also synonymous with 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。Specific examples of the amino-substituted silane compound used in the present invention will be given below.
【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, and the particle size thereof may be one suitable for the intended use, and in particular the specific surface area. It is preferably 50 m 2 / g or more.
【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, the mixture is allowed to stand for 10 minutes, and a small amount of suspension is extracted from the bottom of the flask. The transmittance of this liquid for light having a wavelength of 550 nm, where 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 way, 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 expressed as a triboelectric charge amount with respect to iron. The method of measuring the triboelectric charge amount on iron is described in the literature, for example, “Coloring Material” (55, 9, 630-63).
6, 1982) and the like.
【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 powder surface, but the treatment amount of the compound is preferably the metal oxide powder powder. 5% to 40% by weight
And particularly preferably 10 to 30% by weight. Further, it is also possible to carry out the treatment simultaneously or sequentially in combination with the organopolysiloxane. When the treatments are carried out in order, either the amino-substituted silane compound or the organopolysiloxane may be treated first. In the method of 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 hydrocarbon can be used as a diluent. After adding the treating agent, 100 ℃ under nitrogen atmosphere
Heat at a temperature in the range of ~ 300 ° C to complete the reaction and remove the solvent. In this way, the present invention can provide a hydrophobic metal oxide powder having a negative charging property, and by mixing the powder with a toner to produce a developer for electrophotography, the charging stability can be improved. Environmental resistance,
For example, the stability against 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 has the following general formula [I] and general formula [II]:
By having a phenyl group directly bonded to the nitrogen atom, good hydrophobicity is obtained and negative charge is controlled,
Further, it is possible to obtain a hydrophobic metal oxide powder having excellent charge stability and environmental stability.
【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 in detail below 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 heat-dried as shown in Table 1
g was placed in a stainless steel container, and was placed in a floating state while stirring under a nitrogen atmosphere, and the treating agent shown in Table 1 was sprayed onto the powder at room temperature. After the spraying is completed, the mixture is further stirred at room temperature for 30 minutes, and then externally heated under a nitrogen stream for 15 minutes over 15 minutes.
The temperature was raised to 0 ° C., treated at this temperature for 1 hour, and then allowed to cool to room temperature. In this way, Examples 1-5 and Comparative Examples 1-
The powder obtained in Example 5 was measured for hydrophobicity and triboelectricity with respect to iron by the transmittance method. The results obtained are shown in Table 1.
【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 clear from Table 1, all of the metal oxide powders treated with the amino-substituted silane compound according to the present invention are excellent in negative triboelectric charging property and good in hydrophobicity. On the other hand, it can be seen that the comparative example has a negative hydrophobicity but is poor in practicality although it is negatively charged.
【発明の効果】本発明は、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。INDUSTRIAL APPLICABILITY According to the present invention, since the metal oxide powder is treated with the amino-substituted silane compound having a phenyl group directly bonded to a nitrogen atom, not only it has good hydrophobicity but also negative charge is controlled. Also, a hydrophobic metal oxide powder is obtained, and an electrophotographic developer produced by using the powder is excellent in charging stability and environmental stability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｋ 9/06 ＫＣＱ (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─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical display location C08K 9/06 KCQ (72) Inventor Hideaki Sakurai 1-297 Kitabukurocho, Omiya-shi, Saitama Mitsubishi Materials Central Research Institute Co., Ltd.
Claims (4)
属酸化物であって、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 treated metal oxide has a negative charging property and a hydrophobicity measured by a transmittance method of 60% or more. Characteristic hydrophobic metal oxide powder.
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１】 〔式中、Ｒ1 、Ｒ2 、Ｒ3 は水素原子又は炭素数が１〜
５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のアルキル基
又はフェニル基である。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 [I]
The hydrophobic metal oxide powder according to claim 1, which is a compound represented by: Embedded image [In the formula, R 1 , R 2 , and R 3 each have a hydrogen atom or a carbon number of 1 to
5 is an alkyl group (however, the main chain of the alkyl group may include a VIB group atom), X is an alkoxy group having 1 to 3 carbon atoms, and Y is an alkyl group having 1 to 3 carbon atoms. Or a phenyl group. n is an integer of 2 to 4, and m is an integer of 1 to 3. ]
Ｉ〕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１〜５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のアルキル基又はフ
ェニル基である。ｎは２〜４の整数であり、ｍは１〜３
の整数である。〕3. An amino-substituted silane compound represented by the general formula [I
A compound represented by the formula [I].
The hydrophobic metal oxide powder according to item 1. Embedded image [In the formula, R 1 and R 2 are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (provided that the main chain of the alkyl group may contain a VIB group atom), and X has 1 to 5 carbon atoms. 3 is an alkoxy group, and Y is an alkyl group having 1 to 3 carbon atoms or a phenyl group. n is an integer of 2 to 4, and m is 1 to 3.
Is an integer. ]
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。4. A fluidity improver comprising the hydrophobic metal oxide powder according to any one of claims 1 to 3.
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 true JPH08194332A (en) | 1996-07-30 |
| JP3267087B2 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000004029A3 (en) * | 1998-07-15 | 2001-05-25 | Great Lakes Chemical Europ | Phenylenediamine silanes as antiozonants and antioxidants for rubbers |
| CN113252588A (en) * | 2021-05-11 | 2021-08-13 | 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
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000004029A3 (en) * | 1998-07-15 | 2001-05-25 | Great Lakes Chemical Europ | Phenylenediamine silanes as antiozonants and antioxidants for rubbers |
| CN113252588A (en) * | 2021-05-11 | 2021-08-13 | 西南科技大学 | Organic clay, preparation method thereof, and color development system and method for detecting hydroquinone |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3267087B2 (en) | 2002-03-18 |
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