JP5468463B2 - Surface-modified spherical silica powder and method for producing the same - Google Patents
Surface-modified spherical silica powder and method for producing the same Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 190
- 239000000377 silicon dioxide Substances 0.000 title claims description 94
- 239000000843 powder Substances 0.000 title claims description 82
- 238000004519 manufacturing process Methods 0.000 title description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000009826 distribution Methods 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 18
- 239000003607 modifier Substances 0.000 description 15
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000008859 change Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000001485 argon Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005443 coulometric titration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Description
本発明は、表面改質球状シリカ粉末及びその製造方法に関する。 The present invention relates to a surface-modified spherical silica powder and a method for producing the same.
従来、デジタル複写機やレーザープリンタ等に使用される静電荷像現像用トナーにおいて、その流動性改善や帯電特性の安定化のために、疎水化処理された球状シリカがトナー外添剤として用いられている。この球状シリカに要求される特性は、湿度による帯電量の変化を少なくするため高い疎水性を有し、しかも帯電特性を均一にする為に、球状シリカを均一に表面改質することである。疎水化処理された球状シリカの疎水化度分布について、未だ満足のいくものはなく、高い疎水化度を有する球状シリカであっても経時変化で若干の水分を含んでいく。その水分を含んだ球状シリカが感光体ドラム上に残留し、画像不良を引き起こすといった問題が生じてきた。 Conventionally, in electrostatic charge image developing toners used in digital copying machines, laser printers, and the like, hydrophobic silica is used as an external additive for improving fluidity and stabilizing charging characteristics. ing. The properties required for the spherical silica are to have a high hydrophobicity in order to reduce the change in charge amount due to humidity, and to uniformly modify the surface of the spherical silica in order to make the charging properties uniform. There is still no satisfactory hydrophobization degree distribution of the spherical silica that has been subjected to the hydrophobization treatment, and even spherical silica having a high degree of hydrophobization contains some water over time. There has been a problem that the spherical silica containing the moisture remains on the photosensitive drum and causes an image defect.
シリカと表面改質剤の反応速度は遅く、また表面改質剤の揮発性が高いことから、表面改質剤が反応を起こす前に系外へ揮発してしまい高い疎水性を発現することはできない。そこで、密閉型の混合装置、例えばヘンシェルミキサーを用い、表面改質剤とシリカ粒子の接触時間を長くすることで高い疎水性を実現する方法が提案（特許文献１）された。しかし、この方法では、ミキサーのブレード部分等でシリカ粒子の凝集が発生するため、分散性が損なわれるという問題がある。 Since the reaction rate between silica and the surface modifier is slow, and the volatility of the surface modifier is high, the surface modifier volatilizes out of the system before the reaction occurs and expresses high hydrophobicity. Can not. In view of this, a method has been proposed (Patent Document 1) that achieves high hydrophobicity by increasing the contact time between the surface modifier and the silica particles using a closed mixing device, for example, a Henschel mixer. However, this method has a problem in that dispersibility is impaired because aggregation of silica particles occurs in the blade portion of the mixer.
この問題を解決する方法として、循環ガスで原料球状シリカを浮遊（流動化）させた状態で、表面改質剤を噴霧する方法が提案（特許文献２）された。しかし、疎水化度の均一性という点では未だ満足のいくものではなく、更なる技術改善が求められている。 As a method for solving this problem, a method has been proposed (Patent Document 2) in which the surface modifier is sprayed in a state where the raw spherical silica is suspended (fluidized) with a circulating gas. However, it is still not satisfactory in terms of the uniformity of the degree of hydrophobicity, and further technical improvements are required.
本発明は、高温高湿下においても含有水分量の増加が極めて少ない高疎水性の球状シリカ粉末を提供することである。 An object of the present invention is to provide a highly hydrophobic spherical silica powder in which the increase in water content is extremely small even under high temperature and high humidity.
本発明は、上記の課題を解決するために、以下の手段を採用する。
（１）原料球状シリカ粉末のＢＥＴ比表面積が３０〜８０ｍ ２ ／ｇであり、メタノール滴定法における球状シリカ粉末が１００質量％沈降した時の疎水化度Ａと、球状シリカ粉末が５質量％沈降した時の疎水化度Ｂが式（１）及び式（２）を満たす疎水化度分布を有し、高温高湿（温度５０℃湿度７０％）の試験条件下において、試験前と２４時間後の含有水分量の増加量が０．０２質量％以下であることを特徴とする球状シリカ粉末。
７４％≦Ａ≦７５％ ・・・式（１）
Ａ−Ｂ≦９％ ・・・式（２）
（２）前記（１）に記載の球状シリカ粉末を用いたことを特徴とする静電荷像現像用トナー外添剤。
The present invention employs the following means in order to solve the above problems.
(1) The raw spherical silica powder has a BET specific surface area of 30 to 80 m 2 / g, the hydrophobicity A when the spherical silica powder in the methanol titration method settles to 100% by mass, and the spherical silica powder settles to 5% by mass. The hydrophobization degree B at the time of the test has a hydrophobization degree distribution satisfying the formulas (1) and (2), under the test conditions of high temperature and high humidity (temperature: 50 ° C., humidity: 70%) before and after 24 hours. A spherical silica powder characterized in that the increase in water content is 0.02% by mass or less.
74% ≦ A ≦ 75% Formula (1)
A−B ≦ 9 % (2)
(2) A toner external additive for developing an electrostatic charge image, wherein the spherical silica powder described in (1) is used.
本発明の球状シリカ粉末は、高温高湿下においても含有水分量の増加が極めて少ない。 The spherical silica powder of the present invention has very little increase in water content even under high temperature and high humidity.
本発明の球状シリカ粉末は、メタノール滴定法における球状シリカ粉末が１００質量％沈降した時の疎水化度Ａが式（１）を満たすものである。
６５％≦Ａ ・・・式（１）
疎水化度６５％未満のシリカ粉末は、保存雰囲気中の水分の影響を受け、シリカ表面の水分量が増加する。疎水化度の上限には制約はなく、大きいほどよい。
In the spherical silica powder of the present invention, the degree of hydrophobicity A when the spherical silica powder in the methanol titration method settles to 100% by mass satisfies the formula (1).
65% ≦ A Formula (1)
Silica powder having a hydrophobization degree of less than 65% is affected by moisture in the storage atmosphere, and the moisture content on the silica surface increases. There is no restriction on the upper limit of the degree of hydrophobicity, and the higher the better.
また、球状シリカ粉末の疎水化度分布については、メタノール滴定法における球状シリカ粉末が１００質量％沈降した時の疎水化度Ａと、球状シリカ粉末が５質量％沈降した時の疎水化度Ｂが式（２）を満たすものが好ましい。より好ましくは式（３）を満たすものである。
Ａ−Ｂ≦１５％ ・・・式（２）
Ａ−Ｂ≦１０％ ・・・式（３）
シャープな疎水化度分布を有する球状シリカ粉末は、高温高湿（温度５０℃湿度７０％）の条件下における、試験前と２４時間後の含有水分量の増加量が０．０２質量％以下と著しく低下させることができる。
Further, regarding the hydrophobicity distribution of the spherical silica powder, the hydrophobization degree A when the spherical silica powder is precipitated by 100% by mass in the methanol titration method and the hydrophobization degree B when the spherical silica powder is precipitated by 5% by mass. What satisfy | fills Formula (2) is preferable. More preferably, it satisfies the formula (3).
A-B ≦ 15% (2)
A-B ≦ 10% Formula (3)
The spherical silica powder having a sharp hydrophobization degree distribution is 0.02% by mass or less in water content before and after 24 hours under the conditions of high temperature and high humidity (temperature 50 ° C., humidity 70%). Can be significantly reduced.
本発明における高温高湿の条件とは、球状シリカ粉末を恒温恒湿槽、例えば「ＡＧ−２２５」（ＡＤＶＡＮＴＥＣ社製）にて温度５０℃湿度７０％に保持することで、球状シリカ粉末の水分変化を加速することができる。 The condition of high temperature and high humidity in the present invention means that the spherical silica powder is kept at a temperature of 50 ° C. and a humidity of 70% in a constant temperature and humidity chamber, for example, “AG-225” (manufactured by ADVANTEC), so Change can be accelerated.
本発明の静電荷像現像用トナー外添剤は、本発明の球状シリカ粉末からなるものである。本発明の外添剤は、従来のシリカからなる外添剤と同様にして使用することができる。その一例は、特開２０００−３３０３２８号公報に記載されている。 The toner external additive for developing an electrostatic charge image of the present invention comprises the spherical silica powder of the present invention. The external additive of the present invention can be used in the same manner as conventional external additives made of silica. One example is described in Japanese Patent Application Laid-Open No. 2000-330328.
本発明の球状シリカ粉末は、原料球状シリカ粉末をガスで浮遊させた状態で表面改質剤を噴霧する。反応容器中の空間率を０．８５〜０．９９とし、含有水分量が０．２０質量％以下の原料シリカ粉末に水と表面改質剤を噴霧することによって製造することができる。 The spherical silica powder of the present invention is sprayed with the surface modifier in a state where the raw spherical silica powder is suspended with a gas. It can be produced by spraying water and a surface modifier onto a raw silica powder having a space ratio in the reaction vessel of 0.85 to 0.99 and a water content of 0.20% by mass or less.
反応容器中の空間率を０．８５〜０．９９とすることで原料球状シリカ粉末の凝集が少なく、高分散状態での表面改質が可能である。空間率０．８５未満では原料球状シリカ粉末の凝集が発生し、均一な表面改質ができない。空間率が０．９９超では、原料球状シリカ粉末の均一な表面改質は可能だが、効率が悪く製造には向かない。空間率は、例えばガスライン上のバルブ開度等でガス流量を調整することにより維持できる。原料球状シリカ粉末を高分散状態で表面改質することで、高疎水性を発現することができる。 By setting the space ratio in the reaction vessel to 0.85 to 0.99, there is little aggregation of the raw spherical silica powder, and surface modification in a highly dispersed state is possible. When the space ratio is less than 0.85, the raw spherical silica powder is aggregated and uniform surface modification cannot be performed. When the space ratio exceeds 0.99, uniform surface modification of the raw spherical silica powder is possible, but the efficiency is low and it is not suitable for production. The space ratio can be maintained by adjusting the gas flow rate with, for example, a valve opening degree on the gas line. By modifying the surface of the raw spherical silica powder in a highly dispersed state, high hydrophobicity can be expressed.
本発明に用いる反応容器に特に指定はなく、例えば振動流動層装置「ＶＵＡ−１５型」（中央化工機社製）のような装置を用いることができる。なお、本発明中の空間率とは、反応容器中で浮遊している原料球状シリカ粉末の見掛け体積中におけるガスの体積の割合を示したものである。 The reaction vessel used in the present invention is not particularly specified, and for example, an apparatus such as a vibrating fluidized bed apparatus “VUA-15 type” (manufactured by Chuo Kako Co., Ltd.) can be used. In addition, the space ratio in this invention shows the ratio of the volume of the gas in the apparent volume of the raw material spherical silica powder floating in the reaction container.
上記の表面改質剤を噴霧する工程において、原料球状シリカ粉末の含有水分量を０．２０質量％以下にして、表面改質剤を噴霧することによって原料球状シリカ粉末の凝集が少なく、高い表面反応性を与えることができる。 In the step of spraying the surface modifying agent, the water content of the raw spherical silica powder is reduced to 0.20% by mass or less, and the surface modifying agent is sprayed to reduce the aggregation of the raw spherical silica powder and to increase the surface. It can provide reactivity.
通常、シリカ表面の水分はシリカの凝集に寄与しており、表面改質剤の加水分解に十分に作用しない。原料球状シリカ粉末の含有水分量が０．２０質量％を超えると、凝集が発生しており均一な表面改質ができない。そこで、原料球状シリカ粉末の含有水分量を０．２０質量％以下にすることで、原料球状シリカ粉末の凝集を著しく緩和し、高分散状態を作り出すことができる。原料球状シリカ粉末の含有水分量を０．２０質量％以下に低下させる方法としては、例えば原料球状シリカ粉末を乾燥ガスに接触させることが挙げられる。乾燥ガスとしては、作業性や安全性の面から液体Ｎ２ガスを用いることが好ましい。 Usually, the moisture on the silica surface contributes to the aggregation of the silica and does not sufficiently act on the hydrolysis of the surface modifier. If the water content of the raw spherical silica powder exceeds 0.20% by mass, aggregation occurs and uniform surface modification cannot be performed. Therefore, by setting the water content of the raw spherical silica powder to 0.20% by mass or less, aggregation of the raw spherical silica powder can be remarkably relieved and a highly dispersed state can be created. Examples of a method for reducing the water content of the raw material spherical silica powder to 0.20% by mass or less include bringing the raw material spherical silica powder into contact with a dry gas. As the dry gas, liquid N 2 gas is preferably used from the viewpoint of workability and safety.
原料球状シリカ粉末に水と表面改質剤を噴霧することによって、噴霧した水が表面改質剤の加水分解に好適に作用し、高い表面反応性を与えることができる。水と表面改質剤を噴霧する条件は、特に制限なく適用できるが、均一な表面改質を行うため、例えば２流体ノズル等を用いて液滴径を細かくして噴霧することが好ましい。また、水と表面改質剤は、別々に噴霧しても良いし、同時に噴霧しても良い。 By spraying water and the surface modifier on the raw spherical silica powder, the sprayed water suitably acts on the hydrolysis of the surface modifier and can impart high surface reactivity. The conditions for spraying water and the surface modifying agent can be applied without any particular limitation. However, in order to perform uniform surface modification, for example, it is preferable to spray with a fine droplet diameter using a two-fluid nozzle or the like. Moreover, water and a surface modifier may be sprayed separately, and may be sprayed simultaneously.
原料球状シリカ粉末をガスに浮遊させる条件としては、反応容器中の下部から上部へ向けてガスを流し、０．００５〜５ｍ／ｓの流速となるようガス流量を調整した。表面改質に対する水及び表面改質剤の噴霧量は、原料球状シリカ粉末１００質量部対し、水が０．３〜５質量部、表面改質剤が０．５〜１０質量部である。 As conditions for suspending the raw spherical silica powder in the gas, the gas was flowed from the lower part to the upper part in the reaction vessel, and the gas flow rate was adjusted to a flow rate of 0.005 to 5 m / s. The spray amount of water and the surface modifier for the surface modification is 0.3 to 5 parts by mass of water and 0.5 to 10 parts by mass of the surface modifier with respect to 100 parts by mass of the raw spherical silica powder.
本発明の表面改質剤としては、ヘキサメチルジシラザンを用いることができ、高い疎水性が発現できる。 As the surface modifier of the present invention, hexamethyldisilazane can be used, and high hydrophobicity can be expressed.
原料球状シリカ粉末の製造方法としては、例えばシリコン粒子を化学炎や電気炉等で形成された高温場に投じて酸化反応させながら球状化する方法（例えば特許第１５６８１６８号明細書）、シリコン粒子スラリーを火炎中に噴霧して酸化反応させながら球状化する方法（例えば特開２０００−２４７６２６号公報）などによって製造することができる。 As a method for producing the raw material spherical silica powder, for example, a method in which silicon particles are spheroidized while being subjected to an oxidation reaction by being put in a high temperature field formed by a chemical flame or an electric furnace (for example, Japanese Patent No. 1568168), a silicon particle slurry Can be produced by a method of spheroidizing while spraying into a flame to cause an oxidation reaction (for example, JP-A-2000-247626).
原料球状シリカ粉末の比表面積としては、３〜１５０ｍ２／ｇであることが好ましく、より好ましくは１５〜９５ｍ２／ｇである。比表面積は、ＢＥＴ測定機、例えば「Ｍａｃｓｏｒｂ ＨＭ Ｍｏｄｅｌ−１２０１」（マウンテック社製）で測定することができる。 The specific surface area of the raw material spherical silica powder is preferably 3~150m 2 / g, more preferably 15~95m 2 / g. The specific surface area can be measured with a BET measuring device, for example, “Macsorb HM Model-1201” (manufactured by Mountec).
原料球状シリカ粉末の「球状」の程度としては、平均球形度が０．８５以上であることが好ましい。平均球形度は、実体顕微鏡、例えば「モデルＳＭＺ−１０型」（ニコン社製）、走査型電子顕微鏡、透過型電子顕微鏡等にて撮影した粒子像を画像解析装置、例えば（日本アビオニクス社製など）に取り込み、次のようにして測定することができる。すなわち、写真から粒子の投影面積（Ｃ）と周囲長（ＰＭ）を測定する。周囲長（ＰＭ）に対応する真円の面積を（Ｄ）とすると、その粒子の球形度はＣ／Ｄとして表示できる。そこで、資料粒子の周囲長（ＰＭ）と同一の周囲長を持つ真円を想定すると、ＰＭ＝２πｒ、Ｄ＝πｒ２であるから、Ｄ＝π×（ＰＭ／２π）２となり、個々の粒子の球形度は、球形度＝Ｃ／Ｄ＝Ｃ×４π／（ＰＭ）２として算出することができる。このようにして得られた任意の粒子２００個の球形度を求めその平均値を平均球形度とする。 As the degree of “spherical” of the raw spherical silica powder, the average sphericity is preferably 0.85 or more. The average sphericity is measured by using a stereomicroscope such as “Model SMZ-10” (manufactured by Nikon Corp.), a scanning electron microscope, a transmission electron microscope, or the like as an image analysis apparatus such as (manufactured by Nippon Avionics Co., Ltd.). ) And can be measured as follows. That is, the projected area (C) and the perimeter (PM) of particles are measured from a photograph. When the area of a perfect circle corresponding to the perimeter (PM) is (D), the sphericity of the particle can be displayed as C / D. Therefore, assuming a perfect circle having the same circumference as the circumference of the material particle (PM), PM = 2πr and D = πr 2 , so that D = π × (PM / 2π) 2 , and each particle Can be calculated as sphericity = C / D = C × 4π / (PM) 2 . The sphericity of 200 arbitrary particles thus obtained is obtained, and the average value is defined as the average sphericity.
本発明の球状シリカ粉末は、原料球状シリカ粉末の表面改質剤による処理物からなるものであり、その疎水化度は以下のメタノール滴定法によって算出した。
すなわち、２００ｍｌのビーカーにイオン交換水５０ｍｌを入れ０．２ｇの試料を添加する。攪拌しながら、ビュレットからメタノールを加え、液面上に試料が認められなくなった点を終点として要したメタノール量から、下記の式（４）により疎水化度を算出する。式中のＧはメタノール使用量（ｍｌ）を表す。
疎水化度（％）＝（Ｇ／Ｇ＋５０）×１００ ・・・式（４）
式（４）より、疎水化度とメタノール使用量の関係を表すと以下のようになる。
疎水化度（％） メタノール使用量（ｍｌ）
０ ０
１０ ５．５
２０ １７
３０ ２１
４０ ３３
５０ ５０
６０ ７５
７０ １１６
８０ ２００
９０ ４５０
The spherical silica powder of the present invention consists of a treated product of the raw spherical silica powder with a surface modifier, and the degree of hydrophobicity was calculated by the following methanol titration method.
That is, 50 ml of ion-exchanged water is put into a 200 ml beaker, and a 0.2 g sample is added. While stirring, methanol is added from the burette, and the degree of hydrophobicity is calculated by the following formula (4) from the amount of methanol required with the point where the sample is no longer recognized on the liquid surface. G in the formula represents the amount of methanol used (ml).
Hydrophobic degree (%) = (G / G + 50) × 100 (4)
From the equation (4), the relationship between the degree of hydrophobicity and the amount of methanol used is expressed as follows.
Hydrophobicity (%) Methanol consumption (ml)
0 0
10 5.5
20 17
30 21
40 33
50 50
60 75
70 116
80 200
90 450
また、疎水化度分布は以下のように求められる。
０．２ｇの試料を２００ｍｌのビンにイオン交換水５０ｍｌとメタノールを疎水化度１０％に対応する量加え、１分間振り混ぜた後、１時間静置し、沈んだ試料を分離する。それを蒸発皿に移し、溶液を蒸発乾固し、デシケーター中で放冷する。蒸発乾固後の試料（ｇ）を測定し、下記の式（５）より沈降量（質量％）を測定する。
沈降量（質量％）＝蒸発乾固後の試料量（ｇ）／試料量０．２（ｇ）×１００ 式（５）
次に、疎水化度が１０，２０，３０，４０，５０，６０，７０，８０，９０（％）に対するメタノール量を順次使用し、上記と同様にして沈降量を測定する。疎水化度と沈降量の関係をグラフに表すことによって疎水化度分布が明瞭に表される。例えば、後述する実施例１の疎水化度分布が図１に明確に示されている。
The hydrophobicity distribution is obtained as follows.
A 0.2 g sample is added to a 200 ml bottle with 50 ml of ion-exchanged water and methanol in an amount corresponding to a hydrophobicity of 10%, shaken for 1 minute, and allowed to stand for 1 hour to separate a sunk sample. It is transferred to an evaporating dish and the solution is evaporated to dryness and allowed to cool in a desiccator. The sample (g) after evaporation to dryness is measured, and the amount of sediment (mass%) is measured from the following formula (5).
Sedimentation amount (% by mass) = sample amount after evaporation to dryness (g) / sample amount 0.2 (g) × 100 formula (5)
Next, the amount of methanol with respect to the degree of hydrophobicity of 10, 20, 30, 40, 50, 60, 70, 80, 90 (%) is sequentially used, and the amount of sedimentation is measured in the same manner as described above. By expressing the relationship between the degree of hydrophobicity and the amount of sedimentation in a graph, the degree of hydrophobicity distribution is clearly expressed. For example, the hydrophobization degree distribution of Example 1 described later is clearly shown in FIG.
本発明における含有水分量は、カールフィッシャー電量滴定法で測定される。カールフィッシャー微量水分測定装置、例えば「ＣＡ−１００」（三菱化学社製）にて測定することができる。具体的には、試料を水分気化装置に入れ、電気ヒーターで２００℃まで加熱昇温しながら、脱水処理されたアルゴンガスをキャリアガスとして供給し、試料の表面吸着水を測定することができる。 The water content in the present invention is measured by the Karl Fischer coulometric titration method. It can be measured by a Karl Fischer trace moisture measuring device, for example, “CA-100” (manufactured by Mitsubishi Chemical Corporation). Specifically, the sample surface adsorbed water can be measured by putting the sample in a moisture vaporizer and supplying the dehydrated argon gas as a carrier gas while heating up to 200 ° C. with an electric heater.
本発明における含有水分量の増加量は、球状シリカ粉末の表面改質直後の含有水分量と、高温高湿（温度５０℃湿度７０％）の条件下においての２４時間後の含有水分量の差により求めることができる。 The increase in the water content in the present invention is the difference between the water content immediately after the surface modification of the spherical silica powder and the water content after 24 hours under conditions of high temperature and high humidity (temperature: 50 ° C., humidity: 70%). It can ask for.
実施例１
ＢＥＴ比表面積８０ｍ２／ｇで平均球形度が０．９０の原料球状シリカ粉末５００ｇを反応容器に仕込み、Ｎ２ガスで浮遊させながら原料球状シリカ粉末の含有水分量を０．１７３（質量％）にした。空間率を０．９７に調整し、次いで水２０ｇとヘキサメチルジシラザン４０ｇを噴霧し、球状シリカ粉末を得た。得られた球状シリカ粉末の疎水化度と含有水分変化量を測定した。それらの結果を表１に示す。
Example 1
500 g of raw spherical silica powder having a BET specific surface area of 80 m 2 / g and an average sphericity of 0.90 was charged into a reaction vessel, and the water content of the raw spherical silica powder was 0.173 (mass%) while being suspended in N 2 gas. I made it. The porosity was adjusted to 0.97, and then 20 g of water and 40 g of hexamethyldisilazane were sprayed to obtain a spherical silica powder. The degree of hydrophobicity and the amount of change in water content of the obtained spherical silica powder were measured. The results are shown in Table 1.
実施例２
ＢＥＴ比表面積３０ｍ２／ｇで平均球形度が０．９３の原料球状シリカ粉末１０００ｇを反応容器に仕込み、Ｎ２ガスで浮遊させながら原料球状シリカ粉末の含有水分量を０．１４８（質量％）にした。空間率を０．９２に調整し、次いで水１５ｇとヘキサメチルジシラザン３０ｇを噴霧し、球状シリカ粉末を得た。得られた球状シリカ粉末の疎水化度と含有水分変化量を測定した。それらの結果を表１に示す。
Example 2
1000 g of raw spherical silica powder having a BET specific surface area of 30 m 2 / g and an average sphericity of 0.93 was charged into a reaction vessel, and the water content of the raw spherical silica powder was 0.148 (mass%) while being suspended in N 2 gas. I made it. The porosity was adjusted to 0.92, and then 15 g of water and 30 g of hexamethyldisilazane were sprayed to obtain a spherical silica powder. The degree of hydrophobicity and the amount of change in water content of the obtained spherical silica powder were measured. The results are shown in Table 1.
実施例３
ＢＥＴ比表面積３０ｍ２／ｇで平均球形度が０．９３の原料球状シリカ粉末１０００ｇを反応容器に仕込み、Ｎ２ガスで浮遊させながら原料球状シリカ粉末の含有水分量を０．０９７（質量％）にした。空間率を０．９７に調整し、次いで水１５ｇとヘキサメチルジシラザン３０ｇを噴霧し、球状シリカ粉末を得た。得られた球状シリカ粉末の疎水化度と含有水分変化量を測定した。それらの結果を表１に示す。
Example 3
1000 g of raw spherical silica powder having a BET specific surface area of 30 m 2 / g and an average sphericity of 0.93 was charged into a reaction vessel, and the water content of the raw spherical silica powder was 0.097 (mass%) while being suspended in N 2 gas. I made it. The porosity was adjusted to 0.97, and then 15 g of water and 30 g of hexamethyldisilazane were sprayed to obtain a spherical silica powder. The degree of hydrophobicity and the amount of change in water content of the obtained spherical silica powder were measured. The results are shown in Table 1.
実施例４
ＢＥＴ比表面積１２ｍ２／ｇで平均球形度が０．９２の原料球状シリカ粉末２０００ｇを反応容器に仕込み、Ｎ２ガスで浮遊させながら原料球状シリカ粉末の含有水分量を０．０６０（質量％）にした。空間率を０．８６に調整し、次いで水１５ｇとヘキサメチルジシラザン３０ｇを噴霧し、球状シリカ粉末を得た。得られた球状シリカ粉末の疎水化度と含有水分変化量を測定した。それらの結果を表１に示す。
Example 4
2000 g of raw spherical silica powder having a BET specific surface area of 12 m 2 / g and an average sphericity of 0.92 was charged into a reaction vessel, and the water content of the raw spherical silica powder was 0.060 (mass%) while floating in N 2 gas. I made it. The porosity was adjusted to 0.86, and then 15 g of water and 30 g of hexamethyldisilazane were sprayed to obtain a spherical silica powder. The degree of hydrophobicity and the amount of change in water content of the obtained spherical silica powder were measured. The results are shown in Table 1.
実施例５
ＢＥＴ比表面積１００ｍ２／ｇで平均球形度が０．８９の原料球状シリカ粉末５００ｇを反応容器に仕込み、Ｎ２ガスで浮遊させながら原料球状シリカ粉末の含有水分量を０．１８９（質量％）にした。空間率を０．９８に調整し、次いで水２０ｇとヘキサメチルジシラザン４０ｇを噴霧し、球状シリカ粉末を得た。得られた球状シリカ粉末の疎水化度と含有水分変化量を測定した。それらの結果を表１に示す。
Example 5
500 g of raw spherical silica powder having a BET specific surface area of 100 m 2 / g and an average sphericity of 0.89 was charged into a reaction vessel, and the water content of the raw spherical silica powder was 0.189 (mass%) while being suspended in N 2 gas. I made it. The porosity was adjusted to 0.98, and then 20 g of water and 40 g of hexamethyldisilazane were sprayed to obtain a spherical silica powder. The degree of hydrophobicity and the amount of change in water content of the obtained spherical silica powder were measured. The results are shown in Table 1.
実施例６
ＢＥＴ比表面積７ｍ２／ｇで平均球形度が０．９１の原料球状シリカ粉末４０００ｇを反応容器に仕込み、Ｎ２ガスで浮遊させながら原料球状シリカ粉末の含有水分量を０．０５７（質量％）にした。空間率を０．９４に調整し、次いで水１５ｇとヘキサメチルジシラザン３０ｇを噴霧し、球状シリカ粉末を得た。得られた球状シリカ粉末の疎水化度と含有水分変化量を測定した。それらの結果を表１に示す。
Example 6
4000 g of raw spherical silica powder having a BET specific surface area of 7 m 2 / g and an average sphericity of 0.91 was charged into a reaction vessel, and the water content of the raw spherical silica powder was 0.057 (mass%) while being suspended in N 2 gas. I made it. The porosity was adjusted to 0.94, and then 15 g of water and 30 g of hexamethyldisilazane were sprayed to obtain a spherical silica powder. The degree of hydrophobicity and the amount of change in water content of the obtained spherical silica powder were measured. The results are shown in Table 1.
比較例１
空間率を０．８３に調整したこと以外は実施例４と同様にし、球状シリカ粉末を得た。得られた球状シリカ粉末の疎水化度と含有水分変化量を測定した。それらの結果を表１に示す。
Comparative Example 1
A spherical silica powder was obtained in the same manner as in Example 4 except that the porosity was adjusted to 0.83. The degree of hydrophobicity and the amount of change in water content of the obtained spherical silica powder were measured. The results are shown in Table 1.
比較例２
原料球状シリカ粉末の含有水分量を０．２１３（質量％）としたこと以外は実施例２と同様にし、球状シリカ粉末を得た。得られた球状シリカ粉末の疎水化度と含有水分変化量を測定した。それらの結果を表１に示す。
Comparative Example 2
A spherical silica powder was obtained in the same manner as in Example 2 except that the water content of the raw material spherical silica powder was 0.213 (mass%). The degree of hydrophobicity and the amount of change in water content of the obtained spherical silica powder were measured. The results are shown in Table 1.
比較例３
原料球状シリカ粉末の含有水分量を０．２１２（質量％）とし、空間率を０．８０に調整したこと以外は実施例６と同様にし、球状シリカ粉末を得た。得られた球状シリカ粉末の疎水化度と含有水分変化量を測定した。それらの結果を表１に示す。
Comparative Example 3
A spherical silica powder was obtained in the same manner as in Example 6 except that the water content of the raw material spherical silica powder was 0.212 (mass%) and the porosity was adjusted to 0.80. The degree of hydrophobicity and the amount of change in water content of the obtained spherical silica powder were measured. The results are shown in Table 1.
実施例と比較例の対比から分かるように、本発明の球状シリカ粉末は、高温高湿下においても含有水分量の増加量が極めて少ないものである。本発明の製造方法を用いることで、高温高湿の条件下においても含有水分量の増加量が極めて少ない球状シリカ粉末を製造することができる。 As can be seen from the comparison between the examples and the comparative examples, the spherical silica powder of the present invention has an extremely small increase in water content even under high temperature and high humidity. By using the production method of the present invention, it is possible to produce a spherical silica powder with an extremely small increase in the water content even under high temperature and high humidity conditions.
本発明の球状シリカ粉末は特に、静電荷像現像用トナー外添剤に好適に用いることができ、安定した高い印字性を期待できる。
In particular, the spherical silica powder of the present invention can be suitably used for an external toner additive for developing an electrostatic image, and stable high printability can be expected.
Claims (2)
７４％≦Ａ≦７５％ ・・・式（１）
Ａ−Ｂ≦９％ ・・・式（２） When the raw spherical silica powder has a BET specific surface area of 30 to 80 m 2 / g, the hydrophobicity A when the spherical silica powder in the methanol titration method settles 100 mass%, and the spherical silica powder sediments 5 mass% Has a hydrophobicity distribution satisfying the formulas (1) and (2), and is contained before and after the test under the test conditions of high temperature and high humidity (temperature 50 ° C., humidity 70%). A spherical silica powder characterized in that the increase in water content is 0.02 mass% or less.
74% ≦ A ≦ 75% Formula (1)
A−B ≦ 9 % (2)
A toner external additive for developing an electrostatic charge image, wherein the spherical silica powder according to claim 1 is used.
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