JP2015059054A - Surface organic resin-coated hydrophobic spherical silica fine particle, production method of the same, and toner external additive for electrostatic charge image development using the same - Google Patents
Surface organic resin-coated hydrophobic spherical silica fine particle, production method of the same, and toner external additive for electrostatic charge image development using the same Download PDFInfo
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本発明は、表面有機樹脂被覆疎水性球状シリカ微粒子、その製造方法及びそれを用いた静電荷像現像用トナー外添剤に関する。 The present invention relates to surface organic resin-coated hydrophobic spherical silica fine particles, a method for producing the same, and a toner external additive for developing an electrostatic image using the same.
電子写真法等で使用する乾式現像剤は、結着樹脂中に着色剤を分散したトナーそのものを用いる一成分現像剤と、そのトナーにキャリアを混合した二成分現像剤とに大別でき、そしてこれらの現像剤を用いてコピー操作を行う場合、プロセス適合性を有するためには、現像剤が流動性、耐ケーキング性、定着性、帯電性、クリーニング性等に優れていることが必要である。そして特に、流動性、耐ケーキング性、定着性、クリーニング性を高めるために、無機微粒子をトナーに添加することがしばしば行われている。 Dry developers used in electrophotography and the like can be broadly classified into a one-component developer using a toner itself in which a colorant is dispersed in a binder resin, and a two-component developer in which the toner is mixed with a carrier, and When performing a copying operation using these developers, in order to have process compatibility, the developer needs to be excellent in fluidity, caking resistance, fixing properties, charging properties, cleaning properties, and the like. . In particular, in order to improve fluidity, caking resistance, fixability, and cleaning properties, inorganic fine particles are often added to the toner.
トナーに添加する無機微粒子としては一般的にシリカ微粒子が好適に使用されている。シリカ微粒子は、その製法によって、シラン化合物を燃焼させて得られる燃焼法シリカ（即ち、ヒュームドシリカ）、金属珪素粉を爆発的に燃焼させて得られる爆燃法シリカ、珪酸ナトリウムと鉱酸との中和反応によって得られる湿式シリカ（このうち、アルカリ条件で合成し凝集させたものを沈降法シリカ、酸性条件で合成し凝集させたものをゲル法シリカという）、珪酸ナトリウムからイオン交換樹脂で脱ナトリウムして得られた酸性珪酸をアルカリ性にして重合することで得られるコロイダルシリカ（シリカゾル）、ヒドロカルビルオキシシランの加水分解によって得られるゾルゲル法シリカ（いわゆるＳｔｏｅｂｅｒ法）などに大別される。 In general, silica fine particles are preferably used as the inorganic fine particles added to the toner. Silica fine particles are produced by combustion method silica obtained by burning a silane compound (ie fumed silica), deflagration silica obtained by explosively burning metal silicon powder, sodium silicate and mineral acid. Wet silica obtained by neutralization reaction (of which, synthesized and aggregated under alkaline conditions is precipitated silica, and synthesized and aggregated under acidic conditions is gel silica), dehydrated from sodium silicate with ion exchange resin Colloidal silica (silica sol) obtained by polymerizing acidic silicic acid obtained by sodium to alkalinity, and sol-gel silica obtained by hydrolysis of hydrocarbyloxysilane (so-called Stöber method) are roughly classified.
電子写真用トナーの外添剤としては、疎水化表面処理をしたシリカ微粒子粉体が好適に用いられている。
疎水化表面処理方法としては、シリカ微粒子粉体に、疎水化剤、例えば界面活性剤、シリコーンオイル、又はアルキルハロゲノシラン、アルキルアルコキシシラン、アルキルジシラザンなどのシリル化剤の気体を接触させ疎水化処理する方法、水と親水性有機混合溶媒中でシリル化剤に接触させ疎水化処理する方法等が挙げられる。
As an external additive for an electrophotographic toner, silica fine particle powder subjected to a hydrophobic surface treatment is preferably used.
Hydrophobic surface treatment is performed by bringing silica fine particle powder into contact with a hydrophobizing agent such as a surfactant, silicone oil, or a silylating agent such as alkylhalogenosilane, alkylalkoxysilane, or alkyldisilazane. The method of processing, the method of contacting with a silylating agent in water and a hydrophilic organic mixed solvent, and the method of hydrophobizing are mentioned.
そのような疎水化表面処理をしたシリカ微粒子粉体は、電子写真用トナーの外添剤として好適に用いられているが、これはトナー母体の比重に対して１．５〜１．８倍（シリカ比重は１．８〜２．２）と、かなりトナー母体と比重差があるため、トナー母体に混合する操作を行なう際、分散させ難かったり、トナー母体と固着しても経時的にトナー母体からシリカ微粒子が脱落しやすいなどの問題が指摘されていた。 The silica fine particle powder subjected to such a hydrophobic surface treatment is suitably used as an external additive for an electrophotographic toner, which is 1.5 to 1.8 times the specific gravity of the toner base ( The specific gravity of silica is 1.8 to 2.2), which is considerably different from that of the toner base. Therefore, when mixing with the toner base, it is difficult to disperse or even if the toner base adheres to the toner base over time. From the above, problems such as easy removal of silica fine particles have been pointed out.
このような問題を解決する従来技術としては、一旦金属酸化物からなる外添剤をトナーに付着させた後、脱落を防止するために有機樹脂粒子を更に被覆するという技術がある（特許文献１）。しかしこの方法は、外添剤よりも小さくて均一な有機樹脂粒子がないことや、その有機樹脂粒子が現像機内で飛散・遊離して画像に悪影響を及ぼしたり、帯電を悪くする等の問題を有していた。 As a conventional technique for solving such a problem, there is a technique in which an external additive made of a metal oxide is once attached to a toner and then further coated with organic resin particles in order to prevent dropping (Patent Document 1). ). However, this method has problems such as that there are no organic resin particles that are smaller and uniform than the external additive, that the organic resin particles are scattered and released in the developing machine, adversely affecting the image, and charging becomes worse. Had.
従って、本発明は、トナー母体に混合したときに高い分散状態を保ち、トナー母体との付着強度も強く、更にトナー表面から離脱し帯電に悪影響を与えるような現象がない表面有機樹脂被覆疎水性球状シリカ微粒子、その製造方法及びそれを用いた静電荷像現像用トナー外添剤を提供することを目的とする。 Therefore, the present invention maintains a high dispersion state when mixed with the toner base, has a strong adhesion strength to the toner base, and further has a surface organic resin-coated hydrophobicity that does not cause a phenomenon that is separated from the toner surface and adversely affects charging. An object of the present invention is to provide spherical silica fine particles, a process for producing the same, and an external toner additive for developing an electrostatic image using the same.
斯かる実情に鑑み、本発明者は鋭意研究を行った結果、下記シリカ微粒子がトナー母体に混合したときに高い分散状態を保ち、付着強度も強く、更にトナー表面から離脱し帯電に悪影響を与えるような現象がないことを見出し本発明を完成した。
即ち本発明は、次に示すものである。
In view of such circumstances, the present inventor has conducted intensive research. As a result, when the following silica fine particles are mixed in the toner base, the present invention maintains a high dispersion state and has a high adhesion strength, and further departs from the toner surface and adversely affects charging. The present invention was completed by finding that there was no such phenomenon.
That is, the present invention is as follows.
＜１＞
１次粒子の平均粒子径が体積基準メジアン径で０．０１〜５μｍであり、表面の少なくとも一部がガラス転移温度が６５〜１２０℃である有機樹脂被膜で被覆された、表面有機樹脂被覆疎水性球状シリカ微粒子。
<1>
Surface organic resin-coated hydrophobic, in which the average particle diameter of primary particles is 0.01-5 μm in volume-based median diameter, and at least a part of the surface is coated with an organic resin film having a glass transition temperature of 65-120 ° C. Spherical silica fine particles.
＜２＞
（Ａ１）下記一般式（Ｉ）：
Ｓｉ（ＯＲ3）4 （Ｉ）
（但し、Ｒ3は同一又は異種の炭素原子数１〜６の一価炭化水素基である。）
で示される４官能性シラン化合物、その部分加水分解生成物又はこれらの混合物を、塩基性物質の存在下で親水性有機溶媒と水の混合液中で加水分解、縮合することによって、ＳｉＯ2単位を含む親水性球状シリカ微粒子の混合溶媒分散液を得る工程と、
（Ａ２）該親水性球状シリカ微粒子の混合溶媒分散液に、下記一般式（ＩＩ）：
Ｒ1Ｓｉ（ＯＲ4）3 （ＩＩ）
（但し、Ｒ1は置換又は非置換の炭素原子数１〜２０の一価炭化水素基であり、Ｒ4は同一又は異種の炭素原子数１〜６の一価炭化水素基である。）
で示される３官能性シラン化合物、その部分加水分解生成物又はこれらの混合物を添加して、前記親水性球状シリカ微粒子の表面を処理することにより、該親水性球状シリカ微粒子の表面にＲ1ＳｉＯ3/2単位（但し、Ｒ1は前記と同じである。）を導入し、第一の表面疎水化球状シリカ微粒子の混合溶媒分散液を得る工程と、
（Ａ３）該第一の表面疎水化球状シリカ微粒子の混合溶媒分散液又はその濃縮液に下記一般式（ＩＩＩ）：
Ｒ2 3ＳｉＮＨＳｉＲ2 3 （ＩＩＩ）
（但し、Ｒ2は同一又は異種の置換又は非置換の炭素原子数１〜６の一価炭化水素基である）
で示されるシラザン化合物、
下記一般式（ＩＶ）：
Ｒ2 3ＳｉＸ （ＩＶ）
（但し、Ｒ2は同一又は異種の置換又は非置換の炭素原子数１〜６の一価炭化水素基であり、ＸはＯＨ基又は加水分解性基である。）
で示される１官能性シラン化合物又はこれらの混合物を添加し、該第一の表面疎水化球状シリカ微粒子の表面を処理して、該第一の表面疎水化球状シリカ微粒子の表面にＲ2 3ＳｉＯ1/2単位（但し、Ｒ2は前記と同じである。）を導入することにより第二の疎水性球状シリカ微粒子を得る工程と、
（Ａ４）該第二の疎水性球状シリカ微粒子の分散液に、ガラス転移温度が６５〜１２０℃の有機樹脂を溶解せしめ、該第二の疎水性球状シリカ微粒子の表面の少なくとも一部に有機樹脂被覆を形成して有機樹脂被覆疎水性球状シリカ微粒子を得る工程と、
を有することを特徴とする＜１＞に記載の表面有機樹脂被覆疎水性球状シリカ微粒子の製造方法。
<2>
(A1) The following general formula (I):
Si (OR 3 ) 4 (I)
(However, R 3 is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms.)
By hydrolyzing and condensing a tetrafunctional silane compound represented by the formula, a partial hydrolysis product thereof or a mixture thereof in a mixture of a hydrophilic organic solvent and water in the presence of a basic substance, SiO 2 unit Obtaining a mixed solvent dispersion of hydrophilic spherical silica fine particles comprising:
(A2) In the mixed solvent dispersion of the hydrophilic spherical silica fine particles, the following general formula (II):
R 1 Si (OR 4 ) 3 (II)
(However, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 4 is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms.)
Is added to the surface of the hydrophilic spherical silica fine particles to add R 1 SiO to the surface of the hydrophilic spherical silica fine particles. Introducing 3/2 units (where R 1 is as defined above) to obtain a mixed solvent dispersion of the first surface-hydrophobized spherical silica fine particles;
(A3) A mixed solvent dispersion of the first surface-hydrophobized spherical silica fine particles or a concentrated liquid thereof has the following general formula (III):
R 2 3 SiNHSiR 2 3 (III)
(Wherein R 2 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms)
A silazane compound represented by
The following general formula (IV):
R 2 3 SiX (IV)
(Wherein R 2 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and X is an OH group or a hydrolyzable group.)
A monofunctional silane compound represented by the formula (1) or a mixture thereof is added, and the surface of the first surface hydrophobized spherical silica fine particles is treated to form R 2 3 SiO on the surface of the first surface hydrophobized spherical silica fine particles. A step of obtaining second hydrophobic spherical silica fine particles by introducing 1/2 unit (wherein R 2 is the same as above);
(A4) An organic resin having a glass transition temperature of 65 to 120 ° C. is dissolved in the dispersion liquid of the second hydrophobic spherical silica fine particles, and the organic resin is formed on at least a part of the surface of the second hydrophobic spherical silica fine particles. Forming an organic resin-coated hydrophobic spherical silica fine particle by forming a coating;
<1> The method for producing hydrophobic spherical silica fine particles coated with surface organic resin according to <1>.
＜３＞
＜２＞に記載の製造方法により製造された表面有機樹脂被覆疎水性球状シリカ微粒子。
＜４＞
＜１＞又は＜３＞に記載の表面有機樹脂被覆疎水性球状シリカ微粒子からなる静電荷像現像用トナー外添剤。
＜５＞
＜１＞又は＜３＞に記載の表面有機樹脂被覆疎水性球状シリカ微粒子を含有する静電荷像現像用トナー。
<3>
Surface organic resin-coated hydrophobic spherical silica fine particles produced by the production method according to <2>.
<4>
<1> or <3> a toner external additive for developing an electrostatic image comprising the surface organic resin-coated hydrophobic spherical silica fine particles.
<5>
<1> or <3> A toner for developing an electrostatic charge image, comprising the surface organic resin-coated hydrophobic spherical silica fine particles.
このような表面有機樹脂被覆疎水性球状シリカ微粒子をトナー外添剤として用いれば、トナーに混合したときに高分散状態を保ちながら付着強度の高い状態を有し、トナー表面から離脱したものが帯電に悪影響を与えるような現象を抑制することができる。 When such surface organic resin-coated hydrophobic spherical silica fine particles are used as an external toner additive, when mixed with the toner, it has a high adhesion state while maintaining a high dispersion state, and the one separated from the toner surface is charged. It is possible to suppress a phenomenon that adversely affects the image.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
＜表面有機樹脂被覆疎水性球状シリカ微粒子の特徴＞
まず、本発明の表面有機樹脂被覆疎水性球状シリカ微粒子の特徴について説明する。本発明の微粒子は、１次粒子の平均粒子径が体積基準メジアン径で０．０１〜５μｍの、表面の少なくとも一部が有機樹脂被覆処理された球状シリカ微粒子である。球状でありながら、有機樹脂が表面に被覆されているため、トナー母体と比重差があるにも関らずトナー母体に固着して脱落性が大きく改善できる。これは、トナー母体とシリカ表面の有機樹脂との摩擦帯電極性が同じになり、それぞれの有機樹脂が類似構造のため着きやすい、すなわち似たもの同士が着きやすいという特性からではないかと推測される。
<Features of surface organic resin-coated hydrophobic spherical silica fine particles>
First, the characteristics of the surface organic resin-coated hydrophobic spherical silica fine particles of the present invention will be described. The fine particles of the present invention are spherical silica fine particles whose primary particles have an average particle diameter of 0.01 to 5 μm in volume basis median diameter and whose surface is at least partially coated with an organic resin. Although it is spherical, since the surface is coated with an organic resin, it adheres to the toner base and can largely improve the drop-off property despite a difference in specific gravity from the toner base. This is presumed to be due to the characteristics that the toner base and the organic resin on the silica surface have the same triboelectric charge polarity, and each organic resin is easy to wear because of its similar structure, that is, similar things are easy to wear. .
本発明の表面有機樹脂被覆疎水性球状シリカ微粒子について、「球状」とは、真球だけでなく、若干歪んだ球も含む。具体的には、「球状」であるとは粒子を二次元に投影したときの円形度が０．８〜１の範囲にあることを意味する。ここで円形度とは、（実際の粒子を二次元投影したときの図形の面積と等しい真円の周囲長）／（実際の粒子を二次元投影したときの図形の面積の周囲長）を意味する。 Regarding the surface organic resin-coated hydrophobic spherical silica fine particles of the present invention, “spherical” includes not only true spheres but also slightly distorted spheres. Specifically, “spherical” means that the circularity when particles are projected two-dimensionally is in the range of 0.8-1. Here, the circularity means (peripheral length of a perfect circle equal to the area of the figure when an actual particle is projected two-dimensionally) / (perimeter of the area of the figure when an actual particle is projected two-dimensionally) To do.
本発明の表面有機樹脂被覆疎水性球状シリカ微粒子の粒子径は、１次粒子の平均粒子径が体積基準メジアン径で０．０１〜５μｍであり、好ましくは０．０５〜０．５μｍである。この粒子径が０．０１μｍより小さい場合には、上記微粒子が凝集してしまい、現像剤の流動性、耐ケーキング性、定着性等を得ることができない。また、この粒子径が５μｍより大きい場合には、感光体の変質や削れ、微粒子のトナーへの付着性の低下といった不都合が生じる。なお、本発明において、微粒子の粒度分布は、動的光散乱法／レーザードップラー法ナノトラック粒度分布測定装置（日機装株式会社製、商品名：UPA-EX150）により測定し、その体積基準メジアン径を粒子径とした。なお、メジアン径とは粒度分布を累積分布として表した時の累積５０％に相当する粒子径である。 The particle diameter of the surface organic resin-coated hydrophobic spherical silica fine particles of the present invention is such that the average particle diameter of the primary particles is 0.01 to 5 μm, preferably 0.05 to 0.5 μm in terms of volume-based median diameter. When the particle diameter is smaller than 0.01 μm, the fine particles are aggregated, and the fluidity, caking resistance, fixability, and the like of the developer cannot be obtained. On the other hand, when the particle diameter is larger than 5 μm, problems such as deterioration or abrasion of the photoconductor and reduction in adhesion of fine particles to the toner occur. In the present invention, the particle size distribution of the fine particles is measured by a dynamic light scattering method / laser Doppler nanotrack particle size distribution measuring apparatus (trade name: UPA-EX150, manufactured by Nikkiso Co., Ltd.), and the volume-based median diameter is The particle diameter was taken. The median diameter is a particle diameter corresponding to 50% cumulative when the particle size distribution is expressed as a cumulative distribution.
シリカ表面の被覆に用いられる有機樹脂は、ガラス転移温度が６５〜１２０℃のものである。このガラス転移温度が６５℃未満のものでは高温高湿下でのトナーの保管性が悪化する場合があり好ましくない。一方、ガラス転移温度が１２０℃を超えるようなものは、定着時に阻害要素、すなわち、軟化するのに必要な熱量が多くなることから、トナーへ付与されるべき熱量が奪われることとなり、好ましくない。 The organic resin used for coating the silica surface has a glass transition temperature of 65 to 120 ° C. If the glass transition temperature is less than 65 ° C., the storage stability of the toner under high temperature and high humidity may deteriorate, which is not preferable. On the other hand, those having a glass transition temperature exceeding 120 ° C. are not preferable because the amount of heat to be imparted to the toner is deprived because the amount of heat necessary for softening is increased during the fixing process. .
本発明に用いられる有機樹脂としては、トナー用のスチレン−アクリル樹脂やポリエステル樹脂のほか、ポリスチレン樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、フッ化ビニリデン樹脂やその他のフッ素系樹脂、溶剤可溶性ナイロン樹脂、ブチラール樹脂、フェノキシ樹脂、ポリカーボネート樹脂などが挙げられる。これらの内、スチレン−アクリル樹脂やポリエステル樹脂が特に好ましい。 As the organic resin used in the present invention, in addition to styrene-acrylic resin and polyester resin for toner, polystyrene resin, vinyl chloride resin, vinylidene chloride resin, vinylidene fluoride resin and other fluorine-based resins, solvent-soluble nylon resins, Examples include butyral resin, phenoxy resin, and polycarbonate resin. Of these, styrene-acrylic resins and polyester resins are particularly preferred.
本発明においては、シリカ微粒子の表面の少なくとも一部が上記有機樹脂で被覆されているが、具体的には、シリカ微粒子表面の１〜９０％の面積が有機樹脂被膜で被覆されていることが好ましく、更に５〜７０％の面積が有機樹脂被膜で被覆されていることが好ましい。 In the present invention, at least a part of the surface of the silica fine particles is coated with the organic resin. Specifically, the area of 1 to 90% of the surface of the silica fine particles is covered with the organic resin film. It is preferable that an area of 5 to 70% is further covered with an organic resin film.
＜表面有機樹脂被覆疎水性球状シリカ微粒子の製造方法＞
次に、本発明の表面有機樹脂被覆疎水性球状シリカ微粒子は、例えば、以下の製造方法により、製造することができる。
合成シリカ微粒子は、その製法によって、燃焼法シリカ（即ち、ヒュームドシリカ）、爆燃法シリカ、湿式シリカ、ゾルゲル法シリカ（いわゆるＳｔｏｅｂｅｒ法）に大別される。本発明で用いるシリカ微粒子は、ゾルゲル法シリカに属する。
<Method for producing surface organic resin-coated hydrophobic spherical silica fine particles>
Next, the surface organic resin-coated hydrophobic spherical silica fine particles of the present invention can be produced, for example, by the following production method.
Synthetic silica fine particles are roughly classified into combustion method silica (that is, fumed silica), deflagration method silica, wet silica, and sol-gel method silica (so-called Stober method) depending on the production method. The silica fine particles used in the present invention belong to sol-gel silica.
本発明の表面疎水化球状シリカ微粒子は、
工程（Ａ１）：親水性球状シリカ微粒子の合成工程と、
工程（Ａ２）：３官能性シラン化合物による表面処理工程と、
工程（Ａ３）：１官能性シラン化合物による表面処理工程と、
工程（Ａ４）：有機樹脂による表面被覆処理工程と、
によって得られる。以下各工程を順を追って説明する。
The surface hydrophobized spherical silica fine particles of the present invention are:
Step (A1): Step of synthesizing hydrophilic spherical silica fine particles;
Step (A2): a surface treatment step with a trifunctional silane compound;
Step (A3): a surface treatment step with a functional silane compound;
Step (A4): Surface coating treatment step with an organic resin,
Obtained by. Each process will be described below in order.
−工程（Ａ１）：親水性球状シリカ微粒子の合成工程−
本工程では、一般式（Ｉ）：
Ｓｉ（ＯＲ3）4 （Ｉ）
（但し、各Ｒ3は同一又は異種の炭素原子数１〜６の一価炭化水素基である。）
で示される４官能性シラン化合物、その部分加水分解生成物又はこれらの混合物を、塩基性物質の存在下で親水性有機溶媒と水の混合液中で加水分解、縮合することによって親水性球状シリカ微粒子混合溶媒分散液を得る。
-Step (A1): Step of synthesizing hydrophilic spherical silica fine particles-
In this step, the general formula (I):
Si (OR 3 ) 4 (I)
(However, each R 3 is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms.)
Hydrophilic spherical silica by hydrolyzing and condensing a tetrafunctional silane compound represented by the formula, a partial hydrolysis product thereof, or a mixture thereof in a mixture of a hydrophilic organic solvent and water in the presence of a basic substance. A fine particle mixed solvent dispersion is obtained.
上記一般式（Ｉ）：Ｓｉ（ＯＲ3）4中、Ｒ3は、炭素原子数１〜６の一価炭化水素基であるが、好ましくは炭素原子数１〜４、特に好ましくは１〜２の１価炭化水素基である。Ｒ3で表される１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、フェニル基等、好ましくは、メチル基、エチル基、プロピル基、ブチル基、特に好ましくは、メチル基、エチル基が挙げられる。 In the above general formula (I): Si (OR 3 ) 4 , R 3 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms. These are monovalent hydrocarbon groups. Examples of the monovalent hydrocarbon group represented by R 3 include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group, preferably a methyl group, an ethyl group, a propyl group, and a butyl group, and particularly preferably , Methyl group, and ethyl group.
上記一般式（Ｉ）：Ｓｉ（ＯＲ3）4で示される４官能性シラン化合物としては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のテトラアルコキシシラン、テトラフェノキシシラン等が挙げられ、好ましくは、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、特に好ましくは、テトラメトキシシラン、テトラエトキシシランが挙げられる。また、一般式（Ｉ）で示される４官能性シラン化合物の部分加水分解縮合生成物としては、例えば、メチルシリケート、エチルシリケート等が挙げられる。 Examples of the tetrafunctional silane compound represented by the general formula (I): Si (OR 3 ) 4 include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and tetraphenoxysilane. Preferably, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and particularly preferably tetramethoxysilane, tetraethoxysilane. Examples of the partial hydrolysis-condensation product of the tetrafunctional silane compound represented by the general formula (I) include methyl silicate and ethyl silicate.
前記親水性有機溶媒としては、上記一般式（Ｉ）：Ｓｉ（ＯＲ3）4で示される４官能性シラン化合物と、この部分加水分解縮合生成物と、水とを溶解するものであれば特に制限されず、例えば、アルコール類； メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、酢酸セロソルブ等のセロソルブ類； アセトン、メチルエチルケトン等のケトン類；ジオキサン、テトラヒドロフラン等のエーテル類等が挙げられ、好ましくは、アルコール類、セロソルブ類、特に好ましくはアルコール類が挙げられる。 The hydrophilic organic solvent is not particularly limited as long as it dissolves the tetrafunctional silane compound represented by the general formula (I): Si (OR 3 ) 4 , the partial hydrolysis-condensation product, and water. Without limitation, for example, alcohols; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate; ketones such as acetone and methylethylketone; ethers such as dioxane and tetrahydrofuran; preferably alcohols; Cellosolves, particularly preferably alcohols are mentioned.
ここで、アルコール類としては、一般式（Ｖ）：
Ｒ5ＯＨ （Ｖ）
（式中、Ｒ5は炭素原子数１〜６の１価炭化水素基である）
で示されるアルコールが挙げられる。
Here, as alcohols, general formula (V):
R 5 OH (V)
(Wherein R 5 is a monovalent hydrocarbon group having 1 to 6 carbon atoms)
The alcohol shown by is mentioned.
上記一般式（Ｖ）：Ｒ5ＯＨ中、Ｒ5は、好ましくは炭素原子数１〜４、特に好ましくは１〜２の１価炭化水素基である。Ｒ5で表される１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基等のアルキル基等、好ましくはメチル基、エチル基、プロピル基、イソプロピル基、より好ましくはメチル基、エチル基が挙げられる。上記一般式（Ｖ）で示されるアルコールとしては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等、好ましくは、メタノール、エタノールが挙げられる。アルコールの炭素原子数が増えると、生成する球状シリカ微粒子の粒子径が大きくなる。従って、目的とする小粒径シリカ微粒子を得るためにはメタノールが好ましい。 In the general formula (V): R 5 OH, R 5 is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms. Examples of the monovalent hydrocarbon group represented by R 5 include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, More preferably, a methyl group and an ethyl group are mentioned. Examples of the alcohol represented by the general formula (V) include methanol, ethanol, propanol, isopropanol, butanol, and preferably methanol and ethanol. As the number of carbon atoms in the alcohol increases, the particle size of the spherical silica fine particles to be generated increases. Therefore, methanol is preferred in order to obtain the desired small particle size silica fine particles.
また、上記塩基性物質としてはアンモニア、ジメチルアミン、ジエチルアミン等が挙げられ、好ましくは、アンモニア、ジエチルアミン、特に好ましくはアンモニアが挙げられる。これらの塩基性物質は、所要量を水に溶解した後、得られた水溶液（塩基性）を前記親水性有機溶媒と混合すればよい。 Examples of the basic substance include ammonia, dimethylamine, diethylamine and the like, preferably ammonia, diethylamine, and particularly preferably ammonia. These basic substances may be dissolved in water in a required amount, and the obtained aqueous solution (basic) may be mixed with the hydrophilic organic solvent.
塩基性物質の量は、上記一般式（Ｉ）：Ｓｉ（ＯＲ3）4で示される４官能性シラン化合物および／又はその部分加水分解縮合生成物、のヒドロカルビルオキシ基の合計１モルに対して０．０１〜２モルであることが好ましく、０．０２〜０．５モルであることがより好ましく、０．０４〜０．１２モルであることが特に好ましい。このとき、塩基性物質の量が少ないほど所望の小粒径シリカ微粒子となる。 The amount of the basic substance is based on 1 mol of the total hydrocarbyloxy group of the tetrafunctional silane compound represented by the above general formula (I): Si (OR 3 ) 4 and / or a partial hydrolysis-condensation product thereof. The amount is preferably 0.01 to 2 mol, more preferably 0.02 to 0.5 mol, and particularly preferably 0.04 to 0.12 mol. At this time, the smaller the amount of the basic substance, the desired small particle size silica fine particles.
上記加水分解及び縮合で使用される水の量は、上記一般式（Ｉ）：Ｓｉ（ＯＲ3）4で示される４官能性シラン化合物および／又はその部分加水分解縮合生成物のヒドロカルビルオキシ基の合計１モルに対して０．５〜５モルであることが好ましく、０．６〜２モルであることがより好ましく、０．７〜１モルであることが特に好ましい。水に対する親水性有機溶媒の比率は、質量比で０．５〜１０であることが好ましく、３〜９であることがより好ましく、５〜８であることが特に好ましい。このとき、親水性有機溶媒の量が多いほど所望の小粒径シリカ微粒子となる。 The amount of water used in the hydrolysis and condensation is the amount of the hydrocarbyloxy group of the tetrafunctional silane compound represented by the general formula (I): Si (OR 3 ) 4 and / or the partial hydrolysis condensation product thereof. The amount is preferably 0.5 to 5 mol, more preferably 0.6 to 2 mol, and particularly preferably 0.7 to 1 mol with respect to 1 mol in total. The ratio of the hydrophilic organic solvent to water is preferably 0.5 to 10 in terms of mass ratio, more preferably 3 to 9, and particularly preferably 5 to 8. At this time, as the amount of the hydrophilic organic solvent increases, the desired small particle size silica fine particles are obtained.
上記一般式（Ｉ）：Ｓｉ（ＯＲ3）4で示される４官能性シラン化合物等の加水分解および縮合は、周知の方法、即ち、塩基性物質を含む親水性有機溶媒と水との混合物中に、上記一般式（Ｉ）で示される４官能性シラン化合物等を添加することにより行われる。 The hydrolysis and condensation of the tetrafunctional silane compound represented by the general formula (I): Si (OR 3 ) 4 is performed by a well-known method, that is, in a mixture of a hydrophilic organic solvent containing a basic substance and water. Is performed by adding a tetrafunctional silane compound or the like represented by the above general formula (I).
本工程（Ａ１）で得られる親水性球状シリカ微粒子混合溶媒分散液中のシリカ微粒子の濃度は一般に３〜１５質量％であり、好ましくは５〜１０質量％である。 The concentration of silica fine particles in the hydrophilic spherical silica fine particle mixed solvent dispersion obtained in this step (A1) is generally 3 to 15% by mass, preferably 5 to 10% by mass.
−工程（Ａ２）：３官能性シラン化合物による表面処理工程−
本工程は、工程（Ａ１）において得られた親水性球状シリカ微粒子混合溶媒分散液に、一般式（ＩＩ）：
Ｒ1Ｓｉ（ＯＲ4）3 （ＩＩ）
（但し、Ｒ1は置換又は非置換の炭素原子数１〜２０の一価炭化水素基、Ｒ4は同一又は異種の炭素原子数１〜６の一価炭化水素基である）で示される３官能性シラン化合物、その部分加水分解生成物又はこれらの混合物を添加して親水性球状シリカ微粒子表面をこれにより処理することにより、前記親水性球状シリカ微粒子の表面にＲ1ＳｉＯ3/2単位（但し、Ｒ1は前記式（ＩＩ）の定義と同じである。）を導入し、第一の表面疎水化球状シリカ微粒子の混合溶媒分散液を得る工程である。
-Step (A2): Surface treatment step with trifunctional silane compound-
In this step, the hydrophilic spherical silica fine particle mixed solvent dispersion obtained in the step (A1) is added to the general formula (II):
R 1 Si (OR 4 ) 3 (II)
Wherein R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 4 is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms. By adding a functional silane compound, a partially hydrolyzed product thereof or a mixture thereof and treating the surface of the hydrophilic spherical silica fine particles with this, R 1 SiO 3/2 units ( However, R 1 is the same as the definition of the formula (II).) To obtain a mixed solvent dispersion of the first surface hydrophobized spherical silica fine particles.
本工程（Ａ２）は、後の工程においてシリカ微粒子の凝集を抑制するために不可欠である。凝集を抑制できないと、得られるシリカ系粉体の個々の粒子は一次粒子径を維持できないため、工程（A４）に移行したときに表面の有機樹脂被覆がうまくいかない場合があり、更に表面有機樹脂被覆疎水性球状シリカ微粒子をトナーに添加した時の流動性付与能が悪くなる場合があり好ましくない。 This step (A2) is indispensable for suppressing aggregation of silica fine particles in the subsequent step. If the agglomeration cannot be suppressed, the individual particles of the resulting silica-based powder cannot maintain the primary particle size, so the surface organic resin coating may not work well when the process (A4) is entered, and the surface organic resin coating When the hydrophobic spherical silica fine particles are added to the toner, the fluidity imparting ability may deteriorate, which is not preferable.
上記一般式（ＩＩ）：Ｒ1Ｓｉ（ＯＲ4）3中、Ｒ1は、炭素原子数１〜２０、好ましくは炭素原子数１〜３、特に好ましくは１〜２の１価炭化水素基である。Ｒ1で表される１価炭化水素基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ブチル基、ヘキシル基等のアルキル基等が挙げられ、好ましくは、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、特に好ましくは、メチル基、エチル基が挙げられる。また、これらの１価炭化水素基の水素原子の一部又は全部が、フッ素原子、塩素原子、臭素原子等のハロゲン原子、好ましくはフッ素原子で置換されていてもよい。 In the above general formula (II): R 1 Si (OR 4 ) 3 , R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 3 carbon atoms, particularly preferably 1 to 2 carbon atoms. is there. Examples of the monovalent hydrocarbon group represented by R 1 include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, and a hexyl group, preferably a methyl group, An ethyl group, an n-propyl group, and an isopropyl group, particularly preferably a methyl group and an ethyl group are exemplified. Further, some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom, preferably fluorine atom.
上記一般式（ＩＩ）：Ｒ1Ｓｉ（ＯＲ4）3中、Ｒ4は、炭化水素数１〜６、好ましくは炭素原子数１〜３、特に好ましくは１〜２の１価炭化水素基である。Ｒ4で表される１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等のアルキル基等が挙げられ、好ましくは、メチル基、エチル基、プロピル基、特に好ましくは、メチル基、エチル基が挙げられる。 In the general formula (II): R 1 Si (OR 4 ) 3 , R 4 is a monovalent hydrocarbon group having 1 to 6 hydrocarbons, preferably 1 to 3 carbon atoms, particularly preferably 1 to 2 carbon atoms. is there. Examples of the monovalent hydrocarbon group represented by R 4 include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a methyl group, an ethyl group, and a propyl group, and particularly preferably Includes a methyl group and an ethyl group.
上記一般式（ＩＩ）：Ｒ1Ｓｉ（ＯＲ4）3で示される３官能性シラン化合物としては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、イソプロピルトリメトキシシラン、イソプロピルトリエトキシシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、ヘキシルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘプタデカフルオロデシルトリメトキシシラン等のトリアルコキシシラン等が挙げられ、好ましくは、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、より好ましくは、メチルトリメトキシシラン、メチルトリエトキシシラン、又は、これらの部分加水分解縮合生成物が挙げられる。 Examples of the trifunctional silane compound represented by the general formula (II): R 1 Si (OR 4 ) 3 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n- Propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxy Trialkoxysilanes such as silane, etc., preferably methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, more preferably methyltrimethoxy Shishiran, methyltriethoxysilane, or their partially hydrolyzed condensation products thereof.
上記一般式（ＩＩ）：Ｒ1Ｓｉ（ＯＲ4）3で示される３官能性シラン化合物の添加量は、使用された親水性球状シリカ微粒子のＳｉ原子１モル当り０．００１〜１モルが好ましく、特に０．０１〜０．１モル、更に０．０１〜０．０５モルが好ましい。添加量が０．０１モル以上であれば、分散性が良いのでトナー外添加剤として使用した際の流動性が良くなり好ましい。また１モル以下であれば、シリカ微粒子の凝集が生じることもなく好ましい。 The addition amount of the trifunctional silane compound represented by the above general formula (II): R 1 Si (OR 4 ) 3 is preferably 0.001 to 1 mole per mole of Si atoms of the used hydrophilic spherical silica fine particles. In particular, 0.01 to 0.1 mol, more preferably 0.01 to 0.05 mol is preferable. An addition amount of 0.01 mol or more is preferable because the dispersibility is good and the fluidity when used as an additive outside the toner is improved. Moreover, if it is 1 mol or less, it is preferable, without agglomeration of a silica particle.
本工程（Ａ２）で得られる第一の表面疎水化球状シリカ微粒子の混合溶媒分散液中の該シリカ微粒子の濃度は通常３質量％以上１５質量％未満である。 The concentration of the silica fine particles in the mixed solvent dispersion of the first surface-hydrophobized spherical silica fine particles obtained in this step (A2) is usually 3% by mass or more and less than 15% by mass.
次の工程（Ａ３）において表面処理剤として使用される一般式（ＩＩＩ）で表されるシラザン化合物および一般式（ＩＶ）で表される一官能性シラン化合物が、アルコールや水と反応して表面処理が不十分となり、その後に乾燥を行う時に凝集を生じ、得られるシリカ粉体は一次粒子径を維持できず、工程（A４）に移行したときに表面の有機樹脂被覆がうまくいかない場合があったり、更に表面有機樹脂被覆疎水性球状シリカ微粒子をトナーに添加した時の流動性付与能が悪くなるといった不具合を抑制するために、工程（Ａ２）の後に濃縮工程を設けることが好ましい。 The silazane compound represented by the general formula (III) and the monofunctional silane compound represented by the general formula (IV) used as a surface treating agent in the next step (A3) react with alcohol or water to produce a surface. Insufficient treatment and subsequent aggregation may cause agglomeration, and the resulting silica powder may not be able to maintain the primary particle size, and the surface may not be covered with the organic resin when transferred to step (A4). Further, in order to suppress the problem that the fluidity imparting ability deteriorates when the surface organic resin-coated hydrophobic spherical silica fine particles are added to the toner, it is preferable to provide a concentration step after the step (A2).
濃縮工程は、上記工程（Ａ２）で得られた第一の表面疎水化球状シリカ微粒子混合溶媒分散液から親水性有機溶媒と水の一部を除去することにより第一の表面疎水化球状シリカ微粒子の混合溶媒濃縮分散液を得る工程である。この際、疎水性有機溶媒をあらかじめ、或いは工程中に加えてもよい。使用する疎水性溶媒は、炭化水素系、ケトン系溶媒が好ましい。具体的には、トルエン、キシレン、メチルエチルケトン、メチルイソブチルケトン等が挙げられ、好ましくはメチルイソブチルケトンが好ましい。親水性有機溶媒と水の一部を除去する方法としては、例えば留去、減圧留去などが挙げられる。得られる濃縮分散液はシリカ微粒子濃度が１５〜４０質量％のものが好ましく、２０〜３５質量％のものがでがより好ましく、２５〜３０質量％のものが特に好ましい。この濃度が１５質量％以上であれば、後工程の表面処理がうまくゆき、４０質量％以下であればシリカ微粒子の凝集が生じることもなく好都合である。 In the concentration step, the first surface hydrophobized spherical silica fine particles are removed by removing a part of the hydrophilic organic solvent and water from the first surface hydrophobized spherical silica fine particle mixed solvent dispersion obtained in the step (A2). Is a step of obtaining a concentrated dispersion liquid of At this time, a hydrophobic organic solvent may be added in advance or in the process. The hydrophobic solvent used is preferably a hydrocarbon solvent or a ketone solvent. Specific examples include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and the like, preferably methyl isobutyl ketone. Examples of the method for removing a part of the hydrophilic organic solvent and water include distillation and distillation under reduced pressure. The obtained concentrated dispersion has a silica fine particle concentration of preferably 15 to 40% by mass, more preferably 20 to 35% by mass, and particularly preferably 25 to 30% by mass. If the concentration is 15% by mass or more, the surface treatment in the subsequent process is successful, and if it is 40% by mass or less, the silica fine particles are not agglomerated, which is convenient.
−工程（Ａ３）：１官能性シラン化合物による表面処理工程−
工程（Ａ２）で得られた第一の表面疎水化球状シリカ微粒子の混合溶媒（濃縮）分散液に、下記一般式（ＩＩＩ）：
Ｒ2 3ＳｉＮＨＳｉＲ2 3 （ＩＩＩ）
（但し、Ｒ2は同一又は異種の置換又は非置換の炭素原子数１〜６の一価炭化水素基である）で示されるシラザン化合物、又は下記一般式（ＩＶ）：
Ｒ2 3ＳｉＸ （ＩＶ）
（但し、Ｒ2は同一又は異種の置換又は非置換の炭素原子数１〜６の一価炭化水素基であり、ＸはＯＨ基又は加水分解性基である。）
で示される１官能性シラン化合物又はこれらの混合物を添加し、これにより前記第一の表面疎水化球状シリカ微粒子表面を処理して前記第一の表面疎水化球状シリカ微粒子の表面にＲ2 3ＳｉＯ1/2単位（但し、Ｒ2は前記と同じである。）を導入して第二の表面疎水性球状シリカ微粒子を得る。この工程では、上記の処理により第一の表面疎水化球状シリカ微粒子の表面に残存するシラノール基をトリオルガノシリル化する形でＲ2 3ＳｉＯ1/2単位が該表面に導入される。この工程で表面の疎水性を高めておくことで、工程Ａ４での表面有機樹脂被覆をしやすくなるため、この工程は必須である。この工程がないと表面が親水性のシラノールにより、有機樹脂被覆は疎水性表面に比べて悪くなるため好ましくない。
-Step (A3): Surface treatment step with a functional silane compound-
In the mixed solvent (concentrated) dispersion of the first surface-hydrophobized spherical silica fine particles obtained in the step (A2), the following general formula (III):
R 2 3 SiNHSiR 2 3 (III)
(Wherein R 2 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms), or the following general formula (IV):
R 2 3 SiX (IV)
(Wherein R 2 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and X is an OH group or a hydrolyzable group.)
A monofunctional silane compound represented by formula (1) or a mixture thereof is added, whereby the surface of the first surface hydrophobized spherical silica fine particles is treated to form R 2 3 SiO on the surface of the first surface hydrophobized spherical silica fine particles. 1/2 unit (wherein R 2 is the same as described above) is introduced to obtain second surface hydrophobic spherical silica fine particles. In this step, R 2 3 SiO 1/2 units are introduced to the surface in the form of triorganosilylation of the silanol groups remaining on the surface of the first surface-hydrophobized spherical silica fine particles by the above treatment. This step is indispensable because the surface hydrophobicity in the step A4 is facilitated by increasing the surface hydrophobicity in this step. Without this step, the organic resin coating becomes worse than the hydrophobic surface due to the silanol having a hydrophilic surface, which is not preferable.
上記一般式（ＩＩＩ）：Ｒ2 3ＳｉＮＨＳｉＲ2 3および（ＩＶ）：Ｒ2 3ＳｉＸ中、Ｒ2は、炭素原子数１〜６の一価炭化水素基であるが、炭素原子数１〜４、特に１〜２の１価炭化水素基が好ましい。Ｒ2で表される１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基等のアルキル基等、好ましくは、メチル基、エチル基、プロピル基、特に好ましくは、メチル基、エチル基が挙げられる。また、これらの１価炭化水素基の水素原子の一部又は全部が、フッ素原子、塩素原子、臭素原子等のハロゲン原子、好ましくは、フッ素原子で置換されていてもよい。 In the general formula (III): R 2 3 SiNHSiR 2 3 and (IV): R 2 3 SiX, R 2 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, but 1 to 4 carbon atoms. In particular, a monovalent hydrocarbon group of 1 to 2 is preferable. The monovalent hydrocarbon group represented by R 2 is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, preferably a methyl group, an ethyl group, or a propyl group. Includes a methyl group and an ethyl group. Further, some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom, preferably fluorine atom.
上記一般式（ＩＶ）：Ｒ2 3ＳｉＸ中のＸで表される加水分解性基としては、例えば、塩素原子、アルコキシ基、アミノ基、アシルオキシ基等が挙げられ、好ましくは、アルコキシ基、アミノ基、特に好ましくは、アルコキシ基が挙げられる。 Examples of the hydrolyzable group represented by X in the general formula (IV): R 2 3 SiX include a chlorine atom, an alkoxy group, an amino group, an acyloxy group, and the like, preferably an alkoxy group, an amino group, and the like. A group, particularly preferably an alkoxy group.
上記一般式（ＩＩＩ）：Ｒ2 3ＳｉＮＨＳｉＲ2 3で示されるシラザン化合物としては、例えば、ヘキサメチルジシラザン、ヘキサエチルジシラザン等が挙げられ、好ましくはヘキサメチルジシラザンが挙げられる。上記一般式（ＩＶ）：Ｒ2 3ＳｉＸで示される１官能性シラン化合物としては、例えば、トリメチルシラノール、トリエチルシラノール等のモノシラノール化合物、トリメチルクロロシラン、トリエチルクロロシラン等のモノクロロシラン、トリメチルメトキシシラン、トリメチルエトキシシラン等のモノアルコキシシラン、トリメチルシリルジメチルアミン、トリメチルシリルジエチルアミン等のモノアミノシラン、トリメチルアセトキシシラン等のモノアシルオキシシランが挙げられ、好ましくは、トリメチルシラノール、トリメチルメトキシシラン、トリメチルシリルジエチルアミン、特に好ましくは、トリメチルシラノール、トリメチルメトキシシランが挙げられる。 Examples of the silazane compound represented by the general formula (III): R 2 3 SiNHSiR 2 3 include hexamethyldisilazane and hexaethyldisilazane, and preferably hexamethyldisilazane. Examples of the monofunctional silane compound represented by the general formula (IV): R 2 3 SiX include monosilanol compounds such as trimethylsilanol and triethylsilanol, monochlorosilanes such as trimethylchlorosilane and triethylchlorosilane, trimethylmethoxysilane, and trimethyl. Examples include monoalkoxysilanes such as ethoxysilane, monoaminosilanes such as trimethylsilyldimethylamine and trimethylsilyldiethylamine, and monoacyloxysilanes such as trimethylacetoxysilane, preferably trimethylsilanol, trimethylmethoxysilane, trimethylsilyldiethylamine, particularly preferably trimethylsilanol. And trimethylmethoxysilane.
上記シラザン化合物及び／又は１官能性シラン化合物の使用量は、使用した親水性球状シリカ微粒子のＳｉ原子１モルに対して０．１〜０．５モルが好ましく、特に０．２〜０．４モル、更に０．２５〜０．３５モルが好ましい。使用量が０．１モル以上であれば、トナー外添加剤として使用した際の流動性が良好であり好ましい。また０．５モル以下であれば経済的に有利であり好ましい。 The amount of the silazane compound and / or monofunctional silane compound used is preferably 0.1 to 0.5 mol, particularly 0.2 to 0.4, relative to 1 mol of Si atoms in the used hydrophilic spherical silica fine particles. Mol, more preferably 0.25 to 0.35 mol. If the amount used is 0.1 mol or more, the fluidity when used as an additive outside the toner is good, which is preferable. Moreover, if it is 0.5 mol or less, it is economically advantageous and preferable.
本工程により得られる表面疎水性球状シリカ微粒子は、分散液のまま次の工程（Ａ４）移行してもよいし、ここで一旦常圧乾燥、減圧乾燥等の常法によって粉体として得た後、再度溶剤に分散させて工程（Ａ４）移行してもよい。 The surface hydrophobic spherical silica fine particles obtained in this step may be transferred to the next step (A4) as a dispersion, or once obtained as a powder by a conventional method such as normal pressure drying or reduced pressure drying. , It may be dispersed again in the solvent and transferred to step (A4).
−工程（Ａ４）：有機樹脂による表面被覆処理工程−
工程（Ａ３）で得られた第二の疎水性球状シリカ微粒子の分散溶液はそのまま本工程に用いることができる。一方、第二の疎水性球状シリカ微粒子を一旦乾燥させて乾燥粉体にしたものは、再度溶媒に分散させた分散溶液とする。この時に第二の疎水性球状シリカ微粒子を分散させる溶剤としては、使用する樹脂が可溶なものであればよく、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤、各種脂肪族炭化水素やトルエン、キシレンなどの芳香族炭化水素およびそれらの誘導体、各種アルコール、エステル系溶媒、ＴＨＦ（テトラヒドロフラン）などの環状エーテルなど、各種の有機溶媒が挙げられる。
-Step (A4): Surface coating treatment step with organic resin-
The dispersion solution of the second hydrophobic spherical silica fine particles obtained in the step (A3) can be used in this step as it is. On the other hand, the second hydrophobic spherical silica fine particles once dried to form a dry powder are used as a dispersion solution again dispersed in a solvent. As the solvent for dispersing the second hydrophobic spherical silica fine particles at this time, it is sufficient that the resin to be used is soluble. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and various aliphatic hydrocarbons. And various organic solvents such as aromatic hydrocarbons such as toluene and xylene and derivatives thereof, various alcohols, ester solvents, and cyclic ethers such as THF (tetrahydrofuran).
表面に被覆する有機樹脂としては、ガラス転移温度が６５〜１２０℃の有機樹脂である。このガラス転移温度が６５℃未満のものは高温高湿下でのトナーの保管性が悪化する場合があり好ましくない。一方、ガラス転移温度が１２０℃を超えるものは、定着時に阻害要素、すなわち、軟化するのに必要な熱量が多くなることから、トナーへ付与されるべき熱量が奪われることとなり、好ましくない。 The organic resin to be coated on the surface is an organic resin having a glass transition temperature of 65 to 120 ° C. Those having a glass transition temperature of less than 65 ° C. are not preferable because the storage stability of the toner under high temperature and high humidity may deteriorate. On the other hand, those having a glass transition temperature exceeding 120 ° C. are not preferable because the amount of heat to be imparted to the toner is deprived because the amount of heat necessary for softening is increased during the fixing process.
ここで用いられる有機樹脂は、トナー用のスチレン−アクリル樹脂やポリエステル樹脂のほか、ポリスチレン樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、フッ化ビニリデン樹脂やその他のフッ素系樹脂、溶剤可溶性ナイロン樹脂、ブチラール樹脂、フェノキシ樹脂、ポリカーボネート樹脂などが挙げられる。この内、特に好ましいものはスチレン−アクリル樹脂やポリエステル樹脂である。 Organic resins used here include styrene-acrylic resins and polyester resins for toner, polystyrene resins, vinyl chloride resins, vinylidene chloride resins, vinylidene fluoride resins and other fluorine resins, solvent-soluble nylon resins, butyral resins , Phenoxy resin, polycarbonate resin and the like. Of these, styrene-acrylic resins and polyester resins are particularly preferable.
被覆する有機樹脂の量は第二の疎水性球状シリカ微粒子１００質量部に対して０．１〜５０質量部が好ましい。より好ましくは３〜３０質量部である。この量が０．１質量部よりも少ないとトナーへの付着性が低下するため好ましくない。またこの量が５０質量部より多いと帯電が悪化したり、乾燥時融着等が起こりやすくなるため好ましくない。 The amount of the organic resin to be coated is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the second hydrophobic spherical silica fine particles. More preferably, it is 3-30 mass parts. If the amount is less than 0.1 parts by mass, the adhesion to the toner is lowered, which is not preferable. On the other hand, when the amount is more than 50 parts by mass, charging is deteriorated and fusion during drying is likely to occur.
有機樹脂の被覆は、例えば有機樹脂を有機溶剤に溶解させた有機樹脂溶解溶液を、疎水性球状シリカ微粒子が有機溶剤に分散している分散溶液中に混合し、乾燥することによりシリカ表面に有機樹脂を被覆することができる。上記混合条件としては、反応温度２０〜１００℃、反応時間１〜８時間行うことが好ましい。更に好ましくは反応温度２０〜８０℃、反応時間２〜８時間で行う方がより好ましい。 For example, the organic resin coating is performed by mixing an organic resin-dissolved solution obtained by dissolving an organic resin in an organic solvent into a dispersion solution in which hydrophobic spherical silica fine particles are dispersed in an organic solvent, and then drying the organic resin. Resin can be coated. As said mixing conditions, it is preferable to carry out reaction temperature 20-100 degreeC and reaction time 1-8 hours. More preferably, the reaction temperature is 20 to 80 ° C. and the reaction time is 2 to 8 hours.
有機樹脂を被覆後、常法により乾燥することにより、本発明の有機樹脂被覆疎水性球状シリカ微粒子を得ることができる。 After coating the organic resin, the organic resin-coated hydrophobic spherical silica fine particles of the present invention can be obtained by drying by a conventional method.
また、本発明により得られる有機樹脂被覆疎水性球状シリカ微粒子は、必要に応じて種々のシランカップリング剤、ジメチルジメトキシシラン等のシランで表面処理してもよい。 Moreover, the organic resin-coated hydrophobic spherical silica fine particles obtained by the present invention may be surface-treated with various silane coupling agents and silanes such as dimethyldimethoxysilane as necessary.
＜有機樹脂被覆疎水性球状シリカ微粒子を用いたトナー外添剤＞
本発明の有機樹脂被覆疎水性球状シリカ微粒子又は本発明方法により製造される有機樹脂被覆疎水性球状シリカ微粒子は、トナー外添剤等、特に静電荷像現像用トナー外添剤として好適に用いることができる。該有機樹脂被覆疎水性球状シリカ微粒子を用いたトナー外添剤のトナーに対する配合量は、トナー１００質量部に対して、０．０１〜２０質量部が好ましく、さらに好ましくは０．１〜５重量部である。この配合量が、０．０１質量部以上であれば、トナーへの付着量が十分で、トナーの流動性が十分得られるため好ましく、２０質量部以下であれば、トナーの帯電性に好影響を及ぼし、経済的にも好ましい。
<External toner additive using hydrophobic spherical silica particles coated with organic resin>
The organic resin-coated hydrophobic spherical silica fine particles of the present invention or the organic resin-coated hydrophobic spherical silica fine particles produced by the method of the present invention are suitably used as a toner external additive, particularly as a toner external additive for developing electrostatic images. Can do. The blending amount of the toner external additive using the organic resin-coated hydrophobic spherical silica fine particles with respect to the toner is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the toner. Part. If the blending amount is 0.01 parts by mass or more, it is preferable because the adhesion amount to the toner is sufficient and sufficient fluidity of the toner is obtained, and if it is 20 parts by mass or less, the chargeability of the toner is positively affected. It is economically preferable.
本発明の表有機樹脂被覆疎水性球状シリカ微粒子又は本発明により製造される有機樹脂被覆疎水性球状シリカ微粒子を用いたトナー外添剤が添加されるトナー粒子としては、結着樹脂と着色剤を主成分として構成される公知のものが使用できる。また、必要に応じて帯電制御剤が添加されていてもよい。 As the toner particles to which the external toner additive using the surface organic resin-coated hydrophobic spherical silica fine particles of the present invention or the organic resin-coated hydrophobic spherical silica fine particles produced according to the present invention is added, a binder resin and a colorant are used. A well-known thing comprised as a main component can be used. Moreover, the charge control agent may be added as needed.
本発明の有機樹脂被覆疎水性球状シリカ微粒子又は本発明により製造される有機樹脂被覆疎水性球状シリカ微粒子を用いたトナー外添剤が添加されたトナーは、一成分現像剤として使用できるが、また、それをキャリアと混合して二成分現像剤として使用することもできる。二成分現像剤として使用する場合においては、上記トナー外添剤は予めトナー粒子に添加せず、トナーとキャリアの混合時に添加してトナーの表面被覆を行ってもよい。キャリアとしては、鉄粉等、あるいはそれらの表面に樹脂コーティングされた公知のものが使用される。 The toner to which an organic resin-coated hydrophobic spherical silica fine particle of the present invention or an organic resin-coated hydrophobic spherical silica fine particle produced according to the present invention is added can be used as a one-component developer. It can also be mixed with a carrier and used as a two-component developer. When used as a two-component developer, the toner external additive may not be added to the toner particles in advance, but may be added when the toner and the carrier are mixed to coat the surface of the toner. As the carrier, iron powder or the like, or a known one whose surface is resin-coated is used.
以下、実施例および比較例を示して本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to these Examples.
＜有機樹脂（スチレン−アクリル樹脂）合成例１＞
撹拌機及び温度計を備えた反応容器に、脱イオン水１６０質量部、ポリアクリル酸ソーダ水溶液（固形分３．３質量％）０．０４質量部、硫酸ナトリウム０．４質量部を仕込み、次いで単量体成分としてスチレン８５質量部、ブチルアクリレート１５質量部、トリメチロールプロパントリアクリレート０．３質量部、及び重合開始剤としてベンゾイルパーオキサイド２質量部、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカーボネート０．５質量部を添加した。内容物を攪拌しながら４０℃から１３０℃まで６５分間で昇温し、１３０℃に到達した後、さらに２時間３０分攪拌した後、冷却し、重合体粒子の懸濁液を得た。重合体を分離、洗浄、乾燥し、スチレン−アクリル樹脂Ａを得た。このもののガラス転移点は１００℃まで昇温した後、ＤＳＣ（Rigaku製、Thermo plusＤＳＣ８２３０システム）を用い、昇温速度１０／ｍｉｎの条件下で測定したショルダー値で計測した。このスチレン−アクリル樹脂Ａのガラス転移温度は７０℃であった。
<Organic resin (styrene-acrylic resin) synthesis example 1>
In a reaction vessel equipped with a stirrer and a thermometer, 160 parts by mass of deionized water, 0.04 parts by mass of a sodium polyacrylate aqueous solution (solid content: 3.3% by mass), and 0.4 parts by mass of sodium sulfate were charged. 85 parts by mass of styrene as monomer components, 15 parts by mass of butyl acrylate, 0.3 parts by mass of trimethylolpropane triacrylate, and 2 parts by mass of benzoyl peroxide as a polymerization initiator, t-butylperoxy-2-ethylhexyl monocarbonate 0.5 parts by weight were added. While stirring the contents, the temperature was raised from 40 ° C. to 130 ° C. over 65 minutes, and after reaching 130 ° C., the contents were further stirred for 2 hours 30 minutes and then cooled to obtain a suspension of polymer particles. The polymer was separated, washed and dried to obtain styrene-acrylic resin A. The glass transition point of this product was measured with the shoulder value measured under the condition of a temperature increase rate of 10 / min using DSC (manufactured by Rigaku, Thermo plus DSC8230 system) after increasing the temperature to 100 ° C. The glass transition temperature of this styrene-acrylic resin A was 70 ° C.
＜有機樹脂（スチレン−アクリル樹脂）合成例２＞
上記合成例１のスチレンを９８質量部、ブチルアクリレートを２質量部とした以外は同様に合成し、スチレン−アクリル樹脂Ｂを得た。このもののガラス転移温度は１２０℃まで昇温した後、ＤＳＣ（Rigaku製、Thermo plusＤＳＣ８２３０システム）を用い、昇温速度１０／ｍｉｎの条件下で測定したショルダー値で計測した。このスチレン−アクリル樹脂Ｂのガラス転移温度は１００℃であった。
<Organic resin (styrene-acrylic resin) synthesis example 2>
A styrene-acrylic resin B was obtained in the same manner except that 98 parts by mass of styrene and 2 parts by mass of butyl acrylate in Synthesis Example 1 were used. The glass transition temperature of this product was raised to 120 ° C., and then measured with a shoulder value measured using DSC (Rigaku, Thermo plus DSC 8230 system) under a temperature raising rate of 10 / min. The glass transition temperature of this styrene-acrylic resin B was 100 ° C.
＜実施例１＞
［有機樹脂被覆疎水性球状シリカ微粒子の合成］
−工程（Ａ１）：親水性球状シリカ微粒子の合成工程−
攪拌機と、滴下ロートと、温度計とを備えた３リットルのガラス製反応器にメタノール９８９．５ｇと、水１３５．５ｇと、２８％アンモニア水６６．５ｇとを入れて混合した。この溶液を３５℃となるように調整し、攪拌しながらテトラメトキシシラン４３６．５ｇ（２．８７モル）を６時間かけて滴下した。この滴下が終了した後も、さらに０．５時間攪拌を継続して加水分解を行うことにより、親水性球状シリカ微粒子の懸濁液を得た。
<Example 1>
[Synthesis of organic resin-coated hydrophobic spherical silica fine particles]
-Step (A1): Step of synthesizing hydrophilic spherical silica fine particles-
In a 3 liter glass reactor equipped with a stirrer, a dropping funnel, and a thermometer, 989.5 g of methanol, 135.5 g of water, and 66.5 g of 28% aqueous ammonia were mixed. This solution was adjusted to 35 ° C., and 436.5 g (2.87 mol) of tetramethoxysilane was added dropwise over 6 hours while stirring. Even after the completion of the dropwise addition, the suspension was further stirred for 0.5 hours for hydrolysis to obtain a suspension of hydrophilic spherical silica fine particles.
−工程（Ａ２）：３官能性シラン化合物による表面処理工程−
上記で得られた懸濁液に室温でメチルトリメトキシシラン４．４ｇ（０．０３モル）を０．５時間かけて滴下し、滴下後も１２時間攪拌を継続し、シリカ微粒子表面を疎水化処理することにより、疎水化球状シリカ微粒子分散液を得た。
-Step (A2): Surface treatment step with trifunctional silane compound-
To the suspension obtained above, 4.4 g (0.03 mol) of methyltrimethoxysilane was added dropwise at room temperature over 0.5 hours, and stirring was continued for 12 hours after the addition to hydrophobize the silica fine particle surface. By processing, a hydrophobized spherical silica fine particle dispersion was obtained.
次いで、ガラス製反応器にエステルアダプターと冷却管とを取り付け、得られた分散液を６０〜７０℃に加熱してメタノールと水の混合物１０２１ｇを留去し、疎水化球状シリカ微粒子混合溶媒濃縮分散液を得た。このとき、濃縮分散液中の疎水化球状シリカ微粒子含有量は２８質量％であった。 Next, an ester adapter and a condenser tube are attached to a glass reactor, and the resulting dispersion is heated to 60 to 70 ° C. to distill off a mixture of methanol and water, and the concentrated dispersion of hydrophobic spherical silica fine particles is dispersed. A liquid was obtained. At this time, the content of hydrophobized spherical silica fine particles in the concentrated dispersion was 28% by mass.
−工程（Ａ３）：１官能性シラン化合物による表面処理工程−
前工程で得られた濃縮分散液に、室温において、ヘキサメチルジシラザン１３８．４ｇ（０．８６モル）を添加した後、この分散液を５０〜６０℃に加熱し、９時間反応させることにより、分散液中のシリカ微粒子をトリメチルシリル化した。次いで、この分散液中の溶媒を１３０℃、減圧下（６６５０Ｐａ）で留去することにより、疎水性球状シリカ微粒子（１）１８６ｇを得た。
-Step (A3): Surface treatment step with a functional silane compound-
By adding 138.4 g (0.86 mol) of hexamethyldisilazane to the concentrated dispersion obtained in the previous step at room temperature, the dispersion is heated to 50-60 ° C. and reacted for 9 hours. The silica fine particles in the dispersion were trimethylsilylated. Next, the solvent in this dispersion was distilled off at 130 ° C. under reduced pressure (6650 Pa) to obtain 186 g of hydrophobic spherical silica fine particles (1).
−工程（Ａ４）：有機樹脂による表面被覆処理工程−
次に、ニーダー中にＴＨＦ（テトラヒドロフラン）２５ｇ投入して攪拌しながら、上記（Ａ３）で得られた疎水性球状シリカ微粒子（１）１００ｇを加えて混合した。この混合物を混練しながら、スチレン−アクリル樹脂Ａの１０質量％ＴＨＦを５０ｇ滴下し、さらに混合した。その後乾燥させて、シリカ微粒子−（１）を１０３ｇを得た。
-Step (A4): Surface coating treatment step with organic resin-
Next, 25 g of THF (tetrahydrofuran) was added to the kneader and 100 g of the hydrophobic spherical silica fine particles (1) obtained in the above (A3) were added and mixed while stirring. While kneading this mixture, 50 g of 10% by mass THF of styrene-acrylic resin A was added dropwise and further mixed. Thereafter, drying was performed to obtain 103 g of silica fine particles- (1).
工程（Ａ１）で得られた親水性球状シリカ微粒子について下記の測定方法１に従って測定を行った。また、上記の工程（Ａ１）〜（Ａ４）の各段階を経て得られた有機樹脂被覆疎水性球状シリカ微粒子について、下記の測定方法１、２に従って測定を行った。なお、得られた結果を表１に示す。 The hydrophilic spherical silica fine particles obtained in the step (A1) were measured according to the following measuring method 1. Further, the organic resin-coated hydrophobic spherical silica fine particles obtained through the respective steps (A1) to (A4) were measured according to the following measurement methods 1 and 2. The obtained results are shown in Table 1.
［測定方法１］
−シリカ微粒子の粒子径測定−
メタノールにシリカ微粒子懸濁液又はシリカ微粒子粉体を、シリカ微粒子が０．５質量％となるように添加し、１０分間超音波にかけることにより、該微粒子を分散させた。このように処理した微粒子の粒度分布を、動的光散乱法／レーザードップラー法ナノトラック粒度分布測定装置（日機装株式会社製、商品名：ＵＰＡ−ＥＸ１５０）により測定し、その体積基準メジアン径を粒子径とした。なお、メジアン径とは粒度分布を累積分布として表した時の累積５０％に相当する粒子径である。
[Measurement method 1]
-Particle size measurement of silica fine particles-
Silica fine particle suspension or silica fine particle powder was added to methanol so that the silica fine particle was 0.5 mass%, and the fine particles were dispersed by applying ultrasonic waves for 10 minutes. The particle size distribution of the fine particles treated in this way is measured with a dynamic light scattering method / laser Doppler nanotrack particle size distribution measuring device (trade name: UPA-EX150, manufactured by Nikkiso Co., Ltd.), and the volume-based median diameter is measured as particles. The diameter. The median diameter is a particle diameter corresponding to 50% cumulative when the particle size distribution is expressed as a cumulative distribution.
［測定方法２］
−有機樹脂被覆疎水性球状シリカ微粒子の形状測定−
電子顕微鏡（日立製作所製、商品名：Ｓ−４７００型、倍率：１０万倍）によって観察を行い、形状を確認した。「球状」とは、真球だけでなく、若干歪んだ球も含む。
[Measurement method 2]
-Shape measurement of organic resin-coated hydrophobic spherical silica particles-
The shape was confirmed by observation with an electron microscope (manufactured by Hitachi, trade name: S-4700 type, magnification: 100,000 times). The term “spherical” includes not only a true sphere but also a slightly distorted sphere.
＜実施例２＞
工程（Ａ１）でメタノール、水、及び２８％アンモニア水の量をメタノール１０４５．７ｇ、水１１２．６ｇ、２８％アンモニア水３３．２ｇに変えたこと以外は実施例１と同様にして、シリカ微粒子−（２）１０４ｇを得た。得られた有機樹脂被覆疎水性球状シリカ微粒子を用いて実施例１と同様に測定した。この結果を表１に示す。
<Example 2>
Silica fine particles in the same manner as in Example 1 except that the amounts of methanol, water, and 28% ammonia water were changed to 1045.7 g of methanol, 112.6 g of water, and 33.2 g of 28% ammonia water in step (A1). -104 g of (2) was obtained. Measurement was performed in the same manner as in Example 1 using the obtained organic resin-coated hydrophobic spherical silica fine particles. The results are shown in Table 1.
＜実施例３＞
撹拌機、滴下ロート、温度計を備えた３リットルのガラス製反応器にメタノール６２３．７ｇ、水４１．４ｇ、２８％アンモニア水４９．８ｇを添加して混合した。この溶液を３５℃に調整し、撹拌しながらテトラメトキシシラン１１６３．７ｇおよび５．４％アンモニア水４１８．１ｇを同時に添加開始し、前者は６時間、そして後者は４時間かけて滴
下した。テトラメトキシシラン滴下後も０．５時間撹拌を続け加水分解を行いシリカ微粒子の懸濁液を得た。
<Example 3>
623.7 g of methanol, 41.4 g of water, and 49.8 g of 28% aqueous ammonia were added to and mixed with a 3 liter glass reactor equipped with a stirrer, a dropping funnel and a thermometer. The solution was adjusted to 35 ° C., and 1163.7 g of tetramethoxysilane and 418.1 g of 5.4% aqueous ammonia were simultaneously added with stirring. The former was added dropwise over 6 hours and the latter over 4 hours. After the tetramethoxysilane was dropped, the mixture was stirred for 0.5 hours for hydrolysis to obtain a silica fine particle suspension.
こうして得られた懸濁液に室温でメチルトリメトキシシラン１１．６ｇ（テトラメトキシシランに対してモル比で０．０１相当量）を０．５時間かけて滴下し、滴下後も１２時間撹拌しシリカ微粒子表面の処理を行った。 To the suspension thus obtained, 11.6 g of methyltrimethoxysilane (molar ratio of 0.01 equivalent to tetramethoxysilane) was added dropwise at room temperature over 0.5 hours and stirred for 12 hours after the addition. The surface of silica fine particles was treated.
該ガラス製反応器にエステルアダプターと冷却管を取り付け、上記の表面処理を施したシリカ微粒子を含む分散液にメチルイソブチルケトン１４４０ｇを添加した後、８０〜１１０℃に加熱しメタノール水を７時間かけて留去した。 An ester adapter and a condenser tube were attached to the glass reactor, and 1440 g of methyl isobutyl ketone was added to the dispersion containing silica fine particles subjected to the above surface treatment, and then heated to 80 to 110 ° C. and methanol water was added for 7 hours. Distilled off.
こうして得られた分散液に室温でヘキサメチルジシラザン３５７．６ｇを添加し１２０℃に加熱し３時間反応させ、シリカ微粒子をトリメチルシリル化した。その後溶媒を減圧下で留去して疎水性球状シリカ微粒子４７２ｇを得た。得られたシリカ微粒子１００ｇを実施例１と同様にスチレン−アクリル樹脂Ａの１０質量％ＴＨＦを５０ｇ滴下し、さらに混合した。その後乾燥させて、シリカ微粒子−（３）を得た。結果を表１に示す。 To the dispersion thus obtained, 357.6 g of hexamethyldisilazane was added at room temperature, heated to 120 ° C. and reacted for 3 hours to trimethylsilylate the silica fine particles. Thereafter, the solvent was distilled off under reduced pressure to obtain 472 g of hydrophobic spherical silica fine particles. 50 g of 10 mass% THF of styrene-acrylic resin A was added dropwise to 100 g of the obtained silica fine particles in the same manner as in Example 1, and further mixed. Thereafter, drying was performed to obtain silica fine particles- (3). The results are shown in Table 1.
＜実施例４＞
スチレン−アクリル樹脂Ａの１０質量％ＴＨＦを１５０ｇとした以外は、実施例３と同様に処理し、シリカ微粒子−（４）１０４ｇを得た。得られた有機樹脂被覆疎水性球状シリカ微粒子を用いて実施例１と同様に測定した。この結果を表１に示す。
<Example 4>
The same treatment as in Example 3 was conducted except that 10 g of THF of styrene-acrylic resin A was changed to 150 g, to obtain 104 g of silica fine particles (4). Measurement was performed in the same manner as in Example 1 using the obtained organic resin-coated hydrophobic spherical silica fine particles. The results are shown in Table 1.
＜実施例５＞
ガラス転移温度が１００℃のスチレン−アクリル樹脂Ｂの１０質量％ＴＨＦを５０ｇ用いた以外は、実施例３と同様に処理し、シリカ微粒子−（５）１０３ｇを得た。得られた有機樹脂被覆疎水性球状シリカ微粒子を用いて実施例１と同様に測定した。この結果を表１に示す。
<Example 5>
The same treatment as in Example 3 was carried out except that 50 g of 10% by mass of styrene-acrylic resin B having a glass transition temperature of 100 ° C. was used to obtain 103 g of silica fine particles (5). Measurement was performed in the same manner as in Example 1 using the obtained organic resin-coated hydrophobic spherical silica fine particles. The results are shown in Table 1.
＜比較例１〜６＞
実施例１〜３の有機樹脂被覆工程（Ａ４）を行わず、（Ａ３）工程で仕上げた疎水性球状シリカ粒子−（６）〜（８）を得た。更に実施例１〜３の（Ａ３）工程を行わずに仕上げた有機樹脂被覆シリカ粒子（９）〜（１１）を得た。
<Comparative Examples 1-6>
Hydrophobic spherical silica particles (6) to (8) finished in the step (A3) were obtained without performing the organic resin coating step (A4) in Examples 1 to 3. Furthermore, the organic resin-coated silica particles (9) to (11) finished without performing the step (A3) of Examples 1 to 3 were obtained.
＜注＞
１）工程（Ａ１）で得られた分散液の親水性球状シリカ微粒子
２）最終的に得られた有機樹脂被覆疎水性球状シリカ微粒子
<Note>
1) Hydrophilic spherical silica fine particles of dispersion obtained in step (A1) 2) Finally obtained organic resin-coated hydrophobic spherical silica fine particles
上記表に示すように、本発明方法によれば、有機樹脂被覆を行っても、元々のシリカ微粒子由来の形状を保つことが分かり、また、粒度分布を悪くすることはなかった。 As shown in the above table, according to the method of the present invention, it was found that even when organic resin coating was performed, the original shape derived from silica fine particles was maintained, and the particle size distribution was not deteriorated.
＜トナー帯電量、外添剤遊離率＞
上記得られた実施例１〜５、比較例１〜６［シリカ微粒子（１）〜（１１）］の有機樹脂被覆シリカ粒子のトナー帯電量、外添剤遊離率の測定を以下のように行った。
<Toner charge amount, external additive release rate>
The toner charge amount and external additive release rate of the organic resin-coated silica particles of Examples 1 to 5 and Comparative Examples 1 to 6 [Silica fine particles (1) to (11)] obtained above were measured as follows. It was.
（トナー帯電量の測定方法）
シリカ微粒子０．４ｇと負帯電性トナー（８μｍ）４０ｇとをミキサーにて攪拌混合してトナー組成物２ｇとし、これとフェライトキャリア４８ｇとをポリプロピレン容器（１００ｍｌ容量）に入れ、２５℃／５０％ＲＨ環境下（NN環境下）に２４時間放置する。２４時間放置したトナー組成物とフェライトキャリアの混合物をそれぞれターブラミキサーで１０分振とうする。このトナー組成物とフェライトキャリアの混合物から０．２ｇ採取し、ブローオフ帯電量測定装置（東芝ケミカル社製品：ＴＢ−２００型）で１分間窒素ブローした後の値をトナー組成物の帯電量とする。その結果を表２に示す。
また、その後それぞれターブラミキサーで更に２０分振とうする。トータル３０分振とう後の帯電量も表２に示す。
(Measurement method of toner charge)
0.4 g of silica fine particles and 40 g of negatively chargeable toner (8 μm) are stirred and mixed with a mixer to obtain 2 g of a toner composition. This and 48 g of ferrite carrier are placed in a polypropylene container (100 ml capacity) and 25 ° C./50%. Leave in an RH environment (NN environment) for 24 hours. The mixture of the toner composition and the ferrite carrier left for 24 hours is each shaken with a turbula mixer for 10 minutes. The amount obtained by taking 0.2 g from the toner composition and ferrite carrier mixture and blowing with nitrogen for 1 minute with a blow-off charge measuring device (product of Toshiba Chemical Co., Ltd .: Model TB-200) is taken as the charge amount of the toner composition. . The results are shown in Table 2.
After that, shake for another 20 minutes with a tumbler mixer. The charge amount after shaking for 30 minutes is also shown in Table 2.
（外添剤遊離率）
上記で得られた各トナー組成物におけるトナー粒子からのシリカ微粒子の離脱率Ｄ
を以下にしたがって測定した。トナー組成物２ｇに対し、界面活性剤（重合度１０のポリオキシエチレンオクチルフェニルエーテル）０．２ｗｔ％水溶液を充分に浸漬させ、超音波式ホモジナイザー（ＵＳ１２００Ｔ；日本精機製作所社製）を用いて、その分散液中に超音波振動子を浸し、周波数１５ＫＨｚ、出力４０Ｗで１分間超音波振動させることにより、トナー粒子表面から表面に付着させた微粒子外添剤を離脱させた。その後、分散液をデカンテーション（静置）により上澄み液と沈殿物（トナー）に分離し、離脱した添加剤粒子が含まれる上澄み液を除去した。沈殿物（トナー）を純水で穏やかに洗浄し、乾燥させた。乾燥したトナーを蛍光Ｘ線分析にかけ、トナー粒子表面に残存するシリカ微粒子の定量を行い、トナー粒子に添加されたシリカ微粒の重量に対し、離脱したシリカ微粒子の重量の比率（重量比）を離脱率Ｄとして算出し、下記のように判断した。その結果も表２に示す。
〔評価基準〕
○：離脱率Ｄの値が、２０％以下
△：離脱率Ｄの値が、２１％〜４５％
×：離脱率Ｄの値が、４６％以上
(External additive release rate)
Separation rate D of silica fine particles from toner particles in each toner composition obtained above
Was measured according to the following. A surfactant (polyoxyethylene octylphenyl ether having a polymerization degree of 10) in an amount of 0.2 wt% is sufficiently immersed in 2 g of the toner composition, and an ultrasonic homogenizer (US1200T; manufactured by Nippon Seiki Seisakusho Co., Ltd.) is used. An ultrasonic vibrator was immersed in the dispersion and subjected to ultrasonic vibration for 1 minute at a frequency of 15 KHz and an output of 40 W, whereby the fine particle external additive adhered to the surface was separated from the surface of the toner particles. Thereafter, the dispersion was separated into a supernatant and a precipitate (toner) by decantation (standing), and the supernatant containing the detached additive particles was removed. The precipitate (toner) was gently washed with pure water and dried. The dried toner is subjected to fluorescent X-ray analysis to determine the amount of silica particles remaining on the toner particle surface, and the ratio of the weight of the separated silica particles to the weight of the silica particles added to the toner particles is removed. It was calculated as a rate D and judged as follows. The results are also shown in Table 2.
〔Evaluation criteria〕
○: The value of the separation rate D is 20% or less. Δ: The value of the separation rate D is 21% to 45%.
X: The value of the withdrawal rate D is 46% or more
表２より、本発明の製造方法により製造された表面有機樹脂被覆疎水性球状シリカ微粒子（実施例１〜５）は、本発明の製造方法により製造されたものではない表面疎水化球状シリカ微粒子（比較例１〜６）と比べて帯電安定性つまり、高分散性、付着性が強いこと、また遊離率も少ないことが明らかとなった。 From Table 2, the surface organic resin-coated hydrophobic spherical silica fine particles (Examples 1 to 5) produced by the production method of the present invention were not produced by the production method of the present invention. As compared with Comparative Examples 1 to 6), it was revealed that the charging stability, that is, the high dispersibility and adhesion are strong, and the liberation rate is small.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.
Claims (5)
Ｓｉ（ＯＲ3）4 （Ｉ）
（但し、Ｒ3は同一又は異種の炭素原子数１〜６の一価炭化水素基である。）
で示される４官能性シラン化合物、その部分加水分解生成物又はこれらの混合物を、塩基性物質の存在下で親水性有機溶媒と水の混合液中で加水分解、縮合することによって、ＳｉＯ2単位を含む親水性球状シリカ微粒子の混合溶媒分散液を得る工程と、
（Ａ２）該親水性球状シリカ微粒子の混合溶媒分散液に、下記一般式（ＩＩ）：
Ｒ1Ｓｉ（ＯＲ4）3 （ＩＩ）
（但し、Ｒ1は置換又は非置換の炭素原子数１〜２０の一価炭化水素基であり、Ｒ4は同一又は異種の炭素原子数１〜６の一価炭化水素基である。）
で示される３官能性シラン化合物、その部分加水分解生成物又はこれらの混合物を添加して、前記親水性球状シリカ微粒子の表面を処理することにより、該親水性球状シリカ微粒子の表面にＲ1ＳｉＯ3/2単位（但し、Ｒ1は前記と同じである。）を導入し、第一の表面疎水化球状シリカ微粒子の混合溶媒分散液を得る工程と、
（Ａ３）該第一の表面疎水化球状シリカ微粒子の混合溶媒分散液又はその濃縮液に下記一般式（ＩＩＩ）：
Ｒ2 3ＳｉＮＨＳｉＲ2 3 （ＩＩＩ）
（但し、Ｒ2は同一又は異種の置換又は非置換の炭素原子数１〜６の一価炭化水素基である）
で示されるシラザン化合物、
下記一般式（ＩＶ）：
Ｒ2 3ＳｉＸ （ＩＶ）
（但し、Ｒ2は同一又は異種の置換又は非置換の炭素原子数１〜６の一価炭化水素基であり、ＸはＯＨ基又は加水分解性基である。）
で示される１官能性シラン化合物又はこれらの混合物を添加し、該第一の表面疎水化球状シリカ微粒子の表面を処理して、該第一の表面疎水化球状シリカ微粒子の表面にＲ2 3ＳｉＯ1/2単位（但し、Ｒ2は前記と同じである。）を導入することにより第二の疎水性球状シリカ微粒子を得る工程と、
（Ａ４）該第二の疎水性球状シリカ微粒子の分散液に、ガラス転移温度が６５〜１２０℃の有機樹脂を溶解せしめ、該第二の疎水性球状シリカ微粒子の表面の少なくとも一部に有機樹脂被覆を形成して有機樹脂被覆疎水性球状シリカ微粒子を得る工程と、
を有することを特徴とする請求項１に記載の表面有機樹脂被覆疎水性球状シリカ微粒子の製造方法。 (A1) The following general formula (I):
Si (OR 3 ) 4 (I)
(However, R 3 is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms.)
By hydrolyzing and condensing a tetrafunctional silane compound represented by the formula, a partial hydrolysis product thereof or a mixture thereof in a mixture of a hydrophilic organic solvent and water in the presence of a basic substance, SiO 2 unit Obtaining a mixed solvent dispersion of hydrophilic spherical silica fine particles comprising:
(A2) In the mixed solvent dispersion of the hydrophilic spherical silica fine particles, the following general formula (II):
R 1 Si (OR 4 ) 3 (II)
(However, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 4 is the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms.)
Is added to the surface of the hydrophilic spherical silica fine particles to add R 1 SiO to the surface of the hydrophilic spherical silica fine particles. Introducing 3/2 units (where R 1 is as defined above) to obtain a mixed solvent dispersion of the first surface-hydrophobized spherical silica fine particles;
(A3) A mixed solvent dispersion of the first surface-hydrophobized spherical silica fine particles or a concentrated liquid thereof has the following general formula (III):
R 2 3 SiNHSiR 2 3 (III)
(Wherein R 2 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms)
A silazane compound represented by
The following general formula (IV):
R 2 3 SiX (IV)
(Wherein R 2 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and X is an OH group or a hydrolyzable group.)
A monofunctional silane compound represented by the formula (1) or a mixture thereof is added, and the surface of the first surface hydrophobized spherical silica fine particles is treated to form R 2 3 SiO on the surface of the first surface hydrophobized spherical silica fine particles. A step of obtaining second hydrophobic spherical silica fine particles by introducing 1/2 unit (wherein R 2 is the same as above);
(A4) An organic resin having a glass transition temperature of 65 to 120 ° C. is dissolved in the dispersion liquid of the second hydrophobic spherical silica fine particles, and the organic resin is formed on at least a part of the surface of the second hydrophobic spherical silica fine particles. Forming an organic resin-coated hydrophobic spherical silica fine particle by forming a coating;
The method for producing surface-organic-resin-coated hydrophobic spherical silica fine particles according to claim 1, wherein:
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| CN115304404A (en) * | 2022-07-27 | 2022-11-08 | 航天特种材料及工艺技术研究所 | SiO (silicon dioxide) 2f /SiO 2 Composite hydrophobic coating and preparation method thereof |
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