JP7406354B2 - Surface treatment precipitated silica for water-based paints - Google Patents

Surface treatment precipitated silica for water-based paints Download PDF

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JP7406354B2
JP7406354B2 JP2019209954A JP2019209954A JP7406354B2 JP 7406354 B2 JP7406354 B2 JP 7406354B2 JP 2019209954 A JP2019209954 A JP 2019209954A JP 2019209954 A JP2019209954 A JP 2019209954A JP 7406354 B2 JP7406354 B2 JP 7406354B2
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precipitated silica
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JP2021080393A (en
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遥 谷本
英紀 中上
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Tosoh Silica Corp
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Priority to KR1020227005321A priority patent/KR102645214B1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/159—Coating or hydrophobisation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Silicon Compounds (AREA)
  • Paints Or Removers (AREA)

Description

本発明は、水性塗料の艶消し剤として使用される表面処理沈降シリカに関する。詳細には、水性塗料に直接添加しても凝集を起こすこと無く短時間で濡れることができ、経時変化によって沈澱しても再分散性が良好な表面処理シリカに関する。 The present invention relates to surface-treated precipitated silica used as a matting agent in water-based paints. In particular, it relates to surface-treated silica that can be added directly to water-based paints without causing aggregation and can be wetted in a short time, and that has good redispersibility even if it precipitates over time.

沈降シリカ(precipitated silica)は、ゲルシリカとともに湿式法シリカに大別される非晶質合成シリカの1種である。沈降シリカが塗料の艶消し剤として使用されていることは知られており、特に粉砕や分級等の処理によってミクロンサイズ制御された沈降シリカは金属塗料やプラスチック塗料の艶消し剤として広く利用されている。一方で、それらのシリカに表面処理を施して特定の機能を持たせた塗料用の表面処理シリカも知られている。例えば、特許文献1では、湿式法シリカを多鎖型非イオン界面活性剤で表面処理することにより、塗料中で沈澱しても再分散性が良好な表面処理シリカが開示されている。特許文献2では、特定の細孔容積を有する非晶質シリカに一定量のポリエチレンワックスを被覆した艶消し剤が開示されている。 Precipitated silica is a type of amorphous synthetic silica that is broadly classified into wet process silica along with gel silica. It is known that precipitated silica is used as a matting agent for paints, and in particular, precipitated silica whose micron size has been controlled through processes such as crushing and classification is widely used as a matting agent for metal paints and plastic paints. There is. On the other hand, surface-treated silica for paints is also known, which is obtained by subjecting such silica to surface treatment to give it a specific function. For example, Patent Document 1 discloses surface-treated silica that has good redispersibility even if it precipitates in a paint by surface-treating wet-process silica with a multi-chain nonionic surfactant. Patent Document 2 discloses a matting agent in which amorphous silica having a specific pore volume is coated with a certain amount of polyethylene wax.

特開平9-25440号公報Japanese Patent Application Publication No. 9-25440 特表平11-512124号公報Special Publication No. 11-512124

近年、人の呼吸器官に有害な影響を及ぼすとして、大気中に排出されるVOCの規制がより厳しくなり、また、環境への配慮からも、人体に有害な溶剤を使用した塗料から、水性或いは溶剤を使用しない無溶剤の塗料へと変化しつつある。これに伴い、艶消し剤として使用されるシリカも水性に適したものが求められるようになっている。 In recent years, regulations on VOCs emitted into the atmosphere have become stricter due to their harmful effects on human respiratory organs, and due to environmental considerations, paints that use solvents that are harmful to the human body are being replaced with water-based or There is a shift towards solvent-free paints that do not use solvents. Along with this, silica used as a matting agent is also required to be water-based.

特許文献1の表面処理シリカは、溶剤塗料用としては再分散性等良好であるが、水性塗料に使用した場合は、シリカ同士が凝集沈澱を起こしてハードケークを形成し再分散出来ない状態になる問題があった。 The surface-treated silica of Patent Document 1 has good redispersibility when used in solvent-based paints, but when used in water-based paints, the silica coagulates with each other to form a hard cake, making it impossible to redisperse. There was a problem.

特許文献2の艶消し剤は、溶剤を使用しない（又は低溶剤の）UV硬化型の塗料用としては良好な艶消し性能を有するが、表面処理剤のワックスが水に馴染まないので水性塗料には十分に分散せず、艶消し効果を発揮出来ない問題があった。 The matting agent of Patent Document 2 has good matting performance for UV-curable paints that do not use solvents (or low solvents), but it is not suitable for water-based paints because the wax of the surface treatment agent is not compatible with water. There was a problem in that it was not sufficiently dispersed and could not produce a matting effect.

艶消し剤として沈降シリカを水性塗料に直接添加した場合、沈降シリカが凝集を起こして塗料中で分散せず、所謂ブツを発生する、或いは経時で沈澱してハードケークを形成するなどの問題がある。そのため、一般に、シリカ艶消し剤は予め濃度10～20％程度のシリカ分散液を調製しておき、必要に応じて樹脂や顔料等が入った水性塗料に添加して使用されている。 When precipitated silica is added directly to water-based paints as a matting agent, there are problems such as the precipitated silica coagulating and not being dispersed in the paint, causing so-called lumps, or settling over time to form a hard cake. be. Therefore, silica matting agents are generally used by preparing a silica dispersion liquid with a concentration of about 10 to 20% in advance and adding it to water-based paints containing resins, pigments, etc. as necessary.

しかし、溶剤塗料とは異なり、水性塗料へ濃度10～20％程度のシリカ分散液を添加すると、塗料全体が希釈されて低濃度の塗料になってしまうため、塗膜厚の変化や、乾燥に要する時間およびエネルギーが溶剤塗料と比べて増加するなどの問題があった。さらに工数削減という観点からもシリカ分散液を調製する工程は無い方が好ましいとされている。 However, unlike solvent paints, when a silica dispersion with a concentration of 10 to 20% is added to water-based paints, the entire paint is diluted and becomes a low-concentration paint, resulting in changes in film thickness and drying problems. There were problems such as increased time and energy required compared to solvent paints. Furthermore, from the viewpoint of reducing the number of man-hours, it is said that it is preferable not to include the step of preparing the silica dispersion.

そこで本発明が解決すべき課題は、水性塗料に粉体のまま直接添加しても凝集を起こすこと無く短時間で濡れることができ、かつ経時により沈澱しても再分散性が良好な表面処理シリカを開発することであり、これらの課題を解決した表面処理シリカを提供することを本発明の目的とする。 Therefore, the problem to be solved by the present invention is to provide a surface treatment that can be added directly to a water-based paint as a powder without causing agglomeration and can be wetted in a short time, and that has good redispersibility even if it settles over time. It is an object of the present invention to develop silica and to provide surface-treated silica that solves these problems.

本発明者らは、上記課題を解決するために、水性塗料に直接添加しても凝集を起こすこと無く短時間で濡れることができ、かつ経時変化によって沈澱しても再分散性が良好な表面処理シリカの開発について鋭意検討した。その結果、アルミニウムを一定量含有した所定の沈降シリカの表面をエーテル系非イオン界面活性剤で処理したシリカが有効であることを見出して本発明を完成した。とりわけ、ポリオキシアルキレンアルキルエーテル非イオン界面活性剤で処理を行えば、経時により沈澱しても再分散性が特に良好である。 In order to solve the above problems, the present inventors have developed a surface that can be wetted in a short time without causing agglomeration even when directly added to a water-based paint, and that has good redispersibility even if sedimentation occurs over time. The development of treated silica was intensively studied. As a result, the present invention was completed by discovering that silica obtained by treating the surface of a predetermined precipitated silica containing a certain amount of aluminum with an ether-based nonionic surfactant is effective. In particular, when treated with a polyoxyalkylene alkyl ether nonionic surfactant, redispersibility is particularly good even if precipitation occurs over time.

本発明は以下の通りである。
［１］
沈降シリカの表面に0.5～5.0％のエーテル系非イオン界面活性剤を有する、水性塗料用表面処理沈降シリカであって、前記表面処理沈降シリカは、アルミニウム含有量がAl2O3換算で0.30～1.00質量％の範囲にあり、レーザー回折法による体積平均粒子径D50が3.0～10.0μmの範囲であり、かつレーザー回折法で測定した粒度分布における下位からの体積積算累積値の90％である粒子径D90とD50との比D90/D50が2.0以下である、前記表面処理沈降シリカ。
［２］
前記表面処理沈降シリカはBET比表面積が60～280m2/gの範囲である、［１］に記載の表面処理沈降シリカ。
［３］
前記エーテル系非イオン界面活性剤が、ポリオキシアルキレンアルキルエーテル非イオン界面活性剤である、［１］又は［２］に記載の表面処理沈降シリカ。
［４］
前記エーテル系非イオン界面活性剤は、HLBが10.0～15.0の範囲である、［１］～［３］のいずれかに記載の表面処理沈降シリカ。
［５］
前記表面処理沈降シリカは、加熱減量が9.0％以下であり、見掛比重が0.05～0.30g/mLの範囲にある、［１］～［４］のいずれかに記載の表面処理沈降シリカ。 The invention is as follows.
[1]
A surface-treated precipitated silica for water-based paints having 0.5 to 5.0% of an ether nonionic surfactant on the surface of the precipitated silica, wherein the surface-treated precipitated silica has an aluminum content of 0.30 to 0.30 in terms of Al 2 O 3 Particles that are in the range of 1.00% by mass, have a volume average particle diameter D50 of 3.0 to 10.0 μm as measured by laser diffraction, and are 90% of the volume cumulative value from the bottom in the particle size distribution measured by laser diffraction. The surface-treated precipitated silica has a diameter D90 to D50 ratio D90/D50 of 2.0 or less.
[2]
The surface-treated precipitated silica according to [1], wherein the surface-treated precipitated silica has a BET specific surface area in the range of 60 to 280 m 2 /g.
[3]
The surface-treated precipitated silica according to [1] or [2], wherein the ether-based nonionic surfactant is a polyoxyalkylene alkyl ether nonionic surfactant.
[4]
The surface-treated precipitated silica according to any one of [1] to [3], wherein the ether type nonionic surfactant has an HLB in the range of 10.0 to 15.0.
[5]
The surface-treated precipitated silica according to any one of [1] to [4], wherein the surface-treated precipitated silica has a heating loss of 9.0% or less and an apparent specific gravity in the range of 0.05 to 0.30 g/mL.

本発明によれば、水性塗料に直接添加しても凝集を起こすことなく短時間で濡れることができ、経時により沈澱しても再分散性が良好な表面処理沈降シリカを提供することができ、この表面処理沈降シリカは、水性塗料の艶消し剤として有用である。 According to the present invention, it is possible to provide surface-treated precipitated silica that can be wetted in a short time without causing agglomeration even when directly added to a water-based paint, and has good redispersibility even if it settles over time, This surface-treated precipitated silica is useful as a matting agent in water-based paints.

本発明の表面処理沈降シリカは、沈降シリカの表面に0.5～5.0％のエーテル系非イオン界面活性剤を有する、水性塗料用表面処理沈降シリカであって、前記表面処理沈降シリカは、アルミニウム含有量がAl2O3換算で0.30～1.00質量％の範囲にあり、レーザー回折法による体積平均粒子径D50が3.0～10.0μmの範囲であり、かつレーザー回折法で測定した粒度分布における下位からの体積積算累積値の90％である粒子径D90とD50との比D90/D50が2.0以下である。本発明の表面処理沈降シリカは、水性塗料用であり、水性塗料の艶消し剤として有用である。本発明での水性塗料は、水溶性樹脂塗料およびディスパージョン塗料、エマルジョン塗料を指す。 The surface-treated precipitated silica of the present invention is a surface-treated precipitated silica for water-based paints that has 0.5 to 5.0% of an ether-based nonionic surfactant on the surface of the precipitated silica, and the surface-treated precipitated silica has an aluminum content. is in the range of 0.30 to 1.00 mass% in terms of Al 2 O 3 , the volume average particle diameter D50 by laser diffraction is in the range of 3.0 to 10.0 μm, and the volume from the bottom in the particle size distribution measured by laser diffraction is The ratio D90/D50 between particle diameter D90 and D50, which is 90% of the integrated cumulative value, is 2.0 or less. The surface-treated precipitated silica of the present invention is for water-based paints and is useful as a matting agent for water-based paints. The water-based paint in the present invention refers to a water-soluble resin paint, a dispersion paint, and an emulsion paint.

本発明の表面処理沈降シリカは、アルミニウム含有量がAl2O3換算で0.30～1.00質量％の範囲にある。アルミニウム含有量がAl2O3換算で0.30質量％未満のアルミニウムが少ない沈降シリカの場合、水、特に工業用水などミネラルを含んだ水に馴染みにくく、たとえエーテル系非イオン界面活性剤で表面処理しても塗料が増粘しかつ沈澱し易くなる等の問題がある。一方、アルミニウム含有量がAl2O3換算で1.00質量％ 超の沈降シリカの場合、沈降シリカの湿式合成の際にアルミニウムを多く添加する必要がある。しかし、アルミニウムを多く添加すると、合成途中のシリカの凝集が強くなるために得られる沈降シリカ粒子が硬くなりすぎて、粉砕しても粗大粒子が残ってしまう。さらに、アルミニウム含有量がAl2O3換算で1.00質量％ 超の沈降シリカをエーテル系非イオン界面活性剤で表面処理しても凝集粒子が経時沈澱し易くなる。 The surface-treated precipitated silica of the present invention has an aluminum content in the range of 0.30 to 1.00% by mass in terms of Al 2 O 3 . In the case of precipitated silica with low aluminum content, which has an aluminum content of less than 0.30% by mass in terms of Al 2 O 3 , it is difficult to be compatible with water, especially water containing minerals such as industrial water, and even if the surface is treated with an ether-based nonionic surfactant, However, there are problems such as the paint becoming thicker and more likely to precipitate. On the other hand, in the case of precipitated silica having an aluminum content of more than 1.00% by mass in terms of Al 2 O 3 , it is necessary to add a large amount of aluminum during wet synthesis of the precipitated silica. However, if a large amount of aluminum is added, the agglomeration of silica during synthesis becomes stronger, resulting in the resulting precipitated silica particles becoming too hard, and coarse particles remaining even after pulverization. Furthermore, even if precipitated silica with an aluminum content of more than 1.00% by mass calculated as Al 2 O 3 is surface-treated with an ether nonionic surfactant, aggregated particles tend to settle over time.

アルミニウム含有量(Al2O3換算)は、好ましくは0.40～0.90質量％ の範囲、より好ましくは0.45～0.85質量％の範囲である。 The aluminum content (in terms of Al 2 O 3 ) is preferably in the range of 0.40 to 0.90% by mass, more preferably in the range of 0.45 to 0.85% by mass.

表面処理沈降シリカとしたときに上記範囲のアルミニウム含有量となる沈降シリカの調製は、常法で行うことができ、常法におけるアルミニウムの添加方法には、特に限定はない。但し、表面処理沈降シリカを水性塗料に添加して用いることを考慮すると、塗料中の他の添加剤との相互作用を引き起こさないという観点では、沈降シリカへのアルミニウムの添加は表面処理による添加ではなく、沈降シリカの湿式合成時に、合成原料に添加するか、または合成途中に添加することが好ましい。 Precipitated silica having an aluminum content within the above range when surface-treated precipitated silica can be prepared by a conventional method, and there are no particular limitations on the method of adding aluminum in the conventional method. However, considering that surface-treated precipitated silica is used by adding it to water-based paints, from the viewpoint of not causing interaction with other additives in the paint, aluminum cannot be added to precipitated silica by surface treatment. Rather, it is preferable to add it to the synthesis raw materials during the wet synthesis of precipitated silica, or to add it during the synthesis.

本発明の表面処理沈降シリカは、レーザー回折法による体積平均粒子径D50が3.0～10.0μmの範囲であり、かつレーザー回折法で測定した粒度分布における下位からの体積積算累積値の90％である粒子径D90とD50との比D90/D50が2.0以下である。D50が3.0～10.0μmの範囲であり、かつ比D90/D50が2.0以下である表面処理沈降シリカであれば、艶消し剤としての所望の機能を十分に発揮できる。D50が3.0μm未満の場合は、粒子径が小さすぎるためにシリカ粒子が塗膜に埋もれてしまい、十分な艶消し効果を得ることができない。D50が10.0μmより大きい場合は、塗膜表面がざらつき、意匠を損なうため艶消し用途には適さない。比D90/D50が2.0より大きくなると、水性塗料に本発明の表面処理沈降シリカを直接添加した場合、凝集沈澱を発生することや、塗料中でのいわゆるブツ発生要因となる。D50は、好ましくは3.5～9.0μmの範囲である。比D90/D50の下限は、特に限定はないが、例えば、0.5であり、好ましくは1.0である。比D90/D50は、好ましくは1.2～2.0、より好ましくは1.4～1.9の範囲である。 The surface-treated precipitated silica of the present invention has a volume average particle diameter D50 of 3.0 to 10.0 μm as measured by laser diffraction, and is 90% of the volume cumulative value from the bottom in the particle size distribution measured by laser diffraction. The ratio D90/D50 between particle diameter D90 and D50 is 2.0 or less. A surface-treated precipitated silica having a D50 in the range of 3.0 to 10.0 μm and a ratio D90/D50 of 2.0 or less can sufficiently exhibit the desired function as a matting agent. When D50 is less than 3.0 μm, the particle size is too small and the silica particles are buried in the coating film, making it impossible to obtain a sufficient matting effect. If D50 is larger than 10.0 μm, the coating surface becomes rough and the design is impaired, making it unsuitable for matte applications. When the ratio D90/D50 is greater than 2.0, when the surface-treated precipitated silica of the present invention is directly added to an aqueous paint, it may cause agglomerated sedimentation or cause so-called lumps in the paint. D50 preferably ranges from 3.5 to 9.0 μm. The lower limit of the ratio D90/D50 is, for example, 0.5, preferably 1.0, although there is no particular limitation. The ratio D90/D50 preferably ranges from 1.2 to 2.0, more preferably from 1.4 to 1.9.

本発明の表面処理沈降シリカは、沈降シリカの表面に0.5～5.0％のエーテル系非イオン界面活性剤を有する。エーテル系非イオン界面活性剤の量が少ないと浸透効果（以下、湿潤性）が少なく、多いと溶出して塗料に悪影響を及ぼすので上記範囲とする。エーテル系非イオン界面活性剤の量は、好ましくは1.0～4.0％、さらに好ましくは2.0～3.0％の範囲である。 The surface-treated precipitated silica of the present invention has 0.5 to 5.0% of an ether type nonionic surfactant on the surface of the precipitated silica. If the amount of the ether type nonionic surfactant is small, the permeation effect (hereinafter referred to as wettability) will be small, and if the amount is large, it will elute and adversely affect the paint, so it is set in the above range. The amount of ether type nonionic surfactant is preferably in the range of 1.0 to 4.0%, more preferably 2.0 to 3.0%.

本発明においてエーテル系非イオン界面活性剤は、水への湿潤性が良好でかつ塗料中の樹脂成分や他に添加する顔料や添加剤に対しても実質的に影響を及ぼさないので有効である。特に、本発明者らが多くのエーテル系非イオン界面活性剤について調査した結果、ポリオキシアルキレンアルキルエーテル類で良好な結果が得られた。この理由は定かではなくこの理由に拘泥する意図はないが、ポリオキシアルキレン部がシリカ表面と適切に親和するため良好な結果が得られたと推測される。ポリオキシアルキレンアルキルエーテル類のより具体的な例を以下に挙げる。以下の例はいずれも市販品として入手可能である。ポリオキシアルキレン分岐デシルエーテル（ノイゲンXL、ノイゲンLF：ポリオキシアルキレン部分はポリオキシ短鎖アルキレンとポリオキシエチレンの重合体よりなる。第一工業製薬社製など）、ポリオキシエチレンイソデシルエーテル（ノイゲンSD：第一工業製薬社製など）、ポリオキシエチレンラウリルエーテル（DKSNL：第一工業製薬社製など）、ポリオキシエチレントリデシルエーテル（ノイゲンTDS：第一工業製薬社製など）、ポリオキシアルキレントリデシルエーテル（ノイゲンTDX：ポリオキシアルキレン部分はポリオキシプロピレンとポリオキシエチレンの重合体よりなる。第一工業製薬社製など）、ポリオキシエチレンポリオキシプロピレンアルキルエーテル（エマルゲンLS：花王社製、ペポールAS：東邦化学工業社製など）、ポリオキシエチレンアルキルエーテル（ナロアクティーCL、三洋化成工業社製など）、ポリオキシエチレン2-エチルヘキシルエーテル（ニューコール1000系：日本乳化剤社製など）、ポリオキシエチレンセチルエーテル（ニューコール1600系：日本乳化剤社製など）、ポリオキシエチレンオレイルエーテル（エマルゲン408：花王社製、ニューコール1200系：日本乳化剤社製など）などが挙げられる。 In the present invention, ether type nonionic surfactants are effective because they have good water wettability and do not substantially affect resin components in paints or other pigments and additives. . In particular, as a result of the inventors' investigation of many ether-based nonionic surfactants, good results were obtained with polyoxyalkylene alkyl ethers. Although the reason for this is not clear and there is no intention to be bound by this reason, it is presumed that the good results were obtained because the polyoxyalkylene moiety has an appropriate affinity with the silica surface. More specific examples of polyoxyalkylene alkyl ethers are listed below. All of the following examples are commercially available. Polyoxyalkylene branched decyl ether (Noigen XL, Noigen LF: The polyoxyalkylene portion consists of a polymer of polyoxy short-chain alkylene and polyoxyethylene. Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., etc.), polyoxyethylene isodecyl ether (Noigen SD) : manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene lauryl ether (DKSNL: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., etc.), polyoxyethylene tridecyl ether (Neugen TDS: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., etc.), polyoxyalkylene tridecane Decyl ether (Neugen TDX: The polyoxyalkylene part is made of a polymer of polyoxypropylene and polyoxyethylene. Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., etc.), polyoxyethylene polyoxypropylene alkyl ether (Emulgen LS: Kao Corporation, Pepol) AS: manufactured by Toho Chemical Industries, Ltd., etc.), polyoxyethylene alkyl ether (NAROACTY CL, manufactured by Sanyo Chemical Industries, Ltd., etc.), polyoxyethylene 2-ethylhexyl ether (Nukol 1000 series: manufactured by Nippon Nyukazai Co., Ltd., etc.), polyoxy Examples include ethylene cetyl ether (Nukol 1600 series: manufactured by Nippon Nyukazai Co., Ltd., etc.), polyoxyethylene oleyl ether (Emulgen 408: manufactured by Kao Corporation, Nucol 1200 series: manufactured by Nippon Nyukazai Co., Ltd., etc.).

これらのうち、ノイゲンXL-61（ポリオキシエチレントリデシルエーテル。HLB：13）、エマルゲンLS-106（ポリオキシエチレンポリオキシプロピレンアルキルエーテル。HLB：13）などを使用することが本発明には好ましい。 Among these, it is preferable for the present invention to use Neugen XL-61 (polyoxyethylene tridecyl ether. HLB: 13), Emulgen LS-106 (polyoxyethylene polyoxypropylene alkyl ether. HLB: 13), etc. .

本発明の表面処理沈降シリカは、沈降シリカの表面にエーテル系非イオン界面活性剤を提供する方法により調製することができ、そのような調製方法(処理方法)としては、沈降シリカと界面活性剤を高速流動ミキサー等で混合する乾式処理法、またはシリカスラリーに界面活性剤溶液を混合し乾燥を行う湿式処理法などを挙げることができる。但し、処理方法に限定はない。乾式処理法における混合方法にはFMミキサーやアキシャルミキサーなどを用いることができる。湿式処理法における乾燥方法にはスピンフラッシュドライヤー(SFD)やスプレードライヤー(SD)などがあるが、瞬間乾燥が可能であるSDが好ましい。 The surface-treated precipitated silica of the present invention can be prepared by a method of providing an ether-based nonionic surfactant on the surface of precipitated silica, and such a preparation method (treatment method) includes the following: Examples include a dry processing method in which a surfactant solution is mixed with a silica slurry using a high-speed fluid mixer, and a wet processing method in which a surfactant solution is mixed with a silica slurry and dried. However, there are no limitations on the processing method. For the mixing method in the dry processing method, an FM mixer, an axial mixer, etc. can be used. Drying methods in the wet processing method include a spin flash dryer (SFD) and a spray dryer (SD), but SD is preferred because it allows instant drying.

エーテル系非イオン界面活性剤のHLBが低いと、界面活性剤が水と混ざりにくいため、表面処理沈降シリカになったときに湿潤効果が低下する傾向がある。エーテル系非イオン界面活性剤のHLBが高いと親水性が高くなり、処理後のシリカ表面から界面活性剤が溶液側(塗料側)に脱離しやすくなり、効果が低下する傾向がある。このような観点から、エーテル系非イオン界面活性剤は、HLBが、好ましくは10.0～15.0、より好ましくは11.0～14.0、さらに好ましくは11.0～13.0の範囲である。 When the HLB of an ether type nonionic surfactant is low, the surfactant is difficult to mix with water, so the wetting effect tends to decrease when surface-treated precipitated silica is formed. When the HLB of an ether type nonionic surfactant is high, its hydrophilicity becomes high, and the surfactant tends to be easily desorbed from the treated silica surface to the solution side (paint side), which tends to reduce its effectiveness. From this viewpoint, the HLB of the ether type nonionic surfactant is preferably in the range of 10.0 to 15.0, more preferably 11.0 to 14.0, and still more preferably 11.0 to 13.0.

本発明の表面処理沈降シリカは、BET比表面積が60～280m2/gの範囲であることが好ましい。ここでのBET比表面積は、表面処理後のシリカ(表面処理沈降シリカ)のBET比表面積を指し、60m2/g以上であることで、シリカの艶消し効果がより大きくなる。280m2/g以下であることで、沈降シリカの製造が容易であり、シリカ一次粒子同士の凝集力も強過ぎず水性塗料に添加しても沈澱し難い表面処理沈降シリカが得られる。 The surface-treated precipitated silica of the present invention preferably has a BET specific surface area in the range of 60 to 280 m 2 /g. The BET specific surface area here refers to the BET specific surface area of silica after surface treatment (surface treated precipitated silica), and when it is 60 m 2 /g or more, the matting effect of silica becomes greater. When the amount is 280 m 2 /g or less, it is easy to produce precipitated silica, and the cohesive force between primary silica particles is not too strong, so surface-treated precipitated silica is obtained that is difficult to precipitate even when added to a water-based paint.

本発明の表面処理沈降シリカは、加熱減量が好ましくは9.0％以下である。加熱減量が小さいほど、艶消しに有効なシリカ分が多くなるので好ましい。本発明の表面処理沈降シリカは、見掛け比重が好ましくは0.05～0.30 g/mLの範囲である。見掛け比重がこの範囲であることで、ハンドリングが良好(比重がある程度大きいため)であり、沈澱した際にハードケークを形成し難い(比重が大き過ぎないため)という利点がある。 The surface-treated precipitated silica of the present invention preferably has a heat loss of 9.0% or less. The smaller the loss on heating is, the more silica content that is effective for matting increases, which is preferable. The surface-treated precipitated silica of the present invention preferably has an apparent specific gravity in the range of 0.05 to 0.30 g/mL. When the apparent specific gravity is within this range, it has the advantage of being easy to handle (because the specific gravity is high to some extent) and hard to form a hard cake when precipitated (because the specific gravity is not too high).

本発明の表面処理沈降シリカは、市販の水性塗料に好適に使用することができる。水性塗料は、ベースとなる水溶性樹脂塗料またはディスパージョン塗料またはエマルジョン塗料に、必要に応じて、着色用の顔料、添加剤などが配合されている。水性塗料の固形分濃度は10～50％、粘度は数十～数千センチポイズに調整されている。本発明の表面処理沈降シリカは、プラスチック製品、木材製品、金属製品、コンクリート製品、モルタル製品、紙製品、レザー製品(皮革製品および合成皮革製品)の塗装に使用される水性塗料に最も適している。 The surface-treated precipitated silica of the present invention can be suitably used in commercially available water-based paints. A water-based paint is a base water-soluble resin paint, dispersion paint, or emulsion paint, and pigments for coloring, additives, etc. are blended as necessary. The solid content concentration of water-based paints is adjusted to 10 to 50%, and the viscosity is adjusted to several tens to several thousand centipoise. The surface-treated precipitated silica of the present invention is most suitable for water-based paints used for coating plastic products, wood products, metal products, concrete products, mortar products, paper products, and leather products (leather products and synthetic leather products). .

以下、本発明を実施例に基づいて更に詳細に説明する。但し、実施例は本発明の例示であって、本発明は実施例に限定される意図ではない。 Hereinafter, the present invention will be explained in more detail based on examples. However, the examples are illustrative of the present invention, and the present invention is not intended to be limited to the examples.

＜表面処理沈降シリカの評価＞
1）表面処理沈降シリカ中のアルミニウム含有量の測定
走査型蛍光Ｘ線分析装置（型式：ZSX PrimusII、リガク社製）を用いて表面処理沈降シリカ中のアルミニウム(Al)含有量を定量した。Al質量％濃度が既知である標準サンプルの蛍光X線強度測定を行い、Al元素の蛍光X線強度と濃度との間の関係を求め、表面処理沈降シリカの蛍光X線強度からAl元素の含有量(質量％濃度)を算出する、検量線法を用いて、Al質量％濃度の定量分析を行った。定量したアルミニウム含有量を、装置付属の解析ソフトで酸化物換算し、Al2O3質量％濃度を算出した。測定試料は、表面処理沈降シリカをリング状の型に入れプレスする加圧成型法により作製した。 <Evaluation of surface treated precipitated silica>
1) Measurement of aluminum content in surface-treated precipitated silica The aluminum (Al) content in surface-treated precipitated silica was quantified using a scanning fluorescent X-ray analyzer (model: ZSX Primus II, manufactured by Rigaku Corporation). Measure the fluorescent X-ray intensity of a standard sample whose Al mass % concentration is known, determine the relationship between the fluorescent X-ray intensity and concentration of the Al element, and determine the Al element content from the fluorescent X-ray intensity of the surface-treated precipitated silica. Quantitative analysis of Al mass % concentration was performed using a calibration curve method to calculate the amount (mass % concentration). The quantified aluminum content was converted into oxides using analysis software attached to the device, and the Al 2 O 3 mass% concentration was calculated. The measurement sample was prepared by a pressure molding method in which surface-treated precipitated silica was placed in a ring-shaped mold and pressed.

2）表面処理沈降シリカの平均粒子径（D50、D90、D90/D50）
レーザー回折式粒度分布測定装置（型式：マイクロトラックMT-3000、マイクロトラック・ベル社製）を用いて粒度分布を測定し、粒度分布における体積積算累積値の50％の値（D50）、90％の値（D90）、D90とD50の比(D90/D50)を求めた。 2) Average particle diameter of surface treated precipitated silica (D50, D90, D90/D50)
The particle size distribution was measured using a laser diffraction particle size distribution analyzer (model: Microtrac MT-3000, manufactured by Microtrac Bell), and the 50% value (D50) and 90% of the cumulative volume value in the particle size distribution were measured. The value of (D90) and the ratio of D90 and D50 (D90/D50) were determined.

3）表面処理沈降シリカの加熱減量
ＪＩＳ Ｋ－５１０１に基づき、105℃、2時間乾燥後の重量減量値から求めた。 3) Heating loss of surface-treated precipitated silica Based on JIS K-5101, it was determined from the weight loss value after drying at 105°C for 2 hours.

4）表面処理沈降シリカの見掛比重
ＪＩＳ Ｋ－６２２０による、見掛比重測定法に準じて測定した。シリンダー(内径22.00mm、深さ100mm)にシリカ1.0gを注ぎこみ打撃を与えてシリカ上面を平らにした後、ピストン(外径21.80mm、長さ115mm、質量190g)を上から緩やかに落とし込み、シリンダーの上部に突出したピストン高さから以下の計算により見掛け比重を算出した。
G = S/[(H2-H1)×0.7854D2]
G:見掛け比重(g/cm3)
S：試料の重量(g)
H2：試料の存在するときのピストンとシリンダーの高さの差(cm)
H1：試料の存在しないときのピストンとシリンダーの高さの差(cm)
D：シリンダーの直径(cm) 4) Apparent specific gravity of surface-treated precipitated silica It was measured according to the apparent specific gravity measuring method according to JIS K-6220. After pouring 1.0 g of silica into a cylinder (inner diameter 22.00 mm, depth 100 mm) and giving a blow to flatten the top surface of the silica, a piston (outer diameter 21.80 mm, length 115 mm, mass 190 g) was gently dropped from above. The apparent specific gravity was calculated from the height of the piston protruding from the top of the cylinder using the following calculation.
G = S/[(H 2 -H 1 )×0.7854D 2 ]
G: Apparent specific gravity (g/cm3)
S: Weight of sample (g)
H 2 : Difference in height between piston and cylinder when sample is present (cm)
H 1 : Difference in height between piston and cylinder when no sample is present (cm)
D: Cylinder diameter (cm)

5）表面処理沈降シリカのBET比表面積
表面処理沈降シリカのBET比表面積は、全自動比表面積測定装置（型式：Macsorb(R) HM model-1200、マウンテック社製）を用いて1点法で測定を行った。 5) BET specific surface area of surface-treated precipitated silica The BET specific surface area of surface-treated precipitated silica is measured using a one-point method using a fully automatic specific surface area measuring device (model: Macsorb(R) HM model-1200, manufactured by Mountech). I did it.

＜表面処理沈降シリカの湿潤性と塗料評価＞
6）湿潤性；湿潤速度の評価
200mLの目盛つきディスポカップに50mLの水（pH7.0、電気伝導度100μS/cm）を張り、上から1gの表面処理沈降シリカを一気に投入して全量が水に完全に馴染むまでの時間を湿潤速度として測定した。評価は、湿潤速度が60秒未満の場合をA、60～180秒をB、180秒以上をCとし、Aのみを合格とした。 <Wettability of surface treated precipitated silica and paint evaluation>
6) Wettability; evaluation of wetting rate
Pour 50 mL of water (pH 7.0, electrical conductivity 100 μS/cm) into a 200 mL disposable cup with a scale, pour 1 g of surface-treated precipitated silica from above at once, and wait until the entire amount is completely absorbed into the water. Measured as speed. The evaluation was A when the wetting speed was less than 60 seconds, B when it was 60 to 180 seconds, and C when it was 180 seconds or more, with only A passing.

7）水性塗料評価
200mLの目盛つきディスポカップに水性エマルジョン塗料（商品名：バーノックWE-301；DIC社製）60g、純水20g、表面処理沈降シリカ3gを入れてハイスピードミキサー（型式：ラボリューション；プライミクス 社製）で750rpm、5分間分散し、塗料とした。 7) Water-based paint evaluation
Put 60 g of water-based emulsion paint (product name: Burnock WE-301; manufactured by DIC), 20 g of pure water, and 3 g of surface-treated precipitated silica into a 200 mL disposable cup with a scale, and mix it with a high-speed mixer (model: Lalaboration; manufactured by Primix). The mixture was dispersed at 750 rpm for 5 minutes to form a paint.

7-a）分散性
塗料をNo.20バーコーターで市販のABS板（100mm×200mm、黒色 コーティングテスタ―社製）に塗布し、任意の8.9mm×6.7mmの範囲に存在する200μm以上の沈降シリカ凝集物（いわゆるブツ）の個数をビデオマイクロスコープでカウントした。なお結果は、場所を変えて5か所測定し、その合計値をブツの累計個数とした。
評価は次のAからCの3段階で判定し、Aのみを合格とした。
A：ブツの累計個数 0
B：ブツの累計個数 1～4
C：ブツの累計個数 5以上 7-a) Dispersibility Apply the paint to a commercially available ABS board (100 mm x 200 mm, black, manufactured by Coating Tester Co., Ltd.) using a No. 20 bar coater, and remove sediments of 200 μm or more that exist within an arbitrary 8.9 mm x 6.7 mm area. The number of silica aggregates (so-called lumps) was counted using a video microscope. The results were measured at 5 different locations, and the total value was used as the cumulative number of particles.
The evaluation was based on the following three levels from A to C, with only A passing.
A: Cumulative number of items 0
B: Cumulative number of items 1 to 4
C: Cumulative number of items 5 or more

7-b）再分散性評価
塗料30gを50mL蓋付容器に入れ、2週間静置し、その後、振とう器(型式：V-SX、イワキ社製)にて1分間振とうさせて、沈降状態の観察試料とした。沈降状態は、蓋が底面になるように容器を反転させた際の容器底に残るシリカの割合にて確認した。沈降状態の評価は以下のA～Cの3段階で行い、Aのみを合格とした。（沈降試験の状態[写真付き]も参照）
A：振とう・反転後、容器の底にシリカの沈澱が確認できない状態。
B：振とう・反転後、容器の底に少量のシリカの沈澱が確認される状態。
C：振とう・反転後、容器の底に多量のシリカが確認される状態。 7-b) Evaluation of redispersibility Put 30 g of paint into a 50 mL container with a lid, let it stand for 2 weeks, and then shake it for 1 minute in a shaker (model: V-SX, manufactured by Iwaki Co., Ltd.) to cause sedimentation. This was used as a condition observation sample. The state of sedimentation was confirmed by the percentage of silica remaining at the bottom of the container when the container was inverted so that the lid was on the bottom. The sedimentation state was evaluated using the following three levels A to C, and only A was considered to be a pass. (See also conditions of sedimentation test [with photos])
A: No silica precipitate can be observed at the bottom of the container after shaking and inversion.
B: After shaking and inversion, a small amount of silica precipitates can be observed at the bottom of the container.
C: A large amount of silica is observed at the bottom of the container after shaking and inversion.

実施例１
攪拌機と循環ポンプを備えたジャケット付き240Lステンレス容器に温水93.5kgと、3号ケイ曹(SiO2濃度10.0wt％、SiO2/Na2Oモル比3.2)をpHが10.5になるまで加え、攪拌と循環を行いながら86.0℃に昇温した（以後、攪拌および循環、温度条件は反応が停止するまで同一条件で実施した）。次いで前記3号ケイ曹66.5kg、98.0wt％濃硫酸、30.0wt％硫酸アルミニウム水溶液0.674kgをpHが10.0～11.0を維持するよう攪拌と循環を行いながら200分かけて同時に滴下して中和反応を行い、中和反応終了後は、硫酸をpH3となるまで添加して反応を完全に停止させた。その後、得られた反応物をフィルタープレスで濾過、水洗してシリカケークを得た。 Example 1
Add 93.5 kg of warm water and No. 3 silica soda (SiO 2 concentration 10.0 wt%, SiO 2 /Na 2 O molar ratio 3.2) to a jacketed 240 L stainless steel container equipped with a stirrer and circulation pump until the pH reaches 10.5, and stir. The temperature was raised to 86.0° C. while circulating the mixture (stirring, circulation, and temperature conditions were kept the same until the reaction stopped). Next, 66.5 kg of No. 3 silica soda, 98.0 wt% concentrated sulfuric acid, and 0.674 kg of a 30.0 wt% aluminum sulfate aqueous solution were simultaneously added dropwise over 200 minutes while stirring and circulating to maintain the pH between 10.0 and 11.0 for a neutralization reaction. After the neutralization reaction was completed, sulfuric acid was added until the pH reached 3 to completely stop the reaction. Thereafter, the obtained reaction product was filtered using a filter press and washed with water to obtain a silica cake.

得られたシリカケークを往復回転式撹拌機（型式：アジターAP04型：島崎エンジニアリング社製）を用いてスラリー化し、市販のポリオキシアルキレンアルキルエーテル非イオン界面活性剤（商品名：ノイゲンXL-61；第一工業製薬社製、HLB：13）をシリカに対して2.0％添加、再攪拌後、ディスク式噴霧乾燥機（型式：スプレードライヤーAN-40R型 アシザワ・ニロアトマイザー社製）にて出口温度110℃の条件で噴霧乾燥させたのち、ジェットミル（型式：PJM-100NP；日本ニューマチック工業社製）で粉砕を行い、風力分級機（型式：クラッシールN-5型 セイシン企業社製）にて粗粒子を取り除き、表面処理沈降シリカ（Al2O3濃度：0.80質量％）を得た。 The obtained silica cake was made into a slurry using a reciprocating rotary stirrer (model: Agitator AP04, manufactured by Shimazaki Engineering Co., Ltd.), and a commercially available polyoxyalkylene alkyl ether nonionic surfactant (trade name: Neugen XL-61; After adding 2.0% of silica (manufactured by Ichi Kogyo Seiyaku Co., Ltd., HLB: 13) and stirring again, use a disc spray dryer (model: Spray Dryer AN-40R, manufactured by Ashizawa Niro Atomizer Co., Ltd.) at an outlet temperature of 110°C. After spray drying under the following conditions, pulverize with a jet mill (model: PJM-100NP; manufactured by Nippon Pneumatic Industries Co., Ltd.), and coarsely crush with an air classifier (model: Claseal N-5, manufactured by Seishin Enterprise Co., Ltd.). The particles were removed to obtain surface-treated precipitated silica (Al 2 O 3 concentration: 0.80% by mass).

実施例２
ポリオキシアルキレンアルキルエーテル非イオン界面活性剤の量を沈降シリカに対して0.5％添加した以外は実施例１と同様な方法で表面処理沈降シリカを得た。 Example 2
Surface-treated precipitated silica was obtained in the same manner as in Example 1, except that 0.5% of the polyoxyalkylene alkyl ether nonionic surfactant was added to the precipitated silica.

実施例３
ポリオキシアルキレンアルキルエーテル非イオン界面活性剤の量を沈降シリカに対して4.5％添加した以外は実施例１と同様な方法で表面処理沈降シリカを得た。 Example 3
Surface-treated precipitated silica was obtained in the same manner as in Example 1, except that 4.5% of the polyoxyalkylene alkyl ether nonionic surfactant was added to the precipitated silica.

実施例４
実施例１と同一の容器、原料において、容器内温度を84.0℃に、温水を74.0kgに、3号ケイ曹を86.5kgに、硫酸アルミニウム水溶液を0.933kgに変更した以外は、実施例１と同様の方法で表面処理沈降シリカを得た。この表面処理沈降シリカは、実施例１と比較してBET比表面積が低めかつ粒子径が大きめである。 Example 4
Same container and raw materials as Example 1, except that the temperature inside the container was changed to 84.0°C, the hot water was changed to 74.0 kg, the No. 3 silica was changed to 86.5 kg, and the aluminum sulfate aqueous solution was changed to 0.933 kg. Surface-treated precipitated silica was obtained in a similar manner. This surface-treated precipitated silica has a lower BET specific surface area and a larger particle size than Example 1.

実施例５
実施例１において、硫酸アルミニウム水溶液を0.337kgに変更した以外は、実施例１と同様の方法で表面処理沈降シリカ（Al2O3濃度：0.40質量％）を得た。 Example 5
Surface-treated precipitated silica (Al 2 O 3 concentration: 0.40% by mass) was obtained in the same manner as in Example 1, except that the aluminum sulfate aqueous solution was changed to 0.337 kg.

実施例６
市販の沈降シリカであるNipsil E-150J（東ソー・シリカ社製）を原粉とし、これをスラリー化したのちに実施例１と同一の方法でポリオキシアルキレンアルキルエーテル非イオン界面活性剤を沈降シリカに対して2.0％添加し、乾燥、粉砕、分級を経て表面処理沈降シリカを得た。 Example 6
Commercially available precipitated silica Nipsil E-150J (manufactured by Tosoh Silica Co., Ltd.) was used as a raw powder, and after slurrying this, a polyoxyalkylene alkyl ether nonionic surfactant was added to the precipitated silica in the same manner as in Example 1. The surface-treated precipitated silica was obtained by adding 2.0% of the silica and drying, pulverizing, and classifying.

比較例１
実施例１において、界面活性剤を添加しなかったこと以外は実施例１と同様な方法で表面未処理の沈降シリカを得た。 Comparative example 1
In Example 1, surface-untreated precipitated silica was obtained in the same manner as in Example 1, except that no surfactant was added.

比較例２
実施例１のポリオキシアルキレンアルキルエーテル非イオン界面活性剤をアニオン界面活性剤（商品名：ネオコールYSK；第一工業製薬社製、HLB：11）に変更した以外は実施例４と同様な方法で表面処理沈降シリカを得た。 Comparative example 2
In the same manner as in Example 4, except that the polyoxyalkylene alkyl ether nonionic surfactant in Example 1 was changed to an anionic surfactant (trade name: Neocol YSK; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB: 11). Surface treated precipitated silica was obtained.

比較例３
実施例１において、硫酸アルミニウム水溶液を0.169kgに変更したこと以外は、実施例１と同様の方法で表面処理沈降シリカ（Al2O3濃度：0.20質量％）を得た。 Comparative example 3
Surface-treated precipitated silica (Al 2 O 3 concentration: 0.20% by mass) was obtained in the same manner as in Example 1, except that the aluminum sulfate aqueous solution was changed to 0.169 kg.

比較例４
特開平9-25440号(特許文献１)の実施例４と同様の方法で、シリカに対して多鎖型非イオン界面活性剤を2.0％添加した表面処理沈降シリカを得た。すなわち、市販の沈降シリカであるNipsil E-200A（東ソー・シリカ社製）1,000gをヘンシェルミキサーに仕込み、分子量90,000の多鎖型非イオン界面活性剤であるディスコール206（第一工業製薬社製、HLB：6.0）20gを40mLのエタノールに溶解した溶液を、前記シリカ全体に均一になるように、攪拌混合下、噴霧添加した。更に10 分間の混合処理の後、取り出してアルコールが完全に飛散するまで乾燥を行ない、多鎖型非イオン界面活性剤による表面処理沈降シリカを得た。 Comparative example 4
Surface-treated precipitated silica was obtained by adding 2.0% of a multi-chain nonionic surfactant to silica using a method similar to Example 4 of JP-A-9-25440 (Patent Document 1). That is, 1,000 g of Nipsil E-200A (manufactured by Tosoh Silica Co., Ltd.), a commercially available precipitated silica, was charged into a Henschel mixer, and Diskol 206 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), a multichain nonionic surfactant with a molecular weight of 90,000, was charged into a Henschel mixer. , HLB: 6.0) dissolved in 40 mL of ethanol was sprayed and added to the silica while stirring so that it was uniformly distributed throughout the silica. After a further 10 minutes of mixing treatment, it was taken out and dried until the alcohol was completely dispersed, yielding precipitated silica surface-treated with a multi-chain nonionic surfactant.

比較例５
実施例1において硫酸アルミニウム水溶液を1.01kgに変更した以外は、実施例１と同様の方法で表面処理沈降シリカ（Al2O3濃度：1.2質量％）を得た。 Comparative example 5
Surface-treated precipitated silica (Al 2 O 3 concentration: 1.2% by mass) was obtained in the same manner as in Example 1, except that the aluminum sulfate aqueous solution in Example 1 was changed to 1.01 kg.

比較例６
実施例１において粉砕後の平均粒子径(D50)が11.5μmになるようにジェットミルでの粉砕条件を変更した以外は、実施例１と同様の方法で表面処理沈降シリカを得た。 Comparative example 6
Surface-treated precipitated silica was obtained in the same manner as in Example 1, except that the pulverization conditions in the jet mill were changed so that the average particle diameter (D50) after pulverization was 11.5 μm.

*1 エーテル非イオン界面活性剤 ポリオキシエチレントリデシルエーテルノイゲンXL-61；第一工業製薬社製
*2 アニオン界面活性剤 ネオコールYSK；第一工業製薬社製
*3 多鎖型非イオン界面活性剤 ディスコール206；第一工業製薬社製
*4 エーテル非イオン界面活性剤 ポリオキシエチレンオレイルエーテルエマルゲン408；花王社製 *1 Ether nonionic surfactant polyoxyethylene tridecyl ether Neugen XL-61; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
*2 Anionic surfactant Neocol YSK; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
*3 Multi-chain nonionic surfactant Diskol 206; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
*4 Ether nonionic surfactant polyoxyethylene oleyl ether emulgen 408; manufactured by Kao Corporation

本発明は、水性塗料の艶消し剤に関連する分野に有用である。 The present invention is useful in fields related to matting agents for water-based paints.

Claims (2)

沈降シリカの表面に0.5～5.0％の、HLBが10.0～15.0の範囲であるポリオキシアルキレンアルキルエーテル非イオン界面活性剤を有する、水性塗料用表面処理沈降シリカであって、前記表面処理沈降シリカは、アルミニウム含有量がAl2O3換算で0.30～1.00質量％の範囲にあり、レーザー回折法による体積平均粒子径D50が3.0～10.0μmの範囲であり、レーザー回折法で測定した粒度分布における下位からの体積積算累積値の90％である粒子径D90とD50との比D90/D50が2.0以下であり、かつBET比表面積が60～280m2/gの範囲である、前記表面処理沈降シリカ。 A surface-treated precipitated silica for water-based paints having 0.5 to 5.0% of a polyoxyalkylene alkyl ether nonionic surfactant with an HLB in the range of 10.0 to 15.0 on the surface of the precipitated silica , the surface-treated precipitated silica comprising: , the aluminum content is in the range of 0.30 to 1.00 mass% in terms of Al 2 O 3 , the volume average particle diameter D50 as measured by laser diffraction is in the range of 3.0 to 10.0 μm, and it is at the bottom of the particle size distribution measured by laser diffraction. The surface-treated precipitated silica, wherein the ratio D90/D50 of the particle diameter D90 and D50, which is 90% of the volumetric cumulative value from the above, is 2.0 or less, and the BET specific surface area is in the range of 60 to 280 m 2 /g. 前記表面処理沈降シリカは、加熱減量が9.0％以下であり、見掛比重が0.05～0.30g/mLの範囲にある、請求項１に記載の表面処理沈降シリカ。 The surface-treated precipitated silica according to claim 1 , wherein the surface-treated precipitated silica has a heat loss of 9.0% or less and an apparent specific gravity in the range of 0.05 to 0.30 g/mL.
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