WO2021100400A1 - Surface-treated precipitated silica for aqueous paint - Google Patents

Surface-treated precipitated silica for aqueous paint Download PDF

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Publication number
WO2021100400A1
WO2021100400A1 PCT/JP2020/039659 JP2020039659W WO2021100400A1 WO 2021100400 A1 WO2021100400 A1 WO 2021100400A1 JP 2020039659 W JP2020039659 W JP 2020039659W WO 2021100400 A1 WO2021100400 A1 WO 2021100400A1
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Prior art keywords
precipitated silica
treated precipitated
treated
silica
range
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PCT/JP2020/039659
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French (fr)
Japanese (ja)
Inventor
遥 谷本
英紀 中上
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東ソー・シリカ株式会社
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Application filed by 東ソー・シリカ株式会社 filed Critical 東ソー・シリカ株式会社
Priority to CN202080059407.5A priority Critical patent/CN114302922B/en
Priority to KR1020227005321A priority patent/KR102645214B1/en
Publication of WO2021100400A1 publication Critical patent/WO2021100400A1/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

Definitions

  • the present invention relates to surface-treated precipitated silica used as a matting agent for water-based paints. More specifically, the present invention relates to a surface-treated silica which can be wetted in a short time without causing agglomeration even when directly added to a water-based paint and has good redispersibility even when precipitated over time.
  • Cross-reference to related applications This application claims the priority of Japanese Patent Application No. 2019-209954 filed on November 20, 2019, the full description thereof of which is incorporated herein by reference in particular.
  • Precipitated silica is a type of amorphous synthetic silica that is roughly classified into wet method silica together with gel silica. It is known that precipitated silica is used as a matting agent for paints. In particular, precipitated silica whose micron size is controlled by processing such as crushing and classification is widely used as a matting agent for metal paints and plastic paints. Has been done. On the other hand, surface-treated silicas for paints, in which these silicas are surface-treated to have a specific function, are also known. For example, Patent Document 1 discloses surface-treated silica having good redispersibility even when precipitated in a coating material by surface-treating wet silica with a multi-chain nonionic surfactant. Patent Document 2 discloses a matting agent in which an amorphous silica having a specific pore volume is coated with a certain amount of polyethylene wax.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 9-25440
  • Patent Document 2 Japanese Patent Application Laid-Open No. 11-512124 All descriptions of Patent Documents 1 and 2 are particularly incorporated herein by reference.
  • Patent Document 1 The surface-treated silica of Patent Document 1 has good redispersibility for solvent-based paints, but when used for water-based paints, the silicas coagulate and precipitate to form hard cakes and cannot be redispersed. There was a problem of becoming.
  • the matting agent of Patent Document 2 has good matting performance for solvent-free or low-solvent UV-curable paints. However, since this matting agent is surface-treated with wax, it is not sufficiently dispersed in the water-based paint, and there is a problem that the matting effect cannot be exhibited.
  • a silica dispersion having a concentration of about 10 to 20% is prepared in advance, and if necessary, it is added to a water-based paint containing a resin, a pigment, or the like for use.
  • the silica dispersion when added to the water-based paint, the entire paint is diluted and the paint becomes a low-concentration paint. As a result, there are problems such as a change in the coating thickness and an increase in the time and energy required for drying as compared with the solvent-based paint. Further, from the viewpoint of reducing man-hours, it is preferable that there is no step of preparing the silica dispersion.
  • an object of the present invention is to develop a surface-treated silica that can be wetted in a short time without causing agglomeration even if it is directly added as a powder to a water-based paint and has good redispersibility even if it precipitates over time. It is to be.
  • the present inventors can wet the surface in a short time without causing aggregation even if it is directly added to the water-based paint, and the surface treatment has good redispersibility even if it precipitates over time.
  • the present inventors have found 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, and completed the present invention.
  • silica polyoxyalkylene alkyl ether nonionic surfactant it is possible to provide surface-treated precipitated silica having particularly good redispersibility even if it precipitates over time.
  • the present invention is as follows. [1] Surface-treated precipitated silica for water-based paints having 0.5 to 5.0% ether-based nonionic surfactant on the surface of the precipitated silica.
  • the surface-treated precipitated silica has an aluminum content of 0.30 to Al 2 O 3 in terms of Al 2 O 3. It is in the range of 1.00 mass%, the volume average particle size D50 measured by laser diffraction is in the range of 3.0 to 10.0 ⁇ m, and the ratio D90 / D50 is 2.0 or less, except that D90 is measured by laser diffraction.
  • the surface-treated precipitated silica, wherein the cumulative volume-accumulated value from the bottom in the particle size distribution is the particle size at 90%.
  • a surface-treated precipitated silica that can be wetted in a short time without causing agglomeration even if it is directly added to a water-based paint and has good redispersibility even if it precipitates over time.
  • This surface-treated precipitated silica is useful as a matting agent for water-based paints.
  • the surface-treated precipitated silica of the present invention is a surface-treated precipitated silica for water-based paints having 0.5 to 5.0% of an ether-based nonionic surfactant on the surface of the precipitated silica.
  • the surface-treated precipitated silica has an aluminum content in the range of 0.30 to 1.00 mass% in terms of Al 2 O 3 , a volume average particle size D50 measured by a laser diffraction method in the range of 3.0 to 10.0 ⁇ m, and a ratio.
  • D90 / D50 is 2.0 or less, where D90 is the particle size when the cumulative volume integration value from the bottom in the particle size distribution measured by the laser diffraction method is 90%.
  • 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.
  • 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.
  • Precipitated silica with an aluminum content of less than 0.30% by mass in terms of Al 2 O 3 is difficult to be compatible with water, especially water containing minerals such as industrial water, and even if it is surface-treated with an ether-based nonionic surfactant. Also, the paint becomes thickened and easily precipitates.
  • precipitated silica having an aluminum content of more than 1.00% by mass in terms of Al 2 O 3 a large amount of aluminum is added during wet synthesis, so that silica aggregation during synthesis becomes strong.
  • the obtained precipitated silica particles become too hard, and coarse particles remain even when pulverized. Therefore, even if the precipitated silica having an aluminum content of more than 1.00% by mass in terms of Al 2 O 3 is surface-treated with an ether-based nonionic surfactant, the aggregated particles are likely to precipitate over time.
  • 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.
  • Preparation of precipitated silica in which the aluminum content of the surface-treated precipitated silica is within the above range can be performed by a conventional method, and the method of adding aluminum in the conventional method is not particularly limited.
  • the addition of aluminum to the precipitated silica is not an addition by surface treatment, but is used as a synthetic raw material during the synthesis of the precipitated silica. It is preferably added or added during the synthesis.
  • the surface-treated precipitated silica of the present invention has a volume average particle diameter D50 measured by a laser diffraction method in the range of 3.0 to 10.0 ⁇ m and a ratio D90 / D50 of 2.0 or less.
  • D90 is the particle size when the cumulative volume integration value from the lower part in the particle size distribution measured by the laser diffraction method is 90%.
  • a surface-treated precipitated silica having a D50 in the range of 3.0 to 10.0 ⁇ m and a ratio of D90 / D50 of 2.0 or less can sufficiently exhibit the desired function as a matting agent.
  • D50 is less than 3.0 ⁇ m, the silica particles are buried in the coating film because the particle size is too small, and a sufficient matting effect cannot be obtained.
  • D50 is larger than 10.0 ⁇ m, the surface of the coating film becomes rough and the design is impaired, so it is not suitable for matte use.
  • the ratio D90 / D50 is larger than 2.0, when the surface-treated precipitated silica of the present invention is directly added to the water-based paint, cohesive precipitation occurs and so-called lumps are generated in the paint.
  • D50 is preferably in the range of 3.5 to 9.0 ⁇ m.
  • the lower limit of the ratio D90 / D50 is not particularly limited, but is, for example, 0.5, preferably 1.0.
  • the ratio D90 / D50 is preferably in the range of 1.2 to 2.0, more preferably 1.4 to 1.9.
  • the surface-treated precipitated silica of the present invention has 0.5 to 5.0% of an ether-based nonionic surfactant on the surface of the precipitated silica. If the amount of the ether-based nonionic surfactant is small, the penetrating effect (hereinafter, wettability) is small, and if it is large, it elutes and adversely affects the paint, so it is within the above range.
  • the amount of the ether-based nonionic surfactant is preferably in the range of 1.0 to 4.0%, more preferably 2.0 to 3.0%.
  • the ether-based nonionic surfactant has good wettability to water and does not substantially affect the resin component in the paint and other pigments and additives to be added.
  • good results were obtained with polyoxyalkylene alkyl ethers. The reason for this is not clear and there is no intention to stick to this reason, but it is presumed that good results were obtained because the polyoxyalkylene portion has an appropriate affinity with the silica surface. More specific examples of polyoxyalkylene alkyl ethers are given below. All of the following examples are available as commercial products.
  • Polyoxyalkylene branched decyl ether (Neugen XL, Neugen LF: The polyoxyalkylene part is composed of a polymer of polyoxy short chain alkylene and polyoxyethylene, etc.), Polyoxyethylene isodecyl ether (Neugen SD) : Daiichi Kogyo Seiyaku Co., Ltd., etc.), Polyoxyethylene lauryl ether (DKSNL: Daiichi Kogyo Seiyaku Co., Ltd., etc.), Polyoxyethylene tridecyl ether (Neugen TDS: Daiichi Kogyo Seiyaku Co., Ltd., etc.), Polyoxyalkylene tri Decyl ether (Neugen TDX: polyoxyalkylene part consists of polymer of polyoxypropylene and polyoxyethylene, etc.), polyoxyethylene polyoxypropylene alkyl ether (Emargen LS: manufactured by Kao, Pepol) AS: Toho Chemical Industry Co., Ltd., etc.), Poly
  • Neugen XL-61 polyoxyethylene tridecyl ether. HLB: 13
  • Emargen LS-106 polyoxyethylene polyoxypropylene alkyl ether. HLB: 13
  • 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 the precipitated silica.
  • the preparation method includes a dry treatment method in which precipitated silica and a surfactant are mixed with a high-speed flow mixer or the like, or a wet treatment method in which a surfactant solution is mixed with a silica slurry and dried. ..
  • the processing method is not limited.
  • An FM mixer, an axial mixer, or the like can be used as the mixing method in the dry processing method.
  • the drying method in the wet treatment method includes a spin flash dryer (SFD) and a spray dryer (SD), but SD capable of instant drying is preferable.
  • the ether-based nonionic surfactant has an HLB in the range of preferably 10.0 to 15.0, more preferably 11.0 to 14.0, and further preferably 11.0 to 13.0.
  • the BET specific surface area of the surface-treated precipitated silica of the present invention is preferably 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 (surface-treated precipitated silica) after surface treatment , and when it is 60 m 2 / g or more, the matting effect of silica becomes larger.
  • the size is 280 m 2 / g or less, the precipitated silica can be easily produced, and the surface-treated precipitated silica that does not easily precipitate even when added to the water-based paint is obtained because the cohesive force between the primary silica particles is not too strong.
  • the heat loss of the surface-treated precipitated silica of the present invention is preferably 9.0% or less.
  • 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 density is in this range, there is an advantage that the handling is good because the specific gravity is large to some extent, and it is difficult to form a hard cake when it precipitates because the specific density is not too large.
  • the surface-treated precipitated silica of the present invention can be suitably used for commercially available water-based paints.
  • a water-soluble resin paint, a dispersion paint, or an emulsion paint as a base is mixed with a pigment for coloring, an additive, or the like, if necessary.
  • the solid content concentration of the water-based paint is adjusted to 10 to 50%, and the viscosity is adjusted to several tens to several thousand centipoise. However, it is not intended to be limited to the solid content concentration and viscosity in this range.
  • the surface-treated precipitated silica of the present invention is most suitable for water-based paints used for painting plastic products, wood products, metal products, concrete products, mortar products, paper products, and leather products (leather products and synthetic leather products). ..
  • the quantified aluminum content was converted into oxides using the 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.
  • Average particle size of surface-treated precipitated silica (D50, D90, D90 / D50) Measure the particle size distribution using a laser diffraction type particle size distribution measuring device (model: Microtrack MT-3000, manufactured by Microtrac Bell), and the value is 50% of the cumulative volume integration value from the bottom of the particle size distribution (D50). , 90% value (D90), and the ratio of D90 to D50 (D90 / D50) were determined respectively.
  • G S / ⁇ (H 2 -H 1 ) ⁇ 0.7854 D 2 ⁇ G: Apparent specific density (g / cm 3 )
  • S Sample weight (g) H 2 : Difference in height between piston and cylinder in the presence of sample (cm) H 1 : Difference in height between piston and cylinder in the absence of sample (cm)
  • D Cylinder diameter (cm)
  • BET specific surface area of surface-treated precipitated silica is measured by a one-point method using a fully automatic specific surface area measuring device (model: Macsorb (R) HM model-1200, manufactured by Mountec). Was done.
  • wetness of surface-treated precipitated silica and paint evaluation> 6 Wetness: Evaluation of wetting rate 50 mL of water (pH 7.0, electrical conductivity 100 ⁇ S / cm) is placed in a 200 mL graduated disposable cup, and 1 g of surface-treated precipitated silica is added at once from above to make the entire amount water. The time required for complete acclimation was measured as the wetting rate. The evaluation was A when the wetting speed was less than 60 seconds, B for 60 to 180 seconds, C for 180 seconds or more, and only A passed.
  • Dispersive paint is applied to a commercially available ABS plate (100 mm x 200 mm, manufactured by Black Coating Tester) with a No. 20 bar coater, and sedimentation of 200 ⁇ m or more existing in an arbitrary range of 8.9 mm ⁇ 6.7 mm.
  • the number of silica aggregates was counted with a video microscope. The number of lumps was measured at 5 different locations, and the total number of lumps was used to evaluate the dispersibility. The evaluation was judged in the following three stages from A to C, and only A was accepted.
  • B Cumulative number of things 1 to 4
  • C Cumulative number of stuff 5 or more
  • Example 1 Add 93.5 kg of hot water and No. 3 silica (SiO 2 concentration 10.0 wt%, SiO 2 / Na 2 O molar ratio 3.2) to a 240 L stainless steel container with a jacket equipped with a stirrer and a circulation pump until the pH reaches 10.5, and stir. The temperature was raised to 86.0 ° C. (after that, stirring, circulation, and temperature conditions were carried out under the same conditions until the reaction was stopped). Next, 66.5 kg of No.
  • silica SiO 2 concentration 10.0 wt%, SiO 2 / Na 2 O molar ratio 3.2
  • silica cake was pulverized using a reciprocating rotary stirrer (model: Agitator AP04 type: manufactured by Shimazaki Engineering Co., Ltd.), and a commercially available polyoxyalkylene alkyl ether nonionic surfactant (trade name: Neugen XL-61; No. Add 2.0% of HLB: 13) to silica, re-stirred, and then use a disc-type spray dryer (model: spray dryer AN-40R, manufactured by Ashizawa Niro Atomizer) at an outlet temperature of 110 ° C.
  • a reciprocating rotary stirrer model: Agitator AP04 type: manufactured by Shimazaki Engineering Co., Ltd.
  • a commercially available polyoxyalkylene alkyl ether nonionic surfactant trade name: Neugen XL-61; No. Add 2.0% of HLB: 13
  • 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.
  • 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.
  • Example 4 In the same container and raw material as in Example 1, except that the temperature inside the container was changed to 84.0 ° C, hot water was changed to 74.0 kg, No. 3 Keiso 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 the same manner. This surface-treated precipitated silica has a lower BET specific surface area and a larger particle size as compared with Example 1.
  • 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 aqueous aluminum sulfate solution was changed to 0.337 kg.
  • Example 6 Nipsil E-150J (manufactured by Tosoh Silica Co., Ltd.), which is a commercially available precipitated silica, was used as a raw powder, and this was slurried. Then, 2.0% of a polyoxyalkylene alkyl ether nonionic surfactant was added to the precipitated silica by the same method as in Example 1, and the surface-treated precipitated silica was obtained through drying, pulverization, and classification.
  • a polyoxyalkylene alkyl ether nonionic surfactant was added to the precipitated silica by the same method as in Example 1, and the surface-treated precipitated silica was obtained through drying, pulverization, and classification.
  • Example 1 surface-untreated precipitated silica was obtained in the same manner as in Example 1 except that no surfactant was added.
  • Comparative Example 2 The same method as in Example 4 except that the polyoxyalkylene alkyl ether nonionic surfactant of Example 1 was changed to an anionic surfactant (trade name: Neocol YSK; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., HLB: 11). Surface-treated precipitated silica was obtained.
  • 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 aqueous aluminum sulfate solution was changed to 0.169 kg in Example 1.
  • Example 4 Surface-treated precipitated silica was obtained by adding 2.0% of a multi-chain nonionic surfactant to silica in the same manner as in Example 4 of JP-A-9-25440 (Patent Document 1). That is, 1,000 g of commercially available precipitated silica Nipsil E-200A (manufactured by Toso Silica) was charged into a Henschel mixer, and Discol 206 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), a multi-chain nonionic surfactant having a molecular weight of 90,000, was charged.
  • Patent Document 1 1,000 g of commercially available precipitated silica Nipsil E-200A (manufactured by Toso Silica) was charged into a Henschel mixer, and Discol 206 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), a multi-chain nonionic surfactant having a molecular
  • Comparative Example 6 Surface-treated precipitated silica was obtained in the same manner as in Example 1 except that the pulverization conditions in a jet mill were changed so that the average particle size (D50) after pulverization was 11.5 ⁇ m in Example 1.
  • Ether nonionic surfactant Polyoxyethylene tridecyl ether Neugen XL-61; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • Anionic surfactant Neocol YSK manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • Multi-chain nonionic surfactant DISCOR 206 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • the present invention is useful in the field related to matting agents for water-based paints.

Abstract

The present invention relates to a surface-treated precipitated silica for aqueous paint, comprising 0.5–5.0% of an ether-based ion surfactant on the surface of precipitated silica, wherein the surface-treated precipitated silica has an aluminum content in the range 0.30–1.00% by mass in Al2O3 equivalent, the volume-average particle diameter D50 measured by laser diffractometry is in the range 3.0–10.0 μm, and the ratio D90/D50 is 2.0 or less, where D90 is the particle diameter at which the cumulative value of the volume integral from the bottom of the granularity distribution, as measured by laser diffractometry, is 90%. With the present invention, a surface-treated silica can be provided that can be wetted in a short period of time without causing agglutination, even when added directly in powder form to an aqueous paint, and has good redispersibility even if the surface-treated silica precipitates over time.

Description

水性塗料用表面処理沈降シリカSurface-treated precipitated silica for water-based paints
　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（surface-treated precipitated silica）に関する。詳細に説明すると、本発明は、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。
関連出願の相互参照
　本出願は、２０１９年１１月２０日出願の日本特願２０１９－２０９９５４号の優先権を主張し、それらの全記載は、ここに特に開示として援用される。 The present invention relates to surface-treated precipitated silica used as a matting agent for water-based paints. More specifically, the present invention relates to a surface-treated silica which can be wetted in a short time without causing agglomeration even when directly added to a water-based paint and has good redispersibility even when precipitated over time.
Cross-reference to related applications This application claims the priority of Japanese Patent Application No. 2019-209954 filed on November 20, 2019, the full description thereof of which is incorporated herein by reference in particular.
　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用塗料やプラスチック用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 roughly classified into wet method silica together with gel silica. It is known that precipitated silica is used as a matting agent for paints. In particular, precipitated silica whose micron size is controlled by processing such as crushing and classification is widely used as a matting agent for metal paints and plastic paints. Has been done. On the other hand, surface-treated silicas for paints, in which these silicas are surface-treated to have a specific function, are also known. For example, Patent Document 1 discloses surface-treated silica having good redispersibility even when precipitated in a coating material by surface-treating wet silica with a multi-chain nonionic surfactant. Patent Document 2 discloses a matting agent in which an amorphous silica having a specific pore volume is coated with a certain amount of polyethylene wax.
特許文献１：特開平９－２５４４０号公報
特許文献２：特表平１１－５１２１２４号公報
特許文献１及び２の全記載は、ここに特に開示として援用される。 Patent Document 1: Japanese Patent Application Laid-Open No. 9-25440 Patent Document 2: Japanese Patent Application Laid-Open No. 11-512124 All descriptions of Patent Documents 1 and 2 are particularly incorporated herein by reference.
　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っている。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、水性塗料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, the regulation of VOCs emitted into the atmosphere has become stricter as it has a harmful effect on the human respiratory organs. In consideration of the environment, paints using solvents harmful to the human body are changing to water-based paints or solvent-free paints that do not use solvents. Along with this, silica used as a matting agent is also required to be suitable for aqueous use.
　特許文献1の表面処理シリカは、溶剤系塗料用としては再分散性が良好であるが、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 for solvent-based paints, but when used for water-based paints, the silicas coagulate and precipitate to form hard cakes and cannot be redispersed. There was a problem of becoming.
　特許文献2の艶消し剤は、無溶剤又は低溶剤のUV硬化型の塗料用としては良好な艶消し性能を有する。しかし、この艶消し剤はワックスで表面処理されているので、水性塗料中では十分に分散せず、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 solvent-free or low-solvent UV-curable paints. However, since this matting agent is surface-treated with wax, it is not sufficiently dispersed in the water-based paint, and there is a problem that the matting effect cannot be exhibited.
　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、一般的には、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 directly added to the water-based paint as a matting agent, there are problems such as the precipitated silica agglomerating and not dispersing in the paint, causing so-called lumps, or precipitating over time to form hard cakes. is there. Therefore, in general, a silica dispersion having a concentration of about 10 to 20% is prepared in advance, and if necessary, it is added to a water-based paint containing a resin, a pigment, or the like for use.
　しかし、水性塗料へ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。その結果、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系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。 However, when the silica dispersion is added to the water-based paint, the entire paint is diluted and the paint becomes a low-concentration paint. As a result, there are problems such as a change in the coating thickness and an increase in the time and energy required for drying as compared with the solvent-based paint. Further, from the viewpoint of reducing man-hours, it is preferable that there is no step of preparing the silica dispersion.
　そこで本発明の目的は、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る。 Therefore, an object of the present invention is to develop a surface-treated silica that can be wetted in a short time without causing agglomeration even if it is directly added as a powder to a water-based paint and has good redispersibility even if it precipitates over time. It is to be.
　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、本発明者らは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な表面処理沈降シリカが提供できる。 In order to solve the above problems, the present inventors can wet the surface in a short time without causing aggregation even if it is directly added to the water-based paint, and the surface treatment has good redispersibility even if it precipitates over time. We diligently examined the development of silica. As a result, the present inventors have found 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, and completed the present invention. In particular, by treating with a polyoxyalkylene alkyl ether nonionic surfactant, it is possible to provide surface-treated precipitated silica having particularly good redispersibility even if it precipitates 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、レーザー回折法で測定した体積平均粒子径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、但し、D90は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が90％における粒子径である、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％以下である、［１］～［４］のいずれかに記載の表面処理沈降シリカ。
［６］
見掛比重が0.05～0.30g/mLの範囲にある、［１］～［５］のいずれかに記載の表面処理沈降シリカ。
［７］
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0.45～0.85質量％の範囲にある、［１］～［６］のいずれかに記載の表面処理沈降シリカ。
［８］
前記レーザー回折法で測定した体積平均粒子径D50が3.5～9.0μmの範囲である、［１］～［７］のいずれかに記載の表面処理沈降シリカ。
［９］
前記比D90/D50が1.4～1.9である、［１］～［８］のいずれかに記載の表面処理沈降シリカ。 The present invention is as follows.
[1]
Surface-treated precipitated silica for water-based paints having 0.5 to 5.0% ether-based nonionic surfactant on the surface of the precipitated silica. The surface-treated precipitated silica has an aluminum content of 0.30 to Al 2 O 3 in terms of Al 2 O 3. It is in the range of 1.00 mass%, the volume average particle size D50 measured by laser diffraction is in the range of 3.0 to 10.0 μm, and the ratio D90 / D50 is 2.0 or less, except that D90 is measured by laser diffraction. The surface-treated precipitated silica, wherein the cumulative volume-accumulated value from the bottom in the particle size distribution is the particle size at 90%.
[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-based 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 heat loss of 9.0% or less.
[6]
The surface-treated precipitated silica according to any one of [1] to [5], which has an apparent specific gravity in the range of 0.05 to 0.30 g / mL.
[7]
The surface-treated precipitated silica according to any one of [1] to [6], wherein the surface-treated precipitated silica has an aluminum content in the range of 0.45 to 0.85% by mass in terms of Al 2 O 3.
[8]
The surface-treated precipitated silica according to any one of [1] to [7], wherein the volume average particle diameter D50 measured by the laser diffraction method is in the range of 3.5 to 9.0 μm.
[9]
The surface-treated precipitated silica according to any one of [1] to [8], wherein the ratio D90 / D50 is 1.4 to 1.9.
　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る。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 a surface-treated precipitated silica that can be wetted in a short time without causing agglomeration even if it is directly added to a water-based paint and has good redispersibility even if it precipitates over time. This surface-treated precipitated silica is useful as a matting agent for 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る。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、レーザー回折法で測定した体積平均粒子径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、但し、D90は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が90％における粒子径である。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 having 0.5 to 5.0% of an ether-based nonionic surfactant on the surface of the precipitated silica. The surface-treated precipitated silica has an aluminum content in the range of 0.30 to 1.00 mass% in terms of Al 2 O 3 , a volume average particle size D50 measured by a laser diffraction method in the range of 3.0 to 10.0 μm, and a ratio. D90 / D50 is 2.0 or less, where D90 is the particle size when the cumulative volume integration value from the bottom in the particle size distribution measured by the laser diffraction method is 90%. 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は、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。一方、アルミニウム含有量がAl2O3換算で1.00質量％超の沈降シリカは、湿式合成の際にアルミニウムが多く添加されるため、合成途中のシリカの凝集が強くなる。そのため、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。したがって、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. Precipitated silica with an aluminum content of less than 0.30% by mass in terms of Al 2 O 3 is difficult to be compatible with water, especially water containing minerals such as industrial water, and even if it is surface-treated with an ether-based nonionic surfactant. Also, the paint becomes thickened and easily precipitates. On the other hand, for precipitated silica having an aluminum content of more than 1.00% by mass in terms of Al 2 O 3, a large amount of aluminum is added during wet synthesis, so that silica aggregation during synthesis becomes strong. Therefore, the obtained precipitated silica particles become too hard, and coarse particles remain even when pulverized. Therefore, even if the precipitated silica having an aluminum content of more than 1.00% by mass in terms of Al 2 O 3 is surface-treated with an ether-based nonionic surfactant, the aggregated particles are likely to precipitate 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のアルミニウム含有量が上記範囲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が水性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。 Preparation of precipitated silica in which the aluminum content of the surface-treated precipitated silica is within the above range can be performed by a conventional method, and the method of adding aluminum in the conventional method is not particularly limited. However, from the viewpoint that the surface-treated precipitated silica does not cause interaction with other additives in the aqueous paint, the addition of aluminum to the precipitated silica is not an addition by surface treatment, but is used as a synthetic raw material during the synthesis of the precipitated silica. It is preferably added or added during the synthesis.
　本発明の表面処理沈降シリカは、レーザー回折法で測定した体積平均粒子径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。但し、D90は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が90％における粒子径である。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 measured by a laser diffraction method in the range of 3.0 to 10.0 μm and a ratio D90 / D50 of 2.0 or less. However, D90 is the particle size when the cumulative volume integration value from the lower part in the particle size distribution measured by the laser diffraction method is 90%. A surface-treated precipitated silica having a D50 in the range of 3.0 to 10.0 μm and a ratio of 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 silica particles are buried in the coating film because the particle size is too small, and a sufficient matting effect cannot be obtained. If D50 is larger than 10.0 μm, the surface of the coating film becomes rough and the design is impaired, so it is not suitable for matte use. When the ratio D90 / D50 is larger than 2.0, when the surface-treated precipitated silica of the present invention is directly added to the water-based paint, cohesive precipitation occurs and so-called lumps are generated in the paint. D50 is preferably in the range of 3.5 to 9.0 μm. The lower limit of the ratio D90 / D50 is not particularly limited, but is, for example, 0.5, preferably 1.0. The ratio D90 / D50 is preferably in the range of 1.2 to 2.0, more preferably 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-based nonionic surfactant on the surface of the precipitated silica. If the amount of the ether-based nonionic surfactant is small, the penetrating effect (hereinafter, wettability) is small, and if it is large, it elutes and adversely affects the paint, so it is within the above range. The amount of the ether-based 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。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, the ether-based nonionic surfactant has good wettability to water and does not substantially affect the resin component in the paint and other pigments and additives to be added. In particular, as a result of investigations by the present inventors on many ether-based nonionic surfactants, good results were obtained with polyoxyalkylene alkyl ethers. The reason for this is not clear and there is no intention to stick to this reason, but it is presumed that good results were obtained because the polyoxyalkylene portion has an appropriate affinity with the silica surface. More specific examples of polyoxyalkylene alkyl ethers are given below. All of the following examples are available as commercial products. Polyoxyalkylene branched decyl ether (Neugen XL, Neugen LF: The polyoxyalkylene part is composed of a polymer of polyoxy short chain alkylene and polyoxyethylene, etc.), Polyoxyethylene isodecyl ether (Neugen SD) : Daiichi Kogyo Seiyaku Co., Ltd., etc.), Polyoxyethylene lauryl ether (DKSNL: Daiichi Kogyo Seiyaku Co., Ltd., etc.), Polyoxyethylene tridecyl ether (Neugen TDS: Daiichi Kogyo Seiyaku Co., Ltd., etc.), Polyoxyalkylene tri Decyl ether (Neugen TDX: polyoxyalkylene part consists of polymer of polyoxypropylene and polyoxyethylene, etc.), polyoxyethylene polyoxypropylene alkyl ether (Emargen LS: manufactured by Kao, Pepol) AS: Toho Chemical Industry Co., Ltd., etc.), Polyoxyethylene alkyl ether (Naroacty CL, Sanyo Kasei Kogyo Co., Ltd., etc.), Polyoxyethylene 2-ethylhexyl ether (Newcol 1000 series: Nippon Emulsifier Co., Ltd., etc.), Polyoxy Examples thereof include ethylene cetyl ether (Newcol 1600 series: manufactured by Nippon Emulsifier Co., Ltd.), polyoxyethylene oleyl ether (Emargen 408: manufactured by Kao Co., Ltd., Newcol 1200 series: manufactured by Japan Emulsifier 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。 Of these, it is preferable to use Neugen XL-61 (polyoxyethylene tridecyl ether. HLB: 13), Emargen LS-106 (polyoxyethylene polyoxypropylene alkyl ether. HLB: 13) and the like in the present invention. ..
　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る。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 the precipitated silica. Examples of the preparation method (treatment method) include a dry treatment method in which precipitated silica and a surfactant are mixed with a high-speed flow mixer or the like, or a wet treatment method in which a surfactant solution is mixed with a silica slurry and dried. .. However, the processing method is not limited. An FM mixer, an axial mixer, or the like can be used as the mixing method in the dry processing method. The drying method in the wet treatment method includes a spin flash dryer (SFD) and a spray dryer (SD), but SD capable of instant drying is preferable.
　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の湿潤効果が低下する。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、シリカ表面から界面活性剤が溶液側または塗料側に脱離しやすくなる。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。 If the HLB of the ether-based nonionic surfactant is low, the surfactant is difficult to mix with water, so that the wetting effect of the surface-treated precipitated silica is reduced. When the HLB of the ether-based nonionic surfactant is high, the hydrophilicity becomes high, and the surfactant is easily desorbed from the silica surface to the solution side or the paint side. From this point of view, the ether-based nonionic surfactant has an HLB in the range of preferably 10.0 to 15.0, more preferably 11.0 to 14.0, and further preferably 11.0 to 13.0.
　本発明の表面処理沈降シリカのBET比表面積は、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 BET specific surface area of the surface-treated precipitated silica of the present invention is preferably 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 (surface-treated precipitated silica) after surface treatment , and when it is 60 m 2 / g or more, the matting effect of silica becomes larger. When the size is 280 m 2 / g or less, the precipitated silica can be easily produced, and the surface-treated precipitated silica that does not easily precipitate even when added to the water-based paint is obtained because the cohesive force between the primary silica particles is not too strong.
　本発明の表面処理沈降シリカの加熱減量は、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、比重がある程度大きいためハンドリングが良好であり、比重が大き過ぎないため沈澱した際にハードケークを形成し難いという利点がある。 The heat loss of the surface-treated precipitated silica of the present invention is preferably 9.0% or less. The smaller the heat loss, the larger the silica content effective for matting, 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 density is in this range, there is an advantage that the handling is good because the specific gravity is large to some extent, and it is difficult to form a hard cake when it precipitates because the specific density is not too large.
　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。一般に、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。但し、この範囲の固形分濃度及び粘度に限定する意図ではない。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 for commercially available water-based paints. In the water-based paint, a water-soluble resin paint, a dispersion paint, or an emulsion paint as a base is mixed with a pigment for coloring, an additive, or the like, if necessary. Generally, the solid content concentration of the water-based paint is adjusted to 10 to 50%, and the viscosity is adjusted to several tens to several thousand centipoise. However, it is not intended to be limited to the solid content concentration and viscosity in this range. The surface-treated precipitated silica of the present invention is most suitable for water-based paints used for painting 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 described in more detail based on examples. However, the examples are examples 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). Fluorescent X-ray intensity measurement of a standard sample with a known Al mass% concentration was performed to determine the relationship between the fluorescent X-ray intensity and concentration of the Al element, and the Al element content was determined from the fluorescent X-ray intensity of the surface-treated precipitated silica. Quantitative analysis of Al mass% concentration was performed using the calibration curve method for calculating the amount (mass% concentration). The quantified aluminum content was converted into oxides using the 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、粒度分布における下位からの体積積算累積値の50％の値（D50）、90％の値（D90）、及びD90とD50の比(D90/D50)をそれぞれ求めた。 2) Average particle size of surface-treated precipitated silica (D50, D90, D90 / D50)
Measure the particle size distribution using a laser diffraction type particle size distribution measuring device (model: Microtrack MT-3000, manufactured by Microtrac Bell), and the value is 50% of the cumulative volume integration value from the bottom of the particle size distribution (D50). , 90% value (D90), and the ratio of D90 to D50 (D90 / D50) were determined respectively.
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) Heat 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。つぎに、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を測定し、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 weight of surface-treated precipitated silica Measured according to the apparent specific weight measurement method according to JIS K-6220. 1.0 g of silica was poured into a cylinder (inner diameter 22.00 mm, depth 100 mm) and hit to flatten the upper surface of the silica. Next, the piston (outer diameter 21.80 mm, length 115 mm, mass 190 g) was gently dropped from above, the height of the piston protruding from the top of the cylinder was measured, and the apparent specific gravity was calculated by the following calculation.
G = S / {(H 2 -H 1 ) × 0.7854 D 2 }
G: Apparent specific density (g / cm 3 )
S: Sample weight (g)
H 2 : Difference in height between piston and cylinder in the presence of sample (cm)
H 1 : Difference in height between piston and cylinder in the absence of sample (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 by a one-point method using a fully automatic specific surface area measuring device (model: Macsorb (R) HM model-1200, manufactured by Mountec). Was done.
＜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。 <Wetness of surface-treated precipitated silica and paint evaluation>
6) Wetness: Evaluation of wetting rate 50 mL of water (pH 7.0, electrical conductivity 100 μS / cm) is placed in a 200 mL graduated disposable cup, and 1 g of surface-treated precipitated silica is added at once from above to make the entire amount water. The time required for complete acclimation was measured as the wetting rate. The evaluation was A when the wetting speed was less than 60 seconds, B for 60 to 180 seconds, C for 180 seconds or more, and only A passed.
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) Evaluation of water-based paint Put 60 g of water-based emulsion paint (trade name: Barnock WE-301; manufactured by DIC), 20 g of pure water, and 3 g of surface-treated precipitated silica in a 200 mL graduated disposable cup and put it in a high-speed mixer (model: laboratory). Dispersed at 750 rpm for 5 minutes at 750 rpm (manufactured by Primix Corporation) to prepare 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。ブツの個数は場所を変えて5か所測定し、そのブツの累計個数で分散性を評価した。
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) Dispersive paint is applied to a commercially available ABS plate (100 mm x 200 mm, manufactured by Black Coating Tester) with a No. 20 bar coater, and sedimentation of 200 μm or more existing in an arbitrary range of 8.9 mm × 6.7 mm. The number of silica aggregates (so-called lumps) was counted with a video microscope. The number of lumps was measured at 5 different locations, and the total number of lumps was used to evaluate the dispersibility.
The evaluation was judged in the following three stages from A to C, and only A was accepted.
A: Cumulative number of stuff 0
B: Cumulative number of things 1 to 4
C: Cumulative number of stuff 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。
　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 in a container with a 50 mL lid, let stand for 2 weeks, and then shake with a shaker (model: V-SX, manufactured by Iwaki) for 1 minute to settle. The state was used as an observation sample. The sedimentation state was confirmed by the ratio of silica remaining on the bottom of the container when the container was inverted so that the lid was on the bottom. The evaluation of the sedimentation state was performed in the following three stages from A to C, and only A was accepted.
A: After shaking and reversing, silica precipitation cannot be confirmed on the bottom of the container.
B: A state in which a small amount of silica precipitates is confirmed on the bottom of the container after shaking and reversing.
C: A state in which a large amount of silica is confirmed on the bottom of the container after shaking and reversing.
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 hot water and No. 3 silica (SiO 2 concentration 10.0 wt%, SiO 2 / Na 2 O molar ratio 3.2) to a 240 L stainless steel container with a jacket equipped with a stirrer and a circulation pump until the pH reaches 10.5, and stir. The temperature was raised to 86.0 ° C. (after that, stirring, circulation, and temperature conditions were carried out under the same conditions until the reaction was stopped). Next, 66.5 kg of No. 3 Keiso, 98.0 wt% concentrated sulfuric acid, and 0.674 kg of 30.0 wt% aluminum sulfate aqueous solution were simultaneously added dropwise over 200 minutes while stirring and circulating so as to maintain a pH of 10.0 to 11.0 for a neutralization reaction. After the neutralization reaction was completed, sulfuric acid was added until the pH reached 3, and the reaction was completely stopped. Then, the obtained reaction product was filtered with 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 pulverized using a reciprocating rotary stirrer (model: Agitator AP04 type: manufactured by Shimazaki Engineering Co., Ltd.), and a commercially available polyoxyalkylene alkyl ether nonionic surfactant (trade name: Neugen XL-61; No. Add 2.0% of HLB: 13) to silica, re-stirred, and then use a disc-type spray dryer (model: spray dryer AN-40R, manufactured by Ashizawa Niro Atomizer) at an outlet temperature of 110 ° C. After spray-drying under the conditions of, crush with a jet mill (model: PJM-100NP; manufactured by Nippon Pneumatic Industries, Ltd.), and coarsely with a wind classifier (model: Classile 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
In the same container and raw material as in Example 1, except that the temperature inside the container was changed to 84.0 ° C, hot water was changed to 74.0 kg, No. 3 Keiso 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 the same manner. This surface-treated precipitated silica has a lower BET specific surface area and a larger particle size as compared with 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
In Example 1, 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 aqueous aluminum sulfate 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。その後、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
Nipsil E-150J (manufactured by Tosoh Silica Co., Ltd.), which is a commercially available precipitated silica, was used as a raw powder, and this was slurried. Then, 2.0% of a polyoxyalkylene alkyl ether nonionic surfactant was added to the precipitated silica by the same method as in Example 1, and the surface-treated precipitated silica was obtained through drying, pulverization, and classification.
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
The same method as in Example 4 except that the polyoxyalkylene alkyl ether nonionic surfactant of Example 1 was changed to an anionic surfactant (trade name: Neocol YSK; manufactured by Dai-ichi 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 aqueous aluminum sulfate solution was changed to 0.169 kg in Example 1.
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 in the same manner as in Example 4 of JP-A-9-25440 (Patent Document 1). That is, 1,000 g of commercially available precipitated silica Nipsil E-200A (manufactured by Toso Silica) was charged into a Henschel mixer, and Discol 206 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), a multi-chain nonionic surfactant having a molecular weight of 90,000, was charged. , HLB: 6.0) A solution prepared by dissolving 20 g in 40 mL of ethanol was added by spraying under stirring and mixing so as to be uniform over the entire silica. After a further 10-minute mixing treatment, the mixture was taken out and dried until the alcohol was completely scattered to obtain surface-treated precipitated silica 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 aqueous aluminum sulfate solution was changed to 1.01 kg in Example 1.
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 a jet mill were changed so that the average particle size (D50) after pulverization was 11.5 μm in Example 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
*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 * 1 Ether nonionic surfactant Polyoxyethylene tridecyl ether Neugen XL-61; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
* 2 Anionic surfactant Neocol YSK; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
* 3 Multi-chain nonionic surfactant DISCOR 206; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　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 the field related to matting agents for water-based paints.

Claims (9)

  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、レーザー回折法で測定した体積平均粒子径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、但し、D90は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が90％における粒子径である、前記表面処理沈降シリカ。 Surface-treated precipitated silica for water-based paints having 0.5 to 5.0% ether-based nonionic surfactant on the surface of the precipitated silica. The surface-treated precipitated silica has an aluminum content of 0.30 to Al 2 O 3 in terms of Al 2 O 3. It is in the range of 1.00 mass%, the volume average particle size D50 measured by laser diffraction is in the range of 3.0 to 10.0 μm, and the ratio D90 / D50 is 2.0 or less, except that D90 is measured by laser diffraction. The surface-treated precipitated silica, wherein the cumulative volume-accumulated value from the bottom in the particle size distribution is the particle size at 90%.
  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、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 BET specific surface area in the range of 60 to 280 m 2 / g.
  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、請求項１又は２に記載の表面処理沈降シリカ。 The surface-treated precipitated silica according to claim 1 or 2, wherein the ether-based nonionic surfactant is a polyoxyalkylene alkyl ether nonionic surfactant.
  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、請求項1～３のいずれかに記載の表面処理沈降シリカ。 The surface-treated precipitated silica according to any one of claims 1 to 3, wherein the ether-based nonionic surfactant has an HLB in the range of 10.0 to 15.0.
  5. 前記表面処理沈降シリカは、加熱減量が9.0％以下である、請求項１～４のいずれかに記載の表面処理沈降シリカ。 The surface-treated precipitated silica according to any one of claims 1 to 4, wherein the surface-treated precipitated silica has a heat loss of 9.0% or less.
  6. 見掛比重が0.05～0.30g/mLの範囲にある、請求項１～５のいずれかに記載の表面処理沈降シリカ。 The surface-treated precipitated silica according to any one of claims 1 to 5, wherein the apparent specific gravity is in the range of 0.05 to 0.30 g / mL.
  7. 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0.45～0.85質量％の範囲にある、請求項１～６のいずれかに記載の表面処理沈降シリカ。 The surface-treated precipitated silica according to any one of claims 1 to 6, wherein the surface-treated precipitated silica has an aluminum content in the range of 0.45 to 0.85% by mass in terms of Al 2 O 3.
  8. 前記レーザー回折法で測定した体積平均粒子径D50が3.5～9.0μmの範囲である、請求項１～７のいずれかに記載の表面処理沈降シリカ。 The surface-treated precipitated silica according to any one of claims 1 to 7, wherein the volume average particle diameter D50 measured by the laser diffraction method is in the range of 3.5 to 9.0 μm.
  9. 前記比D90/D50が1.4～1.9である、請求項１～８のいずれかに記載の表面処理沈降シリカ。
     
          The surface-treated precipitated silica according to any one of claims 1 to 8, wherein the ratio D90 / D50 is 1.4 to 1.9.
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