WO2021246191A1 - 塗料艶消し用表面処理含水ケイ酸及びその製造方法 - Google Patents

塗料艶消し用表面処理含水ケイ酸及びその製造方法 Download PDF

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WO2021246191A1
WO2021246191A1 PCT/JP2021/019277 JP2021019277W WO2021246191A1 WO 2021246191 A1 WO2021246191 A1 WO 2021246191A1 JP 2021019277 W JP2021019277 W JP 2021019277W WO 2021246191 A1 WO2021246191 A1 WO 2021246191A1
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silicic acid
hydrous silicic
group
treated
mass
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French (fr)
Japanese (ja)
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大祐 古城
英紀 中上
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Tosoh Silica Corp
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Tosoh Silica Corp
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Priority to JP2022528737A priority Critical patent/JP7439257B2/ja
Priority to CN202180035864.5A priority patent/CN115667436A/zh
Priority to KR1020227044168A priority patent/KR102747609B1/ko
Publication of WO2021246191A1 publication Critical patent/WO2021246191A1/ja
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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
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • 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
    • C09C1/30—Silicic acid
    • 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
    • C09C3/12—Treatment with organosilicon 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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

Definitions

  • the present invention relates to a surface-treated hydrous silicic acid used for matting paints, inks and the like (hereinafter, these are collectively referred to as paints). More specifically, the present invention is a novel luster capable of exhibiting excellent scratch resistance and matting performance in a well-balanced manner by sufficiently binding a surface treatment agent having a reactive functional group to the surface of hydrous silicic acid. Provided is a surface-treated hydrous silicic acid for erasing.
  • the matte coating film has been used because it has a high-class appearance and has the effect of hiding molding unevenness and scratches on the surface of the object to be coated.
  • hydrous silicic acid whose particle size distribution is controlled to a micron size by pulverization, classification, etc. has been conventionally used as a matting agent for paints.
  • Hydrous silicic acid is suitable as a matting agent because it is excellent in handling and matting performance.
  • the matte coating film is often used for parts where appearance is important, it is required to be resistant to scratches that lead to deterioration of appearance. With such increasing demands, the applicable range of cross-linked or polymerized paints such as energy ray-curable type having excellent scratch resistance has expanded.
  • crosslinked or polymerized paint examples include epoxy resin paint, aminoalkido resin paint, phenol resin paint, heat-curable acrylic resin paint, urethane resin paint, and UV and EB curable paint. Since these paints are paints that are cured by heat, a catalyst, energy rays, or the like, the paint resin molecules are bonded to each other directly or via a cross-linking agent during curing to form a strong coating film.
  • Patent Document 1 Japanese Patent Publication No. 2010-521539 (WO2008 / 068003)
  • Patent Document 2 Japanese Patent Application Laid-Open No. 11-60231 (EP0884277 A1) The entire description of Patent Documents 1 and 2 is incorporated herein by reference in particular.
  • the scratch resistance of the coating film is improved by surface-treating the hydrous silicic acid with wax.
  • the wax and the hydrous silicic acid are not bonded, and the share is applied when the paint is blended, so that the paint temperature rises and the wax may elute in the paint.
  • the improvement of scratch resistance by blending hydrous silicic acid having a dense aggregated structure as in Patent Document 2 is expected to have a certain effect.
  • hydrophobization treatment with dimethyl silicone oil or the like is also known, and the possibility of bleeding is low because less elution into paint than wax.
  • dimethylsilicone oil and the like do not interact with the paint resin component and do not form a bond, no improvement effect can be expected in terms of scratch resistance.
  • the present inventors have an excellent balance between matte performance and scratch resistance, focusing on the fact that there is little elution into the paint, the adhesion to the paint resin component is high, and the water-containing silicic acid does not easily fall off from the paint film.
  • a surface treatment agent having a functional group that interacts with or forms a bond with the resin component of the paint and also binds to the surface of the hydrous silicic acid can be bonded to 95% or more of the hydrous silicic acid, and the amount of the surface treatment agent can be obtained. It has been found that by adjusting the M value of the surface-treated hydrous silicic acid to be 0 vol% and having a predetermined scratch resistance, the matting performance is high, and both scratch resistance and reduction of surface treatment agent elution can be achieved.
  • the present invention is as follows. [1] Hydrous silicic acid surface-treated with organosilicon compound residues, (1)
  • the organic silicon compound residue has at least one functional group selected from the group consisting of an amino group, an epoxy group, an isocyanate group, a vinyl group, a metaacryloyl group, and an acryloyl group.
  • the M value is 0 vol%
  • the amount of carbon measured by the carbon analyzer is in the range of 0.5 to 6% by mass, and (4) the carbon is dispersed in toluene at a concentration of 2% by mass, and carbon analysis is performed at 20 ° C. for about 24 hours.
  • the bond ratio between the organosilicon compound residue represented by the ratio of the carbon content measured by the apparatus (however, the carbon content before the lapse is 100%) and the hydrous silicic acid is 95% or more.
  • Surface treatment Hydrous silicic acid [2] The surface-treated hydrous silicic acid according to [1], wherein the organosilicon compound residue has at least one functional group selected from the group consisting of a vinyl group, a metaacryloyl group, and an acryloyl group. [3] The surface-treated hydrous silicic acid according to [1] or [2], wherein the amount of aluminum measured by fluorescent X-ray quantitative analysis is in the range of 0.1 to 1.5% by mass in terms of Al 2 O 3.
  • [4] The surface-treated hydrous silicic acid according to any one of [1] to [3], wherein the volume average particle diameter D50 value measured by a laser diffraction method is in the range of 1 to 20 ⁇ m.
  • [5] The surface-treated hydrous silicic acid according to any one of [1] to [4], wherein the maximum particle size measured by a laser diffraction method is 5 to 70 ⁇ m.
  • [6] The surface-treated hydrous silicic acid according to any one of [1] to [5], wherein the ratio D90 / D50 of the D90 value to the D50 value measured by the laser diffraction method is less than 1.8.
  • the surface-treated hydrous silicic acid according to any one of [1] to [6], which has a DBA adsorption amount of 30 mmol / kg or more.
  • the hydrous silicic acid was heated at a temperature in the range of 80 to 200 ° C. in the presence of water and surface-treated with the organic silicon compound residue derived from the silane coupling agent.
  • the organic silicon compound residue comprises obtaining an acid and has at least one functional group selected from the group consisting of an amino group, an epoxy group, an isocyanate group, a vinyl group, a metaacryloyl group, and an acryloyl group.
  • the method for producing a surface-treated hydrous silicic acid according to any one of [1] to [7].
  • a surface-treated water-containing silicic acid for matting which is excellent in matting performance and scratch resistance, reduces elution of the surface treatment agent, and is less likely to cause appearance defects.
  • FIG. 1 shows an ultra-depth shape measurement micrograph of the coating film state after the scratch resistance test (Canvas No. 6 5,000 reciprocations) in Example 1.
  • FIG. 2 shows an ultra-depth shape measurement micrograph of the coating film state after the scratch resistance test (Canvas No. 6 5,000 round trips) in Reference Example 4.
  • the surface-treated hydrous silicic acid of the present invention is a hydrous silicic acid surface-treated with organosilicon compound residues.
  • the organic silicon compound residue has at least one functional group selected from the group consisting of an amino group, an epoxy group, an isocyanate group, a vinyl group, a metaacryloyl group, and an acryloyl group.
  • the M value is 0 vol%
  • the amount of carbon measured by the carbon analyzer is in the range of 0.5 to 6% by mass, and (4) the carbon is dispersed in toluene at a concentration of 2% by mass, and carbon analysis is performed at 20 ° C. for about 24 hours.
  • the hydrous silicic acid surface-treated with the organosilicon compound residue of the present invention is a hydrous silicic acid produced by a wet method.
  • the hydrous silicic acid is not particularly limited.
  • the hydrous silicic acid produced by the wet method includes both the precipitation method hydrous silicic acid and the gel method hydrous silicic acid.
  • Organic silicon compound residue The organic silicon compound residue has at least one functional group selected from the group consisting of an amino group, an epoxy group, an isocyanate group, a vinyl group, a metaacryloyl group, and an acryloyl group.
  • the organosilicon compound residue for surface-treating the hydrous silicic acid of the present invention is derived from the silane coupling agent.
  • the silane coupling agent has two or more different functional groups, and one functional group is hydrolyzed to become a hydrolysis intermediate having a silanol group.
  • the silanol group of the hydrolysis intermediate reacts with the silanol group on the hydrous silicic acid to fix the organosilicon compound residue on the surface of the hydrous silicic acid.
  • Some or all of the remaining functional groups are at least one functional group selected from the group consisting of the above amino group, epoxy group, isocyanate group, vinyl group, metaacryloyl group, and acryloyl group, and these functional groups are used.
  • the group is reactive with the organic compounds contained in the paint. Therefore, it can be expected that the water-containing silicic acid and the resin are brought into close contact with each other by forming an interaction or bond with the resin of the paint to improve the scratch resistance and prevent the water-containing silicic acid particles from falling off.
  • These functional groups can be appropriately determined in consideration of the reactivity with the organic compound contained in the coating material.
  • These functional groups are preferably an amino group, an epoxy group, a vinyl group, a metaacryloyl group and an acryloyl group, more preferably a vinyl group, an epoxy group, a metaacryloyl group and an acryloyl group, and further preferably a vinyl group.
  • a functional group having an ethylenic double bond consisting of a metaacryloyl group and an acryloyl group. Most preferably, it is a metaacryloyl group and an acryloyl group.
  • the surface-treated hydrous silicic acid of the present invention has an M value of 0 vol%.
  • the method of measuring the M value will be described in Examples.
  • the M value is the minimum concentration of methanol in which a predetermined amount of surface-treated hydrous silicic acid sample is placed in a mixed solution with water in which the concentration of methanol is changed at intervals of 5 vol%, and the mixed solution is suspended after shaking and allowing to stand. Indicated by.
  • a M value of 0 vol% means that it is also suspended in water that does not contain methanol.
  • the surface of the hydrous silicic acid maintains hydrophilicity, or the hydrophobized surface has a certain amount of hydrophilic portions and is not completely hydrophobized.
  • the surface-treated hydrous silicic acid of the present invention is the latter of the above. Therefore, when blended in a paint, it exhibits matting performance and has good settling stability.
  • the M value exceeds 0 vol% and becomes hydrophobic, for example, 5 vol% or more, it is difficult to form floculate in the paint, so that unevenness cannot be formed on the coating film surface and the matting performance deteriorates. In addition, sedimentation stability is reduced and tends to form non-redispersible hard cakes.
  • the surface-treated hydrous silicic acid of the present invention has a carbon content in the range of 0.5 to 6% by mass as measured by a carbon analyzer.
  • the carbon measured by the carbon analyzer is mainly derived from the organosilicon compound residues used as the surface treatment agent.
  • the carbon content is in this range, the surface of the hydrous silicic acid can be effectively covered with the organosilicon compound residue, and the effect of improving the scratch resistance is enhanced. If the amount of carbon is less than 0.5% by mass, the amount of surface treatment is small and the effect of improving scratch resistance cannot be sufficiently obtained.
  • the carbon content exceeds 6% by mass the coating of the organosilicon compound residue becomes excessive, and the surface of the hydrous silicic acid and the unreacted surface treatment agent increase.
  • the surface treatment of the surface treatment agent may cause bleeding from the water-containing silicic acid to the coating film, deterioration of the appearance due to foaming of the coating film, or deterioration of the matting performance.
  • the carbon content is preferably in the range of 0.6 to 5.8% by mass, more preferably in the range of 0.7 to 5.5% by mass.
  • the surface-treated hydrous silicic acid of the present invention is dispersed in toluene at a concentration of 2% by mass, and is an organic represented by the ratio of the amount of carbon measured by a carbon analyzer at 20 ° C. for about 24 hours.
  • the binding rate between the silicon compound residue and the hydrous silicic acid is 95% or more.
  • the carbon content in the surface-treated hydrous silicic acid before the lapse of time, that is, before the elution test to toluene is 100%.
  • the binding rate indicates the ratio of organosilicon compound residues chemically bound to hydrous silicic acid, and at 95% or more, most of the organosilicon compound residues derived from the surface treatment agent are bound to hydrous silicic acid. There is. As a result, when blended in the paint film, the surface treatment agent is not liberated in the paint film and the appearance of the paint film is not deteriorated, and a paint film having excellent scratch resistance is formed. When the binding rate is less than 95%, the appearance is deteriorated due to the release of the treatment agent and the scratch resistance effect is deteriorated.
  • the binding rate is more preferably 96% or more, still more preferably 97% or more.
  • the surface-treated hydrous silicic acid of the present invention has an aluminum amount measured by fluorescent X-ray quantitative analysis in the range of 0.1 to 1.5% (mass basis) in terms of Al 2 O 3. Is preferable. Within this range, the amount of solid acid present on the surface of the hydrous silicic acid increases, the reactivity with the silane coupling agent which is the surface treatment agent becomes high, and the amount of coating with the organosilicon compound residue is the same. Also, a surface-treated hydrous silicic acid having a high binding rate can be obtained. When the amount of aluminum is 0.1% or more in terms of Al 2 O 3 , the reactivity with the surface treatment agent is good.
  • the amount of aluminum in the hydrous silicic acid increases, the cohesiveness of the hydrous silicic acid tends to increase.
  • the amount of aluminum is 1.5% or less in terms of Al 2 O 3 , it is possible to avoid deterioration of the appearance of the coating film due to the appearance of agglomerates on the surface of the coating film due to cohesiveness.
  • the amount of aluminum is preferably in the range of 0.2 to 1.3%, more preferably in the range of 0.3 to 1.1% in terms of Al 2 O 3.
  • the surface-treated hydrous silicic acid of the present invention preferably has a volume average particle diameter D50 value in the range of 1 to 20 ⁇ m as measured by a laser diffraction method. When the D50 value is in this range, sufficient matting performance is exhibited. If the D50 value is less than 1 ⁇ m, the particle size is too small and it tends to be difficult to obtain sufficient matting performance. If the volume average particle diameter D50 value exceeds 20 ⁇ m, the matte surface is too rough when used in a paint, and the appearance may be deteriorated.
  • the D50 value is preferably in the range of 1 to 18 ⁇ m, more preferably 1 to 16 ⁇ m, still more preferably 1 to 14 ⁇ m, and most preferably 1.5 to 10 ⁇ m.
  • the surface-treated hydrous silicic acid of the present invention preferably has a maximum particle size measured by a laser diffraction method in the range of 5 to 70 ⁇ m.
  • the maximum particle size is in this range, the particles are not too rough and the appearance when formed into a coating film is excellent.
  • the maximum particle size is preferably 6 to 65 ⁇ m, more preferably 7 to 60 ⁇ m.
  • the surface-treated hydrous silicic acid of the present invention preferably has a ratio D90 / D50 of the D90 value to the D50 value measured by the laser diffraction method of less than 1.8.
  • the surface-treated hydrous silicic acid having a D90 / D50 of less than 1.8 has a sharp particle size distribution and is excellent in matting performance.
  • D90 / D50 is preferably less than 1.7.
  • the surface-treated hydrous silicic acid of the present invention preferably has a DBA adsorption amount of 30 mmol / kg or more.
  • Surface-treated hydrous silicic acid having a DBA adsorption amount of 30 mmol / kg or more has an appropriate surface treatment, and no deterioration in appearance or matting performance is observed.
  • the amount of DBA adsorbed is preferably 40 mmol / kg or more, more preferably 50 mmol / kg or more, still more preferably 60 mmol / kg or more, and most preferably 80 mmol / kg or more.
  • the surface-treated water-containing silicic acid of the present invention is for matting paint.
  • the biggest feature is that the surface treatment agent that interacts with or bonds with the resin of the paint sufficiently binds to the hydrous silicic acid and does not elute into the paint, so that the appearance of the paint film is not impaired and the scratch resistance is greatly improved. There is.
  • the matte surface-treated water-containing silicic acid of the present invention can be used regardless of the type of paint. Particularly preferred is to be used in energy ray-curable paints such as UV (ultraviolet) and EB (electron beam), and more prominently if the surface-treated hydrous silicic acid of the present invention is used in these paints. A coating film with improved scratch resistance can be realized.
  • energy ray-curable paints such as UV (ultraviolet) and EB (electron beam
  • ⁇ Manufacturing method> For the surface-treated hydrous silicic acid of the present invention, after mixing the hydrous silicic acid and the silane coupling agent, 0.05 to 15 parts by mass of water is added to 100 parts by mass of the hydrous silicic acid, and 80 parts by mass is added under reduced pressure conditions. It is produced by a method comprising heating to a temperature in the range of ⁇ 200 ° C. to obtain hydrous silicic acid surface-treated with organic silicon compound residues.
  • the hydrous silicic acid used as a raw material is the same as described above, and is not particularly limited as long as it is a hydrous silicic acid produced by a wet method, but it is considered that the surface-treated hydrous silicic acid of the present invention is used for matting. Then, it is appropriate that the BET specific surface area is in the range of 50 to 600 m 2 / g. Further, the hydrous silicic acid used as a raw material has a surface-treated hydrous silicic acid having a similar volume average particle diameter D50 value that the volume average particle diameter D50 value measured by the laser diffraction method is in the range of 1 to 20 ⁇ m. It is preferable from the viewpoint of obtaining.
  • the silane coupling agent is a precursor of organosilicon compound residues.
  • the organic silicon compound residue of the surface-treated hydrous silicic acid has at least one functional group selected from the group consisting of an amino group, an epoxy group, an isocyanate group, a vinyl group, a metaacryloyl group, and an acryloyl group. .. Silane coupling agents also have similar functional groups.
  • the surface-treated organosilicon compound residue derived from a vinyl group having an ethylenic double bond, a metaacryloyl group, and a silane coupling agent having an acryloyl group is water-containing.
  • Acryloyl showed the best scratch resistance effect.
  • hydrous silicic acid surface-treated with organosilicon compound residues derived from a silane coupling agent having a metaacryloyl group and an acryloyl group exhibited a remarkably excellent scratch resistance effect.
  • silane coupling agent containing an amino group examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-.
  • examples thereof include aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, and N-phenyl-3-aminopropyltrimethoxysilane.
  • silane coupling agent containing an epoxy group examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3 -Glysidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane can be mentioned.
  • silane coupling agent containing an isocyanate group examples include 3-isocyanatepropyltriethoxysilane and ⁇ -isocyanatepropyltrimethoxysilane.
  • silane coupling agent containing a vinyl group examples include vinyltrimethoxysilane and vinyltriethoxysilane.
  • silane coupling agent containing a metaacryloyl group examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxy. Silane can be mentioned.
  • silane coupling agent containing an acryloyl group examples include 3-acryloxypropyltrimethoxysilane.
  • the silane coupling agent having a functional group other than the above group there is one having a sulfide group, a phenyl group, a mercapto group and the like.
  • these functional groups do not have reactivity with the organic compounds contained in the paint. Therefore, the silane coupling agent having these functional groups does not interact with or form a bond with the resin of the paint, and even if the surface treatment is performed, it cannot be expected to improve the scratch resistance and prevent the water-containing silicic acid particles from falling off.
  • silicone oil or the like as a surface treatment agent.
  • straight silicone oil generally used as a hydrophobic agent for hydrous silicic acid does not have an amino group, an epoxy group, an isocyanate group, a vinyl group, a metaacryloyl group, and an acryloyl group. Therefore, even if the surface is treated with straight silicone oil, it does not interact with or bond with the resin of the paint, and it cannot be expected to improve the scratch resistance and prevent the water-containing silicic acid particles from falling off.
  • some have an amino group or an epoxy group.
  • the proportion of reactive functional groups in the molecule is limited, there are few points that interact with or bond with the resin of the paint, and there are no groups that bind to hydrous silicic acid, so the binding rate with hydrous silicic acid can be determined. Difficult to raise. Therefore, even in the case of the modified silicone oil, the effects of improving the scratch resistance and preventing the water-containing silicic acid particles from falling off are limited as compared with the case of using the silane coupling agent.
  • silane coupling agent for mixing the silane coupling agent and the hydrous silicic acid (powder), for example, it is appropriate to add an appropriate amount of the silane coupling agent to the hydrous silicic acid.
  • the addition may be in a stationary state or a mixed state of the hydrous silicic acid, but the addition in the mixed state is preferable from the viewpoint that the silane coupling agent can be uniformly mixed in the water-containing silicic acid.
  • dropping, spraying or the like is preferable, and spray spraying is more preferable.
  • the addition of water to the mixture of hydrous silicic acid and the silane coupling agent may be in a stationary state or a mixed state, but the addition in the mixed state uniformly adds water to the mixture. It is preferable from the viewpoint that it can be added. As a method for adding water, dripping, spray spraying and the like are preferable, and spray spraying is more preferable. Further mixing is also possible after the addition of the silane coupling agent and / or after the addition of water.
  • the order of adding the silane coupling agent and water is important, and water is added after the silane coupling agent is added to the hydrous silicic acid.
  • water is added after the silane coupling agent is added to the hydrous silicic acid.
  • the amount of water added is preferably in the range of 0.05 to 15 parts by mass with respect to 100 parts by mass of hydrous silicic acid. If it is less than 0.05 parts by mass, the amount of water added may be small and the effect may be insufficient. If the amount of water added exceeds 15 parts by mass, the amount added is too large, so that agglomerates of hydrous silicic acid may be formed due to water, and the appearance of the coating film may be deteriorated.
  • the amount of water added is preferably in the range of 0.1 to 12 parts by mass, more preferably 0.15 to 10 parts by mass, and further preferably 0.2 to 8 parts by mass.
  • heat by dry treatment at a temperature in the range of 80 to 200 ° C.
  • various static and batch type mixers and dryers are preferably used.
  • a box-type dryer, a muffle furnace, a continuous heating furnace, or the like is suitable.
  • an FM mixer, a Nesco heater, an axial mixer and the like are preferably used.
  • the heating temperature is in the range of 80 to 200 ° C, preferably in the range of 100 ° C to 180 ° C, and more preferably in the range of 110 to 160 ° C.
  • the heat treatment time is not particularly limited, but is preferably in the range of, for example, 30 minutes to 12 hours from the viewpoint of stabilizing physical properties and productivity. Particularly preferably, it is in the range of 45 minutes to 6 hours.
  • the product may be naturally allowed to cool, or the container may be cooled by water cooling or the like.
  • crushing and classification may be performed to adjust the particle size.
  • the crushing device is not particularly limited.
  • a jet mill, an impact type pin mill, or the like is preferably used.
  • the classifying machine is not particularly limited, but for example, a wind power classifying machine or the like is preferably used.
  • the matte surface-treated water-containing silicic acid of the present invention has a functional group that interacts with the paint resin (for example, polar attraction such as hydrogen bond) or forms a bond. Further, by using a predetermined amount of the surface treatment agent that also binds to the surface of the water-containing silicic acid, the binding rate between the water-containing silicic acid and the surface treatment agent is high in the surface-treated water-containing silicic acid of the present invention. Release from silicic acid can be reduced. It can be expected that the coating film containing the surface-treated water-containing silicic acid of the present invention as a matting agent exhibits excellent matting performance and scratch resistance in a well-balanced manner and does not cause deterioration of the appearance.
  • the paint resin for example, polar attraction such as hydrogen bond
  • M value measuring method Prepare a mixed solution with water in which the concentration of methanol is changed from 0 vol% to 100 vol% at intervals of 5 vol%, and put 5 ml of this in a test tube having a volume of 10 ml. Next, 0.1 to 0.2 g of a surface-treated hydrous silicic acid sample, which is a test powder, is added, shaken and allowed to stand, and then the concentration of the minimum methanol in which the mixed solution is suspended is observed, and this is taken as the M value. ..
  • Carbon content analysis The carbon content of the surface-treated hydrous silicic acid sample is 1,250 ° C, oxygen inflow using the combustion in oxygen stream-non-dispersed infrared absorption method (solid carbon analyzer carbon analyzer EMIA-110 manufactured by Horiba Seisakusho Co., Ltd.).
  • the sample was heat-treated under the conditions of a pressure of 0.07 MPa and a measurement time of 90 seconds, and the carbon content was measured by quantifying CO and CO 2 gas with an infrared detector (NDIR) in the apparatus.
  • NDIR infrared detector
  • the supernatant liquid is discarded again, n-hexane is added to loosen the surface-treated hydrous silicic acid sample, and then the operation of centrifugation is performed twice. After discarding the supernatant, it was dried in a dryer at 80 ° C. for 15 hours or more, and the remaining solid content was used as surface-treated hydrous silicic acid after the elution test, and carbon content analysis was performed.
  • Fluorescent X-ray (aluminum content) analysis The amount of aluminum in the surface-treated hydrous silicic acid was measured using a scanning fluorescent X-ray analyzer ZSX Primus II manufactured by Rigaku Corporation. 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 fluorescent X-ray intensity of the surface-treated hydrous silicic acid was used to determine the Al element. Quantitative analysis of Al mass% concentration was performed using a calibration curve method for calculating the content (mass% concentration). Oxide basis in the analysis software included with the apparatus, the quantitative aluminum amount was calculated Al 2 O 3 wt% concentration.
  • the measurement sample was prepared by a pressure molding method in which surface-treated hydrous silicic acid was placed in a ring-shaped mold and pressed.
  • Table 1 shows the paint composition (mass standard).
  • Oligomer NK oligo UA-1100H manufactured by Shin Nakamura Chemical Industry Co., Ltd. (containing acryloyl (acrylic) group and urethane group)
  • Monomer DPHA manufactured by Dycel Ornex (containing acryloyl (acrylic) group and ether moiety)
  • Photopolymerization Initiator 1 BASF Ormirad 184
  • Photopolymerization Initiator 2 BASF Ormirad TPO H Leveling agent: BYK-UV-3570 manufactured by BYK Chemie
  • Gloss value measurement A 60 ° gloss value was measured using a gloss meter VG7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
  • the appearance of the coating film was visually judged.
  • the one having a uniform appearance without uneven gloss was designated as A
  • the one having a coating film defect such as uneven gloss depending on the location was designated as B
  • the one having a coating film defect as a whole was designated as C.
  • Example 1 As a raw material, 500 g of Nipsil E-220A (BET specific surface area 135 m 2 / g, volume average particle diameter D50 value 4.2 ⁇ m) was used as a precipitation method hydrous silicic acid.
  • a silane coupling agent containing a typical organosilicon compound (OFS-6030 manufactured by Dow Toray Co., Ltd.), which is 6 parts by mass with respect to 100 parts by mass of hydrous silicic acid, is added to hydrous silicic acid by hand spraying. Sprayed. After the spraying of the surface treatment agent was completed, 2 parts by mass of water was sprayed on the hydrous silicic acid in the same manner.
  • OFS-6030 manufactured by Dow Toray Co., Ltd.
  • FIG. 1 shows a micrograph of the ultra-deep shape measurement after the scratch resistance test of the obtained coating film. It can be seen that the coating film surface is clean even after the scratch resistance test.
  • Example 2 4.0 kg of Nipsil E-220A (BET specific surface area 135 m 2 / g, volume average particle diameter D50 value 4.2 ⁇ m) was used as the raw material for the precipitation method hydrous silicic acid, and 12 parts by mass with respect to 100 parts by mass of hydrous silicic acid.
  • a silane coupling agent containing a metaacryloyl group KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.
  • a silane coupling agent was sprayed on the hydrous silicic acid while mixing the hydrous silicic acid using an axial mixer UA-10 manufactured by Sugiyama Heavy Industries.
  • Example 3 Surface treatment was performed in the same manner as in Example 2 except that Nipsil E-200A (BET specific surface area 130 m 2 / g, volume average particle diameter D50 value 5.6 ⁇ m) was used as the raw material for the precipitation method hydrous silicic acid. Treated hydrous silicic acid was obtained.
  • Nipsil E-200A BET specific surface area 130 m 2 / g, volume average particle diameter D50 value 5.6 ⁇ m
  • Example 4 Nipsil E-150J (BET specific surface area 100 m 2 / g, volume average particle diameter D50 value 8.3 ⁇ m) was used as the raw material for the precipitation method hydrous silicic acid, and 12 parts by mass of acryloyl group was used with respect to 100 parts by mass of hydrous silicic acid.
  • the surface treatment was carried out in the same manner as in Example 1 except that the contained silane coupling agent (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to obtain surface-treated water-containing silicic acid.
  • silane coupling agent KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 5 Using NIPGEL BY-800 (BET specific surface area 500 m 2 / g, volume average particle diameter D50 value 14.5 ⁇ m) as the gel method hydrous silicic acid as a raw material, 15 parts by mass of metaacryloyl with respect to 100 parts by mass of hydrous silicic acid.
  • the surface treatment was performed in the same manner as in Example 1 except that the group-containing silane coupling agent (KBM-503) was added and the amount of water added was 10 parts by volume with respect to the hydrous silicic acid. Obtained acid.
  • KBM-503 group-containing silane coupling agent
  • Reference example 1 Surface treatment was performed in the same manner as in Example 3 except that 20 parts by mass of a metaacryloyl group-containing silane coupling agent (KBM-503) was added to 100 parts by mass of hydrous silicic acid to obtain surface-treated hydrous silicic acid. .. The carbon content was 6.3% by mass, and the surface treatment was excessive, resulting in uneven gloss and deterioration of the appearance of the coating film.
  • KBM-503 metaacryloyl group-containing silane coupling agent
  • Reference example 2 12 parts by mass of a metaacryloyl group-containing silane coupling agent (KBM-503) was added to 100 parts by mass of hydrous silicic acid, and surface treatment was performed in the same manner as in Example 1 except that water was not added, and the surface was treated. Treated hydrous silicic acid was obtained. Since no water was added before the vacuum heat treatment, the binding rate was low, and as a result, the scratch resistance was low.
  • KBM-503 metaacryloyl group-containing silane coupling agent
  • Reference example 3 4.0 kg of Nipsil E-220A (BET specific surface area 135 m 2 / g, volume average particle diameter D50 value 4.2 ⁇ m) was used as the raw material for the precipitation method hydrous silicic acid, and 6 mass with respect to 100 parts by mass of hydrous silicic acid. I prepared the water for the club. Water was sprayed on the hydrous silicic acid while mixing the hydrous silicic acid using an axial mixer. After the water spraying was completed, only mixing was performed, and 12 parts by mass of the metaacryloyl group-containing silane coupling agent (KBM-503) was sprayed on the hydrous silicic acid as it was.
  • KBM-503 metaacryloyl group-containing silane coupling agent
  • Example 3 the surface-treated hydrous silicic acid was obtained by the same method as in Example 2 except that water was sprayed first and then the silane coupling agent was sprayed (the order of addition was different). Since water spraying was performed before adding the silane coupling agent to the hydrous silicic acid, the binding rate was low and the wear resistance was deteriorated as compared with Example 2.
  • Reference example 4 When blending the paint, surface-treated water-containing silicic acid is not used, and it is 6 with respect to the commercially available Nipsil E-220A (BET specific surface area 135 m 2 / g, volume average particle diameter D50 value 4.2 ⁇ m) and 100 parts by mass of water-containing silicic acid.
  • a paint was prepared by directly adding a silane coupling agent containing a metaacryloyl group (KBM-503) by mass to the paint. The obtained paint was used for painting in the same manner as in Example 1.
  • FIG. 2 shows a micrograph of the ultra-deep shape measurement after the scratch resistance test on the surface of the coating film. It can be seen that the unevenness disappears from the surface of the coating film, and the coating film is scraped or silica is removed.
  • Table 2 shows the physical characteristics of the hydrous silicic acid of Examples 1 to 5 and Reference Examples 1 to 4 and the evaluation results of the coating film prepared by the coating film preparation method.
  • the present invention is useful in the field of paints related to surface treated hydrous silicic acid.

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  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025119939A1 (en) 2023-12-03 2025-06-12 Aphaia Pharma Ag Treatment of obesity and related conditions by circadian administration of enterokine-stimulating compositions
LU103233B1 (en) 2023-12-21 2025-06-24 Aphaia Ip Ag Treatment of obesity and related conditions by circadian administration of enterokine-stimulating compositions

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04202008A (ja) * 1990-11-29 1992-07-22 Moon Star Co 水系ポリウレタン用フロスト剤およびその製造方法
JPH08245835A (ja) * 1995-03-10 1996-09-24 Nec Corp シリカ粒子を含む樹脂組成物およびシリカ粒子の表面 処理方法
JP2002201380A (ja) * 2000-09-30 2002-07-19 Degussa Ag アルミニウムをドープした沈降珪酸、その製造方法、その使用および沈降珪酸を含有する塗料製剤
JP2004099435A (ja) * 2002-09-06 2004-04-02 Degussa Ag 沈降ケイ酸をベースとする効果的艶消し剤
JP2005307158A (ja) * 2003-12-26 2005-11-04 Fuji Photo Film Co Ltd 無機酸化物微粒子分散物、コーティング組成物、光学フィルム、反射防止フィルム、偏光板、及び液晶表示装置
JP2015528528A (ja) * 2012-09-12 2015-09-28 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． 耐艶性および低光沢性を示す硬化性フィルム形成組成物
JP2016525158A (ja) * 2013-06-26 2016-08-22 モメンティブ パフォーマンス マテリアルズ ゲーエムベーハー 光硬化性コーティング組成物およびその使用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK2099873T3 (en) 2006-12-07 2016-01-25 Grace Gmbh & Co Kg Matting Agent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04202008A (ja) * 1990-11-29 1992-07-22 Moon Star Co 水系ポリウレタン用フロスト剤およびその製造方法
JPH08245835A (ja) * 1995-03-10 1996-09-24 Nec Corp シリカ粒子を含む樹脂組成物およびシリカ粒子の表面 処理方法
JP2002201380A (ja) * 2000-09-30 2002-07-19 Degussa Ag アルミニウムをドープした沈降珪酸、その製造方法、その使用および沈降珪酸を含有する塗料製剤
JP2004099435A (ja) * 2002-09-06 2004-04-02 Degussa Ag 沈降ケイ酸をベースとする効果的艶消し剤
JP2005307158A (ja) * 2003-12-26 2005-11-04 Fuji Photo Film Co Ltd 無機酸化物微粒子分散物、コーティング組成物、光学フィルム、反射防止フィルム、偏光板、及び液晶表示装置
JP2015528528A (ja) * 2012-09-12 2015-09-28 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． 耐艶性および低光沢性を示す硬化性フィルム形成組成物
JP2016525158A (ja) * 2013-06-26 2016-08-22 モメンティブ パフォーマンス マテリアルズ ゲーエムベーハー 光硬化性コーティング組成物およびその使用

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025119939A1 (en) 2023-12-03 2025-06-12 Aphaia Pharma Ag Treatment of obesity and related conditions by circadian administration of enterokine-stimulating compositions
LU103233B1 (en) 2023-12-21 2025-06-24 Aphaia Ip Ag Treatment of obesity and related conditions by circadian administration of enterokine-stimulating compositions

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