WO2024001464A1 - Sol de silice creux, sa méthode de préparation, et composition de revêtement et produit associé - Google Patents

Sol de silice creux, sa méthode de préparation, et composition de revêtement et produit associé Download PDF

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WO2024001464A1
WO2024001464A1 PCT/CN2023/090053 CN2023090053W WO2024001464A1 WO 2024001464 A1 WO2024001464 A1 WO 2024001464A1 CN 2023090053 W CN2023090053 W CN 2023090053W WO 2024001464 A1 WO2024001464 A1 WO 2024001464A1
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hollow silica
silica sol
group
solvent
alkyl
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PCT/CN2023/090053
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赵永亮
朱晓敏
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宁波特粒科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • C01B33/141—Preparation of hydrosols or aqueous dispersions
    • 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
    • C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • Hollow silica particles have the characteristics of high porosity, low refractive index, low dielectric constant, and biological non-toxicity. Therefore, they are widely used in lightweight, low-reflection materials, anti-reflective coatings, semiconductor materials, and active molecule loading and sustained release. and other fields.
  • the present invention is completed to solve at least part of the above problems, and its purpose is to provide a hollow silica sol with reduced viscosity, good stability, high hardness and good wear resistance when forming a coating on a substrate. Improved adhesion to substrate.
  • the transparent coating layer is formed as an anti-reflection layer, the refractive index is reduced, the anti-reflection performance is improved, and the moisture and heat resistance is improved.
  • the aforementioned hollow silica sol is the aforementioned hollow silica sol of the present invention, or is based on the aforementioned hollow silica sol of the present invention.
  • the hollow silica sol is prepared by a preparation method.
  • Q3/(Q1+Q2+Q3+Q4) is 0.01 ⁇ 0.6, and,
  • the preparation method of hollow silica sol according to any one of [6] and [1] to [5] is characterized by comprising the following steps:
  • Hollow silica generation step disperse the aforementioned organosilicon intermediate product P1 into a second solvent, add a second catalyst, and react in the range of 0 to 95°C to obtain a hollow silica sol;
  • R 1 is alkyl, vinylalkyl, vinyl, epoxyalkyl, phenyl, styrylalkyl, methacryloyloxy Alkyl group, acryloyloxyalkyl group, aminoalkyl group, urea alkyl group, chloroalkyl group, mercaptoalkyl group, isocyanate alkyl group, or hydroxyalkyl group.
  • R 1 is optionally the same or different from each other.
  • R 2 is an alkyl group with 1 to 6 carbon atoms.
  • each R 2 may be the same or different from each other; SiO m (OR 3 ) 4-2m
  • Formula II Formula II
  • m is an integer or non-integer
  • R 3 is an alkyl group with 1 to 6 carbon atoms, how many When there are two R 3s , each R 3 may be the same or different from each other.
  • M h is the molecular weight of the hydrophilic part of the aforementioned active compound, and M is the molecular weight of the aforementioned active compound,
  • the weight ratio of the aforementioned active compound to the aforementioned silicon source is (0.05-0.5):1, and the aforementioned active compound may be one type or a mixture of two or more types.
  • the aforementioned second solvent is water, a mixture of water and a hydrophilic organic solvent, or a mixture of water and a hydrophobic organic solvent;
  • the aforementioned second catalyst is acid or alkali
  • the weight percentage of the aforementioned organosilicon intermediate P1 relative to the aforementioned second solvent is 1 to 60%;
  • the weight ratio of the aforementioned second catalyst to the aforementioned organosilicon intermediate product P1 is (0.05-2):1.
  • R 4 is selected from alkyl, vinyl alkyl, epoxy alkyl, styryl alkyl, methacryloyloxyalkyl, acryloxy Alkyl group, aminoalkyl group, urealkyl group, chloroalkyl group, mercaptoalkyl group, isocyanate alkyl group, or hydroxyalkyl group, when there are multiple R 4 , each R 4 is the same or different from each other, and the hydrogen in R 4
  • the atoms may be partially or completely replaced by fluorine atoms,
  • X is selected from an alkoxy group with 1 to 6 carbon atoms, halogen or hydrogen.
  • the aforementioned surface modification step is performed after the aforementioned hollow silica generating step and/or after the hydrothermal treatment step.
  • R 4 is selected from alkyl, vinyl alkyl, epoxy alkyl, styryl alkyl, methacryloyloxyalkyl, acryloxy Alkyl group, aminoalkyl group, urealkyl group, chloroalkyl group, mercaptoalkyl group, isocyanate alkyl group, or hydroxyalkyl group, when there are multiple R 4 , each R 4 is the same or different from each other, and the hydrogen in R 4
  • the atoms may be partially or completely replaced by fluorine atoms,
  • X is selected from an alkoxy group with 1 to 6 carbon atoms, halogen or hydrogen.
  • the aforementioned surface modification step is performed after the aforementioned hollow silica generating step, and/or after the aforementioned hydrothermal treatment step, and/or after the aforementioned solvent replacement step.
  • the hollow silica particles contained have Q4 (ratio of Si atoms bound to 4 -OSi- groups) and Q3 (ratio of Si atoms bound to 3 -OSi- groups and 1 Q1/ (Q1+Q2+Q3+Q4) is substantially 0, Q2/(Q1+Q2+Q3+Q4) is 0.01 to 0.2, Q3/(Q1+Q2+Q3+Q4) is 0.01 to 0.6, and Q4/ (Q1+Q2+Q3+Q4) is 0.2 to 0.98.
  • the pore size of the shell layer of the hollow silica particles is small, thin and dense. Therefore, the hollow silica sol of the present invention has low viscosity and excellent thermal stability.
  • the hollow particles in the hollow silica sol of the present invention have a good shell structure. When formed into a coating, they have high hardness, good wear resistance, and strong adhesion to the substrate. Since the inside of the cavity can be avoided by other Substance filling, which also has a reduced refractive index when formed into a coating. In addition, when the formed coating is used as an anti-reflective layer, the anti-reflective performance and moisture and heat resistance are improved.
  • the hollow silica sol is subjected to hydrothermal treatment, so that the hydroxyl groups on the surface of the hollow silica particles are further condensed, and small, thin and small pores containing the shell layer can be prepared.
  • the coating composition of the present invention can form a coating film with obvious anti-reflection effect, good wear resistance, high hardness and strong adhesion to the substrate.
  • the product of the present invention has excellent anti-reflection effect, good hardness, wear resistance, adhesion to the base material, and excellent moisture and heat resistance and other weather resistance.
  • Figure 1 is a transmission electron microscope photograph of the hollow silica particles obtained in Example 1.
  • Figure 2 is a transmission electron microscope photograph of the hollow silica particles obtained in Example 2.
  • Figure 3 is a transmission electron microscope photograph of the hollow silica particles obtained in Example 3.
  • Figure 4 is a transmission electron microscope photograph of the hollow silica particles obtained in Comparative Example 1.
  • Figure 5 is a transmission electron microscope photograph of the hollow silica particles obtained in Comparative Example 2.
  • the above-mentioned hollow silica particles have a resonance peak area Q1 with a chemical shift of -78 to -88 ppm and a resonance peak area Q2 with a chemical shift of -88 to -98 ppm corresponding to the peak measured by 29 Si nuclear magnetic resonance spectroscopy.
  • the resonance peak area Q3 with a shift of -98 to -108 ppm and the resonance peak area Q4 with a chemical shift of -108 to -117 ppm satisfy:
  • Q2/(Q1+Q2+Q3+Q4) is 0.01 ⁇ 0.2
  • Q3/(Q1+Q2+Q3+Q4) is 0.01 ⁇ 0.6, and,
  • Q4/(Q1+Q2+Q3+Q4) is 0.2 ⁇ 0.98.
  • the peak attributed to Q1 is a peak related to the structure of a silicon atom with one -OSi- group and three hydroxyl groups bonded to the Si atom;
  • the peak attributed to Q2 is related to the structure of the Si atom with two -OSi- groups bonded to it.
  • the peak attributed to Q3 is the peak related to the structure of silicon atoms with 3 -OSi- groups and 1 hydroxyl group bonded to the Si atom;
  • the peak attributed to Q4 It is a peak related to the structure of silicon atoms with four -OSi- groups bonded to Si atoms.
  • Q1/(Q1+Q2+Q3+Q4) is substantially 0” means that there is substantially no peak related to the structure of a silicon atom in which one -OSi- group and three hydroxyl groups are bonded to the Si atom. , but it does not rule out the case where Q1/(Q1+Q2+Q3+Q4) is, for example, 0.0001 or less due to unavoidable peaks caused by detection limits and noise. In this case, it is also considered that Q1/(Q1+ Q2+Q3+Q4) is essentially 0.
  • the aforementioned Q2/(Q1+Q2+Q3+Q4) is 0.2 or less. From the perspective that the hydroxyl groups on the surface of the hollow silica have the hydroxyl groups required for later solvent replacement and/or surface modification, and the adhesion after forming the coating, the aforementioned Q2/(Q1+Q2+Q3+Q4) is preferred. It is 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more.
  • the aforementioned Q3/(Q1+Q2+Q3+Q4) is 0.6 or less. From the perspective that the hydroxyl groups on the surface of the hollow silica have the hydroxyl groups required for later solvent replacement and/or surface modification, and the adhesion after forming the coating, the aforementioned Q3/(Q1+Q2+Q3+Q4) is preferred. is 0.01 or more, more preferably 0.1 or more, More preferably, it is 0.2 or more, still more preferably, it is 0.3 or more, and still more preferably, it is 0.4 or more.
  • Q4/(Q1+Q2+Q3+Q4) is 0.2 or more, considering that the hollow particles have sufficient mechanical properties, are not easily broken, and the internal cavities are not easily filled, and have excellent anti-reflection properties when formed into coatings or products.
  • the Si-O-Si structure which is not completely hydrophobic on the surface, has sufficient hydrophilicity to stabilize the hollow silica sol and is not prone to sedimentation, and the surface can be modified, which is beneficial in other solvents.
  • Q4/(Q1+Q2+Q3+Q4) is preferably 0.98 or less, and more preferably 0.8 or less , more preferably 0.6 or less.
  • the hollow silica sol of the present invention by adjusting the proportions of Q1, Q2, Q3, and Q4 in the hollow silica particles, there are enough hydroxyl groups on the surface of the hollow particles to facilitate dispersion in water and other solvents, forming a stable Silica sol makes subsequent surface functionalization easy to carry out, so that it can be applied to coating compositions of different systems, and it can take into account that the hydroxyl groups on the surface of the hollow particles are not excessive, the surface structure is dense, and the mechanical properties are excellent.
  • the advantages of hollow silica sol Low viscosity and excellent storage stability.
  • (Q2+Q3)/(Q1+Q2+Q3+Q4) is preferably 0.2 or more, and more preferably 0.45 or more.
  • the viscosity of the hollow silica sol of the present invention at 25° C. and a solid content of 20% is, for example, 5 to 200 mPa ⁇ sec. From the viewpoint of good storage stability, the viscosity is preferably 5 to 100 mPa ⁇ sec, and more preferably 5 to 50 mPa. ⁇ sec, more preferably 5 to 20 mPa ⁇ sec.
  • Q1, Q2, Q3, and Q4 satisfy that Q1/(Q1+Q2+Q3+Q4) is substantially 0, and Q2/(Q1+Q2+Q3+Q4) is 0.05 ⁇ 0.1, Q3/(Q1+Q2+Q3+Q4) is 0.2 ⁇ 0.55, and Q4/(Q1+Q2+Q3+Q4) is 0.35 ⁇ 0.75
  • Q1, Q2, Q3, and Q4 satisfy Q1/(Q1+Q2+Q3+Q4) is substantially 0, Q2/(Q1+Q2+Q3+Q4) is 0.05 to 0.2, Q3/(Q1+Q2+Q3+Q4) is 0.35 to 0.6, and, Q4/(Q1+Q2+Q3+Q4) is 0.3 ⁇ 0.65.
  • the aforementioned hollow silica particles are particles whose shell layer contains silica as a main component and the inside of the shell layer is a cavity.
  • the aforementioned "the shell layer contains silica as the main component” means that the main component of the shell layer of the hollow particles is silica, optionally containing a small amount of other oxides and/or organic groups.
  • the thickness of the shell layer of the hollow silica particles is preferably, for example, 3 to 100 nm.
  • the thickness of the shell layer is 3 nm or more, it has sufficient strength, and it is more preferably 4 nm or more.
  • the thickness of the aforementioned shell layer is preferably, for example, 100 nm or less, more preferably 50 nm or less, and more preferably 10 nm or less, which is beneficial to obtaining an appropriate refractive index, and is more preferably 6 nm or less.
  • the thickness of the shell layer can be appropriately adjusted by the amount of reaction raw materials such as silicon source, reaction temperature, etc. in the production conditions of the hollow particles. From the viewpoint of obtaining an excellent refractive index, the thickness of the shell is more preferably 4 to 10 nm.
  • the thickness of the shell layer was measured by observing the hollow particles with a transmission electron microscope (TEM), randomly selecting 100 particles, measuring the thickness of the shell of each hollow particle, and averaging the measured values.
  • TEM transmission electron microscope
  • the shell layer of the hollow silica particles has pores with a diameter distribution of, for example, 0.5 to 4 nanometers.
  • the pores of the shell of the hollow particles are 10 nanometers or less, the hollow particles will have good particle strength.
  • the internal pores will not be easily filled, and good wear resistance and reduction can be obtained. Reflective properties. From the viewpoint of refractive index and relative dielectric constant, it is more preferably 0.5 to 4 nanometers.
  • the pore volume of the hollow silica particles may be, for example, 0.15 to 1.0 cm 3 /g. If the pore volume of the hollow silica particles is 0.15cm 3 /g or more, the particles can have a lower refractive index. When the pore volume of the hollow silica particles is 1.0 cm 3 /g or less, the particles have sufficient strength.
  • the size and pore volume of the aforementioned pores can be measured by the following method: static adsorption measurement at 77K using a Quadrasorb evo specific surface and porosity analyzer (Quantachrome Instruments, USA).
  • the pore size and pore volume on the shell of hollow silica particles were determined using isothermal adsorption curves and Measured by Barrett-Joyner-Halenda (BJH) model.
  • the refractive index of the hollow silica particles may be, for example, 1.10 to 1.45.
  • the refractive index of hollow silica particles is above 1.10, so the hollow particles have good hardness and strength.
  • the refractive index of hollow silica particles is 1.45 or less, which means they have a lower refractive index and perform well in anti-reflective coatings.
  • the relative dielectric constant of the hollow silica particles is, for example, 1.6 to 2.2.
  • the relative dielectric constant of the hollow silica particles is 1.6 or more, the particles have sufficient strength in the composite dielectric material.
  • the relative dielectric constant of the hollow silica particles is 2.2 or less, and more preferably 2.0 or less.
  • the particle size of the hollow silica particles is, for example, 15 to 1000 nm. From the viewpoint of the transparency of the formed optical coating, the thickness is more preferably 20 to 500 nm, and further preferably 20 to 100 nm.
  • the polydispersity index (PDI) of the hollow silica particles is, for example, 0.05 to 0.3.
  • the aforementioned polydispersity index was obtained from dynamic light scattering (DLS) test data of hollow silica sol.
  • the lower the PDI the more uniform the size distribution of the hollow particles is and the more they tend to be monodispersed. If the PDI is below 0.3, the hollow silica particles will have a more uniform size distribution. After being prepared into a coating, the surface of the coating will have lower roughness and better friction resistance.
  • the content of the hollow silica particles is preferably in the range of 0.5% by mass to 70% by mass.
  • the content of hollow silica particles in the hollow silica sol is preferably 0.5% by mass or more from the viewpoint of efficiency in forming a coating, more preferably 5% by mass or more, and even more preferably 10% by mass or more.
  • the content of hollow silica particles in the hollow silica sol is preferably 70 mass% or less from the viewpoint of the storage stability and appropriate viscosity of the hollow silica sol, and is more preferably 60 mass% or less. It is further preferred to 50% by mass or less.
  • the dispersion medium contained in the aforementioned hollow silica sol is water, organic solvent or a combination of both.
  • the aforementioned organic solvent refers to a mobile organic compound containing carbon atoms.
  • the function of the dispersion medium is to make the hollow silica particles exist as single particles in the environment provided by the dispersion medium, so as to avoid the aggregation of the hollow silica particles in the dry state, thereby affecting the optical transparency of the final coating and product.
  • organic solvent examples include methanol, ethanol, isopropyl alcohol, butanol, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, heptanone, hexane, cyclohexane, and heptane.
  • the preparation method of hollow silica sol includes the following steps:
  • Intermediate product generation step mix the silicon source, the first solvent, the first catalyst and the active compound, carry out the reaction in the range of 0 to 150°C, and then remove substances with boiling points less than 300°C to obtain liquid silicone intermediate product P1;
  • Hollow silica generation step disperse the organosilicon intermediate product P1 into a second solvent, add a second catalyst, and react in the range of 0 to 95°C to obtain a hollow silica sol;
  • Hydrothermal treatment step After cleaning as needed, perform hydrothermal treatment in the range of 30 to 300°C.
  • the alkoxy groups in the silicon source are hydrolyzed in the presence of the first solvent to generate silicon hydroxyl groups.
  • the generated silicon hydroxyl groups can further undergo a condensation reaction or can also react with active
  • the hydroxyl group in the compound reacts to generate a high-boiling liquid silicone intermediate product and low-boiling point substances as by-products (substances with a boiling point less than 300°C).
  • the intermediate product is purified to make its molecular weight distribution narrower. Chemical properties are more uniform.
  • composition of the aforementioned silicon source contains an alkoxy group and can be hydrolyzed into a silanol group and further condensed to form a flowable intermediate product.
  • the silicon source is one or more of the silane monomers represented by the following formula I, or a polyalkoxysiloxane oligomer whose simplest formula is represented by the following formula II. , R 1 4-n Si(OR 2 ) nFormula I
  • R 1 is alkyl, vinylalkyl, vinyl, epoxyalkyl, phenyl, styrylalkyl, methacryloyloxy Alkyl group, acryloyloxyalkyl group, aminoalkyl group, urea alkyl group, chloroalkyl group, mercaptoalkyl group, isocyanate alkyl group, or hydroxyalkyl group.
  • R 1 is optionally the same or different from each other.
  • R 2 is an alkyl group with 1 to 6 carbon atoms.
  • each R 2 may be the same or different from each other; SiO m (OR 3 ) 4-2m
  • Formula II Formula II
  • m is an integer or non-integer
  • R 3 is an alkyl group with 1 to 6 carbon atoms, and when there are multiple R 3s , each R 3 may be the same or different from each other.
  • R 1 represents an alkyl group, a vinylalkyl group, a vinyl group, an epoxyalkyl group, a phenyl group, a styrylalkyl group, a methacryloyloxyalkyl group, or an acryloyloxy group.
  • alkyl group in the alkylalkyl group, aminoalkyl group, urealkyl group, chloroalkyl group, mercaptoalkyl group, isocyanate alkyl group or hydroxyalkyl group include alkyl groups having 1 to 22 carbon atoms. It may be an alkyl group having 1 to 10 carbon atoms, and further may be an alkyl group having 1 to 8 carbon atoms.
  • alkyl group having 1 to 8 carbon atoms examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, hexyl, n-pentyl Heptyl group, n-octyl group, etc. are not particularly limited.
  • Examples of the polyalkoxysiloxane oligomer whose simplest formula is Formula II include commercially available silicon 40, silicon 48, silicon 51, silicon 53, and silicon 63.
  • the aforementioned silicon source one or more of the silane monomers having the structure represented by the aforementioned formula I or one or more of the polyalkoxysiloxane oligomers represented by the aforementioned formula II can be used. 2 or more types can also be used in combination.
  • the aforementioned silicon source is selected from the group consisting of tetraethyl silicate, tetramethyl silicate, vinyl triethoxysilane, methyltriethoxysilane, and 3-(methacryloyloxy)propyltriethyl. At least one of oxysilane, silicon 40, silicon 48, and silicon 51.
  • the first solvent is preferably water or a mixed solvent of water and an organic solvent, and more preferably a mixed solvent of water and an organic solvent.
  • examples thereof include aqueous methanol, aqueous ethanol, aqueous isopropyl alcohol, and aqueous butanol.
  • the weight ratio of the water contained in the first solvent to the silicon source is preferably 0.001:1 or more and less than 0.5:1.
  • the alkoxy groups in the silicon source are hydrolyzed when exposed to water and further condensed to form an intermediate product containing a Si-O-Si structure.
  • the weight ratio is 0.001:1 or above, the molecular weight of the obtained intermediate product is high enough, and the hydrophilicity after reacting with the active compound will not be too strong, and interfacial activity can be generated.
  • the weight ratio is less than 0.5:1, some of the alkoxy groups in the silicon source are not completely reacted, which is conducive to subsequent active compounds continuing to react with them.
  • the aforementioned weight ratio of water to silicon source is one of the factors that affects the shell thickness of the hollow silica particles as the final product.
  • the shell thickness of the hollow silica particles increases with the weight ratio of water to silicon source. Big and getting bigger. From the perspective of obtaining a sufficient shell thickness of the hollow silica particles so that the hollow silica particles have sufficient strength, the weight ratio of the aforementioned water to the silicon source is preferably 0.01:1 or more. From the perspective that the shell thickness of the hollow silica particles is not too thick and thus has a low refractive index, the weight ratio of the water to the silicon source is preferably 0.25:1 or less.
  • the purpose of using other solvents except water is to enable water and the silicon source to be quickly and uniformly mixed.
  • the amount added is not particularly limited. From the perspective of saving preparation costs, the preferred amount is to ensure that water Use an amount that can be mixed evenly with the silicon source.
  • the aforementioned first catalyst is acid, alkali, or metal alkoxide or metal carboxylate.
  • acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, acidic cation exchange resin, etc., but are not limited to these.
  • a base include ammonia water, organic amines, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, etc., but are not limited to these.
  • metal alkoxide include titanium alkoxide, aluminum alkoxide, zirconium alkoxide, etc., but are not limited to these.
  • the first catalyst is preferably an acid or titanium alkoxide.
  • titanium alkoxide include titanium tetramethoxide, titanium tetraethoxide, and titanium tetrapropoxide.
  • the weight ratio of the first catalyst to the silicon source is preferably 0.001 to 0.5:1. Controlling the weight ratio to 0.5:1 or less is beneficial to preventing the formation of gel-like solids caused by too fast reaction rates. Controlling the weight ratio to 0.001:1 or above is beneficial to improving catalytic efficiency and obtaining a suitable reaction rate.
  • the aforementioned active compound refers to a compound that plays a role in improving the hydrophilicity of the organic silicon intermediate product.
  • the aforementioned active compounds may be a single substance or a mixture of two or more.
  • the aforementioned active compound include one selected from the group consisting of polyacrylic acid, polyethylene glycol, polyethylene glycol monoether, polyvinyl alcohol, polyglycerin, and copolymers of ethylene oxide and propylene oxide. kind or a combination of 2 or more kinds.
  • the HLB value of the active compound calculated by formula III is lower than 5, the active compound cannot give appropriate hydrophilicity to the organic silicon intermediate product, and hollow silica particles cannot be obtained in subsequent steps.
  • the weight ratio of the aforementioned active compound to the aforementioned silicon source may be, for example, (0.05-0.5):1.
  • the obtained organic silicone intermediate product can be made to have sufficient hydrophilicity, so that it is not easy to agglomerate in the aqueous solvent and can form particles with a hollow structure.
  • the obtained organosilicon intermediate is partially hydrophobic, thereby having appropriate interfacial activity and capable of forming hollow particles in subsequent steps.
  • the removal of the aforementioned by-products with boiling points below 300°C has a key impact on the preparation of hollow silica particles.
  • the hydrolysis and condensation of the silicon source and the condensation with the hydroxyl-containing active compound can proceed forward to obtain higher molecular weight intermediate products and finally form hollow silica particles.
  • the particle size of the prepared hollow silica particles is more uniform and the size is easier to control.
  • the aforementioned organosilicon intermediate product P1 is dispersed in a second solvent, a second catalyst is added, and the reaction is carried out in the range of 0 to 95°C to obtain a hollow silica sol.
  • the aforementioned second solvent is water, or a combination of water and a hydrophilic solvent, or a combination of water and a hydrophobic solvent.
  • hydrophilic solvents include organic solvents miscible with water such as alcohols, ketones, and ethers.
  • hydrophobic solvents include organic solvents such as alkanes, aromatic hydrocarbons, and esters.
  • the organic silicone intermediate product P1 When the aforementioned organic silicone intermediate product P1 is dispersed into the second solvent, the organic silicone intermediate product P1 and the second solvent assemble into a vesicle-like structure, the inside and outside of the vesicle are both aqueous solvents, and the organic silicone The intermediate product P1 is enriched at the interface. Under the action of the second catalyst, the organic silicon intermediate product P1 is rapidly hydrolyzed and condensed to form hollow silica particles with a dense silica shell, thereby obtaining monodispersed hollow silica particles. Sol of silica particles.
  • the pore size, pore volume, and refractive index of the hollow particles can be adjusted by adjusting the type and amount of the second catalyst.
  • the pore size formed by using a base catalyst is larger, the pore volume is higher, and the refractive index is lower than when using an acid catalyst.
  • the aforementioned second catalyst may be, for example, an acid or a base.
  • the acid may be an organic acid or an inorganic acid.
  • inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and the like
  • organic acids include formic acid, acetic acid, acrylic acid, and the like.
  • the base may be an inorganic base or an organic base.
  • the inorganic base include sodium hydroxide, potassium hydroxide, ammonia water, etc.
  • examples of the organic base include triethylamine and the like.
  • the aforementioned second catalyst may be the same as the first catalyst, or may be different from the first catalyst.
  • the weight ratio of the aforementioned second catalyst to the organosilicon intermediate product may be, for example, (0.05-2):1.
  • the weight percentage of the silicone intermediate P1 relative to the second solvent is preferably 1 to 60%.
  • a hollow silica sol with good dispersibility can be obtained.
  • it has not undergone surface densification treatment, and there are excessive hydroxyl groups and defects.
  • the viscosity of this primary hollow silica sol increases over time under high solid content conditions, and even gels appear, which affects subsequent use.
  • Silica spherical shells are relatively soft and have many surface defects. When used as subsequent coating compositions or coating products, they may have poor wear resistance and the hollow structures are easily filled, thus affecting anti-reflective and dielectric properties. And other issues.
  • the hydrothermal treatment step is performed at a temperature of 30 to 300°C.
  • the shell of the hollow silica particles becomes more uniform and denser. Due to surface tension, the particles will be closer to a spherical shape, and the mechanical strength will be greatly improved.
  • the hollow silica sol after the hydrothermal treatment step still maintains a lower viscosity even if it has a higher solid content, which improves the thermal stability and storage stability.
  • the shell layer of the hollow silica particles is denser, surface defects are reduced, the hardness and friction resistance are improved when forming a coating.
  • resins with relatively high refractive index cannot enter the interior of hollow particles, so a coating film with better anti-reflective effect can be obtained.
  • the proportion of hydroxyl groups and other groups on the surface of the hollow silica particles is adjusted so that the obtained hollow silica sol satisfies the aforementioned ranges of Q1, Q2, Q3, and Q4 of the hollow silica sol of the present invention. , thereby enabling the obtained hollow silica sol to contain hollow silica particles with few defects, dense surface structure, excellent mechanical properties, low sol viscosity and other properties, while also taking into account the fact that the surface of the hollow silica particles has sufficient hydroxyl groups. It is easy to disperse in water and other solvents to form a stable silica sol, which makes subsequent surface functionalization easy and can be applied to coating compositions of different systems.
  • the hydrothermal temperature in the aforementioned hydrothermal step is 30°C to 300°C.
  • the hydrothermal temperature is above 30°C, the silica spherical shell can be effectively densified.
  • the hydrothermal temperature exceeds 300°C, the surface of the hollow particles cannot In one step of densification, the performance of the paint and coating formed cannot be further improved. At the same time, it may cause the agglomeration of hollow particles and precipitate from the sol, affecting further use.
  • the hydrothermal treatment temperature is preferably 100°C to 200°C.
  • the hollow silica sol has higher purity and better stability.
  • the preparation method of hollow silica sol of the present invention does not require the steps of removing the internal template by traditional means such as high-temperature calcination, solvent etching or acid-base dissolution, and can obtain hollow particle dispersion with excellent monodispersity and no secondary agglomeration. liquid.
  • hollow silica particles with high mechanical strength, uniform shell layer and dense can be prepared.
  • the particles are used in coating compositions and coatings , can give the coating excellent water resistance, wear resistance, weather resistance and anti-reflective properties.
  • the hollow silica sol obtained above can be used together with a binder to form a coating composition and is widely used to form anti-reflective coatings. Alternatively, various additives may be added to the coating composition according to the performance requirements of the coating formed. Furthermore, the hollow silica sol can also be dried and stored as a powder of hollow silica particles for later use.
  • the shell of the hollow particles contained in the hollow silica sol obtained by the aforementioned preparation method of the hollow silica sol contains pore channels and can be used for coating and sustained release.
  • preparation method of the hollow silica sol of the present invention may further include the following steps:
  • ultrafiltration membranes In the solvent replacement step, ultrafiltration membranes, rotary evaporators, centrifuges and other equipment are used to replace all or part of the original solvent in the obtained hollow silica sol with an organic solvent to obtain a hollow silica organosol.
  • the aforementioned "part” may be, for example, 20% or more, 40% or more, 60% or more, 80% or more, 90% or more, or 99% or more.
  • the solvent used for substitution may be one type or a mixture of two or more solvents.
  • the hollow silica sol that has undergone the solvent replacement step can be applied to most coating systems, and has excellent dispersion properties in the resulting coating composition. In the prepared coatings and products, agglomeration does not occur, giving the coating Better optical transparency to avoid whitening of the coating.
  • the solvent of the hollow silica sol before replacement is water
  • the water in the hollow silica sol can be replaced with methanol to obtain the hollow silica methanosol.
  • the solvent of the hollow silica sol before replacement is methanol
  • a part of the methanol can be replaced with acetone to obtain a methanol/acetone sol of hollow silica.
  • a silane selected from the group consisting of silane represented by the following formula IV and/or its partial hydrolyzate, hexamethyldisiloxane and hexamethyldisilazine (amine) into the hollow silica sol. 1 or 2 or more types are used to modify the surface of hollow silica particles.
  • R 4 is selected from alkyl, vinyl alkyl, epoxy alkyl, styryl alkyl, methacryloxy alkyl, propylene Acyloxyalkyl group, aminoalkyl group, ureaalkyl group, chloroalkyl group, mercaptoalkyl group, isocyanate alkyl group, or hydroxyalkyl group.
  • each R 4 is the same as or different from each other.
  • the hydrogen atoms are optionally partially or completely replaced by fluorine atoms;
  • X is selected from an alkoxy group with 1 to 6 carbon atoms, halogen or hydrogen. When there are multiple Xs, each X may be the same or different from each other.
  • alkyl group vinylalkyl group, epoxyalkyl group, styrylalkyl group, methacryloyloxyalkyl group, acryloyloxyalkyl group, aminoalkyl group, urethane represented by R 4 "alkyl group" in “alkyl group, chloroalkyl group, mercaptoalkyl group, isocyanate alkyl group, or hydroxyalkyl group” includes, for example, an alkyl group having 1 to 22 carbon atoms, which may be an alkyl group having 1 to 10 carbon atoms. The alkyl group may further be an alkyl group having 1 to 8 carbon atoms.
  • alkyl group having 1 to 8 carbon atoms examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, hexyl, n-pentyl Heptyl group, n-octyl group, etc. are not particularly limited. .
  • One or more of the group consisting of hydrolyzate, hexamethyldisiloxane, and hexamethyldisilazine (amine) alkane can modify the surface of the hollow silica particles, thereby enabling the hollow silica particles to be
  • the surface of the particles is modified with organic groups, so that the hollow silica has better dispersion stability in certain organic solvents, and thus has a stronger affinity with the binder in the coating.
  • Binders have stronger interactions, thus giving the coating better adhesion, hardness and wear resistance.
  • the refractive index of the hollow silica particles can be further reduced.
  • the surface of the hollow particles becomes more hydrophobic, so that when used in a coating composition It gives the coating excellent fingerprint resistance, slipperiness, and stain resistance, thereby providing better wear resistance.
  • the above-mentioned surface modification step can be performed at any step after the above-mentioned hollow silica generating step, and/or after the above-mentioned hydrothermal treatment step, and/or after the above-mentioned solvent replacement step.
  • the order of the aforementioned hydrothermal treatment step, solvent replacement step and surface modification step can be randomly selected, or any one or two or more steps can be repeated, as long as the stability of the hollow silica sol and the stability of the coating composition are not damaged. Just disperse it.
  • drying can be performed after any of the steps of generating the hollow silica, the hydrothermal treatment step, the solvent replacement step, and the surface modification step. , or sintering to obtain hollow silica powder.
  • the preparation method of hollow silica sol of the present invention does not use any hard template or soft template, and utilizes the self-assembly behavior of organic silicon intermediate products in water to generate aqueous dispersion of hollow silica particles.
  • there is no need to remove the template through high-temperature calcination, solvent etching, acid-base dissolution, etc., which avoids the agglomeration of hollow particles.
  • hydrothermal treatment the surface of the hollow particles is denser, the shell is more uniform, the mechanical strength is higher, and the weather resistance is better.
  • solvent replacement hollow silica organosilica sols with different dispersion systems are obtained.
  • the dispersion stability of the hollow particles in organic solvents and the affinity of organic resins are further increased, giving coating compositions and coatings excellent Optical properties, mechanical properties and weather resistance.
  • the hollow silica sol preparation method of the present invention not only has excellent low refractive index and can be used for anti-reflective coatings, but also has more excellent low dielectric properties because no metal ions are introduced.
  • the pore structure on the spherical shell allows the hollow silica particles to be used for loading and sustained release of active molecules.
  • the coating composition of the present invention includes the hollow silica sol of the present invention, a binder and as needed Solvents and additives to be used.
  • inorganic binders can be cited, including those precursor compounds that are well known to those skilled in the art and can form corresponding inorganic oxides through hydrolysis and condensation reactions, such as metal alkoxides, metal salts, siloxanes, Silicates and mixtures thereof, organic binders may also be exemplified, including various polymers and monomers and oligomers that can be cured by heat or radiation (such as UV, electron radiation) well known to those skilled in the art.
  • heat or radiation such as UV, electron radiation
  • acrylate monomers including acrylate monomers, methacrylate monomers, and various oligomers derived from the two, such as (meth)acrylate oligomers, polyurethane (meth)acrylate oligomers Polymers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and free radical curable unsaturated polyesters or polyurethanes in acrylates and methacrylates.
  • Examples of the solvent include water, alcohols, ketones, ethers, esters, nitrogen-containing compounds, sulfur-containing compounds, and the like.
  • Examples of alcohols include methanol, ethanol, isopropyl alcohol, and the like.
  • Examples of ketones include acetone, methyl ethyl ketone, and the like.
  • Examples of ethers include tetrahydrofuran, 1,4-dioxane, and the like.
  • Examples of esters include ethyl acetate, methyl acetate, and the like.
  • Examples of nitrogen-containing compounds include N,N-dimethylacetamide, N,N-dimethylformamide, and the like.
  • Examples of sulfur-containing compounds include dimethyl sulfoxide.
  • the coating composition of the present invention may contain hollow particles or solid particles other than the hollow particles of the present invention within a range that does not impair the effects of the present invention.
  • the coating composition of the present invention may also contain other auxiliaries, such as thermal initiators, photoinitiators, antistatic agents, leveling agents, wetting agents, defoaming agents, pigments, dyes, ultraviolet shielding agents, infrared Shielding agents, antioxidants, anti-fingerprint agents, etc.
  • auxiliaries such as thermal initiators, photoinitiators, antistatic agents, leveling agents, wetting agents, defoaming agents, pigments, dyes, ultraviolet shielding agents, infrared Shielding agents, antioxidants, anti-fingerprint agents, etc.
  • the weight ratio of the hollow silica particles to the adhesive may be, for example, 0.1:1 to 5:1, preferably 0.5:1 to 3:1, and more preferably 0.8:1 to 2: 1. If the hollow particle/binder ratio is too low, the anti-reflective performance of the coating will not be obvious. If the ratio is too high, the anti-reflective performance will not be improved and the mechanical properties and weather resistance of the coating will be reduced.
  • the coating composition of the present invention described above contains the hollow particles of the present invention with low refractive index and high particle strength, it can form a coating film with excellent antireflection effect and high wear resistance and hardness.
  • the article of the present invention consists of a base material and a coating on the surface of the base material.
  • the coating layer is one layer or more than two layers, and at least one layer in the coating layer is formed by curing the coating composition of the present invention.
  • the aforementioned coating layer can be formed by applying the coating composition of the present invention on a substrate and drying it.
  • the coating can be further heated, baked, or irradiated.
  • Examples of the base material include glass, transparent polymers, metals, etc., and are not particularly limited.
  • coating methods include bar coating, knife coating, spin coating, dip coating, roller coating, shower coating, spray coating, slit coating, and dimpling coating, and are not particularly limited.
  • the article of the present invention described above is provided with a coating layer formed of the coating composition of the present invention, it has a good anti-reflection effect, good wear resistance, and high hardness.
  • the preparation methods are conventional methods unless otherwise specified, and the raw materials used can be obtained from public commercial sources unless otherwise specified.
  • the percentages refer to mass percentages, and the temperature is in degrees Celsius (°C).
  • Solid content Obtained by solid content analyzer Precisa, XM60, baked at 150°C until constant weight, solid content displayed.
  • Viscosity measured by a rotational viscometer, the temperature is set to 25°C, and the solid content of the hollow silica sol is fixed at 20%.
  • Average particle size In the corresponding TEM photo, 100 particles are randomly selected, the particle size of each particle is measured, and the average value of the measured particle sizes is used as the average particle size of the particles.
  • Shell thickness In the corresponding TEM photo, randomly select 100 particles, measure the wall thickness of each particle, and average the measured shell thickness as the shell thickness.
  • Determination of the proportions of Q1, Q2, Q3, and Q4 After drying the hollow silica sol into powder, use a nuclear magnetic resonance instrument (Bruker AVIII HD 500 spectrometer) to measure the 29 Si NMR spectrum, and then measure the chemical shifts between -78 and - Integrate the resonant peak area Q1 of 88ppm, the resonant peak area Q2 of -88 to -98ppm, the resonant peak area Q3 of -98 to -108ppm, and the resonant peak area Q4 of -108 to -117ppm to calculate Q1, Q2, Q3, The value of Q4.
  • a nuclear magnetic resonance instrument Bruker AVIII HD 500 spectrometer
  • Determination of polydispersity Use a dynamic light scattering instrument (Malven, Zetasizer Nano, ZS90-2027) to measure the dispersion, and obtain the size distribution curve and polydispersity results.
  • hollow silica sol After the aforementioned hollow silica sol was washed with an ultrafiltration membrane, it was hydrothermally treated at 200° C. for 12 hours to obtain hollow silica sol 1.
  • the transmission electron microscope (TEM) photograph of the hollow silica particles in the obtained hollow silica sol 1 is shown in Figure 1.
  • the average particle diameter was determined to be 55 nanometers and the shell thickness was 5.5 nanometers.
  • hollow silica sol After the aforementioned hollow silica sol was washed with an ultrafiltration membrane, it was hydrothermally treated at 150° C. for 24 hours to obtain hollow silica sol 2.
  • the transmission electron microscope (TEM) photo of the hollow silica particles in the obtained hollow silica sol 2 is shown in Figure 2.
  • the average particle diameter was determined to be 70 nanometers and the shell thickness was 6.5 nanometers.
  • hollow silica sol was washed with an ultrafiltration membrane, it was hydrothermally treated at 120° C. for 12 hours to obtain hollow silica sol 3.
  • FIG. 3 A transmission electron microscope (TEM) photograph of the hollow silica particles in the obtained hollow silica sol 3 is shown in FIG. 3 .
  • the average particle size was determined to be 40 nanometers, and the shell thickness was 4.5 nanometers.
  • the hollow silica sol 4 was obtained in the same manner as in Example 1 except that the hydrothermal treatment in Example 1 was not performed.
  • a transmission electron microscope (TEM) photograph of the obtained hollow silica particles 4 is shown in FIG. 4 .
  • the results of dynamic light scattering (DLS) size, PDI, Q1 ⁇ Q4 proportion, pore size distribution, pore volume, dielectric constant and other results are shown in the table 1.
  • the hollow silica sol 5 was obtained in the same manner as in Example 2 except that the hydrothermal treatment in Example 2 was not performed.
  • Example 3 Except that the hydrothermal treatment in Example 3 was not performed, the same procedure as in Example 3 was performed to obtain hollow silica sol 6.
  • the solvent of the hollow silica sol 1 prepared in Example 1 was replaced with isopropyl alcohol using an ultrafiltration membrane and concentrated to obtain a hollow silica isopropyl alcohol sol 7 with a solid content of 20%.
  • hollow silica isopropyl alcohol sol 7 Take 50 grams of the above-mentioned hollow silica isopropyl alcohol sol 7, add 2 grams of ⁇ -methacryloyloxypropyltrimethoxysilane, 0.2 grams of water, heat to 80°C and react for 12 hours, then add 2 grams of orthoformic acid trimethyl ester to obtain hollow silica-modified isopropyl alcohol sol 8 with a solid content of 20.5%.
  • the solvent of the hollow silica sol 2 prepared in Example 2 was replaced with isopropyl alcohol and concentrated to obtain a hollow silica isopropyl alcohol sol 9 with a solid content of 20%.
  • hollow silica isopropyl alcohol sol 9 Take 50 grams of the above-mentioned hollow silica isopropyl alcohol sol 9, add 2 grams of ⁇ -methacryloyloxypropyltrimethoxysilane, 0.2 grams of water, heat to 80°C and react for 12 hours, then add 2 grams of orthoformic acid trimethyl ester to obtain hollow silica-modified isopropyl alcohol sol 10 with a solid content of 20.5%.
  • the solvent of the hollow silica sol 3 prepared in Example 3 was replaced with isopropyl alcohol and concentrated to obtain a hollow silica isopropyl alcohol sol 11 with a solid content of 20%.
  • Each of the sols prepared in the aforementioned Examples 1 to 6 and Comparative Examples 1 to 6 was diluted with methyl isobutyl ketone (MIBK) to a solid content of 10%. Take 10 grams of sol with a solid content of 10%, add 1 gram of dipentaerythritol hexaacrylate (DPHA), 0.05 grams of photoinitiator (Irgacure-184), 38.95 grams of MIBK, and mix evenly to obtain 50 grams of sol with a solid content of 4%. Coating compositions.
  • MIBK methyl isobutyl ketone
  • the above coating composition was coated on the PET film (Yihua Toray, Lumiller PY2, thickness 100 microns) with a 3# wire rod (3 microns), dried in an 80°C oven for 2 minutes, and UV cured ( The energy is 800 ⁇ 1500mJ/cm 2 ), and a PET product containing an anti-reflective coating with a thickness of 100 nanometers is produced. Its reflectivity, haze, moisture and heat resistance, pencil hardness, adhesion, and wear resistance were characterized. The results are shown in Table 2.
  • Haze Use a hazemeter to measure total light transmittance and haze.
  • Heat and humidity resistance Set the temperature of the constant temperature and humidity chamber to 85°C, the humidity to 85%, and the test time to 1000 hours.
  • the resistance to heat and humidity is evaluated by testing the attenuation rate of the total light transmittance of PET products.
  • the resistance to heat and humidity is divided into For the following 3 levels:
  • Attenuation ranges from 0.5 to 1.0%
  • Pencil hardness According to Japanese JIS K 5600, use a pencil scratch tester to measure the pencil hardness of the resulting coating. The resulting coating was scratched about 5cm from above with a pencil at an angle of 45 degrees with a load of 750 grams, and the hardness of the pencil without scratches was expressed as four or more times out of five times.
  • Adhesion Use a knife to draw 100 squares on the surface of the PET coating, stick the transparent tape on it, and then peel off the tape. Evaluate the adhesion by observing the number of remaining squares. The number of remaining squares is divided into the following three levels:
  • Level 4 More than 1 and no more than 10 abrasions occur
  • Level 3 More than 10 and no more than 30 abrasions occur
  • Level 1 The entire surface is scratched or peeled off
  • Examples 1 to 3 show that the sol viscosity is significantly reduced, the surface of the spherical shell is denser, the pore diameter becomes smaller, and the wall thickness of the hollow particles becomes thinner.
  • the corresponding refractive index and relative dielectric constant both decrease, showing excellent low refractive and low dielectric properties.
  • the solution of the present invention combines excellent anti-reflection performance with outstanding mechanical properties and weather resistance.

Abstract

La présente invention concerne un sol de silice creux, sa méthode de préparation, et une composition de revêtement et un produit associé. Le sol de silice creux de la présente invention contient des particules de silice creuses et un milieu de dispersion. Une zone de pic de résonance Q1 avec un déplacement chimique de -78 à -88 ppm, une zone de pic de résonance Q2 avec un déplacement chimique de -88 à -98 ppm, une zone de pic de résonance Q3 avec un déplacement chimique de -98 à -108 ppm, et une zone de pic de résonance Q4 avec un déplacement chimique de -108 à -117 ppm correspondant à des valeurs de pic des particules de silice creuses décrites mesurées au moyen d'une spectroscopie par résonance magnétique nucléaire 29Si satisfont que Q1/(Q1+Q2+Q3+Q4) est sensiblement 0, Q2/(Q1+Q2+Q3+Q4) est de 0,01 à 0,2, Q3/(Q1+Q2+Q3+Q4) est de 0,01 à 0,6, et Q4/(Q1+Q2+Q3+Q4) est de 0,2 à 0,98. Le milieu de dispersion est de l'eau, un solvant organique ou une combinaison des deux. Le sol de silice creux de la présente invention présente une faible viscosité et une bonne stabilité, et dans la condition qu'un revêtement est formé sur un matériau de base, le sol de silice creux a une dureté élevée, une bonne résistance à l'abrasion et une force adhésive améliorée avec le matériau de base.
PCT/CN2023/090053 2022-07-01 2023-04-23 Sol de silice creux, sa méthode de préparation, et composition de revêtement et produit associé WO2024001464A1 (fr)

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CN105283413A (zh) * 2013-06-10 2016-01-27 日产化学工业株式会社 二氧化硅溶胶及二氧化硅溶胶的制造方法
CN110128855A (zh) * 2018-12-04 2019-08-16 上海特栎材料科技有限公司 一种含有二氧化硅空心粒子防反射涂料组合物的制备方法
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US20040198882A1 (en) * 2003-03-31 2004-10-07 Fuji Photo Film Co., Ltd. Silica-containing coating composition for forming films and method for forming silica-containing films
CN101312909A (zh) * 2005-11-25 2008-11-26 触媒化成工业株式会社 中空二氧化硅微粒、含有该微粒的透明涂膜形成用组合物、及覆有透明涂膜的基材
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