WO2024001464A1 - Hollow silica sol, method for preparing same, and coating composition and product thereof - Google Patents

Hollow silica sol, method for preparing same, and coating composition and product thereof 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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French (fr)
Chinese (zh)
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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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Publication of WO2024001464A1 publication Critical patent/WO2024001464A1/en

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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

The present invention relates to a hollow silica sol, a method for preparing same, and a coating composition and a product thereof. The hollow silica sol of the present invention contains hollow silica particles and a dispersion medium. A resonance peak area Q1 with a chemical shift of -78 to -88 ppm, a resonance peak area Q2 with a chemical shift of -88 to -98 ppm, a resonance peak area Q3 with a chemical shift of -98 to -108 ppm, and a resonance peak area Q4 with a chemical shift of -108 to -117 ppm corresponding to peak values of the described hollow silica particles measured by means of a 29Si nuclear magnetic resonance spectroscopy satisfy that Q1/(Q1+Q2+Q3+Q4) is substantially 0, 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 dispersion medium is water, an organic solvent, or a combination of the two. The hollow silica sol of the present invention is low in viscosity and good in stability, and under the condition that a coating is formed on a base material, the hollow silica sol has a high hardness, a good abrasion resistance, and an improved adhesive force with the base material.

Description

中空二氧化硅溶胶、其制备方法、涂料组合物及制品Hollow silica sol, preparation method thereof, coating composition and products
相关申请的交叉引用Cross-references to related applications
本申请要求享有于2022年7月1日提交的名称为“中空二氧化硅溶胶、其制备方法、涂料组合物及制品”的中国专利申请202210773132.2的优先权，该申请的全部内容通过引用并入本文中。This application claims priority to Chinese patent application 202210773132.2 titled "Hollow silica sol, preparation method thereof, coating composition and products" submitted on July 1, 2022, the entire content of which is incorporated by reference. in this article.
技术领域Technical field
本发明涉及中空二氧化硅溶胶、其制备方法、涂料组合物及制品。The present invention relates to hollow silica sol, its preparation method, coating composition and products.
背景技术Background technique
中空二氧化硅粒子具有高孔隙率、低折射率、低介电常数、生物无毒性等特点，因而广泛用于轻量化、低折材料、减反射涂层、半导体材料以及活性分子负载与缓释等领域。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.
在低折射率材料、减反射涂层等应用领域，对中空二氧化硅粒子的尺寸有要求，一般介于几十至几百纳米之间，粒子尺寸过大会导致光学透明性下降，难以被应用。除了粒子本身的尺寸大小，也要求其在使用的过程中具有好的分散稳定性，不发生团聚，因此具有稳定分散性的溶胶使后续使用更加方便，也避免了粉末态粒子使用时带来的分散难点。In application fields such as low refractive index materials and anti-reflective coatings, there are requirements for the size of hollow silica particles, which are generally between tens to hundreds of nanometers. Excessive particle size will lead to a decrease in optical transparency and difficulty in application. . In addition to the size of the particles themselves, they are also required to have good dispersion stability and no agglomeration during use. Therefore, the sol with stable dispersion makes subsequent use more convenient and avoids the problems caused by the use of powdered particles. Spread out the difficulties.
本发明人在CN110128855A中公开了一种中空二氧化硅粒子的制备方法，即先利用硅烷单体在水中的水解与缩合，制备一种双亲性的聚烷氧基硅氧烷，然后利用其在水性介质中自组装行为制得中空二氧化硅粒子。该中空二氧化硅粒子的分散性优异，尺寸可控，在减反射领域有较好的应用。但是，使用该中空粒子制备减反射涂层时，涂层的硬度低、全光线透过率差、反射率较高，另外还存在耐湿热性差、附着力不够、耐磨性差等问题。另外，使用该中空二氧化硅粒子制备的溶胶粘度大、稳定性差，不耐储存。The inventor disclosed a method for preparing hollow silica particles in CN110128855A, that is, first utilizing the hydrolysis and condensation of silane monomers in water to prepare an amphiphilic polyalkoxysiloxane, and then utilizing it in Hollow silica particles were prepared by self-assembly behavior in aqueous media. The hollow silica particles have excellent dispersion and controllable size, and have good applications in the field of anti-reflection. However, when using the hollow particles to prepare an anti-reflective coating, the coating has low hardness, poor total light transmittance, and high reflectivity. In addition, there are also problems such as poor heat and moisture resistance, insufficient adhesion, and poor wear resistance. In addition, the sol prepared using the hollow silica particles has high viscosity, poor stability, and is not resistant to storage.
专利文献1：CN110128855APatent document 1: CN110128855A
发明内容 Contents of the invention
本发明人等面对前述的现有技术存在的问题进行了深入研究后发现，中空二氧化硅溶胶中含有的中空二氧化硅粒子的表面缺陷导致使用该粒子得到的涂层硬度低，耐磨性差。表面缺陷还使得中空粒子内部的空腔容易被粘合剂、溶剂等填充，制备成减反射涂层时折射率降低不明显、减反射性能变差，还存在耐湿热性变差等问题。另外，表面缺陷的存在表明粒子表面含有丰富的羟基，以溶胶形式储存时存在不稳定、粘度大、易凝胶等问题，After conducting in-depth research on the problems existing in the prior art mentioned above, the inventors found that the surface defects of the hollow silica particles contained in the hollow silica sol resulted in a coating obtained using the particles having low hardness and poor wear resistance. Poor sex. Surface defects also make the cavities inside the hollow particles easily filled with adhesives, solvents, etc. When prepared into an anti-reflective coating, the refractive index does not decrease significantly, the anti-reflective performance deteriorates, and there are also problems such as poor heat and humidity resistance. In addition, the existence of surface defects indicates that the surface of the particles contains abundant hydroxyl groups. When stored in sol form, there are problems such as instability, high viscosity, and easy gelation.
本发明是为了解决上述至少一部分问题而完成，其目的在于提供一种中空二氧化硅溶胶，其粘度降低，稳定性好，在基材上形成涂层的情况下硬度高、耐磨性好、与基材的附着力提高。另外，在形成透明涂层作为减反射层时折射率降低、减反射性能提高、耐湿热性提高。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. In addition, when 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.
本发明的目的还在于提供一种中空二氧化硅溶胶的制备方法，通过该制备方法制备得到的中空二氧化硅溶胶的粘度降低，稳定性提高，在基材上形成涂层的情况下硬度、耐磨性提高，与基材的附着力提高。另外，在形成透明的减反射层时折射率降低、减反射性能提高、耐湿热性提高。Another object of the present invention is to provide a method for preparing hollow silica sol. The hollow silica sol prepared by the preparation method has reduced viscosity, improved stability, and hardness, Improved wear resistance and improved adhesion to the substrate. In addition, when a transparent anti-reflection layer is formed, the refractive index is reduced, the anti-reflection performance is improved, and the moisture and heat resistance is improved.
本发明的目的还在于提供一种涂料组合物，其含有中空二氧化硅溶胶以及粘接剂，前述中空二氧化硅溶胶为本发明前述的中空二氧化硅溶胶，或者为根据前述的本发明的中空二氧化硅溶胶制备方法制备得到。It is also an object of the present invention to provide a coating composition, which contains hollow silica sol and an adhesive. 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.
本发明的目的还在于提供一种制品，其在基材表面具有由本发明的涂料组合物固化形成的涂层。该涂层的硬度高、耐磨性好、与基材的附着力提高。另外，在形成透明涂层作为减反射层时折射率降低、减反射性能、耐湿热性提高。Another object of the present invention is to provide an article having a coating formed by curing the coating composition of the present invention on the surface of a substrate. The coating has high hardness, good wear resistance, and improved adhesion to the substrate. In addition, when a clear coating layer is formed as an anti-reflection layer, the refractive index is reduced, and the anti-reflection performance and moisture and heat resistance are improved.
本发明提供下述的技术方案：The present invention provides the following technical solutions:
[1]一种中空二氧化硅溶胶，其含有中空二氧化硅粒子和分散介质，[1] A hollow silica sol containing hollow silica particles and a dispersion medium,
前述中空二氧化硅粒子通过29Si核磁共振谱法测得的与峰值相对应的化学位移在-78～-88ppm的共振峰面积Q1、化学位移在-88～-98ppm的共振峰面积Q2、化学位移在-98～-108ppm的共振峰面积Q3、以及化学位移在-108～-117ppm出现的共振峰面积Q4满足：The aforementioned hollow silica particles measured by 29 Si nuclear magnetic resonance spectroscopy have a chemical shift corresponding to the resonance peak area Q1 of -78 to -88 ppm, a chemical shift of -88 to -98 ppm, a resonance peak area Q2, and a chemical 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:
Q1/(Q1+Q2+Q3+Q4)实质上为0、Q1/(Q1+Q2+Q3+Q4) is essentially 0,
Q2/(Q1+Q2+Q3+Q4)为0.01～0.2、Q2/(Q1+Q2+Q3+Q4) is 0.01～0.2,
Q3/(Q1+Q2+Q3+Q4)为0.01～0.6、以及， Q3/(Q1+Q2+Q3+Q4) is 0.01~0.6, and,
Q4/(Q1+Q2+Q3+Q4)为0.2～0.98，Q4/(Q1+Q2+Q3+Q4) is 0.2~0.98,
前述分散介质为水、有机溶剂或者两者的组合。The aforementioned dispersion medium is water, organic solvent or a combination of both.
[2]、根据[1]记载的中空二氧化硅溶胶，其中，前述中空二氧化硅粒子的壳层的厚度为3～100nm，前述壳层上的孔的孔径分布为0.5～4纳米范围。[2] The hollow silica sol according to [1], wherein the thickness of the shell layer of the hollow silica particles is 3 to 100 nm, and the pore size distribution of the pores in the shell layer is in the range of 0.5 to 4 nm.
[3]、根据[1]或[2]记载的中空二氧化硅溶胶，其中，前述中空二氧化硅粒子的孔容为0.15～1cm3/g，孔隙率为10％～90％，折射率为1.10～1.45。[3]. The hollow silica sol according to [1] or [2], wherein the hollow silica particles have a pore volume of 0.15 to 1 cm 3 /g, a porosity of 10% to 90%, and a refractive index It is 1.10~1.45.
[4]、根据[1]～[3]的任一项记载的中空二氧化硅溶胶，前述中空二氧化硅粒子的相对介电常数为1.6～2.2。[4]. The hollow silica sol according to any one of [1] to [3], wherein the relative dielectric constant of the hollow silica particles is 1.6 to 2.2.
[5]、根据[1]～[4]的任一项记载的中空二氧化硅溶胶，前述中空二氧化硅粒子通过动态光散射测得的粒径为15～1000nm，多分散性指数为0.05～0.3。[5]. The hollow silica sol according to any one of [1] to [4], wherein the particle diameter of the hollow silica particles measured by dynamic light scattering is 15 to 1000 nm, and the polydispersity index is 0.05 ~0.3.
[6]、[1]～[5]的任一项记载的中空二氧化硅溶胶的制备方法，其特征在于，包括以下步骤：The preparation method of hollow silica sol according to any one of [6] and [1] to [5] is characterized by comprising the following steps:
中间产物生成步骤：将硅源、第一溶剂、第一催化剂及活性化合物混合，在0～150℃范围内进行反应，然后去除沸点小于300℃的物质，得到液态有机硅中间产物P1；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;
中空二氧化硅生成步骤：将前述有机硅中间产物P1分散到第二溶剂中，并加入第二催化剂，在0～95℃的范围内进行反应，得到中空二氧化硅溶胶；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;
水热处理步骤：在30～300℃范围内进行水热处理。Hydrothermal treatment step: Hydrothermal treatment is carried out in the range of 30 to 300°C.
[7]、根据[6]记载的中空二氧化硅溶胶的制备方法，其中，前述中间产物生成步骤中，前述硅源为选自下述的式I所示的硅烷单体中的1种或2种以上，或者为最简式为下述式II所示的聚烷氧基硅氧烷低聚物，
R1 4-nSi(OR2)n   式I[7]. The method for preparing hollow silica sol according to [6], wherein in the intermediate product generating step, the silicon source is one selected from the group consisting of silane monomers represented by the following formula I or 2 or more types, or a polyalkoxysiloxane oligomer whose simplest formula is represented by the following formula II,
R 1 4-n Si(OR 2 ) nFormula I
式I中，n＝1、2、3、或者4，R1为烷基、乙烯基烷基、乙烯基、环氧基烷基、苯基、苯乙烯基烷基、甲基丙烯酰氧基烷基、丙烯酰氧基烷基、氨基烷基、脲烷基、氯烷基、巯烷基、异氰酸酯烷基、或者羟基烷基，有多个R1时，各R1彼此任选相同或不同；R2为碳原子数1～6的烷基，有多个R2时各R2彼此任选相同或不同；
SiOm(OR3)4-2m   式IIIn formula I, n=1, 2, 3, or 4, 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. When there are multiple R 1s , each R 1 is optionally the same or different from each other. Different; R 2 is an alkyl group with 1 to 6 carbon atoms. When there are multiple R 2s , each R 2 may be the same or different from each other;
SiO m (OR 3 ) 4-2m Formula II
式II中，0<m<2，m为整数或者非整数，R3为碳原子数1～6的烷基，有多 个R3时各R3彼此任选相同或不同。In formula II, 0<m<2, 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.
[8]、根据[6]或[7]记载的中空二氧化硅溶胶的制备方法，其中，前述中间产物生成步骤中，前述第一溶剂为水、或者为含水的有机溶剂，水与前述硅源的重量比为0.001：1以上且小于0.5：1。[8]. The preparation method of hollow silica sol according to [6] or [7], wherein in the step of generating the intermediate product, the first solvent is water or an organic solvent containing water, and water and the silicon The weight ratio of the sources is above 0.001:1 and less than 0.5:1.
[9]、根据[6]～[8]的任一项记载的中空二氧化硅溶胶的制备方法，其中，前述中间产物生成步骤中，前述第一催化剂为酸或者碱，前述第一催化剂与前述硅源的重量比为(0.001～0.5)：1。[9]. The preparation method of hollow silica sol according to any one of [6] to [8], wherein in the intermediate product generating step, the first catalyst is an acid or a base, and the first catalyst and The weight ratio of the aforementioned silicon source is (0.001~0.5):1.
[10]、根据[6]～[9]的任一项记载的中空二氧化硅溶胶的制备方法，其中，前述中间产物生成步骤中，前述活性化合物含有至少一个OH基团且分子量大于150，并且，前述活性化合物的通过下述式III计算的HLB值大于5，
HLB＝20×Mh/M  式III[10]. The method for preparing hollow silica sol according to any one of [6] to [9], wherein in the intermediate product generating step, the active compound contains at least one OH group and has a molecular weight greater than 150, Furthermore, the HLB value of the aforementioned active compound calculated by the following formula III is greater than 5,
HLB＝20×M h /M Formula III
式III中，Mh为前述活性化合物中亲水部分的分子量，M为前述活性化合物的分子量，In formula III, 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,
前述活性化合物与前述硅源的重量比为(0.05～0.5)：1，前述活性化合物可以为一种或两种以上混合物。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.
[11]、根据[6]～[10]的任一项记载的中空二氧化硅溶胶的制备方法，其中，[11]. The method for preparing hollow silica sol according to any one of [6] to [10], wherein:
前述中空二氧化硅生成步骤中，前述第二溶剂为水、水与亲水性有机溶剂的混合物、或者水与疏水性有机溶剂的混合物；In the aforementioned hollow silica generating step, 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;
前述第二催化剂为酸或者碱；The aforementioned second catalyst is acid or alkali;
前述有机硅中间产物P1相对于前述第二溶剂的重量百分比为1～60％；The weight percentage of the aforementioned organosilicon intermediate P1 relative to the aforementioned second solvent is 1 to 60%;
前述第二催化剂与前述有机硅中间产物P1的重量比为(0.05～2)：1。The weight ratio of the aforementioned second catalyst to the aforementioned organosilicon intermediate product P1 is (0.05-2):1.
[12]、根据[6]～[11]的任一项记载的中空二氧化硅溶胶的制备方法，其还包括：对前述中空二氧化硅溶胶的溶剂进行置换的溶剂置换步骤，[12]. The method for preparing the hollow silica sol according to any one of [6] to [11], further comprising: a solvent replacement step of replacing the solvent of the hollow silica sol,
前述溶剂置换步骤中，通过离心、加热共沸或者超滤操作置换掉前述中空二氧化硅溶胶中的全部或者部分溶剂。In the aforementioned solvent replacement step, all or part of the solvent in the aforementioned hollow silica sol is replaced by centrifugation, heating, azeotroping or ultrafiltration.
[13]、根据[6]～[11]的任一项前述的中空二氧化硅溶胶的制备方法，其还包含下述步骤：[13]. The preparation method of hollow silica sol according to any one of [6] to [11], which further includes the following steps:
表面修饰步骤：在中空二氧化硅溶胶中加入选自下述的式IV所示的硅烷及/或其部分水解物、六甲基二硅氧烷以及六甲基二硅氮(胺)烷组成的组中的 一种或多种物质，对中空二氧化硅粒子表面进行修饰，
R4 p-Si-X4-p     式IVSurface modification step: Add silane represented by Formula IV below and/or its partial hydrolyzate, hexamethyldisiloxane and hexamethyldisilazine (amine) into the hollow silica sol. in the group One or more substances modify the surface of hollow silica particles,
R 4 p -Si-X 4-p Formula IV
式IV中，p＝0、1、2或者3，R4选自烷基、乙烯基烷基、环氧基烷基、苯乙烯基烷基、甲基丙烯酰氧基烷基、丙烯酰氧基烷基、氨基烷基、脲烷基、氯烷基、巯烷基、异氰酸酯烷基、或者、羟基烷基，有多个R4时，各R4彼此相同或者不同，R4中的氢原子可部分或全部被氟原子取代，In formula IV, p=0, 1, 2 or 3, 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选自碳原子数为1-6的烷氧基、卤素或者氢，有多个X时，各X彼此相同或不同，X is selected from an alkoxy group with 1 to 6 carbon atoms, halogen or hydrogen. When there are multiple
前述表面修饰步骤在前述中空二氧化硅生成步骤之后和/或所述水热处理步骤之后进行。The aforementioned surface modification step is performed after the aforementioned hollow silica generating step and/or after the hydrothermal treatment step.
[14]、根据[12]记载的中空二氧化硅溶胶的制备方法，其还包含下述步骤：[14]. The method for preparing hollow silica sol according to [12], which further includes the following steps:
表面修饰步骤：在中空二氧化硅溶胶中加入选自下述的式IV所示的硅烷及/或其部分水解物、六甲基二硅氧烷以及六甲基二硅氮(胺)烷组成的组中的一种或多种物质，对中空二氧化硅粒子表面进行修饰，
R4 p-Si-X4-p  式IVSurface modification step: Add silane represented by Formula IV below and/or its partial hydrolyzate, hexamethyldisiloxane and hexamethyldisilazine (amine) into the hollow silica sol. One or more substances in the group modify the surface of hollow silica particles,
R 4 p -Si-X 4-p Formula IV
式IV中，p＝0、1、2或者3,R4选自烷基、乙烯基烷基、环氧基烷基、苯乙烯基烷基、甲基丙烯酰氧基烷基、丙烯酰氧基烷基、氨基烷基、脲烷基、氯烷基、巯烷基、异氰酸酯烷基、或者、羟基烷基，有多个R4时，各R4彼此相同或者不同，R4中的氢原子可部分或全部被氟原子取代，In formula IV, p=0, 1, 2 or 3, 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选自碳原子数为1-6的烷氧基、卤素或者氢，有多个X时，各X彼此相同或不同，X is selected from an alkoxy group with 1 to 6 carbon atoms, halogen or hydrogen. When there are multiple
前述表面修饰步骤在前述中空二氧化硅生成步骤之后、和/或、前述水热处理步骤之后、和/或、前述溶剂置换步骤之后进行。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.
[15]、根据[14]记载的中空二氧化硅溶胶的制备方法，其中在前述表面修饰步骤之后再次进行前述水热处理步骤或/和前述溶剂置换步骤。[15]. The method for preparing hollow silica sol according to [14], wherein the hydrothermal treatment step or/and the solvent replacement step is performed again after the surface modification step.
[16]、一种涂料组合物，其含有中空二氧化硅溶胶、以及、粘接剂，前述中空二氧化硅溶胶为[1]～[5]的任一项记载的溶胶、或者为根据[6]～[15]的任一项记载的中空二氧化硅溶胶制备方法制备得到。[16] A coating composition containing a hollow silica sol and an adhesive, wherein the hollow silica sol is a sol according to any one of [1] to [5], or a sol according to [1] to [5]. It is prepared by the hollow silica sol preparation method described in any one of 6] to [15].
[17]、一种制品，其在基材表面具有涂层，前述涂层为1层或2层以上， 前述涂层中的至少1层由[16]记载的涂料组合物固化形成。[17]. A product having a coating on the surface of a base material, where the aforementioned coating is 1 layer or more than 2 layers, At least one layer among the coating layers is formed by curing the coating composition described in [16].
发明效果Invention effect
根据本发明的中空二氧化硅溶胶，通过使其含有的中空二氧化硅粒子的Q4(结合有4个-OSi-基的Si原子的比例)、Q3(结合3个-OSi-基和1个羟基的Si原子的比例)、Q2(结合2个-OSi-基和2个羟基的硅原子的比例)、Q1(结合1个-OSi-基和3个羟基的硅原子的比例)满足Q1/(Q1+Q2+Q3+Q4)实质上为0、Q2/(Q1+Q2+Q3+Q4)为0.01～0.2、Q3/(Q1+Q2+Q3+Q4)为0.01～0.6、以及，Q4/(Q1+Q2+Q3+Q4)为0.2～0.98，中空二氧化硅粒子的壳层的细孔尺寸小、薄而致密，从而本发明的中空二氧化硅溶胶粘度低，具有优异的热稳定性和分散稳定性。另外，本发明的中空二氧化硅溶胶中的中空粒子具有良好的壳层结构，形成为涂层时硬度高、耐磨性好、与基材的附着力强，由于能够避免空腔内部被其他物质填充，从而形成为涂层时还具有降低的折射率。另外，在形成的涂层作为减反射层时减反射性能提高、耐湿热性提高。According to the hollow silica sol of the present invention, 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. and dispersion stability. In addition, 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.
根据本发明的中空二氧化硅溶胶的制备方法，对中空二氧化硅溶胶进行水热处理，使得其中的中空二氧化硅粒子表面的羟基进一步缩合，能够制备含有壳层的细孔尺寸小、薄而致密的中空二氧化硅粒子的粘度小的中空二氧化硅溶胶。According to the preparation method of the hollow silica sol of the present invention, 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. Hollow silica sol with dense hollow silica particles and low viscosity.
本发明的涂料组合物能够形成减反射效果明显、耐磨性好、硬度高、与基材的附着力强的涂膜。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.
本发明的制品具有优异的减反射效果、良好的硬度、耐磨性、与基材的附着力以及优异的耐湿热性等耐候性。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.
附图说明Description of drawings
图1为实施例1得到的中空二氧化硅粒子的透射电子显微镜照片。Figure 1 is a transmission electron microscope photograph of the hollow silica particles obtained in Example 1.
图2为实施例2得到的中空二氧化硅粒子的透射电子显微镜照片。Figure 2 is a transmission electron microscope photograph of the hollow silica particles obtained in Example 2.
图3为实施例3得到的中空二氧化硅粒子的透射电子显微镜照片。Figure 3 is a transmission electron microscope photograph of the hollow silica particles obtained in Example 3.
图4为比较例1得到的中空二氧化硅粒子的透射电子显微镜照片。Figure 4 is a transmission electron microscope photograph of the hollow silica particles obtained in Comparative Example 1.
图5为比较例2得到的中空二氧化硅粒子的透射电子显微镜照片。 Figure 5 is a transmission electron microscope photograph of the hollow silica particles obtained in Comparative Example 2.
图6为比较例3得到的中空二氧化硅粒子的透射电子显微镜照片。Figure 6 is a transmission electron microscope photograph of the hollow silica particles obtained in Comparative Example 3.
具体实施方式Detailed ways
[中空二氧化硅溶胶][Hollow silica sol]
本发明的中空二氧化硅溶胶含有中空二氧化硅粒子和分散介质，The hollow silica sol of the present invention contains hollow silica particles and a dispersion medium,
上述中空二氧化硅粒子通过29Si核磁共振谱法测得的与峰值相对应的化学位移在-78～-88ppm的共振峰面积Q1、化学位移在-88～-98ppm的共振峰面积Q2、化学位移在-98～-108ppm的共振峰面积Q3、以及化学位移在-108～-117ppm出现的共振峰面积Q4满足：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:
Q1/(Q1+Q2+Q3+Q4)实质上为0、Q1/(Q1+Q2+Q3+Q4) is essentially 0,
Q2/(Q1+Q2+Q3+Q4)为0.01～0.2、Q2/(Q1+Q2+Q3+Q4) is 0.01～0.2,
Q3/(Q1+Q2+Q3+Q4)为0.01～0.6、以及，Q3/(Q1+Q2+Q3+Q4) is 0.01~0.6, and,
Q4/(Q1+Q2+Q3+Q4)为0.2～0.98。Q4/(Q1+Q2+Q3+Q4) is 0.2~0.98.
其中，归属于Q1的峰是与Si原子上结合有1个-OSi-基和3个羟基的硅原子的结构有关的峰；归属于Q2的峰是与Si原子上结合有2个-OSi-基和2个羟基的硅原子的结构有关的峰；归属于Q3的峰是与Si原子上结合有3个-OSi-基和1个羟基的硅原子的结构有关的峰；归属于Q4的峰是与Si原子上结合有4个-OSi-基的硅原子的结构有关的峰。Among them, 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 peaks related to the structure of silicon atoms with 3 -OSi- groups and 1 hydroxyl group bonded to the Si atom; 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)实质上为0”的意思是指，实质上不含有与Si原子上结合有1个-OSi-基和3个羟基的硅原子的结构有关的峰，但不排除具有由于检测限以及噪音等带来的不可避免的峰而使得Q1/(Q1+Q2+Q3+Q4)为例如0.0001以下的情况，这种情况下，也认为Q1/(Q1+Q2+Q3+Q4)实质上为0。“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.
前述的Q2/(Q1+Q2+Q3+Q4)为0.2以下。从中空二氧化硅表面的羟基具有能够满足后期溶剂置换和/或表面改性所需要的羟基、以及形成涂层后的附着力的角度考虑，前述Q2/(Q1+Q2+Q3+Q4)优选为0.01以上，更优选为0.03以上，进一步优选为0.05以上。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.
前述的Q3/(Q1+Q2+Q3+Q4)为0.6以下。从中空二氧化硅表面的羟基具有能够满足后期溶剂置换和/或表面改性所需要的羟基、以及形成涂层后的附着力的角度考虑，前述Q3/(Q1+Q2+Q3+Q4)优选为0.01以上，更优选为0.1以上， 进一步优选为0.2以上，再优选为0.3以上，更优选为0.4以上。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.
前述的Q4/(Q1+Q2+Q3+Q4)越高，表明球壳结构越完整，表面越致密，力学强度也越高。从中空粒子力学性能足够，不易破碎，内部空腔也不容易被填充，形成为涂层或制成制品时的减反射性能优异考虑，Q4/(Q1+Q2+Q3+Q4)为0.2以上。另一方面，从表面不是完全疏水的Si-O-Si结构，具有使得中空二氧化硅溶胶稳定的足够的亲水性，不容易发生沉降，并且表面能够被改性处理，有利于在其他溶剂体系或者涂料体系中的分散，另外，所得到的涂层或制品的附着力、耐磨擦性差等方面考虑，Q4/(Q1+Q2+Q3+Q4)优选为0.98以下，更优选为0.8以下，更优选为0.6以下。The higher the aforementioned Q4/(Q1+Q2+Q3+Q4), the more complete the spherical shell structure, the denser the surface, and the higher the mechanical strength. 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. On the other hand, 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. Dispersion in the system or coating system, and in consideration of poor adhesion and friction resistance of the resulting coating or product, Q4/(Q1+Q2+Q3+Q4) is preferably 0.98 or less, and more preferably 0.8 or less , more preferably 0.6 or less.
本发明的中空二氧化硅溶胶中，通过调节中空二氧化硅粒子中Q1、Q2、Q3、Q4的占比，使中空粒子表面既有足够的羟基便于在水及其他溶剂中分散，形成稳定的硅溶胶，使得后续的表面功能化处理容易进行，从而能够应用于不同体系的涂料组合物，并且能够兼顾中空粒子表面的羟基不至于过量，表面结构致密，力学性能优异，中空二氧化硅溶胶的粘度小，储存稳定性优异。In 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.
尤其，虽然Q2/(Q1+Q2+Q3+Q4)、Q3/(Q1+Q2+Q3+Q4)越低，所得中空粒子的球壳的致密度、力学强度越高，但是，当Q2/(Q1+Q2+Q3+Q4)、、Q3/(Q1+Q2+Q3+Q4)过分低的情况下，中空二氧化硅表面的羟基过少，难以满足后期用于涂层时所需要的溶剂置换和/或表面改性的需要，导致无法将溶胶的溶剂置换为需要的溶剂、或者、无法通过表面改性赋予需要的量的功能性官能团，另外，还存在后续形成涂层时的附着力不够的问题。因此，中空二氧化硅溶胶的一些实施方式中，优选的是，(Q2+Q3)/(Q1+Q2+Q3+Q4)为0.2以上，更优选为0.45以上。In particular, although the lower Q2/(Q1+Q2+Q3+Q4) and Q3/(Q1+Q2+Q3+Q4), the higher the density and mechanical strength of the spherical shell of the obtained hollow particles, however, when Q2/( When Q1+Q2+Q3+Q4), Q3/(Q1+Q2+Q3+Q4) are too low, there will be too few hydroxyl groups on the surface of the hollow silica, making it difficult to meet the solvent replacement required for later use in coatings. And/or the need for surface modification results in the inability to replace the solvent of the sol with the required solvent, or the inability to impart the required amount of functional functional groups through surface modification. In addition, there is insufficient adhesion when the subsequent coating is formed. The problem. Therefore, in some embodiments of the hollow silica sol, (Q2+Q3)/(Q1+Q2+Q3+Q4) is preferably 0.2 or more, and more preferably 0.45 or more.
本发明的中空二氧化硅溶胶在25℃、固含20％时的粘度为例如5～200mPa·sec，从具有良好的存储稳定性考虑，优选为5～100mPa·sec，更优选为5～50mPa·sec，进一步优选为5～20mPa·sec。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.
本发明的中空二氧化硅溶胶的一些实施方式中，Q1、Q2、Q3、Q4满足Q1/(Q1+Q2+Q3+Q4)实质上为0、Q2/(Q1+Q2+Q3+Q4)为0.05～0.1、Q3/(Q1+Q2+Q3+Q4)为0.2～0.55、以及，Q4/(Q1+Q2+Q3+Q4)为0.35～0.75In some embodiments of the hollow silica sol of the present invention, 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
本发明的中空二氧化硅溶胶的另一些实施方式中，Q1、Q2、Q3、Q4满足 Q1/(Q1+Q2+Q3+Q4)实质上为0、Q2/(Q1+Q2+Q3+Q4)为0.05～0.2、Q3/(Q1+Q2+Q3+Q4)为0.35～0.6、以及，Q4/(Q1+Q2+Q3+Q4)为0.3～0.65。In other embodiments of the hollow silica sol of the present invention, 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.
前述的Q1、Q2、Q3、Q4的测定方法与后述的实施例中记载的测定方法相同，在此不再赘述。The aforementioned measurement methods of Q1, Q2, Q3, and Q4 are the same as the measurement methods described in the Examples to be described later, and will not be described again.
前述中空二氧化硅粒子是壳层以二氧化硅为主要成分、壳层的内部为空腔的粒子。前述的“壳层以二氧化硅为主要成分”是指，中空粒子的壳层中主要成分为二氧化硅，任选包含少量的其他氧化物和/或有机基团。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.
本发明的中空二氧化硅溶胶的一个实施方式中，前述中空二氧化硅粒子的壳层的厚度优选为例如3～100nm。壳层的厚度为3nm以上的情况下，则具有足够的强度，更优选为4nm以上。前述的壳层的厚度优选为例如100nm以下，进一步优选为50nm以下，更优选为10nm以下，由此，有利于获得适宜的折射率，更优选为6nm以下。前述壳层的厚度可以通过中空粒子的制造条件中硅源等反应原料的量、反应温度等适宜调整。从获得优异的折射率的角度考虑，壳的厚度更优选为4～10nm。In one embodiment of the hollow silica sol of the present invention, the thickness of the shell layer of the hollow silica particles is preferably, for example, 3 to 100 nm. When 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.
壳层的厚度通过下述方法测定：通过透射电镜(TEM)观察中空粒子，随机挑选100个粒子，测量各个中空粒子的壳的厚度，将测得的值平均得到。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.
本发明的中空二氧化硅溶胶的一个实施方式中，前述中空二氧化硅粒子的壳层上具有例如直径分布为0.5～4纳米的孔。通过具有0.5纳米以上的孔，从而能够获得高的孔容、孔隙率以及低的折射率和相对介电常数。如果中空粒子的壳的细孔为10纳米以下，则中空粒子具有良好的粒子强度，在用作涂料组合物制成涂膜时，内部孔隙不容易被填充，能够获得良好的耐磨性和减反射性能。从折射率、相对介电常数的角度考虑，更优选为0.5～4纳米。In one embodiment of the hollow silica sol of the present invention, the shell layer of the hollow silica particles has pores with a diameter distribution of, for example, 0.5 to 4 nanometers. By having pores of 0.5 nm or more, high pore volume, porosity, and low refractive index and relative dielectric constant can be obtained. If the pores of the shell of the hollow particles are 10 nanometers or less, the hollow particles will have good particle strength. When used as a coating composition to form a coating film, 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.
本发明的中空二氧化硅溶胶的一个实施方式中，前述中空二氧化硅粒子的孔容可以为例如0.15～1.0cm3/g。中空二氧化硅粒子的孔容为0.15cm3/g以上，则能够使得粒子具有较低的折射率。中空二氧化硅粒子的孔容为1.0cm3/g以下，则粒子有足够的强度。In one embodiment of the hollow silica sol of the present invention, 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.
前述的细孔的尺寸和孔容可以通过如下方法测定的：采用Quadrasorb evo比表面和孔隙率分析仪(Quantachrome Instruments,USA)在77K条件下静态吸附测量。中空二氧化硅粒子外壳上的孔尺寸和孔容是采用等温吸附曲线和 Barrett-Joyner-Halenda(BJH)模型测得。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.
本发明的中空二氧化硅溶胶的一个实施方式中，前述中空二氧化硅粒子的折射率可以为例如1.10～1.45。中空二氧化硅粒子的折射率为1.10以上，从而中空粒子具有较好的硬度和强度。中空二氧化硅粒子的折射率为1.45以下，则具有较低的折射率，在减反射涂层中表现优异。In one embodiment of the hollow silica sol of the present invention, 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.
本发明的中空二氧化硅溶胶的一个实施方式中，中空二氧化硅粒子的相对介电常数为例如1.6～2.2。中空二氧化硅粒子的相对介电常数为1.6以上时，则粒子在复合介电材料中具有足够的强度。从具有优异的介电性能和低的介电损耗的角度考虑，中空二氧化硅粒子的相对介电常数为2.2以下，更优选为2.0以下。In one embodiment of the hollow silica sol of the present invention, the relative dielectric constant of the hollow silica particles is, for example, 1.6 to 2.2. When the relative dielectric constant of the hollow silica particles is 1.6 or more, the particles have sufficient strength in the composite dielectric material. From the viewpoint of having excellent dielectric properties and low dielectric loss, the relative dielectric constant of the hollow silica particles is 2.2 or less, and more preferably 2.0 or less.
本发明的中空二氧化硅溶胶的一个实施方式中，中空二氧化硅粒子的粒径为例如15～1000nm。从所形成光学涂层的透明性角度考虑，更优选为20～500nm，进一步优选为20～100nm。In one embodiment of the hollow silica sol of the present invention, 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.
本发明的中空二氧化硅溶胶的一个实施方式中，中空二氧化硅粒子的多分散性指数(PDI)为例如0.05～0.3。前述的多分散性指数通过中空二氧化硅溶胶的动态光散射(DLS)测试数据获得。PDI越低，说明中空粒子的尺寸分布越均一，越趋向于单分散。PDI为0.3以下，则中空二氧化硅粒子具有较均匀的尺寸分布，在制备成涂层后，涂层表面具有较低的粗糙度，耐摩擦性能更优异。In one embodiment of the hollow silica sol of the present invention, 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.
通过设置适宜尺寸的细孔及壳层厚度，既保证了足够的孔隙率，具有较低的折射率，同时使其他物质无法通过中空粒子壳上的孔隙进入内部空腔，使中空粒子在涂料组合物、涂层、以及含有涂层的制品中，始终具有优异的减反射性能。By setting appropriate sized pores and shell thickness, it not only ensures sufficient porosity and low refractive index, but also prevents other substances from entering the internal cavity through the pores on the hollow particle shell, making the hollow particles in the paint combination It always has excellent anti-reflective properties in objects, coatings, and products containing coatings.
本发明的中空二氧化硅溶胶的一个实施方式中，中空二氧化硅粒子的含量优选为0.5质量％～70质量％的范围。中空二氧化硅溶胶中中空二氧化硅粒子的含量为0.5质量％以上时，从形成涂层时的效率等方面考虑是优选的，更优选为5质量％以上，进一步优选为10质量％以上。中空二氧化硅溶胶中中空二氧化硅粒子的含量为70质量％以下时，从中空二氧化硅溶胶的存储稳定性、具有适宜的粘度的角度考虑是优选的，更优选为60质量％以下，进一步优选为 50质量％以下。In one embodiment of the hollow silica sol of the present invention, 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.
前述中空二氧化硅溶胶中含有的分散介质为水、有机溶剂或者两者的组合。前述的有机溶剂是指含有碳原子的、能够流动的有机化合物。分散介质的作用在于使中空二氧化硅粒子以单个粒子的状态存在于分散介质提供的环境中，避免中空二氧化硅粒子在干燥状态下发生的聚集从而影响最终涂层及制品的光学透明性。前述的有机溶剂可以列举出例如甲醇、乙醇、异丙醇、丁醇、乙酸乙酯、乙酸丁酯、丙酮、丁酮、甲基异丁基甲酮、庚酮、己烷、环己烷、庚烷、辛烷、壬烷、乙二醇、丙二醇、乙二醇甲醚、乙二醇丁醚、丙二醇甲醚、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等，只要不影响中空二氧化硅溶胶及中空二氧化硅粒子的性能就没有特别的限定。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. Examples of the organic solvent include methanol, ethanol, isopropyl alcohol, butanol, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, heptanone, hexane, cyclohexane, and heptane. , octane, nonane, ethylene glycol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide etc., there is no particular limit as long as the properties of the hollow silica sol and hollow silica particles are not affected.
[中空二氧化硅溶胶的制备方法][Preparation method of hollow silica sol]
中空二氧化硅溶胶的制备方法包括以下步骤：The preparation method of hollow silica sol includes the following steps:
中间产物生成步骤：将硅源、第一溶剂、第一催化剂及活性化合物混合，在0～150℃范围内进行反应，然后去除沸点小于300℃的物质，得到液态有机硅中间产物P1；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;
中空二氧化硅生成步骤：将所述有机硅中间产物P1分散到第二溶剂中，并加入第二催化剂，在0～95℃的范围内进行反应，得到中空二氧化硅溶胶；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;
水热处理步骤：根据需要清洗后，在30～300℃范围内进行水热处理。Hydrothermal treatment step: After cleaning as needed, perform hydrothermal treatment in the range of 30 to 300°C.
下面依次对前述步骤进行说明。The above steps are explained in turn below.
[中间产物生成步骤][Intermediate product generation step]
前述的中间产物生成步骤中，在第一催化剂的催化作用下硅源中的烷氧基在第一溶剂存在下发生水解，生成硅羟基，生成的硅羟基可以进一步发生缩合反应，也可以与活性化合物中的羟基发生反应，生成高沸点的液态有机硅中间产物和作为副产物的低沸点物质(沸点小于300℃的物质)，通过去除低沸点物质，纯化中间产物，使其分子量分布更窄，化学性质更加均匀。In the aforementioned intermediate product generation step, under the catalytic action of the first catalyst, 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). By removing the low-boiling point substances, the intermediate product is purified to make its molecular weight distribution narrower. Chemical properties are more uniform.
对前述的硅源组成没有限定，只要含有烷氧基，能够水解成硅羟基并且进一步缩合，形成可流动的中间产物即可。There is no limit to the composition of the aforementioned silicon source, as long as it contains an alkoxy group and can be hydrolyzed into a silanol group and further condensed to form a flowable intermediate product.
优选地，前述硅源为下述的式I所示的硅烷单体中的1种或2种以上，或者为最简式为下述式II所示的聚烷氧基硅氧烷低聚物，
R1 4-nSi(OR2)n   式IPreferably, 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
式I中，n＝1、2、3、或者4，R1为烷基、乙烯基烷基、乙烯基、环氧基烷基、苯基、苯乙烯基烷基、甲基丙烯酰氧基烷基、丙烯酰氧基烷基、氨基烷基、脲烷基、氯烷基、巯烷基、异氰酸酯烷基、或者羟基烷基，有多个R1时，各R1彼此任选相同或不同；R2为碳原子数1～6的烷基，有多个R2时各R2彼此任选相同或不同；
SiOm(OR3)4-2m   式IIIn formula I, n=1, 2, 3, or 4, 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. When there are multiple R 1s , each R 1 is optionally the same or different from each other. Different; R 2 is an alkyl group with 1 to 6 carbon atoms. When there are multiple R 2s , each R 2 may be the same or different from each other;
SiO m (OR 3 ) 4-2m Formula II
式II中，0<m<2，m为整数或者非整数，R3为碳原子数1～6的烷基，有多个R3时各R3彼此任选相同或不同。In Formula II, 0<m<2, 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.
前述的式I中，作为R1所表示的烷基、乙烯基烷基、乙烯基、环氧基烷基、苯基、苯乙烯基烷基、甲基丙烯酰氧基烷基、丙烯酰氧基烷基、氨基烷基、脲烷基、氯烷基、巯烷基、异氰酸酯烷基、或者羟基烷基中的“烷基”，可以列举出例如，碳原子数1～22的烷基，可以为碳原子数1～10的烷基，进一步可以碳原子数为1～8的烷基。In the aforementioned formula I, 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. Examples of the "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.
作为前述的“碳原子数为1～8的烷基”，例如可以列举出甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基、1-甲基丁基、2-甲基丁基、1-乙基丙基、1,2-二甲基丙基、己基、正庚基、正辛基等，没有特别的限定。Examples of the aforementioned "alkyl group having 1 to 8 carbon atoms" 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.
作为前述的最简式为式II所示的聚烷氧基硅氧烷低聚物，可以列举出例如市售的硅40、硅48、硅51、硅53、硅63等。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.
作为前述的硅源，可以使用前述的式I所示结构的硅烷单体中的1种或2种以上或者前述的式II所示的聚烷氧基硅氧烷低聚物中的1种或2种以上，也可以将两者组合使用。优选地，前述硅源为选自硅酸四乙酯、硅酸四甲酯、乙烯基三乙氧基硅烷、甲基三乙氧基硅烷、3-(甲基丙烯酰氧)丙基三乙氧基硅烷、硅40、硅48、硅51中的至少一种。As 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. Preferably, 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.
作为前述的第一溶剂，优选为水、或者，水与有机溶剂的混合溶剂，进一步优选为水与有机溶剂的混合溶剂，可以列举出例如含水甲醇、含水乙醇、含水异丙醇、含水丁醇、含水乙二醇、含水乙二醇丁醚、含水丙二醇、含水丙二醇甲醚中的至少一种。 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. , at least one of aqueous ethylene glycol, aqueous ethylene glycol butyl ether, aqueous propylene glycol, and aqueous propylene glycol methyl ether.
前述第一溶剂中含有的水与前述硅源的重量比优选为0.001：1以上且小于0.5：1。在前述的中间产物生成步骤中，硅源中的烷氧基遇水发生水解，进一步缩合，形成含有Si-O-Si结构的中间产物。当该重量比为0.001：1以上时，所得中间产物分子量足够高，与活性化合物反应后亲水性不会太强，能够产生界面活性。当该重量比小于0.5：1时，硅源中的烷氧基尚有部分未完全反应，有利于后续的活性化合物继续与之反应。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. In the aforementioned intermediate product generation step, 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. When 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. When 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.
另外，前述的水与硅源的重量比是影响作为最终产物的中空二氧化硅粒子的壳层厚度的因素之一，中空二氧化硅粒子的壳层厚度随着水与硅源的重量比增大而变大。从获得足够的中空二氧化硅粒子的壳层厚度从而使得中空二氧化硅粒子具有足够的强度的角度考虑，前述的水与硅源的重量比优选为0.01：1以上。从中空二氧化硅粒子的壳层厚度不过厚从而具有较低折射率的角度考虑，前述的水与硅源的重量比优选为0.25：1以下。In addition, 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.
前述第一溶剂中，除水之外的其他溶剂的使用，目的在于使水与所述硅源能够快速均匀混合，加入的量没有特别限制，从节省制备成本的角度考虑，优选量为保证水与硅源能够混匀的使用量。In the aforementioned first solvent, 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.
前述的第一催化剂为酸、碱、或金属醇盐、金属羧酸盐。作为这样的酸，例如有盐酸、硫酸、硝酸、磷酸、醋酸、草酸、酸性阳离子交换树脂等，但不限于这些。作为这样的碱，例如有氨水、有机胺、氢氧化钠、氢氧化钾、碳酸氢钠、碳酸钠等，但不限于这些。作为这样的金属醇盐，例如有钛醇盐、铝醇盐、锆醇盐等，但不限于这些。作为这样的金属羧酸盐，例如有乙酸锡、乙酸铝、乙酸锆等，但不限于这些。从反应可控性角度考虑，前述第一催化剂优选为酸或钛醇盐。作为钛醇盐，例如可以列举出四甲氧基钛、四乙氧基钛、四丙氧基钛等。The aforementioned first catalyst is acid, alkali, or metal alkoxide or metal carboxylate. Examples of such 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. Examples of such a base include ammonia water, organic amines, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, etc., but are not limited to these. Examples of such metal alkoxide include titanium alkoxide, aluminum alkoxide, zirconium alkoxide, etc., but are not limited to these. Examples of such metal carboxylates include tin acetate, aluminum acetate, zirconium acetate, etc., but are not limited to these. From the perspective of reaction controllability, the first catalyst is preferably an acid or titanium alkoxide. Examples of titanium alkoxide include titanium tetramethoxide, titanium tetraethoxide, and titanium tetrapropoxide.
前述第一催化剂与前述硅源的重量比优选为0.001～0.5：1。控制该重量比为0.5：1以下，有利于防止反应速度过快导致的凝胶状固体的生成，控制该重量比为0.001：1以上，有利于提高催化效率，获得适宜的反应速率。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.
前述的活性化合物是指，起到提高有机硅中间产物亲水性作用的化合物。作为这样的活性化合物，例如可以为，含有至少一个OH基团、分子量大于150、并且通过下述式III计算的HLB值大于5的物质，
HLB＝20×Mh/M  式IIIThe aforementioned active compound refers to a compound that plays a role in improving the hydrophilicity of the organic silicon intermediate product. Such an active compound may be, for example, a substance containing at least one OH group, a molecular weight greater than 150, and an HLB value calculated by the following formula III greater than 5,
HLB＝20×M h /M Formula III
式III中，Mh为活性化合物中亲水部分的分子量，M为活性化合物的分子量。In formula III, M h is the molecular weight of the hydrophilic part of the active compound, and M is the molecular weight of the active compound.
前述活性化合物可以为单一物质或两种以上的混合物。作为前述的活性化合物，可以列举出例如选自聚丙烯酸、聚乙二醇、聚乙二醇单醚、聚乙烯醇、聚甘油、以及、环氧乙烷与环氧丙烷的共聚物中的1种或2种以上的组合。当活性化合物通过式III计算的HLB值低于5时，该活性化合物不能给予有机硅中间产物适当的亲水性，无法在后续步骤中得到中空二氧化硅粒子。The aforementioned active compounds may be a single substance or a mixture of two or more. Examples of 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. When 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.
前述活性化合物与前述硅源的重量比可以为例如(0.05～0.5)：1。通过将该质量比控制为0.05：1以上，能够使得所得的有机硅中间产物具有足够的亲水性，从而不容易在含水溶剂中发生团聚，能够形成具有中空结构的粒子。通过控制该质量比为0.5：1以下，使得所得有机硅中间体具有部分疏水性，从而具有适宜的界面活性，能够在后续的步骤中形成中空粒子。The weight ratio of the aforementioned active compound to the aforementioned silicon source may be, for example, (0.05-0.5):1. By controlling the mass ratio to be 0.05:1 or more, 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. By controlling the mass ratio to be less than 0.5:1, the obtained organosilicon intermediate is partially hydrophobic, thereby having appropriate interfacial activity and capable of forming hollow particles in subsequent steps.
前述的中间产物生成步骤的反应温度为0～150℃，优选为60～100℃。反应时间为例如1～24小时，优选为5～15小时。从兼顾反应充分及反应效率的角度考虑，更优选为8～10小时。The reaction temperature of the aforementioned intermediate product generation step is 0 to 150°C, preferably 60 to 100°C. The reaction time is, for example, 1 to 24 hours, preferably 5 to 15 hours. From the viewpoint of both sufficient reaction and reaction efficiency, 8 to 10 hours is more preferred.
在前述中间产物生成步骤的反应过程中，由于发生硅源中烷氧基的水解缩合反应，在生成有机硅中间产物P1的同时，也会产生一部分沸点低于300℃的副产物。作为这样的沸点低于300℃的副产物可以列举出例如，分子量低于500的中间产物、烷氧基水解缩合生成的小分子醇类化合物等。During the reaction process of the aforementioned intermediate product generation step, due to the hydrolysis and condensation reaction of alkoxy groups in the silicon source, while the organic silicon intermediate product P1 is generated, some by-products with a boiling point lower than 300°C are also generated. Examples of such by-products having a boiling point lower than 300° C. include intermediate products with a molecular weight lower than 500, small-molecule alcohol compounds produced by hydrolysis and condensation of alkoxy groups, and the like.
前述沸点低于300℃副产物的去除对于中空二氧化硅粒子的制备具有关键影响。通过去除其中作为副产物的醇类化合物，使得硅源水解缩合以及与含羟基的活性化合物缩合能够正向进行，得到较高分子量的中间产物，最终形成中空二氧化硅粒子。通过去除分子量低于500的中间产物，使得制备的中空二氧化硅粒子的粒径更均匀，尺寸更容易控制。The removal of the aforementioned by-products with boiling points below 300°C has a key impact on the preparation of hollow silica particles. By removing the alcohol compounds as by-products, 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. By removing intermediate products with a molecular weight lower than 500, the particle size of the prepared hollow silica particles is more uniform and the size is easier to control.
前述的低沸点副产物的除去方法可以列举出例如选自常压蒸馏、减压蒸馏、薄膜蒸发、或者、旋转蒸发中的一种或它们的组合。前述的低沸点副产物的除去可以与水解、缩合反应一起进行，在反应过程中，当观察到有液体被蒸出时，说明副产物正在被去除。在加热反应结束后，可以进一步进行前述的第 一反应副产物的除去，使得副产物充分去除。在除去的过程中，当观察不到有液体被蒸出或者收集瓶中的液体质量持续一定时间不再变化，则认为副产物已被完全去除，保留的为有机硅中间产物P1。The aforementioned method for removing low boiling point by-products may include, for example, one selected from the group consisting of normal pressure distillation, reduced pressure distillation, thin film evaporation, or rotary evaporation, or a combination thereof. The aforementioned removal of low-boiling point by-products can be carried out together with hydrolysis and condensation reactions. During the reaction, when liquid is observed to be evaporated, it indicates that the by-products are being removed. After the heating reaction is completed, the aforementioned third step can be further performed. The removal of reaction by-products ensures that the by-products are fully removed. During the removal process, when no liquid is observed to be evaporated or the quality of the liquid in the collection bottle does not change for a certain period of time, it is considered that the by-product has been completely removed and the remaining organic silicone intermediate product P1 is retained.
[中空二氧化硅生成步骤][Hollow silica production step]
中空二氧化硅生成步骤中，将前述的有机硅中间产物P1分散到第二溶剂中，并加入第二催化剂，在0～95℃的范围内进行反应，得到中空二氧化硅溶胶。In the step of generating hollow silica, 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.
前述的第二溶剂为水、或者水与亲水性溶剂的组合、或者水与疏水性溶剂的组合。作为这样的亲水性溶剂，可以列举出例如醇、酮、醚等能够与水混溶的有机溶剂。作为这样的疏水性溶剂，可以列举出例如烷烃、芳香烃、酯等有机溶剂。The aforementioned second solvent is water, or a combination of water and a hydrophilic solvent, or a combination of water and a hydrophobic solvent. Examples of such hydrophilic solvents include organic solvents miscible with water such as alcohols, ketones, and ethers. Examples of such hydrophobic solvents include organic solvents such as alkanes, aromatic hydrocarbons, and esters.
将前述的有机硅中间产物P1分散到第二溶剂中时，有机硅中间产物P1与第二溶剂组装成类似囊泡(vesicle)的结构，该囊泡的内部和外部均为含水溶剂，有机硅中间产物P1富集在界面处，在第二催化剂的作用下有机硅中间产物P1快速水解、缩合，形成为具有致密二氧化硅壳层的中空二氧化硅粒子，从而得到含有单分散的中空二氧化硅粒子的溶胶。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.
另一方面，在第二催化剂的作用下有机硅中间产物水解、缩合转变成二氧化硅的同时，也会释放小分子醇，在囊泡尺寸基本不变的情况下，小分子醇的释放会在二氧化硅球壳上引入足够多的细孔。On the other hand, when the organic silicon intermediate product is hydrolyzed and condensed into silica under the action of the second catalyst, small molecular alcohols will also be released. When the size of the vesicles remains basically unchanged, the release of small molecular alcohols will increase. Introduce enough pores into the silica spherical shell.
可以通过调整第二催化剂的种类和用量来调节细孔尺寸、孔容、中空粒子的折射率。一般情况下，与使用酸催化剂的情况相比，使用碱催化剂形成的细孔尺寸更大，孔容更高，折射率更低。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. In general, 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.
前述的第二催化剂可以为例如酸或者碱。作为酸，可以为有机酸或无机酸。作为无机酸，例如可以列举出盐酸、硝酸、硫酸等，作为有机酸，可以列举出甲酸、乙酸、丙烯酸等。作为碱，可以为无机碱或者有机碱。作为前述的无机碱，可以列举出氢氧化钠、氢氧化钾、氨水等，作为前述的有机碱，可以列举出三乙胺等。另外，酸式盐、碱式盐等为盐的形式但显示出酸性或者碱性的情况下，只要是能够作为前述的第二催化发挥作用使得有机硅中间产物发生反应生成中空二氧化硅粒子，就认为是属于前述的第二催化剂的范畴。前述的第二催化剂可以与第一催化剂相同，也可以与第一催化剂不同。 The aforementioned second catalyst may be, for example, an acid or a base. The acid may be an organic acid or an inorganic acid. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and the like, and examples of organic acids include formic acid, acetic acid, acrylic acid, and the like. The base may be an inorganic base or an organic base. Examples of the inorganic base include sodium hydroxide, potassium hydroxide, ammonia water, etc., and examples of the organic base include triethylamine and the like. In addition, when an acidic salt, a basic salt, etc. is in the form of a salt but shows acidity or alkalinity, as long as it can function as the aforementioned second catalytic reaction so that the organic silicon intermediate product reacts to generate hollow silica particles, It is considered to belong to the category of the aforementioned second catalyst. The aforementioned second catalyst may be the same as the first catalyst, or may be different from the first catalyst.
前述第二催化剂相对于有机硅中间产物的重量比可以为例如，(0.05～2)：1。The weight ratio of the aforementioned second catalyst to the organosilicon intermediate product may be, for example, (0.05-2):1.
前述的中空二氧化硅粒子生成步骤中，从获得适宜的分散液粘度以及生产效率的角度考虑，有机硅中间产物P1相对于第二溶剂的重量百分比优选为1～60％。In the aforementioned step of generating hollow silica particles, from the perspective of obtaining appropriate dispersion viscosity and production efficiency, the weight percentage of the silicone intermediate P1 relative to the second solvent is preferably 1 to 60%.
通过前述的中空二氧化硅粒子生成步骤，能够获得分散性良好的中空二氧化硅溶胶。但其未经过表面致密化处理，存在过量的羟基以及缺陷，导致这种初级中空二氧化硅溶胶在高固含情况下，粘度随时间而增大，甚至出现凝胶，影响后续使用，另外，二氧化硅球壳相对较软，且表面缺陷较多，在用作后续的涂料组合物或者涂层制品时，可能会出现耐磨性差，中空结构易被填充进而影响减反射性能、介电性能等问题。Through the above-mentioned step of producing hollow silica particles, a hollow silica sol with good dispersibility can be obtained. However, it has not undergone surface densification treatment, and there are excessive hydroxyl groups and defects. As a result, the viscosity of this primary hollow silica sol increases over time under high solid content conditions, and even gels appear, which affects subsequent use. In addition, 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.
[水热处理步骤][Hydrothermal treatment step]
水热处理步骤在30～300℃温度下进行。通过水热处理，中空二氧化硅粒子的壳层变得更均匀、更致密，因为表面张力的原因，粒子会更接近于球形，且力学强度大大提高。与未经过水热处理的中空二氧化硅溶胶相比较，经过了水热处理步骤之后的中空二氧化硅溶胶即使处于较高的固含，依旧保持较低的粘度，提高了热稳定性与储存稳定性，另外，中空二氧化硅粒子的壳层更致密，表面缺陷减少，形成涂层时的硬度提高、耐摩擦性提高。另外，在用于减反射涂料时，相对高折射率的树脂无法进入中空粒子内部，因此能得到减反射效果较好的涂膜。The hydrothermal treatment step is performed at a temperature of 30 to 300°C. Through hydrothermal treatment, 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. Compared with the hollow silica sol that has not undergone hydrothermal treatment, 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. , In addition, 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. In addition, when used in anti-reflective coatings, 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.
通过前述的水热处理，调节中空二氧化硅粒子表面的羟基等基团的比例，使得得到的中空二氧化硅溶胶满足前述的本发明的中空二氧化硅溶胶的Q1、Q2、Q3、Q4的范围，从而能够使得得到的中空二氧化硅溶胶含有的中空二氧化硅粒子的缺陷少、表面结构致密、力学性能优异、溶胶粘度小等性能、又能兼顾使得中空二氧化硅粒子表面具有足够的羟基便于在水及其他溶剂中分散，形成稳定的硅溶胶，使得后续的表面功能化处理容易进行，从而能够应用于不同体系的涂料组合物。Through the aforementioned hydrothermal treatment, 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.
前述水热步骤的水热温度为30℃～300℃。水热温度为30℃以上时，能够有效地致密化二氧化硅球壳，用作涂料及涂层时，能够有效提高涂膜性、减反射性以及涂层的强度。水热温度超过300℃的情况下，中空粒子表面也无法进 一步致密化，所形成的涂料和涂层性能也无法进一步提升，同时可能会造成中空粒子的团聚，从溶胶中析出，影响进一步使用。从形成的涂层的耐水性、耐候性以及耐摩擦性的角度考虑，前述水热处理温度优选为100℃～200℃。The hydrothermal temperature in the aforementioned hydrothermal step is 30°C to 300°C. When the hydrothermal temperature is above 30°C, the silica spherical shell can be effectively densified. When used as a paint and coating, it can effectively improve the coating properties, anti-reflective properties and coating strength. When 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. From the viewpoint of water resistance, weather resistance and friction resistance of the formed coating, the hydrothermal treatment temperature is preferably 100°C to 200°C.
前述的水热处理步骤之前，根据情况，任选地，可以进行超滤、离心、离子交换树脂等公知的清洗步骤，以除去中空二氧化硅溶胶中可能存在的除二氧化硅之外的其他物质或离子，通过清洗步骤，中空二氧化硅溶胶纯度更高、稳定性更好。Before the aforementioned hydrothermal treatment step, depending on the situation, well-known cleaning steps such as ultrafiltration, centrifugation, and ion exchange resin can be performed optionally to remove other substances other than silica that may be present in the hollow silica sol. or ions, through the cleaning step, the hollow silica sol has higher purity and better stability.
本发明的中空二氧化硅溶胶的制备方法，无需进行利用高温煅烧、溶剂刻蚀或酸碱溶解等传统手段去除内部模板的步骤，就能够获得单分散性优异、没有二次团聚的中空粒子分散液。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.
另外，本发明的中空二氧化硅溶胶的制备方法中，通过水热处理步骤，能够制备力学强度高、壳层均匀、致密的中空二氧化硅粒子，将该粒子用于涂料组合物、涂层时，能够赋予涂层优异的耐水性、耐磨性、耐候性以及减反射性能。In addition, in the preparation method of hollow silica sol of the present invention, through the hydrothermal treatment step, hollow silica particles with high mechanical strength, uniform shell layer and dense can be prepared. When the particles are used in coating compositions and coatings , can give the coating excellent water resistance, wear resistance, weather resistance and anti-reflective properties.
以上所得的中空二氧化硅溶胶可以与粘合剂一起组成涂料组合物进行使用，广泛用于形成减反射涂层。或者，根据所形成的涂层的性能要求，可以在涂料组合物中添加各种添加剂。进一步，中空二氧化硅溶胶也可以干燥后作为中空二氧化硅粒子的粉体的形式保存待用。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.
另外，本发明的中空二氧化硅溶胶的制备方法中，不引入任何金属离子，具有优异的低介电特性。In addition, in the preparation method of the hollow silica sol of the present invention, no metal ions are introduced, and it has excellent low dielectric properties.
通过前述的中空二氧化硅溶胶的制备方法得到的中空二氧化硅溶胶中含有的中空粒子的壳层含有细孔通道，能够用于包覆及缓释。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.
可选地，本发明的中空二氧化硅溶胶的制备方法中，还可以进一步包含下述步骤：Optionally, the preparation method of the hollow silica sol of the present invention may further include the following steps:
溶剂置换步骤Solvent replacement step
溶剂置换步骤中，使用超滤膜、旋转蒸发仪、离心机等设备，用有机溶剂置换所得的中空二氧化硅溶胶中的原来的溶剂的全部或者一部分，得到中空二氧化硅有机溶胶。前述的“一部分”可以是例如20％以上、40％以上、60％以上、80％以上、90％以上，或者为99％以上。 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.
用于置换的溶剂可以为1种或2种以上的混合溶剂。经过溶剂置换步骤的中空二氧化硅溶胶，能够适用于绝大多数涂料体系，在所得的涂料组合物中具有优异的分散性能，在制得的涂层及制品中，不发生团聚，赋予涂层较好的光学透明性，避免涂层发白。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.
例如，置换前中空二氧化硅溶胶的溶剂为水的情况下，可以使用甲醇将其中的水进行置换，得到中空二氧化硅甲醇溶胶。For example, if 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.
另一实施方式中，例如，置换前中空二氧化硅溶胶的溶剂为甲醇的情况下，可以使用丙酮将其中一部分甲醇进行置换，得到中空二氧化硅的甲醇/丙酮溶胶。In another embodiment, for example, when 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.
表面修饰步骤Surface modification steps
在中空二氧化硅溶胶中加入选自下述的式IV所示的硅烷及/或其部分水解物、六甲基二硅氧烷以及六甲基二硅氮(胺)烷组成的组中的1种或者2种以上，对中空二氧化硅粒子表面进行修饰。
R4 p-Si-X4-p   式IVAdd 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 p -Si-X 4-p Formula IV
式IV中，p＝0、1、2、或者、3，R4选自烷基、乙烯基烷基、环氧基烷基、苯乙烯基烷基、甲基丙烯酰氧基烷基、丙烯酰氧基烷基、氨基烷基、脲烷基、氯烷基、巯烷基、异氰酸酯烷基、或者、羟基烷基，有多个R4时，各R4彼此相同或者不同，R4中的氢原子任选部分或全部被氟原子取代；In formula IV, p=0, 1, 2, or 3, 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. When there are multiple R 4 , each R 4 is the same as or different from each other. Among R 4 The hydrogen atoms are optionally partially or completely replaced by fluorine atoms;
X选自碳原子数为1-6的烷氧基、卤素或者氢，有多个X时，各X彼此相同或不同。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.
前述的R4所表示的“烷基、乙烯基烷基、环氧基烷基、苯乙烯基烷基、甲基丙烯酰氧基烷基、丙烯酰氧基烷基、氨基烷基、脲烷基、氯烷基、巯烷基、异氰酸酯烷基、或者、羟基烷基”中的“烷基”可以列举出例如，碳原子数1～22的烷基，可以为碳原子数1～10的烷基，进一步可以碳原子数为1～8的烷基。The aforementioned "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.
作为前述的“碳原子数为1～8的烷基”，例如可以列举出甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基、1-甲基丁基、2-甲基丁基、1-乙基丙基、1,2-二甲基丙基、己基、正庚基、正辛基等，没有特别的限定。。Examples of the aforementioned "alkyl group having 1 to 8 carbon atoms" 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. .
通过在中空二氧化硅溶胶中加入前述的选自式IV所示的硅烷及/或其部分 水解物、六甲基二硅氧烷以及六甲基二硅氮(胺)烷组成的组中的1种或者2种以上，对中空二氧化硅粒子表面进行修饰，从而能够在中空二氧化硅粒子表面修饰上有机基团，使中空二氧化硅在某些有机溶剂中具有更优异的分散稳定性，从而与涂料中的粘合剂具有更强的亲和力，在涂层固化的过程中，与粘合剂有更强的相互作用，因而赋予涂层更好的附着力、硬度及耐磨性。By adding the aforementioned silanes and/or parts thereof selected from the group consisting of formula IV into the hollow silica sol 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. During the curing process of the coating, it interacts with Binders have stronger interactions, thus giving the coating better adhesion, hardness and wear resistance.
前述式IV中，通过将R4中的氢原子部分或全部用氟原子取代，能够进一步降低中空二氧化硅粒子的折射率，另外，中空粒子表面更加疏水，从而在用于涂料组合物时能够赋予涂层优异的抗指纹性、爽滑性、耐污性，进而提供更加出色的耐磨性。In the aforementioned formula IV, by replacing part or all of the hydrogen atoms in R 4 with fluorine atoms, the refractive index of the hollow silica particles can be further reduced. In addition, 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.
上述的表面修饰步骤可在前述中空二氧化硅生成步骤之后、和/或、前述水热处理步骤之后、和/或、前述溶剂置换步骤后的任意步骤进行。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.
前述的水热处理步骤、溶剂置换步骤以及表面改性步骤的顺序可随机选择，也可以重复进行任1种或2种以上的步骤，只要不损害中空二氧化硅溶胶的稳定性以及在涂料组合物中的分散即可。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.
另外，可选地，在本发明的中空二氧化硅溶胶的制备方法中，可以在中空二氧化硅生成步骤、水热处理步骤、溶剂置换步骤、表面改性步骤中的某一步骤后，进行干燥，或进行烧结，得到中空二氧化硅粉体。In addition, optionally, in the preparation method of the hollow silica sol of the present invention, 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.
本发明的中空二氧化硅溶胶制备方法，不采用任何硬模板或软模板，利用有机硅中间产物在水中的自组装行为生成中空二氧化硅粒子水分散液。后期不需要通过高温煅烧、溶剂刻蚀、酸碱溶解等方式去除模板，避免了中空粒子的团聚，通过水热处理，使中空粒子表面更致密、壳层更均匀、力学强度更高、耐候性更佳，通过溶剂置换，得到不同分散体系的中空二氧化硅有机硅溶胶，通过表面改性，进一步增加中空粒子在有机溶剂中的分散稳定性和有机树脂的亲和力，赋予涂料组合物及涂层优异的光学性能、力学性能、耐候性。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. In the later stage, 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. Through 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. Through solvent replacement, hollow silica organosilica sols with different dispersion systems are obtained. Through surface modification, 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.
进一步，本发明的中空二氧化硅溶胶制备方法除了具备优异的低折射率可用于减反射涂层外，因为没有金属离子引入，使其具备更加优异的低介电特性。另外，球壳上细孔结构使该中空二氧化硅粒子可用于活性分子的负载与缓释。Furthermore, 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. In addition, the pore structure on the spherical shell allows the hollow silica particles to be used for loading and sustained release of active molecules.
[涂料组合物][Coating composition]
本发明的涂料组合物包含本发明的中空二氧化硅溶胶、粘合剂以及根据需 要使用的溶剂及助剂。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.
作为粘合剂，可以列举出无机粘合剂，包括本领域技术人员所熟知的能够通过水解、缩合反应形成相应无机氧化物的那些前体化合物，如金属醇盐、金属盐、硅氧烷、硅酸盐及其混合物，也可以列举出有机粘接剂，包括本领域技术人员所熟知的各种不同聚合物和可以热固化或者辐射(例如UV、电子辐射)固化的单体和低聚物，包括丙烯酸酯类单体、甲基丙烯酸酯类单体、以及在两者基础上衍生出来的各种低聚物，如(甲基)丙烯酸酯低聚物，聚氨酯(甲基)丙烯酸酯低聚物、环氧(甲基)丙烯酸酯低聚物、聚酯(甲基)丙烯酸酯低聚物以及在丙烯酸酯、甲基丙烯酸酯中可自由基固化的不饱和聚酯或者聚氨酯。As binders, 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. , 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.
作为溶剂，可以列举出例如水、醇类、酮类、醚类、酯类、含氮化合物、含硫化合物等。作为醇类，可以列举出例如甲醇、乙醇、异丙醇等。作为酮类，可以列举出例如丙酮、甲乙酮等。作为醚类，可以列举出例如四氢呋喃、1,4-二恶烷等。作为酯类，可以列举出例如乙酸乙酯、乙酸甲酯等。作为含氮化合物，可以列举出例如N,N-二甲基乙酰胺、N,N-二甲基甲酰胺等。作为含硫化合物，可以列举出例如二甲亚砜等。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.
本发明的涂料组合物中，在不损害本发明的效果的范围内，可以包含本发明的中空粒子以外的其他中空粒子或实心粒子。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.
进一步，本发明的涂料组合物中还可以含有其他助剂，例如热引发剂、光引发剂、抗静电剂、流平剂、润湿剂、消泡剂、颜料、染料、紫外线屏蔽剂、红外屏蔽剂、抗氧剂、抗指纹剂等。Furthermore, 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.
本发明的涂料组合物中，中空二氧化硅粒子与粘接剂的重量比可以为例如0.1：1～5：1，优选为0.5：1～3：1，更优选为0.8：1～2：1。中空粒子/粘接剂比例过低，容易引起涂层的减反射性能不明显，比例过高，并不能继续提升减反射性能，并且容易降低涂层的力学性能和耐候性。In the coating composition of the present invention, 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.
以上所述的本发明的涂料组合物包含折射率低且粒子强度高的本发明的中空粒子，因此，可以形成减反射效果优异且耐磨性和硬度高的涂膜。Since 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.
[制品][Product]
本发明的制品由基材和基材表面的涂层组成。所述涂层为1层或2层以上，所述涂层中的至少1层由本发明所述的涂料组合物固化形成。 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.
前述涂层可以通过在基材上涂布本发明的涂料组合物并干燥而形成。另外，还可以进一步对涂层进行加热或者焙烧或者辐射。The aforementioned coating layer can be formed by applying the coating composition of the present invention on a substrate and drying it. In addition, the coating can be further heated, baked, or irradiated.
作为基材，可以列举出例如玻璃、透明聚合物、金属等，没有特别的限定。Examples of the base material include glass, transparent polymers, metals, etc., and are not particularly limited.
作为涂布方法，可以列举出例如棒涂、刮涂、旋涂、浸涂、辊涂、淋涂、喷涂、狭缝涂布、微凹涂布等，没有特别的限定。Examples of 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.
以上所述的本发明的物品由于具备本发明的涂料组合物形成的涂层，因此减反射效果好，并且耐磨性好、硬度高。Since 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.
实施例Example
为了更清楚地说明本发明，下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。In order to illustrate the present invention more clearly, the present invention will be further described below with reference to preferred embodiments. Those skilled in the art should understand that the content described below is illustrative rather than restrictive, and should not be used to limit the scope of the present invention.
本发明中，制备方法如无特殊说明则均为常规方法，所用的原料如无特别说明均可从公开的商业途径获得，百分比均指质量百分比，温度为摄氏度(℃)。In the present invention, 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).
各实施例中所涉及的符号的具体意义及测试条件如下：The specific meanings and test conditions of the symbols involved in each embodiment are as follows:
固含：通过固含测定仪Precisa,XM60获得，在150℃条件下烘烤，直至恒重，显示固含。Solid content: Obtained by solid content analyzer Precisa, XM60, baked at 150°C until constant weight, solid content displayed.
粘度：通过旋转粘度计测得，温度设定为25℃，中空二氧化硅溶胶的固含固定在20％。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%.
平均粒径：在对应的TEM照片中，随机选100个粒子，测各粒子的粒径，将测量得到的粒径平均后的值作为粒子的平均粒径。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.
壳层厚度：在对应的TEM照片中，随机选100个粒子，测量各粒子的壁厚，将测量得到的壳层厚度平均后的值作为壳层厚度。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.
Q1、Q2、Q3、Q4占比测定：将中空二氧化硅溶胶干燥成粉末后，采用核磁共振仪(Bruker AVIII HD 500 spectrometer)测定29Si NMR谱图，然后分别对化学位移处于-78～-88ppm的共振峰面积Q1、-88～-98ppm的共振峰面积Q2、-98～-108ppm的共振峰面积Q3、以及-108～-117ppm的共振峰面积Q4进行积分，计算Q1、Q2、Q3、Q4的值。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.
多分散性的测定：采用动态光散射仪(Malven,Zetasizer Nano,ZS90-2027)对分散液进行测定，获得尺寸分布曲线以及多分散性结果。 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.
孔尺寸分布、孔容及孔隙率：通过N2吸附测试，采用Quadrasorb evo比表面和孔隙率分析仪(Quantachrome Instruments,USA)在77K条件下静态吸附测量BET。采用等温吸附曲线和Barrett-Joyner-Halenda(BJH)模型测得孔尺寸分布、孔容、孔隙率，并根据下述的折射率计算公式算出折射率RI。
RI＝1.5*(1-Vc)+1.0*VcPore size distribution, pore volume and porosity: Through N2 adsorption test, BET was measured by static adsorption using Quadrasorb evo specific surface and porosity analyzer (Quantachrome Instruments, USA) under 77K conditions. The isothermal adsorption curve and Barrett-Joyner-Halenda (BJH) model were used to measure the pore size distribution, pore volume, and porosity, and the refractive index RI was calculated according to the following refractive index calculation formula.
RI＝1.5*(1-Vc)+1.0*Vc
(其中，1.5表示二氧化硅折射率，1.0表示空气折射率，Vc为孔隙率)(where 1.5 represents the refractive index of silica, 1.0 represents the refractive index of air, and V c is the porosity)
相对介电常数：相对介电常数er通过静电场按如下方式测得，在标准大气压下，首先测定两块极板之间为真空时电容器的电容C0，然后测定电容极板间距离不变但极板间加入电介质后的电容Cx，通过下式计算得到：
er＝Cx/C0 Relative dielectric constant: The relative dielectric constant er is measured by the electrostatic field as follows. Under standard atmospheric pressure, first measure the capacitance C 0 of the capacitor when there is a vacuum between the two plates, and then measure the distance between the capacitor plates. The capacitance C x after adding dielectric between the variable plates is calculated by the following formula:
e r =C x /C 0
实施例1Example 1
将208克四乙氧基硅烷、20克水、5克盐酸(浓度37％)、30克聚乙二醇(分子量500)混合均匀，保持搅拌状态，升温至85℃，反应8小时后，继续升温到135℃并抽真空，直到没有液体被抽出，得到156克具有一定粘度的、透明的有机硅中间产物。Mix 208 grams of tetraethoxysilane, 20 grams of water, 5 grams of hydrochloric acid (concentration 37%), and 30 grams of polyethylene glycol (molecular weight 500) evenly, keep stirring, and raise the temperature to 85°C. After 8 hours of reaction, continue The temperature was raised to 135°C and vacuumed until no liquid was extracted, and 156 grams of a transparent silicone intermediate product with a certain viscosity was obtained.
将前述的得到的156克有机硅中间产物与500克水混合后，开启搅拌，同时快速加入20克氨水(质量浓度25％)，继续搅拌反应24小时，得到中空二氧化硅溶胶，中空二氧化硅粒子的固含为9.2％。After mixing 156 grams of the aforementioned organic silicon intermediate product with 500 grams of water, start stirring, and quickly add 20 grams of ammonia water (mass concentration 25%), continue stirring for 24 hours, and obtain a hollow silica sol. The solid content of silicon particles is 9.2%.
将前述的中空二氧化硅溶胶用超滤膜进行清洗后，在200℃下进行水热处理12小时，得到中空二氧化硅溶胶1。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.
所得中空二氧化硅溶胶1中的中空二氧化硅粒子的透射电镜(TEM)照片示于附图1，测定其平均粒径为55纳米，壳层厚度为5.5纳米。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.
动态光散射(DLS)尺寸、PDI、Q1～Q4占比、孔径分布、孔容、介电常数等结果见表1。The results of dynamic light scattering (DLS) size, PDI, proportion of Q1 to Q4, pore size distribution, pore volume, and dielectric constant are shown in Table 1.
实施例2Example 2
将120克硅48(Gelest Int.，最简式：SiO1.12(OCH2CH3)1.76)、60克乙醇、2.5克水、1.0克氨水(浓度25％)、25克聚乙二醇单甲醚(分子量500)混合均匀，保持搅拌状态，升温至65℃，反应8小时后，继续升温到135℃并抽真空，直到没有液体被抽出，得到150克具有一定粘度的、透明的有机硅中间产 物。Mix 120 grams of silicon 48 (Gelest Int., simplest formula: SiO 1.12 (OCH 2 CH 3 ) 1.76 ), 60 grams of ethanol, 2.5 grams of water, 1.0 grams of ammonia (concentration 25%), 25 grams of polyethylene glycol monomethyl Mix the ether (molecular weight 500) evenly, keep stirring, and raise the temperature to 65°C. After 8 hours of reaction, continue to raise the temperature to 135°C and vacuum until no liquid is extracted, and obtain 150 grams of a transparent silicone intermediate with a certain viscosity. Produce things.
将前述的得到的150克有机硅中间产物与1000克水混合后，开启搅拌，同时快速加入50克氨水(质量浓度25％)，继续搅拌反应24小时，得到中空二氧化硅溶胶，中空二氧化硅粒子的固含为4.8％。After mixing 150 grams of the aforementioned organic silicon intermediate product with 1000 grams of water, start stirring, and quickly add 50 grams of ammonia water (mass concentration 25%), continue stirring for 24 hours, and obtain a hollow silica sol. The solid content of silicon particles is 4.8%.
将前述的中空二氧化硅溶胶用超滤膜进行清洗后，在150℃下进行水热处理24小时，得到中空二氧化硅溶胶2。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.
所得中空二氧化硅溶胶2中的中空二氧化硅粒子的透射电镜(TEM)照片示于附图2，测定其平均粒径为70纳米，壳层厚度为6.5纳米。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.
动态光散射(DLS)尺寸、PDI、Q1～Q4占比、孔径分布、孔容、介电常数等结果见表1。The results of dynamic light scattering (DLS) size, PDI, proportion of Q1 to Q4, pore size distribution, pore volume, and dielectric constant are shown in Table 1.
实施例3Example 3
将145克四甲氧基硅烷、5克甲基三乙氧基硅烷、75克异丙醇、25克水、5克硝酸(浓度63％)、40克聚乙二醇单甲醚(分子量500)混合均匀，保持搅拌状态，升温至85℃，反应8小时后，继续升温到135℃并抽真空，直到没有液体被抽出，得到160克具有一定粘度的、透明的有机硅中间产物。Mix 145 grams of tetramethoxysilane, 5 grams of methyltriethoxysilane, 75 grams of isopropyl alcohol, 25 grams of water, 5 grams of nitric acid (concentration 63%), 40 grams of polyethylene glycol monomethyl ether (molecular weight 500 ), mix evenly, keep stirring, raise the temperature to 85°C, and after 8 hours of reaction, continue to raise the temperature to 135°C and vacuum until no liquid is extracted, and obtain 160 grams of a transparent silicone intermediate product with a certain viscosity.
将前述的得到的160克有机硅中间产物与500克水混合后，开启搅拌，同时快速加入20克氨水(质量浓度25％)，继续搅拌反应24小时，得到中空二氧化硅溶胶，中空二氧化硅粒子的固含为8.6％。After mixing 160 grams of the aforementioned organic silicon intermediate product with 500 grams of water, start stirring, and quickly add 20 grams of ammonia water (mass concentration 25%), continue stirring for 24 hours, and obtain a hollow silica sol. The solid content of silicon particles is 8.6%.
将前述的中空二氧化硅溶胶用超滤膜进行清洗后，在120℃下进行水热处理12小时，得到中空二氧化硅溶胶3。After the aforementioned 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.
所得中空二氧化硅溶胶3中的中空二氧化硅粒子的透射电镜(TEM)照片示于附图3。测定其平均粒径为40纳米，壳层厚度为4.5纳米。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.
动态光散射(DLS)尺寸、PDI、Q1～Q4占比、孔径分布、孔容、介电常数等结果见表1。The results of dynamic light scattering (DLS) size, PDI, proportion of Q1 to Q4, pore size distribution, pore volume, and dielectric constant are shown in Table 1.
对比例1Comparative example 1
除了不进行实施例1中的水热处理之外，其余与实施例1同样地进行，得到中空二氧化硅溶胶4。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.
所得中空二氧化硅粒子4的透射电镜(TEM)照片示于附图4。动态光散射(DLS)尺寸、PDI、Q1～Q4占比、孔径分布、孔容、介电常数等结果见表 1。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.
对比例2Comparative example 2
除了不进行实施例2中的水热处理之外，其余与实施例2同样地进行，得到中空二氧化硅溶胶5。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.
所得中空二氧化硅粒子5的透射电镜(TEM)照片示于附图5。动态光散射(DLS)尺寸、PDI、Q1～Q4占比、孔径分布、孔容、介电常数等结果见表1。A transmission electron microscope (TEM) photograph of the obtained hollow silica particles 5 is shown in Figure 5 . The results of dynamic light scattering (DLS) size, PDI, proportion of Q1 to Q4, pore size distribution, pore volume, and dielectric constant are shown in Table 1.
对比例3Comparative example 3
除了不进行实施例3中的水热处理之外，其余与实施例3同样地进行，得到中空二氧化硅溶胶6。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.
所得中空二氧化硅粒子6的透射电镜(TEM)照片示于附图6。动态光散射(DLS)尺寸、PDI、Q1～Q4占比、孔径分布、孔容、介电常数等结果见表1。A transmission electron microscope (TEM) photograph of the obtained hollow silica particles 6 is shown in Figure 6 . The results of dynamic light scattering (DLS) size, PDI, proportion of Q1 to Q4, pore size distribution, pore volume, and dielectric constant are shown in Table 1.
实施例4Example 4
使用超滤膜将实施例1制备的中空二氧化硅溶胶1的溶剂置换为异丙醇，并进行浓缩，得到固含为20％的中空二氧化硅异丙醇溶胶7。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%.
取50克上述中空二氧化硅异丙醇溶胶7，加入2克γ-甲基丙烯酰氧基丙基三甲氧基硅烷，0.2克水，加热至80℃反应12小时后，加入2克原甲酸三甲酯，得到固含为20.5％的中空二氧化硅改性异丙醇溶胶8。Take 50 grams of the above-mentioned hollow silica isopropyl alcohol sol 7, add 2 grams of γ-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%.
实施例5Example 5
使用超滤膜，将实施例2制备的中空二氧化硅溶胶2的溶剂置换为异丙醇，并进行浓缩，得到固含为20％的中空二氧化硅异丙醇溶胶9。Using an ultrafiltration membrane, 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%.
取50克上述中空二氧化硅异丙醇溶胶9，加入2克γ-甲基丙烯酰氧基丙基三甲氧基硅烷，0.2克水，加热至80℃反应12小时后，加入2克原甲酸三甲酯，得到固含为20.5％的中空二氧化硅改性异丙醇溶胶10。Take 50 grams of the above-mentioned hollow silica isopropyl alcohol sol 9, add 2 grams of γ-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%.
实施例6Example 6
使用超滤膜，将实施例3制备的中空二氧化硅溶胶3的溶剂置换为异丙醇，并进行浓缩，得到固含为20％的中空二氧化硅异丙醇溶胶11。Using an ultrafiltration membrane, 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%.
取50克上述中空二氧化硅异丙醇溶胶11，加入2克γ-甲基丙烯酰氧基丙 基三甲氧基硅烷，0.2克水，加热至80℃反应12小时后，加入2克原甲酸三甲酯，得到固含为20.5％的中空二氧化硅改性异丙醇溶胶12。Take 50 grams of the above-mentioned hollow silica isopropyl alcohol sol 11, add 2 grams of γ-methacryloyloxypropyl Trimethoxysilane and 0.2 g of water were heated to 80° C. and reacted for 12 hours. Then, 2 g of trimethyl orthoformate was added to obtain a hollow silica-modified isopropyl alcohol sol 12 with a solid content of 20.5%.
对比例4Comparative example 4
使用对比例1中得到的中空二氧化硅溶胶4代替实施例4中的中空二氧化硅溶胶1，其余与实施例4同样地进行，得到固含为20.5％的中空二氧化硅改性异丙醇溶胶13。Use the hollow silica sol 4 obtained in Comparative Example 1 instead of the hollow silica sol 1 in Example 4, and proceed in the same manner as in Example 4 to obtain hollow silica modified isopropyl with a solid content of 20.5%. Alcohol Sol 13.
对比例5Comparative example 5
使用对比例2中得到的中空二氧化硅溶胶5代替实施例5中的中空二氧化硅溶胶2，其余与实施例5同样地进行，得到固含为20.5％的中空二氧化硅改性异丙醇溶胶14。Use the hollow silica sol 5 obtained in Comparative Example 2 instead of the hollow silica sol 2 in Example 5, and proceed in the same manner as in Example 5 to obtain hollow silica modified isopropyl with a solid content of 20.5%. Alcohol Sol 14.
对比例6Comparative example 6
使用对比例3中得到的中空二氧化硅溶胶6代替实施例6中的中空二氧化硅溶胶3，其余与实施例6同样地进行，得到固含为20.5％的中空二氧化硅改性异丙醇溶胶15。Use the hollow silica sol 6 obtained in Comparative Example 3 to replace the hollow silica sol 3 in Example 6, and proceed in the same manner as in Example 6 to obtain hollow silica modified isopropyl with a solid content of 20.5%. Alcohol Sol 15.
制备例1～12Preparation Examples 1 to 12
减反射涂料组合物及减反射涂层制备例：Preparation examples of anti-reflective coating composition and anti-reflective coating:
将前述的实施例1～6、对比例1～6制备的各溶胶分别用甲基异丁基甲酮(MIBK)稀释到固含为10％。取10克固含为10％的溶胶，加入1克双季戊四醇六丙烯酸酯(DPHA)，0.05克光引发剂(Irgacure-184)，38.95克MIBK，混合均匀，得到50克固含为4％的涂料组合物。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.
将上述涂料组合物用3#线棒(3微米)涂覆于PET膜(仪化东丽，露米勒PY2，厚度100微米)上，在80℃烘箱中干燥2分钟，并进行UV固化(能量800～1500mJ/cm2)，制得含有100纳米厚度的减反射涂层的PET制品。对其反射率、雾度、耐湿热性、铅笔硬度、附着力、耐磨性能进行表征，结果如表2所示。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.
反射率：利用分光光度计(株式会社岛津制造所制造的UV-3150)测定，在300～800nm波长范围内，以5度入射角测定光谱反射率。取380～760nm范围的平均反射率作为平均反射率。Reflectance: Measured using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation), the spectral reflectance was measured in the wavelength range of 300 to 800 nm at an incident angle of 5 degrees. Take the average reflectance in the range of 380 to 760nm as the average reflectance.
雾度：使用雾度计(Hazemeter)测定全光线透过率及雾度。 Haze: Use a hazemeter to measure total light transmittance and haze.
耐湿热性：将恒温恒湿箱的温度设为85℃，湿度设为85％，测试时间为1000小时，通过测试PET制品全光线透过率衰减率来评价耐湿热性，将耐湿热性分为以下3个等级：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:
◎：衰减小于0.5％◎: Attenuation less than 0.5%
○：衰减介于0.5～1.0％○: Attenuation ranges from 0.5 to 1.0%
●：衰减超过1％●: Attenuation exceeds 1%
铅笔硬度：根据日本JIS K 5600，使用铅笔刮擦测试机，测定所得涂层的铅笔硬度。在所得涂层上，使铅笔呈45度角从上方以750克的负荷刮擦5cm左右，以5次之中4次以上无划伤的铅笔的硬度表示。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.
附着力：在PET涂层表面用刀划出100个方格，将透明胶带粘在其上，然后剥离胶带，通过观察残留的方格子数来评价附着力，将残留方格子数分为以下三个等级：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:
◎：90～100◎：90～100
○：80～89○：80～89
●：少于80●: Less than 80
耐磨性：在2cm×2cm的磨具上装备#0000钢丝绒，施加500g/cm2的负荷并往复100次，通过目视观察擦伤的状况，评价标准如下所述。Wear resistance: Equip a 2cm×2cm abrasive tool with #0000 steel wool, apply a load of 500g/ cm2 and reciprocate 100 times, and visually observe the scratches. The evaluation criteria are as follows.
5级：无擦伤Level 5: No scratches
4级：发生1条以上不超过10条的擦伤Level 4: More than 1 and no more than 10 abrasions occur
3级：发生10条以上不超过30条的擦伤Level 3: More than 10 and no more than 30 abrasions occur
2级：发生30条以上的擦伤Level 2: More than 30 abrasions occur
1级：整个面发生擦伤或者剥离Level 1: The entire surface is scratched or peeled off
表1：中空二氧化硅溶胶及中空二氧化硅粒子的性能

Table 1: Properties of hollow silica sol and hollow silica particles

表2：含有涂层的PET制品的性能
Table 2: Properties of coated PET articles
如表1所示，通过实施例1～3与比较例1～3相比，溶胶粘度大幅下降，同时球壳表面更致密，细孔的孔径变小，同时中空粒子壁厚变薄，与之对应的折射率和相对介电常数均有下降，展现出优异的低折和低介电特性。As shown in Table 1, compared with Comparative Examples 1 to 3, 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.
如表2所示，通过对比发现，执行过水热处理步骤的中空粒子，用于减反射涂料组合物，对PET基材涂布后，发现透过率、反射率、耐湿热性、铅笔硬度、附着力、耐磨性，与未执行水热处理的中空粒子相比，都有明显提升。As shown in Table 2, it was found through comparison that the hollow particles that had undergone the hydrothermal treatment step were used in the anti-reflective coating composition. After coating the PET substrate, it was found that the transmittance, reflectivity, moisture and heat resistance, pencil hardness, Compared with hollow particles that have not undergone hydrothermal treatment, the adhesion and wear resistance are significantly improved.
同时，对比制备例1～3与制备例7～9发现，执行过表面改性的中空粒子用于减反射涂料组合物，对PET基材涂布后，发现透过率、反射率、雾度、耐湿热性、铅笔硬度、附着力、耐磨性，与未表面改性过的中空粒子相比，都有提升，尤其是对于雾度、耐磨性的提升非常明显。At the same time, comparing Preparation Examples 1 to 3 with Preparation Examples 7 to 9, it was found that the surface-modified hollow particles were used in the anti-reflective coating composition. After coating the PET substrate, it was found that the transmittance, reflectivity, and haze , moisture and heat resistance, pencil hardness, adhesion, and wear resistance are all improved compared with hollow particles that have not been surface modified, especially the improvement in haze and wear resistance is very obvious.
因而本发明方案兼具了优异的减反射性能和杰出的力学性能、耐候性。Therefore, the solution of the present invention combines excellent anti-reflection performance with outstanding mechanical properties and weather resistance.
本领域技术人员在考虑说明书及实践这里公开的发明后，将容易想到本发明的其它实施方案。本发明旨在涵盖本发明的任何变型、用途或者适应性变化，这些变型、用途或者适应性变化遵循本发明的一般性原理并包括本发明未公开的本技术领域中的公知常识或惯用技术手段。 Other embodiments of the invention will be readily apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. The present invention is intended to cover any variations, uses, or adaptations of the invention that follow the general principles of the invention and include common knowledge or customary technical means in the technical field that are not disclosed in the invention. .

Claims (17)

  1. 一种中空二氧化硅溶胶，其特征在于：含有中空二氧化硅粒子和分散介质，A hollow silica sol, characterized by: containing hollow silica particles and a dispersion medium,
    所述中空二氧化硅粒子通过29Si核磁共振谱法测得的与峰值相对应的化学位移在-78～-88ppm的共振峰面积Q1、化学位移在-88～-98ppm的共振峰面积The hollow silica particles have a chemical shift corresponding to the resonance peak area Q1 of -78~-88ppm and a chemical shift corresponding to the resonance peak area Q1 of -88~-98ppm measured by 29 Si nuclear magnetic resonance spectroscopy.
    Q2、化学位移在-98～-108ppm的共振峰面积Q3、以及化学位移在-108～-117ppm出现的共振峰面积Q4满足：Q2, the resonance peak area Q3 with the chemical shift at -98~-108ppm, and the resonance peak area Q4 with the chemical shift at -108~-117ppm satisfy:
    Q1/(Q1+Q2+Q3+Q4)实质上为0、Q1/(Q1+Q2+Q3+Q4) is essentially 0,
    Q2/(Q1+Q2+Q3+Q4)为0.01～0.2、Q2/(Q1+Q2+Q3+Q4) is 0.01～0.2,
    Q3/(Q1+Q2+Q3+Q4)为0.01～0.6、以及，Q3/(Q1+Q2+Q3+Q4) is 0.01~0.6, and,
    Q4/(Q1+Q2+Q3+Q4)为0.2～0.98，Q4/(Q1+Q2+Q3+Q4) is 0.2~0.98,
    所述分散介质为水、有机溶剂或者两者的组合。The dispersion medium is water, organic solvent or a combination of both.
  2. 根据权利要求1所述的中空二氧化硅溶胶，其中，所述中空二氧化硅粒子的壳层的厚度为3～100nm，所述壳层上的孔的孔径分布为0.5～4纳米范围。The hollow silica sol according to claim 1, wherein the thickness of the shell layer of the hollow silica particles is 3 to 100 nm, and the pore size distribution of the pores on the shell layer is in the range of 0.5 to 4 nm.
  3. 根据权利要求1或2所述的中空二氧化硅溶胶，其中，所述中空二氧化硅粒子的孔容为0.15～1cm3/g，孔隙率为10％～90％，折射率为1.10～1.45。The hollow silica sol according to claim 1 or 2, wherein the hollow silica particles have a pore volume of 0.15 to 1 cm 3 /g, a porosity of 10% to 90%, and a refractive index of 1.10 to 1.45. .
  4. 根据权利要求1～3的任一项所述的中空二氧化硅溶胶，所述中空二氧化硅粒子的相对介电常数为1.6～2.2。The hollow silica sol according to any one of claims 1 to 3, wherein the relative dielectric constant of the hollow silica particles is 1.6 to 2.2.
  5. 根据权利要求1～4的任一项所述的中空二氧化硅溶胶，所述中空二氧化硅粒子通过动态光散射测得的粒径为15～1000nm，多分散性指数为0.05～0.3。The hollow silica sol according to any one of claims 1 to 4, wherein the hollow silica particles have a particle size measured by dynamic light scattering of 15 to 1000 nm, and a polydispersity index of 0.05 to 0.3.
  6. 一种权利要求1～5的任一项所述的中空二氧化硅溶胶的制备方法，其特征在于，包括以下步骤：A method for preparing hollow silica sol according to any one of claims 1 to 5, characterized in that it includes the following steps:
    中间产物生成步骤：将硅源、第一溶剂、第一催化剂及活性化合物混合，在0～150℃范围内进行反应，然后去除沸点小于300℃的物质，得到液态有机硅中间产物P1；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;
    中空二氧化硅生成步骤：将所述有机硅中间产物P1分散到第二溶剂中，并加入第二催化剂，在0～95℃的范围内进行反应，得到中空二氧化硅溶胶；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;
    水热处理步骤：在30～300℃范围内进行水热处理。Hydrothermal treatment step: Hydrothermal treatment is carried out in the range of 30 to 300°C.
  7. 根据权利要求6所述的中空二氧化硅溶胶的制备方法，其中，所述中 间产物生成步骤中，所述硅源为选自下述的式I所示的硅烷单体中的1种或2种以上，或者为最简式为下述式II所示的聚烷氧基硅氧烷低聚物，
    R1 4-nSi(OR2)n  式I    The preparation method of hollow silica sol according to claim 6, wherein the In the intermediate product generation step, the silicon source is one or more types selected from the silane monomers represented by the following formula I, or is a polyalkoxy group whose simplest formula is represented by the following formula II. silicone oligomers,
    R 1 4-n Si(OR 2 ) nFormula I
    式I中，n＝1、2、3、或者4，R1为烷基、乙烯基烷基、乙烯基、环氧基烷基、苯基、苯乙烯基烷基、甲基丙烯酰氧基烷基、丙烯酰氧基烷基、氨基烷基、脲烷基、氯烷基、巯烷基、异氰酸酯烷基、或者羟基烷基，有多个R1时，各R1彼此任选相同或不同；R2为碳原子数1～6的烷基，有多个R2时各R2彼此任选相同或不同；
    SiOm(OR3)4-2m  式II    In formula I, n=1, 2, 3, or 4, 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. When there are multiple R 1s , each R 1 is optionally the same or different from each other. Different; R 2 is an alkyl group with 1 to 6 carbon atoms. When there are multiple R 2s , each R 2 may be the same or different from each other;
    SiO m (OR 3 ) 4-2m Formula II
    式II中，0<m<2，m为整数或者非整数，R3为碳原子数1～6的烷基，有多个R3时各R3彼此任选相同或不同。In Formula II, 0<m<2, 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.
  8. 根据权利要求6或7所述的中空二氧化硅溶胶的制备方法，其中，所述中间产物生成步骤中，所述第一溶剂为水、或者为含水的有机溶剂，水与所述硅源的重量比为0.001：1以上且小于0.5：1。The method for preparing hollow silica sol according to claim 6 or 7, wherein in the intermediate product generating step, the first solvent is water or an organic solvent containing water, and the difference between water and the silicon source is The weight ratio is 0.001:1 or more and less than 0.5:1.
  9. 根据权利要求6～8的任一项所述的中空二氧化硅溶胶的制备方法，其中，所述中间产物生成步骤中，所述第一催化剂为酸或者碱，所述第一催化剂与所述硅源的重量比为(0.001～0.5)：1。The preparation method of hollow silica sol according to any one of claims 6 to 8, wherein in the intermediate product generating step, the first catalyst is an acid or a base, and the first catalyst and the The weight ratio of silicon source is (0.001~0.5):1.
  10. 根据权利要求6～9的任一项所述的中空二氧化硅溶胶的制备方法，其中，所述中间产物生成步骤中，所述活性化合物含有至少一个OH基团且分子量大于150，并且，所述活性化合物的通过下述式III计算的HLB值大于5，
    HLB＝20×Mh/M   式III    The preparation method of hollow silica sol according to any one of claims 6 to 9, wherein in the intermediate product generating step, the active compound contains at least one OH group and has a molecular weight greater than 150, and, the The active compound has an HLB value calculated by the following formula III that is greater than 5,
    HLB＝20×M h /M Formula III
    式III中，Mh为所述活性化合物中亲水部分的分子量，M为所述活性化合物的分子量，In formula III, M h is the molecular weight of the hydrophilic part of the active compound, and M is the molecular weight of the active compound,
    所述活性化合物与所述硅源的重量比为(0.05～0.5)：1，所述活性化合物可以为一种或两种以上混合物。The weight ratio of the active compound to the silicon source is (0.05-0.5):1, and the active compound may be one type or a mixture of two or more types.
  11. 根据权利要求6～10的任一项所述的中空二氧化硅溶胶的制备方法，其中，The preparation method of hollow silica sol according to any one of claims 6 to 10, wherein,
    所述中空二氧化硅生成步骤中，所述第二溶剂为水、水与亲水性有机溶剂的混合物、或者水与疏水性有机溶剂的混合物； In the step of generating hollow silica, the second solvent is water, a mixture of water and a hydrophilic organic solvent, or a mixture of water and a hydrophobic organic solvent;
    所述第二催化剂为酸或者碱；The second catalyst is acid or alkali;
    所述有机硅中间产物P1相对于所述第二溶剂的重量百分比为1～60％；The weight percentage of the silicone intermediate P1 relative to the second solvent is 1 to 60%;
    所述第二催化剂与所述有机硅中间产物P1的重量比为(0.05～2)：1。The weight ratio of the second catalyst to the organosilicon intermediate product P1 is (0.05-2):1.
  12. 根据权利要求6～11的任一项所述的中空二氧化硅溶胶的制备方法，其还包括：对所述中空二氧化硅溶胶的溶剂进行置换的溶剂置换步骤，The method for preparing hollow silica sol according to any one of claims 6 to 11, further comprising: a solvent replacement step of replacing the solvent of the hollow silica sol,
    所述溶剂置换步骤中，通过离心、加热共沸或者超滤操作置换掉所述中空二氧化硅溶胶中的全部或者部分溶剂。In the solvent replacement step, all or part of the solvent in the hollow silica sol is replaced by centrifugation, heating, azeotroping or ultrafiltration.
  13. 根据权利要求6～11的任一项所述的中空二氧化硅溶胶的制备方法，其还包含下述步骤：The preparation method of hollow silica sol according to any one of claims 6 to 11, further comprising the following steps:
    表面修饰步骤：在中空二氧化硅溶胶中加入选自下述的式IV所示的硅烷及/或其部分水解物、六甲基二硅氧烷以及六甲基二硅氮(胺)烷组成的组中的一种或多种物质，对中空二氧化硅粒子表面进行修饰，
    R4 p-Si-X4-p   式IV    Surface modification step: Add silane represented by Formula IV below and/or its partial hydrolyzate, hexamethyldisiloxane and hexamethyldisilazine (amine) into the hollow silica sol. One or more substances in the group modify the surface of hollow silica particles,
    R 4 p -Si-X 4-p Formula IV
    式IV中，p＝0、1、2或者3，R4选自烷基、乙烯基烷基、环氧基烷基、苯乙烯基烷基、甲基丙烯酰氧基烷基、丙烯酰氧基烷基、氨基烷基、脲烷基、氯烷基、巯烷基、异氰酸酯烷基、或者、羟基烷基，有多个R4时，各R4彼此相同或者不同，R4中的氢原子可部分或全部被氟原子取代，In formula IV, p=0, 1, 2 or 3, 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选自碳原子数为1-6的烷氧基、卤素或者氢，有多个X时，各X彼此相同或不同，X is selected from an alkoxy group with 1 to 6 carbon atoms, halogen or hydrogen. When there are multiple
    所述表面修饰步骤在所述中空二氧化硅生成步骤之后和/或所述水热处理步骤之后进行。The surface modification step is performed after the hollow silica generating step and/or after the hydrothermal treatment step.
  14. 根据权利要求12所述的中空二氧化硅溶胶的制备方法，其还包含下述步骤：The preparation method of hollow silica sol according to claim 12, further comprising the following steps:
    表面修饰步骤：在中空二氧化硅溶胶中加入选自下述的式IV所示的硅烷及/或其部分水解物、六甲基二硅氧烷以及六甲基二硅氮(胺)烷组成的组中的一种或多种物质，对中空二氧化硅粒子表面进行修饰，
    R4 p-Si-X4-p   式IV    Surface modification step: Add silane represented by Formula IV below and/or its partial hydrolyzate, hexamethyldisiloxane and hexamethyldisilazine (amine) into the hollow silica sol. One or more substances in the group modify the surface of hollow silica particles,
    R 4 p -Si-X 4-p Formula IV
    式IV中，p＝0、1、2或者3,R4选自烷基、乙烯基烷基、环氧基烷基、苯乙烯基烷基、甲基丙烯酰氧基烷基、丙烯酰氧基烷基、氨基烷基、脲烷基、氯 烷基、巯烷基、异氰酸酯烷基、或者、羟基烷基，有多个R4时，各R4彼此相同或者不同，R4中的氢原子可部分或全部被氟原子取代，In formula IV, p=0, 1, 2 or 3, R 4 is selected from alkyl, vinyl alkyl, epoxy alkyl, styryl alkyl, methacryloyloxyalkyl, acryloxy Alkyl, aminoalkyl, urealkyl, chlorine Alkyl group, mercaptoalkyl group, isocyanate alkyl group, or hydroxyalkyl group, when there are multiple R 4 , each R 4 is the same as or different from each other, and the hydrogen atoms in R 4 may be partially or completely replaced by fluorine atoms,
    X选自碳原子数为1-6的烷氧基、卤素或者氢，有多个X时，各X彼此相同或不同，X is selected from an alkoxy group with 1 to 6 carbon atoms, halogen or hydrogen. When there are multiple
    所述表面修饰步骤在所述中空二氧化硅生成步骤之后、和/或、所述水热处理步骤之后、和/或、所述溶剂置换步骤之后进行。The surface modification step is performed after the hollow silica generating step, and/or after the hydrothermal treatment step, and/or after the solvent replacement step.
  15. 根据权利要求14所述的中空二氧化硅溶胶的制备方法，其中在所述表面修饰步骤之后再次进行所述水热处理步骤或/和所述溶剂置换步骤。The method for preparing hollow silica sol according to claim 14, wherein the hydrothermal treatment step or/and the solvent replacement step is performed again after the surface modification step.
  16. 一种涂料组合物，其含有中空二氧化硅溶胶、以及、粘接剂，所述中空二氧化硅溶胶为权利要求1～5的任一项所述的溶胶、或者为根据权利要求6～15的任一项所述的中空二氧化硅溶胶制备方法制备得到。A coating composition, which contains a hollow silica sol and an adhesive. The hollow silica sol is the sol according to any one of claims 1 to 5, or the sol according to any one of claims 6 to 15. Prepared by any of the hollow silica sol preparation methods.
  17. 一种制品，其特征在于，在基材表面具有涂层，所述涂层为1层或2层以上，所述涂层中的至少1层由权利要求16所述的涂料组合物固化形成。 A product characterized by having a coating layer on a surface of a base material, the coating layer being one layer or two or more layers, and at least one layer of the coating layer being formed by curing the coating composition according to claim 16.
PCT/CN2023/090053 2022-07-01 2023-04-23 Hollow silica sol, method for preparing same, and coating composition and product thereof WO2024001464A1 (en)

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