JP7422796B2 - Surface-modified hollow silica and dispersion of surface-modified hollow silica - Google Patents

Description

The present invention relates to surface-modified hollow silica and dispersions of surface-modified hollow silica.

Generally, flat panel display devices such as PDPs and LCDs are equipped with an anti-reflection film to minimize reflection of light incident from the outside.

As a method to minimize light reflection, there is a method of dispersing filler such as inorganic fine particles in resin and coating it on the base film to give unevenness (anti-glare; AG coating), and a method of applying refraction on the base film. Examples include a method of forming a plurality of layers with different ratios and using optical interference (anti-reflection; AR coating), or a method of using these in combination.

In addition, until now, in order to improve the scratch resistance of the low refractive index layer contained in antireflection films, various nanometer-sized particles (e.g., particles of silica, alumina, zeolite, etc.) have been added. methods were mainly tried. However, when nanometer-sized particles are used as described above, it is difficult to reduce the reflectance of the low refractive layer, and there is a limit.

For this reason, many studies are being conducted to manufacture hollow silica particles to reduce the absolute amount of light reflected from the outside. It has not been sufficient to produce a hollow silica particle dispersion having .

The present invention is intended to solve the above-mentioned problems, and an object of the present invention is to provide surface-modified hollow silica with excellent optical properties due to its low refractive index and reflectance and high transmittance. An object of the present invention is to provide a surface-modified hollow silica dispersion.

However, the problems to be solved by the present invention are not limited to those mentioned above, and further problems not mentioned can be clearly understood by those skilled in the art from the following description.

A surface-modified hollow silica particle according to an embodiment of the present invention includes a hollow core and a silica shell surrounding the core, and has an organic group directly bonded to a silicon atom on the surface of the silica shell, and has an organic group directly bonded to a silicon atom on the surface of the silica shell. The group includes a group represented by the following general formula (1).
-R-C=CH ₂ (1)
(In general formula (1), R is H or 1 to 12 hydrocarbon groups)

Surface-modified hollow silica particles according to another embodiment of the present invention include a hollow core and a silica shell surrounding the core, and have an organic group directly bonded to a silicon atom on the surface of the silica shell, and The organic group includes a group represented by the following general formula (2).
-R-OC(=O)CCH ₃ =CH ₂ (2)
(In general formula (2), R is a 1 to 12 hydrocarbon group)

A surface-modified hollow silica particle according to a further embodiment of the present invention includes a hollow core and a silica shell surrounding the core, and has an organic group directly bonded to a silicon atom on the surface of the silica shell; The organic group includes a group represented by the following general formula (3).
-R- (3)
(In general formula (3), R is a 1 to 12 hydrocarbon group)

A surface-modified hollow silica particle according to a further embodiment of the present invention includes a hollow core and a silica shell surrounding the core, and has an organic group directly bonded to a silicon atom on the surface of the silica shell; The organic group includes a group represented by the following general formula (4).
-C ₆ H ₅ (4)

A dispersion of surface-modified hollow silica according to a further embodiment of the present invention comprises hollow silica particles comprising a hollow core and a silica shell surrounding the core, a silane coupling agent, and an organic solvent, It has organic groups directly bonded to silicon atoms on its surface.

In one embodiment, the organic group may be at least one selected from the group consisting of groups represented by the following general formulas (1) to (4).
-R-C=CH ₂ (1)
(In general formula (1), R is H or 1 to 12 hydrocarbon groups)
-R-OC(=O)CCH ₃ =CH ₂ (2)
(In general formula (2), R is a 1 to 12 hydrocarbon group)
-R- (3)
(In general formula (3), R is a 1 to 12 hydrocarbon group)
-C ₆ H ₅ (4)

In one embodiment, the silane coupling agent may include at least one selected from the group consisting of alkyl silane, vinyl silane, phenyl silane, glycidyl silane, and methacrylic silane.

In one embodiment, the alkyl group silane is methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane silane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, and methylphenyldimethoxysilane may include at least one.

In one embodiment, the vinyl-based silane is vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri acetoxy silane, vinyl trichlorosilane (vi). nyl trichlorosilane), At least one selected from the group consisting of vinyl tris(methoxyethoxy) silane and vinyl tri-isopropoxy silane may be included.

In one embodiment, the phenyl group silane is phenyltrimethoxysilane, phenyltriethoxysilane, phenylchlorosilane, dichlorodiphenylsilane, phenyltrichlorosilane, dimethoxymethylphenylsilane, diphenyldimethoxysilane, diethoxydiphenylsilane, methylphenyldiethoxy It can contain at least one selected from the group consisting of silane and methylphenyldichlorosilane.

In one embodiment, the glycidyl-based silane is glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltriethoxysilane, Sidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltrimethoxysilane Sidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriethoxysilane Cidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane Cidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethyl Methyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxy Propylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Sidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane , γ-glycidoxypropylvinyldimethoxysilane, and γ-glycidoxypropylvinyldiethoxysilane.

In one embodiment, the methacrylic silane is 3-trimethoxysilylpropyl methacrylate, 3-trimethoxypropyl acrylate, 3-trimethoxysilylethyl methacrylate, 3-triethoxysilylethyl methacrylate, γ-(meth)acrylic Oxymethyltrimethoxysilane, γ-(meth)acrylooxymethyltriethoxysilane, γ-(meth)acrylooxyethyltrimethoxysilane, γ-(meth)acrylooxyethyltriethoxysilane, γ-(meth) It may contain at least one selected from the group consisting of acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, and γ-(meth)acryloxypropyltriethoxysilane.

In one embodiment, the hollow silica particles are 1% to 25% by weight of the surface-modified hollow silica dispersion, and the silane coupling agent is in the surface-modified hollow silica dispersion. It may be 5% to 50% by weight of the dispersion.
In one embodiment, the hollow silica particles may be surface-modified with the silane coupling agent.
In one embodiment, the D50 value of the surface-modified hollow silica dispersion may be between 10 nm and 200 nm.

In one embodiment, the organic solvent is propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone or ethyl lactate, glycol ether derivatives, ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivative, ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylate, ethyl acetate, n -butyl acetate and amyl acetate; carboxylates of dibasic acids, diethyl oxylate, and diethyl malonate; dicarboxylic acids of glycols, ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylic acids, methyl lactate, ethyl lactate , ethyl glycolic acid, and ethyl-3-hydroxypropionic acid; ketone esters, methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters, methyl 3-methoxypropionic acid, ethyl 3-ethoxypropionic acid, ethyl 2-hydroxy-2 - Methylpropionic acid or methylethoxypropionic acid; ketone derivatives, methylethylketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketone ether derivatives, diacetone alcohol methyl ether; ketone alcohol derivatives, acetol or diacetone alcohol; Contains at least one selected from the group consisting of ketals or acetals, 1,3-dioxolane and diethoxypropane; lactones, butyrolactone, and gamma valerolactone; amide derivatives, dimethylacetamide or dimethylformamide, anisole; and mixtures thereof. be able to.

Surface-modified hollow silica particles according to an embodiment of the present invention may have a uniform size.
The surface-modified hollow silica dispersion according to an embodiment of the present invention includes surface-modified hollow silica particles of uniform size, has a high total light transmittance (T.T.), and has a low haze. Since the reflectance is also low, it can have a low refractive index.
A method for producing a surface-modified hollow silica dispersion according to an embodiment of the present invention has a high total light transmittance (T.T) due to the inclusion of hollow silica whose surface has been modified with a silane coupling agent. It was found that the haze was low, and the reflectance was also low, making it possible to produce a dispersion of surface-modified hollow silica with a low refractive index.
A diffusion film containing a cured product of a surface-modified hollow silica dispersion according to an embodiment of the present invention has high transmittance and low reflectance, and thus can realize excellent optical properties. .
The diffusion film and display optical member according to an embodiment of the present invention can be used to manufacture a diffusion film incorporated into a backlight unit of a mobile phone, tablet PC, PDP, notebook computer, monitor, or TV. can.

1 is a flowchart schematically showing a process for producing a surface-modified hollow silica dispersion according to an embodiment of the present invention. 2 is a flowchart schematically showing detailed steps of the core preparation step shown in FIG. 1. FIG. 2 is a flowchart schematically showing detailed steps of the core-shell particle preparation step shown in FIG. 1. FIG. It is a TEM image of hollow silica particles according to a production example of the present invention. 1 is a TEM image of a surface-modified hollow silica dispersion according to Example 1 of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, various changes can be made to the embodiments, and the scope of patent application rights is not restricted or limited by the embodiments. It is to be understood that all modifications, equivalents, and alternatives to the embodiments are within the scope of this invention.

The terminology used herein is used merely to describe particular embodiments and is not intended to limit the invention. A singular expression includes a plural expression unless the context clearly indicates a different meaning. As used herein, terms such as "comprising" or "having" indicate the presence of features, numbers, steps, acts, components, parts, or combinations thereof that are described in the specification. This is to be understood as not excluding in advance the possibility of the presence or addition of one or more other features, figures, steps, acts, components, parts, or combinations thereof.

Unless defined differently, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. has. Commonly used predefined terms should be construed to have meanings consistent with the meanings they have in the context of the relevant art, and unless expressly defined herein, ideal or overly It cannot be interpreted in a formal sense.

Furthermore, in the description with reference to the accompanying drawings, the same components will be given the same reference numerals regardless of the drawing numbers, and redundant explanations thereof will be omitted. In the description of the embodiments, if it is determined that detailed description of related known techniques would unnecessarily obscure the gist of the embodiments, the detailed description will be omitted.

Furthermore, in the description of the constituent elements of the embodiments, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are used only to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order, or sequence of the constituent elements.

Components included in any one embodiment and components having common functions will be described using the same names in other embodiments. Since there is no statement to the contrary, the explanation given for any one embodiment also applies to the other embodiments, and specific explanations will be omitted to the extent that they overlap.

Hereinafter, surface-modified hollow silica and a dispersion of surface-modified hollow silica of the present invention will be specifically described with reference to embodiments and drawings. However, the present invention is not limited to such embodiments and drawings.

A surface-modified hollow silica particle according to an embodiment of the present invention includes a hollow core and a silica shell surrounding the core, and has an organic group directly bonded to a silicon atom on the surface of the silica shell, and has an organic group directly bonded to a silicon atom on the surface of the silica shell. The group includes a group represented by the following general formula (1).
-R-C=CH ₂ (1)
(In general formula (1), R is H or 1 to 12 hydrocarbon groups)

Surface-modified hollow silica particles according to another embodiment of the present invention include a hollow core and a silica shell surrounding the core, and have an organic group directly bonded to a silicon atom on the surface of the silica shell, and The organic group includes a group represented by the following general formula (2).
-R-OC(=O)CCH ₃ =CH ₂ (2)
(In general formula (2), R is a 1 to 12 hydrocarbon group)

A surface-modified hollow silica particle according to a further embodiment of the present invention includes a hollow core and a silica shell surrounding the core, and has an organic group directly bonded to a silicon atom on the surface of the silica shell; The organic group includes a group represented by the following general formula (3).
-R- (3)
(In general formula (3), R is a 1 to 12 hydrocarbon group)

A surface-modified hollow silica particle according to a further embodiment of the present invention includes a hollow core and a silica shell surrounding the core, and has an organic group directly bonded to a silicon atom on the surface of the silica shell; The organic group includes a group represented by the following general formula (4).
-C ₆ H ₅ (4)

In the present invention, "hollow silica" refers to particles that include an empty space (hollow) in the core and a silica shell, and has a structure in which the porous silica shell surrounds the hollow inside. In the present invention, the silica shell has a plurality of small pores in the silica shell wall portion, and therefore, the hollow silica has a hollow inner core, and a plurality of mesopores are dispersed in the silica shell.

A dispersion of surface-modified hollow silica according to a further embodiment of the present invention comprises hollow silica particles comprising a hollow core and a silica shell surrounding said core, a silane coupling agent (SCA), and Contains an organic solvent and has organic groups directly bonded to silicon atoms on the surface.

In one embodiment, the organic group may be at least one selected from the group consisting of groups represented by the following general formulas (1) to (4).
-R-C=CH ₂ (1)
(In general formula (1), R is H or 1 to 12 hydrocarbon groups)
-R-OC(=O)CCH ₃ =CH ₂ (2)
(In general formula (2), R is a 1 to 12 hydrocarbon group)
-R- (3)
(In general formula (3), R is a 1 to 12 hydrocarbon group)
-C ₆ H ₅ (4)

In one embodiment, the silane coupling agent may include at least one selected from the group consisting of alkyl silane, vinyl silane, phenyl silane, glycidyl silane, and methacrylic silane.

In one embodiment, the alkyl group silane is methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane silane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, and methylphenyldimethoxysilane may include at least one.

In one embodiment, the vinyl-based silane is vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri acetoxy silane, vinyl trichlorosilane (vi). nyl trichlorosilane), It may contain at least one member selected from the group consisting of vinyl tris (methoxyethoxy) silane and vinyl tri-isopropoxy silane.

In one embodiment, the phenyl group silane is phenyltrimethoxysilane, phenyltriethoxysilane, phenylchlorosilane, dichlorodiphenylsilane, phenyltrichlorosilane, dimethoxymethylphenylsilane, diphenyldimethoxysilane, diethoxydiphenylsilane, methylphenyldiethoxy It may contain at least one selected from the group consisting of silane and methylphenyldichlorosilane.

In one embodiment, the glycidyl-based silane is glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltriethoxysilane, Sidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltrimethoxysilane Sidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriethoxysilane Cidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane Cidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethyl Methyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxy Propylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Sidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane , γ-glycidoxypropylvinyldimethoxysilane, and γ-glycidoxypropylvinyldiethoxysilane.

In one embodiment, the methacrylic silane is 3-trimethoxysilylpropyl methacrylate, 3-trimethoxypropyl acrylate, 3-trimethoxysilylethyl methacrylate, 3-triethoxysilylethyl methacrylate, γ-(meth)acrylic Oxymethyltrimethoxysilane, γ-(meth)acrylooxymethyltriethoxysilane, γ-(meth)acrylooxyethyltrimethoxysilane, γ-(meth)acrylooxyethyltriethoxysilane, γ-(meth) It may contain at least one selected from the group consisting of acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, and γ-(meth)acrylooxypropyltriethoxysilane.

In one embodiment, the hollow silica particles are 1% to 25% by weight of the surface-modified hollow silica dispersion, and the silane coupling agent is in the surface-modified hollow silica dispersion. It may be 5% to 50% by weight of the dispersion.

In one embodiment, the hollow silica particles are surface-modified with the silane coupling agent.

In one embodiment, the D50 value of the surface-modified hollow silica dispersion may be between 10 nm and 200 nm.

Preferably, the D50 value of the surface-modified hollow silica dispersion is 10 nm to 180 nm, 10 nm to 150 nm, 10 nm to 100 nm, 10 nm to 150 nm, 10 nm to 30 nm, 50 nm to 200 nm, 50 nm to 180 nm, 50 nm to 150 nm. , 50nm to 100nm, 50nm to 80nm, 80nm to 200nm, 80nm to 150nm, 80nm to 130nm, 80nm to 100nm, 100nm to 200nm, 100nm to 150nm, 100nm to 130nm, 150nm to 200nm or 180nm to 200nm It may be nm.

In one embodiment, when the D50 value of the surface-modified hollow silica dispersion is less than 10 nm, the refractive index of the surface-modified hollow silica dispersion may become high, and dispersion due to particle aggregation may occur. Difficult to control sexuality. If it exceeds 200 nm, haze increases and transparency decreases, and the strength of the shell decreases and there is a risk that the shell will break when it is filled into a film.

In one embodiment, the D50 value of the surface-modified hollow silica dispersion is defined as the median of the particle size distribution.

A representative sample of the surface-modified hollow silica dispersion can be collected and the diameter of the surface-modified hollow silica dispersion measured using a scanning electron microscope (SEM). The inner diameter of the hollow portion was measured using a transmission electron microscope (TEM) photograph.

In one embodiment, the core may have an average diameter of 10 nm to 100 nm.

In one embodiment, when the average diameter of the core is less than 10 nm, the refractive index of the surface-modified hollow silica dispersion may become high, making it difficult to control the dispersibility due to particle aggregation. If it exceeds 100 nm, the haze increases, transparency decreases, and the strength of the shell decreases, so that there is a risk that the shell will break when it is filled into a film. The average diameter of the hollow silica finally produced is determined by the average diameter of the core, and by controlling the average diameter of the core, the average diameter of the hollow silica finally produced can be controlled.

In one embodiment, the average thickness of the shell may be between 1 nm and 50 nm.

In one embodiment, when the average thickness of the shell is less than 1 nm, there is a problem that the core is removed and removed together when producing a dispersion of surface-modified hollow silica, and the average thickness of the shell is less than 1 nm. If it exceeds this, there is a problem that the surface-modified hollow silica dispersion becomes opaque and the silica itself exhibits its own characteristics due to the increased proportion of silica.

In one embodiment, the surface area of the surface-modified hollow silica dispersion may be between 30 m ² /g and 150 m ² /g.

Preferably, the surface area of the surface-modified hollow silica dispersion is 30 m ² /g to 140 m ² /g, 30 m ² /g to 120 m ² /g, 30 m ² /g to 100 m ² /g, 30 m ² /g - 50m ² /g, 40m ² /g - 150m ² /g, 40m ² /g - 140m ^{2 /g, 40m 2 /} g - 120m ² /g, 40m ² /g - 100m ² /g, 50m ² /g ~ 150m ² /g, 50m ² /g ~ 140m ² /g, 50m ² /g ~ 120m ² /g, 50m ² /g ~ 100m ² /g, 60m ² /g ~ 150m ² /g, 60m ² /g - 100m ² /g, 30m ² /g - 120m ² /g, 30m ² /g - 100m ² /g, 60m ² /g - 80m ² /g, 70m ² /g - 150m ² /g, 70m ² /g ~ 130m ² /g, 80m ² /g ~ 150m ² /g, 80m ² /g ~ 130m ² /g, 90m ² /g ~ 150m ² /g, 90m ² /g ~ 100m ² /g, 100m ² /g to 150 m ² /g, 100 m ² /g to 130 ^{m 2} /g, 110 m ² /g to 150 m ² /g, or 110 m ² /g to 120 m ² /g.

In one embodiment, when the surface area of the surface-modified hollow silica dispersion is less than 30 m ² /g, there is a problem that the dispersibility decreases due to interparticle aggregation, and when it exceeds 80 m ² /g, the resin and There is a problem that it is difficult to withstand post-processing due to penetration of solvent, and the strength of the shell decreases and the hollow silica structure breaks.

In one embodiment, the pore volume of the shell may be between 0.1 cm ³ /g and 0.7 cm ³ /g. Preferably, the pore volume of the shell is 0.1 ^{cm 3} /g to ^0.5 cm 3 /g, ^{0.2 cm} 3 /g to 0.7 cm 3 /g, 0.2 cm ³ /g ^to 0.6 cm ³ /g. , 0.3 cm ³ /g to 0.7 cm ³ /g, 0.2 ^{cm 3} /g to 0.5 cm ³ /g, or 0.4 cm ³ /g to 0.5 cm ³ /g.

In one embodiment, when the pore volume of the shell is less than 0.1 cm ³ /g, there is a problem that the dispersibility decreases due to interparticle aggregation, and when it exceeds 0.7 cm ³ /g, there is a problem that the pore volume of the shell is reduced due to the penetration of resin and solvent. There is a problem that it is difficult to withstand post-processing, the strength of the shell decreases, and the hollow silica structure breaks.

The surface-modified hollow silica dispersions of the present invention are suitable for use in any liquid, liquefiable or mastic composition containing hollow silica that is converted into a solid film after application to a substrate. As shown, the surface-modified hollow silica dispersion can be applied inside or outside the surface of any structure.

In one embodiment, the organic solvent is propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone or ethyl lactate, glycol ether derivatives, ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether, glycol ether ester derivative, ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA), carboxylate, ethyl acetate, n - butyl acetate and amyl acetate; carboxylic acid salts of dibasic acids, diethyl oxylate and diethyl malonate; dicarboxylic acids of glycols, ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylic acids, methyl lactate, ethyl lactate, Ethyl glycolic acid and ethyl-3-hydroxypropionic acid; ketone ester, methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid ester, methyl 3-methoxypropionic acid, ethyl 3-ethoxypropionic acid, ethyl 2-hydroxy-2- Methylpropionic acid or methylethoxypropionic acid; ketone derivatives, methylethylketone, acetylacetone, cyclopentanone, cyclohexanone or 2-heptanone; ketone ether derivatives, diacetone alcohol methyl ether; ketone alcohol derivatives, acetol or diacetone alcohol; ketal or It may be at least one selected from the group consisting of acetal, 1,3-dioxolane and diethoxypropane; lactone, butyrolactone and gamma valerolactone; amide derivative, dimethylacetamide or dimethylformamide, anisole; and mixtures thereof. .

The surface-modified hollow silica dispersion of the present invention is a surface-modified hollow silica dispersion having high transparency, low reflectance, and anti-dazzle effect as described above, resin, organic solvent, etc. It can be manufactured by mixing.

In order to adjust the refractive index with the surface-modified hollow silica dispersion to produce a transparent composition, the refractive index of the resin is preferably less than 1.5, and preferably UV curing It is preferable to select and use a resin having a refractive index similar to that of the hollow particles from among the resins having a similar refractive index.

In one embodiment, the UV curable resin may include at least one selected from the group consisting of urethane resin, acrylic resin, polyester resin, and epoxy resin.

In one embodiment, the surface-modified hollow silica dispersion may further include a hard coating agent, a UV blocker, or an IR blocker, and the additives may be well-known or other additives. It may further contain additives that provide additional functionality if necessary.

In one embodiment, the surface-modified hollow silica dispersion may be any coating composition and may be applied to any substrate.

The surface-modified hollow silica dispersion of the present invention may be used to manufacture optical members for displays such as polarizing films, prism sheets, and AR sheets.

The surface-modified hollow silica dispersion according to an embodiment of the present invention exhibits low refractive index, anti-reflection, and anti-glare efficiency, thereby achieving excellent optical properties.

The surface-modified hollow silica dispersion according to an embodiment of the present invention includes surface-modified hollow silica particles of uniform size and has an excellent total light transmittance (T.T), It is found that the haze is low, and the reflectance is also low and may have a low refractive index.

In one embodiment, a method for producing a dispersion of surface-modified hollow silica according to another embodiment of the present invention includes the step of preparing a core by synthesizing a cationic surfactant and a monomer, and dispersing the dispersion on the core. preparing core-shell particles by forming a silica shell; preparing hollow silica particles by pre-baking the core-shell particles at a temperature of 800° C. or higher to remove the core; and silane coupling the hollow silica particles. the step of dispersing in the agent.

FIG. 1 is a flowchart schematically showing a process for producing a surface-modified hollow silica dispersion according to an embodiment of the present invention.

Referring to FIG. 1, the method for producing a surface-modified hollow silica dispersion according to an embodiment of the present invention includes a core preparation step S110, a core shell particle preparation step S120, a hollow silica particle preparation step S130, and a dispersion step. Includes S140.

In one embodiment, the core preparation step S110 prepares the core by synthesizing a cationic surfactant and a monomer.

In one embodiment, the step of synthesizing the cationic surfactant and the monomer to prepare the core includes preparing a mixture by adding the cationic surfactant and the monomer to distilled water and purging with nitrogen. After heating the mixture in a temperature range of 50° C. to 100° C., adding a polymerization initiator under a nitrogen atmosphere and stirring for 10 hours to 48 hours to prepare a polymerization solution, and washing the polymerization solution with an organic solvent. and then drying at a temperature range of 60° C. to 120° C. for 10 hours to 48 hours.

FIG. 3 is a flowchart schematically showing detailed steps of the core preparation step shown in FIG. 2.

Referring to FIG. 3, the core preparation step S110 of the present invention includes a mixture preparation step S111, a polymerization solution preparation step S112, and a washing and drying step S113.

In one embodiment, the mixture preparation step S111 is a step of preparing a mixture by adding the cationic surfactant and the monomer to distilled water and purging with nitrogen.

Preferably, distilled water and a cationic surfactant are added, stirred and purged with nitrogen, and then a monomer is added and stirred at a temperature range of 60° C. to 100° C., most preferably 90° C., to prepare a mixture.

In one embodiment, the cationic surfactant is cetyltrimethylammonium bromide (CTAB), hexadecyltrimethylammonium bromide (TMABr), or hexadecyltrimethylammonium bromide (TMABr). Methylpyridinium chloride (hexadecyltrimethylpyridinium chloride; TMPrCl), From tetramethylammonium chloride (TMACl), Pluronic P-123 (Pluronic P-123, EO ₂₀ PO ₇₀ EO ₂₀ ) and trimethylbenzene (TMB) at least one selected from the group May contain one.

In one embodiment, the cationic surfactant may have a molecular weight (Mw) of 10,000 to 2,500,000. Preferably, it may be 100,000 to 2,000,000, 200,000 to 1,500,000, or 200,000 to 1,000,000.

In one embodiment, the monomer may include at least one selected from the group consisting of styrene, methacrylate, acrylate, and vinyl acetate. Preferably, the monomer may be styrene.

In one embodiment, the mixing ratio of the monomer to the cationic surfactant may be 1:0.00001 to 1:0.001. When the mixing ratio of the monomer: the cationic surfactant is less than 1:0.00001, the periphery of the polymerized polystyrene particles is not sufficiently surrounded, so the effect of steric hindrance is small, and there is a risk of aggregation problems. If the ratio exceeds 1:0.001, the surfactant will not be dissolved in the pre-polymerization solution and the viscosity will increase, making it difficult to form uniform polystyrene particles.

In one embodiment, the higher the mixing ratio of the cationic surfactant to the monomer, the smaller the average diameter of the core and the thicker the silica shell; As the mixing ratio of the agents decreases, the average diameter of the core increases and the thickness of the silica shell decreases.

In one embodiment, the polymerization solution preparation step S112 includes heating the mixture in a temperature range of 50° C. to 100°C, adding a polymerization initiator under a nitrogen atmosphere, and stirring for 10 to 48 hours to form a polymerization solution. This is a step to prepare. Preferably, after reaching a temperature range of 75°C to 95°C, most preferably 90°C, the polymerization initiator is introduced under an atmosphere of nitrogen.

In one embodiment, the polymerization initiator is 2,2''-Azobis(2-methylpropionamidine) dihydrochloride (AIBA), 2,2''-Azobis(2-methylpropionamidine) dihydrochloride; Azobisisobutyronitrile (AIBN), 2,2-azobis(2-methylisobutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, selected from the group consisting of methyl ethyl ketone peroxide, t-butyl hydroperoxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, and t-butyl peroxyisobutyrate It may include at least one.

In one embodiment, the washing and drying step S113 is a step of washing the polymerization solution with an organic solvent and then drying the polymer solution at a temperature of 60° C. to 120° C. for 10 hours to 48 hours. Preferably, drying may be carried out at a temperature range of 70°C to 100°C, most preferably at 80°C for a period of 24 hours.

In one embodiment, the organic solvent may include at least one selected from the group consisting of ethanol, methanol, chloroform, chloromethane, dichloromethane, trichloroethane, and dimethyl sulfoxide. Preferably, the core can be obtained by washing the polymerization solution with ethanol.

In one embodiment, the step of preparing core-shell particles by forming a silica shell on the core includes the step of preparing a dispersion by diluting the core in distilled water, and mixing a basic substance into the dispersion. heating the pH-adjusted dispersion in a temperature range of 20°C to 80°C, and then adding a silane coupling agent to prepare a core-shell forming solution; the core-shell forming solution; reacting for 12 to 48 hours at a temperature range of 20°C to 90°C to prepare a core-shell reaction solution, and washing the core-shell reaction solution with an organic solvent and then reacting at a temperature range of 60°C to 120°C for 10 hours. The method may include a step of drying between hours and 48 hours.

FIG. 3 is a flowchart schematically showing detailed steps of the core-shell particle preparation step shown in FIG. 1.

Referring to FIG. 3, the core-shell particle preparation step of the present invention includes a dispersion liquid preparation step S121, a pH adjustment step S122, a core-shell forming solution preparation step S123, a core-shell reaction solution preparation step S124, and a core-shell reaction solution drying step S125. include.

In one embodiment, the dispersion liquid preparation step S121 is a step of preparing a dispersion liquid by diluting the core in distilled water.

In one embodiment, the pH adjustment step S122 is a step of adjusting the pH by mixing a basic substance into the dispersion liquid.

The basic substances include ammonia water, ammonium methyl propanol (AMP), tetra methyl ammonium hydroxide (TMAH), ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, It may contain at least one selected from the group consisting of rubidium hydroxide, cesium hydroxide, sodium hydrogen carbonate, sodium carbonate, imidazole, and salts thereof.

In one embodiment, the step of adjusting the pH of the dispersion by adding a basic substance to the dispersion may adjust the pH of the dispersion to a range of 7 to 12. Preferably, the pH of the dispersion may be 8-11.

In one embodiment, if the pH of the dispersion is low, it approaches neutrality, making it difficult for silane hydrolysis and condensation reactions to occur. If the temperature is high, the rate of hydrolysis and condensation reaction of silane becomes faster, and there is a high possibility that individual spherical silica is formed instead of forming silica around the core.

In one embodiment, the core-shell forming solution preparation step S123 includes heating the pH-adjusted dispersion in a temperature range of 20° C. to 80° C., and then adding a silane coupling agent to prepare the core-shell forming solution. It is a step. Preferably, the silane coupling agent is introduced after reaching a temperature range of 30°C to 50°C, most preferably 30°C.

In one embodiment, the core-shell reaction solution preparation step S124 is a step of preparing a core-shell reaction solution by reacting the core-shell forming solution at a temperature range of 20° C. to 90° C. for 1 hour to 7 hours. Preferably, the reaction may be carried out at a temperature range of 30°C to 80°C, most preferably at 30°C for a period of 12 hours to 48 hours.

In one embodiment, the core-shell reaction solution drying step S125 may dry the core-shell reaction solution to obtain core-shell particles.

In one embodiment, the core-shell reaction solution may be washed with an organic solvent and then dried at a temperature range of 60° C. to 120° C. for 10 hours to 48 hours.

In one embodiment, the step S130 of pre-calcining the core-shell particles and removing the core is performed on the core-shell particles at a temperature range of 800° C. or more and less than 1,000° C. for 1 hour to 10 hours. It is.

In the present invention, in the step of removing the core, as the pre-firing temperature increases to a high temperature of 800°C or higher, the core-shell particles have more bonds between the surrounding SiO ₂ particles, and the empty space is filled and the shell is removed. Density increases and pore volume and surface area decrease.

In one embodiment, when the pre-firing temperature is less than 800°C, the density of the shell becomes low, and when it exceeds 1,000°C, the particles are strongly agglomerated with each other and large aggregates are formed. be.

In one embodiment, the dispersion step S140 consists in dispersing the hollow silica particles in a silane coupling agent.

In one embodiment, the silane coupling agent may include at least one selected from the group consisting of alkyl silane, vinyl silane, phenyl silane, glycidyl silane, and methacrylic silane.

In one embodiment, the alkyl group silane is methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane silane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, and methylphenyldimethoxysilane may include at least one.

In one embodiment, the vinyl-based silane is vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri acetoxy silane, vinyl trichlorosilane (vi). nyl trichlorosilane), It may contain at least one member selected from the group consisting of vinyl tris (methoxyethoxy) silane and vinyl tri-isopropoxy silane.

In one embodiment, the phenyl group silane is phenyltrimethoxysilane, phenyltriethoxysilane, phenylchlorosilane, dichlorodiphenylsilane, phenyltrichlorosilane, dimethoxymethylphenylsilane, diphenyldimethoxysilane, diethoxydiphenylsilane, methylphenyldiethoxy It may contain at least one selected from the group consisting of silane and methylphenyldichlorosilane.

In one embodiment, the glycidyl-based silane is glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltriethoxysilane, Sidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltrimethoxysilane Sidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriethoxysilane Cidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane Cidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethyl Methyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxy Propylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Sidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane , γ-glycidoxypropylvinyldimethoxysilane, and γ-glycidoxypropylvinyldiethoxysilane.

In one embodiment, the methacrylic silane is 3-trimethoxysilylpropyl methacrylate, 3-trimethoxypropyl acrylate, 3-trimethoxysilylethyl methacrylate, 3-triethoxysilylethyl methacrylate, γ-(meth)acrylic Oxymethyltrimethoxysilane, γ-(meth)acrylooxymethyltriethoxysilane, γ-(meth)acrylooxyethyltrimethoxysilane, γ-(meth)acrylooxyethyltriethoxysilane, γ-(meth) It may contain at least one selected from the group consisting of acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, and γ-(meth)acrylooxypropyltriethoxysilane.

In one embodiment, the hollow silica particles are 1% to 25% by weight of the surface-modified hollow silica dispersion, and the silane coupling agent is in the surface-modified hollow silica dispersion. It may be 5% to 50% by weight of the dispersion. If the content of the hollow silica particles is less than 1% by weight, the anti-reflection and anti-glare effects cannot be fully achieved, and if the content exceeds 25% by weight, the transparency will decrease and the resin content will decrease, resulting in hardening. Efficiency may decrease.

A method for producing a surface-modified hollow silica dispersion according to an embodiment of the present invention includes hollow silica surface-modified with a silane coupling agent, so that the total light transmittance (T.T.) is increased. It is possible to produce a dispersion of surface-modified hollow silica having a high refractive index and a low haze, and a low reflectance.

Diffusion films according to further embodiments of the invention include the production of dispersions of surface-modified hollow silica according to one embodiment of the invention and dispersions of surface-modified hollow silica according to other embodiments. The method includes a cured product of a dispersion of surface-modified hollow silica produced by the method.

In one embodiment, the diffusion film may have a transmittance of 94% or more, a haze of 1.2% or less, and a reflectance of 0.8% or less.

In one embodiment, a substrate is prepared, and a dispersion of surface-modified hollow silica according to an embodiment of the present invention is laminated or applied to the substrate and UV-cured to form a coating layer, A cured product can be produced.

In one embodiment, the coating method includes gravure coating, offset gravure coating, two and three roll pressure coating, two and three roll reverse coating, dip coating, one and Two roll kiss coatings, trailing balde coatings, nip coatings, flexographic coatings, inverted knife coatings, polishing bar coatings ) and wire wound doctor coating ( wire wound doctor coating). After coating, the coating layer is cured with UV light, and the curing process is completed within 10 seconds to 1 hour.

A diffusion film according to an embodiment of the present invention is used to manufacture a diffusion film that is included in a backlight unit of a mobile phone, a tablet PC, a PDP, a notebook computer, a monitor, or a TV.

A diffusion film containing a cured product of a surface-modified hollow silica dispersion according to an embodiment of the present invention has high transmittance and low reflectance, so it is possible to achieve excellent optical properties. can.

An optical member for a display according to a further embodiment of the present invention may include a diffusion film according to an embodiment of the present invention.

The diffusion film according to one embodiment of the present invention can be applied to optical members incorporated in backlight units of mobile phones, tablet PCs, PDPs, notebook computers, monitors, and TVs.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
However, the following examples are merely for illustrating the present invention, and the content of the present invention is not limited to the following examples.

[Manufacturing example]
(Manufacture of core)
Distilled water and a cationic surfactant CTAB (Cetyltrimethylammonium bromide) were placed in a 500 ml three-necked flask and stirred. Create a nitrogen atmosphere while raising the temperature to 90°C. Styrene monomer was added at 90° C. and stirred for 30 minutes to prepare a mixture. 2,2''-Azobis(2-methylpropionamidine) dihydrochloride (AIBA) was added as a polymerization initiator and polymerization was carried out by stirring for 24 hours. A solution was prepared.
The polymerized solution was washed with ethanol and dried in an oven at 80° C. for 24 hours to prepare polystyrene (PS) particles.

(Manufacture of hollow silica particles)
The polystyrene (PS) particles prepared above were diluted with distilled water, aqueous ammonia was added thereto, and the mixture was titrated at pH 10. Tetraethylorthosilicate (TEOS) was added at a temperature of 30° C. and stirred for 12 hours to prepare a core-shell forming solution. Thereafter, the core-shell forming solution was dried in an 80° C. oven for 24 hours. The dried core-shell powder was pre-calcined in a Box Furnace at 800° C. for 5 hours to obtain surface-modified hollow silica powder.

[Example 1] Dispersion of hollow silica using a surface treatment agent having a vinyl group In a 500 ml container, 87 g of ethanol and vinyl trimethoxysilane of the following structural formula (1) were added as a surface treatment agent having a vinyl group. Silane (VTMS) (3 g) was added thereto and mixed for 5 minutes using a stirrer bar at a temperature of 25°C.

Thereafter, 10 g of hollow silica was added to the solution, and a mixed solution was formed at 25° C. using a stirrer bar for 30 minutes. Thereafter, 500 g of 10 mm zirconia balls were added to the mixed solution and dispersed for 24 hours using ball mill equipment to obtain a hollow silica ethanol dispersion. A paint shaker was used by putting 50 g of the ethanol dispersion and 50 g of 0.03 mm zirconia beads into a 100 ml capacity paint shaker container. Thereafter, PGMEA was mixed with the solution and ethanol was removed under reduced pressure to obtain a 20 wt % hollow silica-PGMEA dispersion.

[Example 2] Hollow silica dispersion using a surface treatment agent having a methacrylic group As a surface treatment agent having a methacrylic group, 3-trimethoxysilylpropyl methacrylate (3-trimethoxysilylpropyl) having the following structural formula (2) was used. A dispersion of hollow silica was obtained using the same method as in Example 1, except that methacrylate (MPS) was used.

[Example 3] Hollow silica dispersion using a surface treatment agent having an alkyl group Methyltrimethoxysilane (MTMS) having the following structural formula (3) was used as a surface treatment agent having an alkyl group. A hollow silica dispersion was obtained using the same method as in Example 1 except for the following.

[Example 4] Hollow silica dispersion using a surface treatment agent having a phenyl group Phenyltrimethoxysilane (PTMS) having the following structural formula (4) was used as a surface treatment agent having a phenyl group. A hollow silica dispersion was obtained using the same method as in Example 1 except for the following.

[Comparative Example 1] Hollow silica dispersion using a surface treatment agent having a poxy group Glycidoxypropyl trimethoxysilane (GPTMS) having the following structural formula (5) was used as a surface treatment agent having an epoxy group. A dispersion of hollow silica was obtained using the same method as in Example 1, except that .

[Comparative Example 2] Hollow silica dispersion using a surface treatment agent having an amino group As a surface treatment agent having an amino group, aminoethylaminopropyl trimethoxysilane (APTMS) having the following structural formula (6) was used. A dispersion of hollow silica was obtained using the same method as in Example 1, except that:

FIG. 4 is a TEM image of hollow silica particles according to a production example of the present invention, and FIG. 5 is a TEM image of a surface-modified hollow silica dispersion according to Example 1 of the present invention.
Table 1 below shows the physical properties and coating properties of surface-modified hollow silica dispersions according to Examples 1 to 4 of the present invention and Comparative Examples 1 and 2.

Referring to Table 1, the surface-modified hollow silica dispersions of Comparative Examples 1 and 2 were gelled using a silane coupling agent containing an epoxy group and an amino group, and the physical properties of the dispersion and coating were evaluated. I couldn't do that.

The surface-modified hollow silica dispersions of Examples 1 to 4 have uniform surface-modified hollow silica particles, excellent total light transmittance (T.T) of 94% or more, and low haze. It can be seen that the reflectance is low.

Although the embodiments have been described above with reference to limited examples and drawings, various modifications and variations can be made from the above description by those skilled in the art. For example, the techniques described may be performed in a different order than described, and/or the described components may be combined or combined in a different manner than described, or with other components or equivalents. Appropriate results can be achieved even with substitutions and substitutions.
Therefore, other implementations, other embodiments, equivalents to the scope of the claims, etc. are within the scope of the scope of the claims described below.

Claims (5)

hollow silica particles comprising a hollow core and a silica shell surrounding the core;
a silane coupling agent,
an organic solvent;
including;
The hollow silica particles have an organic group directly bonded to a silicon atom on the surface,
The D50 value of the hollow silica particles is 80 nm to 130 nm,
The organic group includes a group represented by the following general formula (1),
The silane coupling agent is a surface-modified hollow silica dispersion containing vinyl-based silane .
-R-C=CH ₂ (1)
(In general formula (1), R is a single bond or 1 to 12 hydrocarbon groups) The vinyl group silane is vinyl trimethoxysilane (Vinyl trimethox
y silane), vinyl triethoxy silane (vinyl triethoxy s
ilane), vinyl triacetoxysilane (vinyl triacetoxysilane),
ilane), vinyl trichlorosilane
), vinyl tris(methoxyethoxy)silane
xyethoxy) silane), and vinyltriisopropoxysilane (Vinyl
The surface-modified hollow silica dispersion according to claim 1 , comprising at least one selected from the group consisting of tri-isopropoxy silane. The hollow silica particles account for 1% to 25% by weight of the surface-modified hollow silica dispersion.
weight%,
The silane coupling agent accounts for 5% by weight of the surface-modified hollow silica dispersion.
A dispersion of surface-modified hollow silica according to claim 1 , which is ˜50% by weight. The surface-modified hollow silica dispersion according to claim 1 , wherein the hollow silica particles are surface-modified with the silane coupling agent. The organic solvent is propylene glycol monomethyl ether acetate (PGMEA).
, cyclohexanone or ethyl lactate, glycol ether derivatives, ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; Glycol ether ester derivatives, ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates, ethyl acetate, n-butyl acetate, and amyl acetate; carboxylate salts of dibasic acids, diethyloxy Lato, and diethyl malonate;
Glycol dicarboxylic acids, ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylic acids, methyl lactate, ethyl lactate, ethyl glycolic acid, and ethyl-3-hydroxypropionic acid; ketone esters, methyl pyruvate or ethyl pyruvate; Alkoxycarboxylic acid ester, methyl 3-methoxypropionic acid,
Ethyl 3-ethoxypropionic acid, ethyl 2-hydroxy-2-methylpropionic acid, or methyl ethoxypropionic acid; ketone derivatives, methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone; ketone ether derivatives, diacetone alcohol Methyl ether; ketone alcohol derivatives, acetol or diacetone alcohol; ketals or acetals, 1,3-dioxolane and diethoxypropane; lactones, butyrolactone and gamma valerolactone; amide derivatives, dimethylacetamide or dimethylformamide, anisole; and their The dispersion of surface-modified hollow silica according to claim 1 , comprising at least one selected from the group consisting of mixtures.