JP2023037553A - Surface-modified hollow silica and surface-modified hollow silica liquid dispersion - Google Patents

Abstract

To provide surface-modified hollow silica particles and a surface-modified hollow silica liquid dispersion.SOLUTION: The surface-modified hollow silica liquid dispersion contains: hollow silica particles each comprising a hollow core and silica shell enclosing the core; a coupling agent; and an organic solvent. A surface has an organic group coupled directly to a silicon atom.SELECTED DRAWING: Figure 1

Description

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

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

As a method for minimizing the reflection of light, a method of dispersing a filler such as inorganic fine particles in a resin and coating it on the base film to give unevenness (anti-glare: AG coating), A method of using light interference (anti-reflection; AR coating) by forming a plurality of layers with different ratios, or a method of using these methods can be used.

In addition, until now, various nanometer-sized particles (such as silica, alumina, and zeolite particles) have been added to improve the scratch resistance of the low-refractive layer included in the anti-reflection film. methods were mainly tried. However, when nanometer-sized particles are used as described above, it is difficult to lower the reflectance of the low-refractive layer, and there is a limit.

Therefore, many studies have been conducted, such as manufacturing hollow silica particles to reduce the absolute amount of reflection of light incident from the outside. was not sufficient to produce a hollow silica particle dispersion having

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

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

A surface-modified hollow silica particle according to one embodiment of the present invention comprises a hollow core and a silica shell surrounding the core, having organic groups directly bonded to silicon atoms on the surface of the silica shell, wherein the organic The group includes a group represented by general formula (1) below.
-RC=CH ₂ (1)
(In general formula (1), R is H or a hydrocarbon group of 1 to 12)

A surface-modified hollow silica particle according to another embodiment of the present invention comprises a hollow core and a silica shell surrounding the core, having organic groups directly bonded to silicon atoms on the surface of the silica shell, The organic group includes a group represented by general formula (2) below.
-R-OC(=O) _CCH3 = _CH2 (2)
(In general formula (2), R is a hydrocarbon group of 1 to 12)

A further embodiment of the present invention is a surface-modified hollow silica particle comprising a hollow core and a silica shell surrounding said core, having organic groups directly bonded to silicon atoms on said silica shell surface, said The organic group includes a group represented by general formula (3) below.
-R- (3)
(In general formula (3), R is a hydrocarbon group of 1 to 12)

A further embodiment of the present invention is a surface-modified hollow silica particle comprising a hollow core and a silica shell surrounding said core, having organic groups directly bonded to silicon atoms on said silica shell surface, said Organic groups include groups represented by the following general formula (4).
_-C6H5 ( 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 said 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).
-RC=CH ₂ (1)
(In general formula (1), R is H or a hydrocarbon group of 1 to 12)
-R-OC(=O) _CCH3 = _CH2 (2)
(In general formula (2), R is a hydrocarbon group of 1 to 12)
-R- (3)
(In general formula (3), R is a hydrocarbon group of 1 to 12)
_-C6H5 ( ₄ )

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

In one embodiment, the alkyl group silane is methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane. selected from the group consisting of silane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, dimethyldimethoxysilane, and methylphenyldimethoxysilane can include at least one of

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

In one embodiment, the phenyl-based silane is phenyltrimethoxysilane, phenyltriethoxysilane, phenylchlorosilane, dichlorodiphenylsilane, phenyltrichlorosilane, dimethoxymethylphenylsilane, diphenyldimethoxysilane, diethoxydiphenylsilane, methylphenyldiethoxy At least one selected from the group consisting of silane and methylphenyldichlorosilane can be included.

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-glycidoxypropyltributoxysilane Sidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane Sidoxybutyltriethoxysilane, 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-glycidoxypropylmethyldiethoxysilane sidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane , γ-glycidoxypropylvinyldimethoxysilane, and γ-glycidoxypropylvinyldiethoxysilane.

In one embodiment, the methacryl-based silane is 3-trimethoxysilylpropyl methacrylate, 3-trimethoxypropyl acrylate, 3-trimethoxysilylethyl methacrylate, 3-triethoxysilylethyl methacrylate, γ-(meth)acryloyl Oxymethyltrimoxysilane, γ-(meth)acrylooxymethyltriethoxysilane, γ-(meth)acrylooxyethyltrimoxysilane, γ-(meth)acrylooxyethyltriethoxysilane, γ-(meth) At least one selected from the group consisting of acrylooxypropyltrimoxysilane, γ-(meth)acrylooxypropyltrimoxysilane, and γ-(meth)acrylooxypropyltriethoxysilane can be included.

In one embodiment, the hollow silica particles are 1% to 25% by weight of the dispersion of the surface-modified hollow silica, and the silane coupling agent is the surface-modified hollow silica. It may be from 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 dispersion of said surface-modified hollow silica may have a D50 value of 10 nm to 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 derivatives, ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylate, ethyl acetate, n butyl acetate and amyl acetate; diacid carboxylates, diethyl oxylate and diethyl malonate; glycol dicarboxylic acids, ethylene glycol diacetate and propylene glycol diacetate; and hydroxy carboxylic acids, methyl lactate, ethyl lactate. , ethyl glycolic acid, and ethyl-3-hydroxypropionate; ketone esters, methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2 - methylpropionic acid or methylethoxypropionic 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, butyrolactones and gamma valerolactones; amide derivatives, dimethylacetamide or dimethylformamide, anisole; and mixtures thereof. be able to.

The surface-modified hollow silica particles according to one embodiment of the invention can have a uniform size.
A dispersion of surface-modified hollow silica according to one embodiment of the present invention comprises uniformly sized surface-modified hollow silica particles, has a high total light transmittance (T.T), and has a low haze of It turns out to be low, and the reflectance is also low, so 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 (TT) by including hollow silica surface-modified with a silane coupling agent. , the haze is found to be low, and the reflectance is also low, allowing the production of dispersions of surface-modified hollow silica having a low refractive index.
A diffusion film containing a cured body 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. .
A diffusion film and an optical member for display according to an embodiment of the present invention can be used to manufacture diffusion films incorporated in backlight units of mobile phones, tablet PCs, PDPs, laptop computers, monitors, and TVs. can.

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

Embodiments will now be described in detail with reference to the accompanying drawings. However, various modifications can be made to the embodiments, and the scope of rights of the patent application is not restricted or restricted by the embodiments. All modifications, equivalents or alternatives to the embodiments must be understood to fall within the scope of rights.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. As used herein, the terms "including" or "having" indicate the presence of the features, numbers, steps, acts, components, parts, or combinations thereof described in the specification. without precluding the possibility of the presence or addition of one or more other features, figures, steps, acts, components, parts, or combinations thereof.

Unless defined otherwise, all terms, including technical or scientific terms, used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. have Commonly used pre-defined terms are to be construed to have a meaning consistent with the meaning they have in the context of the relevant art, and unless expressly defined herein, are ideally or excessively It is not to be interpreted in a formal sense.

Also, in the description with reference to the accompanying drawings, the same constituent elements are given the same reference numerals regardless of the drawing numbers, and duplicate descriptions thereof will be omitted. In the description of the embodiments, if it is determined that a detailed description of related known technologies unnecessarily obscures the gist of the embodiments, the detailed description will be omitted.

Also, terms such as first, second, A, B, (a), and (b) may be used in the description of the constituent elements of the embodiment. Such terms are only used to distinguish the component from other components, and the terms do not limit the nature, order, or order of the relevant component.

Components included in any one embodiment and components having common functions will be described using the same names in other embodiments. As long as there is no description to the contrary, the description given for any one embodiment also applies to the other embodiments, and detailed description will be omitted to the extent that it overlaps.

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

A surface-modified hollow silica particle according to one embodiment of the present invention comprises a hollow core and a silica shell surrounding the core, having organic groups directly bonded to silicon atoms on the surface of the silica shell, wherein the organic The group includes a group represented by general formula (1) below.
-RC=CH ₂ (1)
(In general formula (1), R is H or a hydrocarbon group of 1 to 12)

A surface-modified hollow silica particle according to another embodiment of the present invention comprises a hollow core and a silica shell surrounding the core, having organic groups directly bonded to silicon atoms on the surface of the silica shell, The organic group includes a group represented by general formula (2) below.
-R-OC(=O) _CCH3 = _CH2 (2)
(In general formula (2), R is a hydrocarbon group of 1 to 12)

A further embodiment of the present invention is a surface-modified hollow silica particle comprising a hollow core and a silica shell surrounding said core, having organic groups directly bonded to silicon atoms on said silica shell surface, said The organic group includes a group represented by general formula (3) below.
-R- (3)
(In general formula (3), R is a hydrocarbon group of 1 to 12)

A further embodiment of the present invention is a surface-modified hollow silica particle comprising a hollow core and a silica shell surrounding said core, having organic groups directly bonded to silicon atoms on said silica shell surface, said Organic groups include groups represented by the following general formula (4).
_-C6H5 ( ₄ )

In the present invention, the “hollow silica” is a particle containing an empty core space (hollow) and a silica shell, and has a structure in which a porous silica shell surrounds the inner hollow. 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 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 It contains an organic solvent and 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).
-RC=CH ₂ (1)
(In general formula (1), R is H or a hydrocarbon group of 1 to 12)
-R-OC(=O) _CCH3 = _CH2 (2)
(In general formula (2), R is a hydrocarbon group of 1 to 12)
-R- (3)
(In general formula (3), R is a hydrocarbon group of 1 to 12)
_-C6H5 ( ₄ )

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

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

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

In one embodiment, the phenyl-based silane is phenyltrimethoxysilane, phenyltriethoxysilane, phenylchlorosilane, dichlorodiphenylsilane, phenyltrichlorosilane, dimethoxymethylphenylsilane, diphenyldimethoxysilane, diethoxydiphenylsilane, methylphenyldiethoxy At least one selected from the group consisting of silane and methylphenyldichlorosilane may be included.

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-glycidoxypropyltributoxysilane Sidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane Sidoxybutyltriethoxysilane, 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-glycidoxypropylmethyldiethoxysilane sidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane , γ-glycidoxypropylvinyldimethoxysilane, and γ-glycidoxypropylvinyldiethoxysilane.

In one embodiment, the methacryl-based silane is 3-trimethoxysilylpropyl methacrylate, 3-trimethoxypropyl acrylate, 3-trimethoxysilylethyl methacrylate, 3-triethoxysilylethyl methacrylate, γ-(meth)acryloyl Oxymethyltrimoxysilane, γ-(meth)acrylooxymethyltriethoxysilane, γ-(meth)acrylooxyethyltrimoxysilane, γ-(meth)acrylooxyethyltriethoxysilane, γ-(meth) It may contain at least one selected from the group consisting of acrylooxypropyltrimethoxysilane, γ-(meth)acrylooxypropyltrimethoxysilane, and γ-(meth)acrylooxypropyltriethoxysilane.

In one embodiment, the hollow silica particles are 1% to 25% by weight of the dispersion of the surface-modified hollow silica, and the silane coupling agent is the surface-modified hollow silica. It may be from 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 dispersion of said surface-modified hollow silica may have a D50 value of 10 nm to 200 nm.

Preferably, the dispersion of said surface-modified hollow silica has a D50 value of 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. .

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 be high, and dispersion due to particle aggregation may occur. Gender control is difficult. If it exceeds 200 nm, the haze is increased, the transparency is lowered, and the strength of the shell is lowered, so that the shell may be broken when filling the film.

In one embodiment, the D50 value of the dispersion of surface-modified hollow silica 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 by scanning electron microscopy (SEM). The inner diameter of the hollow portion was measured using a transmission electron microscope (TEM).

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 increase, and it is difficult to control the dispersibility due to particle aggregation. If it exceeds 100 nm, the haze increases, the transparency decreases, and the strength of the shell decreases, which may break the shell when filling the film. The average diameter of the finally produced hollow silica is determined by the average diameter of the core, and the average diameter of the finally produced hollow silica can be controlled by controlling the average diameter of the core.

In one embodiment, the shell may have an average thickness of 1 nm to 50 nm.

In one embodiment, when the average thickness of the shell is less than 1 nm, when producing a dispersion of surface-modified hollow silica, there is a problem that it is removed together with the removal of the core, and the average thickness is 50 nm. If it exceeds, the dispersion liquid of the surface-modified hollow silica becomes opaque, and there is a problem that the characteristics of the silica itself are exhibited due to the increase in the ratio of silica.

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

Preferably, the surface area of said dispersion of surface-modified hollow silica 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 to 50 m ² /g, 40 m ² /g to 150 m ² /g, 40 m ² /g to 140 m ² /g, 40 m ² /g to 120 m ² /g, 40 m ² /g to 100 m ² /g, 50 m ² /g to 150 m ² /g, 50 m ² /g to 140 m ² /g, 50 m ² /g to 120 m ² /g, 50 m ² /g to 100 m ² /g, 60 m ² /g to 150 m ² /g, 60 m ² /g to 100 m ² /g, 30 m ² /g to 120 m ² /g, 30 m ² /g to 100 m ² /g, 60 m ² /g to 80 m ² /g, 70 m ² /g to 150 m ² /g, 70 m ² /g to 130 m ² /g, 80 m ² /g to 150 m ² /g, 80 m ² /g to 130 m ² /g, 90 m ² /g to 150 m ² /g, 90 m ² /g to 100 m ² /g, 100 m 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-modified hollow silica dispersion has a surface area of less than 30 m ² /g, there is a problem of deterioration in dispersibility due to aggregation between particles, and when it exceeds 80 m ² /g, the resin and There is a problem that the penetration of the solvent makes it difficult to withstand the post-process, the strength of the shell is lowered, and the structure of the hollow silica is destroyed.

In one embodiment, the shell may have a pore volume of 0.1 cm ³ /g to 0.7 cm ³ /g. Preferably, the pore volume of said shell is between 0.1 cm ³ /g and 0.5 cm ³ /g, between 0.2 cm 3 /g and 0.7 cm 3 /g, between 0.2 ^{cm 3} /g and 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 of deterioration of dispersibility due to aggregation between particles, and when it exceeds 0.7 cm ³ /g, penetration of resin and solvent may occur. It is difficult to withstand the post-process, and there is a problem that the strength of the shell is lowered and the structure of the hollow silica is destroyed.

The surface-modified hollow silica dispersions of the present invention can be used in any liquid, liquefiable or mastic composition containing hollow silica that is converted to a solid film after application to a substrate. As shown, the surface-modified hollow silica dispersion can be applied to the interior or exterior of 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 derivatives, ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA), carboxylate, ethyl acetate, n butyl acetate and amyl acetate; diacid carboxylates, diethyl oxylate and diethyl malonate; glycol dicarboxylic acids, ethylene glycol diacetate and propylene glycol diacetate; and hydroxy carboxylic acids, methyl lactate, ethyl lactate, Ethyl glycolic acid and ethyl-3-hydroxypropionate; ketone esters, methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2- 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; ketal or 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-glare effect as described above, resin, organic solvent, etc. can be produced by mixing

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

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

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

In one embodiment, the dispersion of surface-modified hollow silica 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 produce display optical members such as polarizing films, prism sheets, and AR sheets.

A dispersion of surface-modified hollow silica according to an embodiment of the present invention can achieve excellent optical properties by exhibiting low refractive index, anti-reflection, and anti-glare efficiency.

A dispersion of surface-modified hollow silica according to an embodiment of the present invention comprises uniformly sized surface-modified hollow silica particles and has excellent total light transmittance (T.T), Haze is found to be low, reflectance is also low and can have a low refractive index.

Another embodiment of the present invention provides a method for preparing a dispersion of surface-modified hollow silica, comprising the steps of: preparing a core by synthesizing a cationic surfactant and a monomer; forming a silica shell to prepare core-shell particles; pre-firing the core-shell particles at a temperature of 800° C. or higher to remove the core to prepare hollow silica particles; and silane coupling the hollow silica particles. dispersing in an agent.

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

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

In one embodiment, the core preparation step S110 synthesizes a cationic surfactant and a monomer to prepare the core.

In one embodiment, synthesizing the cationic surfactant and monomer to prepare the core comprises preparing a mixture of the cationic surfactant and the monomer in 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 nitrogen atmosphere and stirring for 10 hours to 48 hours to prepare a polymerization solution, and washing the polymerization solution with an organic solvent. followed by drying at a temperature ranging from 60° C. to 120° C. for 10 hours to 48 hours.

FIG. 3 is a flow chart schematically showing the details of the core preparation steps shown in FIG.

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 preparing a mixture by adding the cationic surfactant and the monomer in distilled water and purging with nitrogen.

A mixture is prepared, preferably by adding distilled water and cationic surfactant, stirring and purging with nitrogen, then adding monomer and stirring at a temperature ranging from 60°C to 100°C, most preferably at 90°C.

In one embodiment, the cationic surfactant is cetyltrimethylammonium bromide (CTAB), hexadecyltrimethylammonium bromide (TMABr), hexadecyltrimethylpyridinylCl; At least one selected from the group consisting of tetramethylammonium chloride (TMACl), Pluronic P-123 (EO ₂₀ PO ₇₀ EO ₂₀ ) and trimethylbenzene (TMB) 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 from 100,000 to 2,000,000, from 200,000 to 1,500,000, from 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, said monomer may be styrene.

In one embodiment, the mixing ratio of the monomer:the cationic surfactant may be from 1:0.00001 to 1:0.001. If the mixing ratio of the monomer to the cationic surfactant is less than 1:0.00001, the peripheries of the polymerized polystyrene particles are not sufficiently surrounded, so the effect of steric hindrance is small, and aggregation may occur. If the ratio exceeds 1:0.001, the surfactant may not be dissolved in the solution before polymerization and the viscosity may 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 thickness of the silica shell, while the cationic surfactant to the monomer When the mixing ratio of the agent is lowered, the average diameter of the core is increased and the thickness of the silica shell is decreased.

In one embodiment, the polymerization solution preparation step S112 includes heating the mixture to 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 obtain a polymerization solution. is the step of preparing the Preferably, after reaching a temperature range of 75° C. to 95° C., most preferably 90° C., the polymerization initiator is charged under an atmosphere of nitrogen.

In one embodiment, the polymerization initiator is 2,2″-azobis(2-methylpropionamidine) dihydrochloride (2,2″-Azobis(2-methylpropionamidine) dihydrochloride; AIBA), 2,2- 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 At least one may be included.

In one embodiment, the washing and drying step S113 is a step of 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. Preferably, it may be dried at a temperature in the range of 70°C to 100°C, most preferably at 80°C for 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 dimethylsulfoxide. Preferably, the cores can be obtained by washing the polymerization solution with ethanol.

In one embodiment, the step of forming a silica shell on the core to prepare core-shell particles includes diluting the core with distilled water to prepare a dispersion, mixing the dispersion with a basic substance. 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; in a temperature range of 20° C. to 90° C. for 12 hours to 48 hours to prepare a core-shell reaction solution; Drying for between 1 hour and 48 hours may be included.

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

Referring to FIG. 3, the core-shell particle preparation step of the present invention comprises a dispersion liquid preparation step S121, a pH adjustment step S122, a core-shell formation 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 preparation step S121 is a step of diluting the cores in distilled water to prepare a dispersion.

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

The basic substance includes aqueous ammonia, ammonium methyl propanol (AMP), tetramethyl ammonium hydroxide (TMAH), ammonium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, At least one selected from the group consisting of rubidium hydroxide, cesium hydroxide, sodium hydrogen carbonate, sodium carbonate, imidazole, and salts thereof may be included.

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

In one embodiment, if the pH of the dispersion liquid is low, it approaches neutrality, making it difficult for the hydrolysis and condensation reactions of silane to occur. If the temperature is high, the rate of hydrolysis and condensation reaction of silane will increase, and there is a high possibility that individual spherical silica will be formed without 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 a core-shell forming solution. 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 reacting the core-shell forming solution at a temperature range of 20° C. to 90° C. for 1 hour to 7 hours to prepare a core-shell reaction solution. Preferably, the reaction may be carried out at a temperature range of 30° C. to 80° C., most preferably at 30° C. for 12 hours to 48 hours.

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

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

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

In the present invention, in the step of removing the core, as the pre-baking temperature increases to 800° C. or higher, the core-shell particles have more bonds between the peripheral _SiO2 particles, and the empty spaces are filled to form the shell. Density increases and pore volume and surface area decrease.

In one embodiment, when the pre-baking temperature is less than 800° C., the density of the shell is low, and when the pre-baking temperature exceeds 1,000° C., there is a problem in that the particles are strongly aggregated to form large aggregates. be.

In one embodiment, the dispersing 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-based silane, vinyl-based silane, phenyl-based silane, glycidyl-based silane, and methacryl-based silane.

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

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

In one embodiment, the phenyl-based silane is phenyltrimethoxysilane, phenyltriethoxysilane, phenylchlorosilane, dichlorodiphenylsilane, phenyltrichlorosilane, dimethoxymethylphenylsilane, diphenyldimethoxysilane, diethoxydiphenylsilane, methylphenyldiethoxy At least one selected from the group consisting of silane and methylphenyldichlorosilane may be included.

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-glycidoxypropyltributoxysilane Sidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane Sidoxybutyltriethoxysilane, 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-glycidoxypropylmethyldiethoxysilane sidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane , γ-glycidoxypropylvinyldimethoxysilane, and γ-glycidoxypropylvinyldiethoxysilane.

In one embodiment, the methacryl-based silane is 3-trimethoxysilylpropyl methacrylate, 3-trimethoxypropyl acrylate, 3-trimethoxysilylethyl methacrylate, 3-triethoxysilylethyl methacrylate, γ-(meth)acryloyl Oxymethyltrimoxysilane, γ-(meth)acrylooxymethyltriethoxysilane, γ-(meth)acrylooxyethyltrimoxysilane, γ-(meth)acrylooxyethyltriethoxysilane, γ-(meth) It may contain at least one selected from the group consisting of acrylooxypropyltrimethoxysilane, γ-(meth)acrylooxypropyltrimethoxysilane, and γ-(meth)acrylooxypropyltriethoxysilane.

In one embodiment, the hollow silica particles are 1% to 25% by weight of the dispersion of the surface-modified hollow silica, and the silane coupling agent is the surface-modified hollow silica. It may be from 5% to 50% by weight of the dispersion. If the content of the hollow silica particles is less than 1% by weight, sufficient antireflection and glare prevention effects cannot be achieved. 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 (TT) is A dispersion of surface-modified hollow silica can be produced that has been found to have high, low haze, low refractive index, and low reflectance.

A diffusion film according to further embodiments of the present invention includes a dispersion of surface-modified hollow silica according to one embodiment of the present invention, and a dispersion of surface-modified hollow silica according to another embodiment. A hardened body 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 one 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 methods include 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 coatings ( wire wound doctor coating). After coating, the coating layer is cured with UV light, and the curing process is completed between 10 seconds and 1 hour.

The diffusion film according to one embodiment of the present invention is used to manufacture the diffusion film that goes into the backlight units of mobile phones, tablet PCs, PDPs, laptops, monitors, and TVs.

A diffusion film comprising a cured dispersion of surface-modified hollow silica according to an embodiment of the present invention has high transmittance and low reflectance, and thus can realize excellent optical properties. can.

A display optical member according to a further embodiment of the present invention can include the diffusion film of one embodiment of the present invention.

A diffusion film according to an 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.

The present invention will be described in more detail below with reference to examples and comparative examples.
However, the following examples are only 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. A nitrogen atmosphere is created while raising the temperature to 90°C. A mixture was prepared by adding styrene monomer at 90° C. and stirring for 30 minutes. 2,2''-Azobis(2-methylpropionamidine) dihydrochloride (2,2''-Azobis(2-methylpropionamidine) dihydrochloride; AIBA) was added as a polymerization initiator and stirred for 24 hours for polymerization. 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.

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

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

Then, 10 g of hollow silica was added to the solution, and a mixture was formed for 30 minutes using a stirrer bar at a temperature of 25°C. Then, 500 g of 10 mm zirconia balls were added to the mixture and dispersed for 24 hours using ball mill equipment to obtain a hollow silica ethanol dispersion. 50 g of the ethanol dispersion and 50 g of 0.03 mm zirconia beads were placed in a 100 ml container for a paint shaker, and a paint shaker was used. After that, PGMEA was mixed with the solution and ethanol was removed under vacuum pressure reduction to obtain a 20 wt % hollow silica-PGMEA dispersion.

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

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

[Example 4] Dispersion of hollow silica using surface treating agent having phenyl group Phenyltrimethoxysilane (PTMS) represented by the following structural formula (4) was used as the surface treating agent having a phenyl group. A dispersion of hollow silica was obtained in the same manner as in Example 1, except for .

[Comparative Example 1] Dispersion of Hollow Silica Using a Surface Treatment Agent Having a Poxy Group Glycidoxypropyltrimethoxysilane (GPTMS) represented by 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 was used.

[Comparative Example 2] Dispersion of Hollow Silica Using a Surface Treatment Agent Having an Amino Group Aminoethylaminopropyltrimethoxysilane (APTMS) represented by the following structural formula (6) was used as a surface treatment agent having an amino group. A dispersion of hollow silica was obtained using the same method as in Example 1, except that it was used.

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 dispersion of surface-modified hollow silica according to Example 1 of the present invention.
Table 1 below shows the physical properties and coating properties of the surface-modified hollow silica dispersions according to Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention.

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 dispersion and coating physical properties were evaluated. I couldn't.

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

Although the embodiments have been described by way of even limited examples and drawings as described above, various modifications and variations can be made from the foregoing description by those of ordinary skill in the art. For example, the techniques described may be performed in a different order than in the manner described; and/or components described may be combined or combined in forms different from the manner described; Suitable results can be achieved with alternatives and permutations.
Accordingly, other implementations, other embodiments, and equivalents of the claims are within the scope of the following claims.

Claims (16)

comprising a hollow core and a silica shell surrounding said core;
Having an organic group directly bonded to the silicon atom on the silica shell surface,
Surface-modified hollow silica particles, wherein the organic group includes a group represented by the following general formula (1).
-RC=CH ₂ (1)
(In general formula (1), R is H or a hydrocarbon group of 1 to 12) comprising a hollow core and a silica shell surrounding said core;
Having an organic group directly bonded to the silicon atom on the silica shell surface,
Surface-modified hollow silica particles, wherein the organic group includes a group represented by the following general formula (2).
-R-OC(=O) _CCH3 = _CH2 (2)
(In general formula (1), R is a hydrocarbon group of 1 to 12) comprising a hollow core and a silica shell surrounding said core;
Having an organic group directly bonded to the silicon atom on the silica shell surface,
Surface-modified hollow silica particles, wherein the organic group includes a group represented by the following general formula (3).
-R- (3)
(In general formula (3), R is a hydrocarbon group of 1 to 12) comprising a hollow core and a silica shell surrounding said core;
Having an organic group directly bonded to the silicon atom on the silica shell surface,
Surface-modified hollow silica particles, wherein the organic group includes a group represented by the following general formula (4).
_-C6H5 ( ₄ ) hollow silica particles comprising a hollow core and a silica shell surrounding the core;
a silane coupling agent;
an organic solvent;
including
A dispersion of surface-modified hollow silica having organic groups directly bonded to silicon atoms on the surface. The surface-modified hollow silica dispersion according to claim 5, wherein the organic group contains at least one selected from the group consisting of groups represented by the following general formulas (1) to (4). .
-RC=CH ₂ (1)
(In general formula (1), R is H or a hydrocarbon group of 1 to 12)
-R-OC(=O) _CCH3 = _CH2 (2)
(In general formula (2), R is a hydrocarbon group of 1 to 12)
-R- (3)
(In general formula (3), R is a hydrocarbon group of 1 to 12)
_-C6H5 ( ₄ ) The surface modification according to claim 5, wherein the silane coupling agent includes at least one selected from the group consisting of alkyl-based silanes, vinyl-based silanes, phenyl-based silanes, glycidyl-based silanes, and methacrylic-based silanes. hollow silica dispersion. The alkyl group silane includes methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and butyltrimethoxysilane. at least one selected from the group consisting of silane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, dimethyldimethoxysilane, and methylphenyldimethoxysilane 8. The dispersion of surface-modified hollow silica according to claim 7, comprising: The vinyl group silane includes vinyl trimethoxy silane, vinyl triethoxy silane, vinyl triacetoxy silane, vinyl trichlorosilane, vinyl tris(β-methoxy 8. The surface-modified hollow according to claim 7, comprising at least one selected from the group consisting of vinyl tris(methoxyethoxy) silane and vinyl tri-isopropoxy silane. A dispersion of silica. The phenyl group silane includes phenyltrimethoxysilane, phenyltriethoxysilane, phenylchlorosilane, dichlorodiphenylsilane, phenyltrichlorosilane, dimethoxymethylphenylsilane, diphenyldimethoxysilane, diethoxydiphenylsilane, methylphenyldiethoxysilane, and methylphenylsilane. 8. The dispersion of surface-modified hollow silica according to claim 7, comprising at least one selected from the group consisting of dichlorosilane. The glycidyl group silane includes glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane. Silane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxy Silane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane Silane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α -glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane , β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Propoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycid 8. The dispersion of surface-modified hollow silica according to claim 7, comprising at least one selected from the group consisting of xypropylvinyldimethoxysilane and γ-glycidoxypropylvinyldiethoxysilane. The methacryl-group silane includes 3-trimethoxysilylpropyl methacrylate, 3-trimethoxypropyl acrylate, 3-trimethoxysilylethyl methacrylate, 3-triethoxysilylethyl methacrylate, and γ-(meth)acryloxymethyltrimexysilane. , γ-(meth)acryloxymethyltriethoxysilane, γ-(meth)acrylooxyethyltrimethoxysilane, γ-(meth)acryloxyethyltriethoxysilane, γ-(meth)acryloxypropyltrimethylsilane The surface modification according to claim 7, comprising at least one selected from the group consisting of chitosisilane, γ-(meth)acryloxypropyltrimethoxysilane, and γ-(meth)acryloxypropyltriethoxysilane. hollow silica dispersion. The hollow silica particles are 1% to 25% by weight of the surface-modified hollow silica dispersion,
6. The surface-modified hollow silica dispersion of claim 5, wherein the silane coupling agent is 5% to 50% by weight of the surface-modified hollow silica dispersion. 6. The dispersion of surface-modified hollow silica according to claim 5, wherein the hollow silica particles are surface-modified with the silane coupling agent. 6. The dispersion of surface-modified hollow silica according to claim 5, wherein the D50 value of said dispersion of surface-modified hollow silica is from 10 nm to 200 nm. The organic solvent includes 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 dibasic acid carboxylates, diethyl oxylate and diethyl malonate; glycol dicarboxylic acids, ethylene glycol diacetate and propylene glycol diacetate; and hydroxy carboxylic acids, methyl lactate, ethyl lactate, ethyl glycol acid, and ethyl-3-hydroxypropionate; ketone esters, methyl pyruvate or ethyl pyruvate; alkoxycarboxylic acid esters, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methylethoxypropionic 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; ketal or acetal, 1 , 3-dioxolane and diethoxypropane; lactone, butyrolactone, and gamma valerolactone; amide derivatives, dimethylacetamide or dimethylformamide, anisole; and mixtures thereof. A dispersion of the surface-modified hollow silica described.

Images