KR20240083311A - Manufacturing method of silica sol having functionality and functional silica sol manufactured by the method - Google Patents

Abstract

The present invention includes the steps of performing primary surface treatment by adding water and an alkoxy silane to an acidic silica sol and reacting, obtaining an alcohol base silica sol by solvent replacing the primary surface treated silica sol with alcohol, and the alcohol base. It relates to a method for producing silica sol comprising adding an alkoxy silane to silica sol and reacting to perform secondary surface treatment, and to a functional silica sol manufactured using the same. According to the present invention, it has excellent stability, hydrophobicity, excellent compatibility and bonding with resin, and can be made to have flame retardancy, water repellency, or low dielectric property.

Description

Method for producing functional silica sol and functional silica sol manufactured using the same {Manufacturing method of silica sol having functionality and functional silica sol manufactured by the method}

The present invention relates to a method for producing silica sol and a silica sol manufactured using the same. More specifically, it has excellent stability, hydrophobicity, excellent compatibility and bonding with resin, flame retardancy, water repellency, and low dielectric properties. It relates to a method for producing a functional silica sol and a functional silica sol manufactured using the same.

Silica sol is a colloidal solution in which silica particles are dispersed in a solvent and has high transparency. In addition, because silica particles have high hardness and heat resistance, they are mixed with resins and the like and used as a modifier for the purpose of providing hardness and heat resistance to the resin.

Recently, as the IT industry has grown, the demand for printed circuit boards (PCBs) on which components are mounted has increased significantly. As IT components become ultra-fast and multi-functional, high density of PCBs is required. there is.

In order to solve the phenomenon of warping of the board due to heat generation due to increased density of printed circuit boards, low thermal expansion (CTE) characteristics of copper clad layer (CCL) are required. Copper-clad laminate is a core component of printed circuit boards, and is formed by coating both sides of PPG (Prepreg) with copper foil.

Since PPG (Prepreg) must have excellent dielectric and heat resistance properties, the key is nano silica with a size of submicron (0.5-0.7㎛) and tens of nanometers (20-100nm) in glass fiber impregnated with epoxy resin. It is being added as a material. Nano silica contained in PPG must be capable of being highly filled in the resin and must have excellent compatibility and bonding properties with the resin.

Researchers of the present invention have developed a silica sol that can be used as a core material for PPG, which enables high filling of nano-silica in the resin, has excellent compatibility and bonding with the resin, and has flame retardancy, water repellency, or low dielectric properties. A method for producing a silica sol that can be used was studied.

Republic of Korea Patent Publication No. 10-0193279

The problem to be solved by the present invention is a method for producing a functional silica sol that has excellent stability, hydrophobicity, excellent compatibility and bonding with resin, flame retardancy, water repellency, or low dielectric properties, and a method of manufacturing a functional silica sol using the same. To provide functional silica sol.

The present invention includes the steps of (a) performing primary surface treatment by adding water and alkoxy silane to acidic silica sol and reacting, and (b) solvent replacing the primary surface treated silica sol with alcohol to obtain alcohol-based silica sol. and (c) adding an alkoxy silane to the alcohol-based silica sol and reacting to perform secondary surface treatment.

In step (c), a flame retardant may be added and reacted with the alkoxy silane to increase the flame retardancy of the silica sol.

The flame retardant includes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and ammonium polyphosphate. ), Triethyl Phosphate, Melamine polyphosphate, Triphenyl phosphate, Cresyl diphenyl phosphate, Resorcinol bis( diphenyl phosphate)), Bisphenol A diphosphate, Mg(OH) ₂ , Al(OH) ₃ , melamine monomer (2,4,6-triamino-1,3,5-triazine monomer) ( Melamine Monomer (2,4,6-Triamino-1,3,5-triazine Monomer)), Potassium3-(phenylsulfonyl)benzenesulfonate), 1,3,5-Tris( It may contain one or more substances selected from the group consisting of 2-hydroxyethyl)isocyanurate (1,3,5-Tris(2-hydroxyethyl)isocyanurate) and polytetrafluoroethylene.

In step (c), a water repellent agent may be added and reacted with the alkoxy silane to increase the water repellency of the silica sol.

The water repellent may include fluorine-based silane.

The fluorine-based silane is 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane (1H, 1H, 2H, 2H-Perfluorooctyltrimethoxysilane), 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (1H ,1H,2H,2H-Perfluorooctyltriethoxysilane), 1H,1H,2H,2H-Perfluorodecyltrimethoxysilane (1H,1H,2H,2H-Perfluorodecyltrimethoxysilane) and 1H,1H,2H,2H-Perfluorodecyl It may contain one or more substances selected from the group consisting of triethoxysilane (1H, 1H, 2H, 2H-Perfluorodecyltriethoxysilane).

In step (c), a low dielectric material may be added and reacted with the alkoxy silane to lower the dielectric constant of the silica sol.

The low dielectric material is a material with a lower dielectric constant than silica and may include one or more oligomers selected from the group consisting of hydrogen silsesquioxane (HSSQ) and methyl silsesquioxane (MSSQ). .

The alkoxy silanes include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, phenyldimethylmethoxysilane, chloropropyldimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane. Toxysilane, tetrapropoxysilane, tetrabutoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyl. Liethoxysilane, n-octylmethyldiethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenethyltrimethoxysilane, dodecyltrimethoxysilane, n-octadecyl Triethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(βmethoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane , γ-acryloxypropyltrimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, β-(3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β ( Aminoethyl)γ-(aminopropyl)methyldimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)trimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, It may contain one or more materials selected from the group consisting of n-decyltrimethoxysilane, dimethoxydiethoxysilane, bis(triethoxysilyl)ethane, and hexaethoxydisiloxane.

In the method for producing the silica sol, after step (c), the secondary surface-treated silica sol and an organic solvent are charged into a rotary evaporator and distilled under reduced pressure, and the alcohol contained in the secondary surface-treated silica sol is distilled into other substances. A step of substitution with an organic solvent may be further included.

The organic solvent has a boiling point similar to or higher than that of the alcohol contained in the secondary surface-treated silica sol.

In the method for producing the silica sol, after step (c), the secondary surface-treated silica sol and epoxy monomer are charged into a rotary evaporator and distilled under reduced pressure to convert the alcohol contained in the secondary surface-treated silica sol into epoxy. A step of substitution with a monomer may be further included.

The epoxy monomers include 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, and 2,6-diglycidyl ether. Glycidylphenylglycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4 '-Methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, triglycidyl-p- Aminophenol, tetraglycidylmethoxylenediamine, tetraglycidyldiaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane, bisphenol-A-diglycidyl ether, bisphenol-S -Diglycyldyl ether, pentaerythritol tetraglycidyl ether, resorcinol diglycidyl ether, phthalic acid diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrabromobis. Phenol-A-diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, pentaerythritol diglycidyl ether, hydrogenated bisphenol-A-diglycidyl ether, tris-(2,3-epoxypropyl) ) Isocyanurate, 1-{2,3-di(propionyloxy)}-3,5-bis(2,3-epoxypropyl)-1,3,5-triazine-2,4,6- (1H,3H,5H)-trione, 1,3-bis{2,3-di(propionyloxy)}-5-(2,3-epoxypropyl)-1,3,5-triazine-2 ,4,6-(1H,3H,5H)-trione, monoallyl diglycidyl isocyanurate, diglycerol polydiglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl)cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycy. Dyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tertiary butyl phenyl glycidyl ether, diglycidyl ether adipic acid, o-phthalic acid diglycidyl ether, dibromophenyl glycidyl ether. Sidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylolperfluorohexane diglycidyl ether, 4,4'-bis(2,3-epoxypropoxyperfluoroiso Propyl) diphenyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclo Hexyloxirane, 2-(3,4-epoxycyclohexyl)-3',4'-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxybis(3,4- Epoxycyclohexylmethane), 4',5'-epoxy-2'-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate boxylate), bis-(3,4-epoxycyclohexylmethyl) adipate, and bis(2,3-epoxycyclopentyl) ether.

In addition, the present invention is manufactured using the method for producing the silica sol, and the silica particles contained in the silica sol have a core made of silica and a shell surrounding the core composed of a soft organic material. Provided is a silica sol characterized by having a structure of:

According to the present invention, it has excellent stability, hydrophobicity, excellent compatibility and bonding with resin, and can be made to have flame retardancy, water repellency, or low dielectric property.

When the silica sol prepared according to the present invention is mixed with a resin, it is possible to highly fill the resin with nano-silica, and its compatibility with the resin and bonding properties are excellent.

The silica sol prepared according to the present invention can also be used as PPG (Prepreg) for forming a copper clad layer (CCL) of a printed circuit board (PCB).

Figure 1 is a diagram schematically showing a UF module.
Figure 2 is a diagram showing the results of Fourier transform infrared spectroscopy (FT-IR) analysis of the acidic silica sol prepared according to Example 1.
Figure 3 is a diagram showing the results of FT-IR (Fourier transform infrared spectroscopy) analysis of the silica sol subjected to primary surface treatment according to Example 1.
Figure 4 is a diagram showing the results of Fourier transform infrared spectroscopy (FT-IR) analysis of the 1,4-butanediol diglycidyl ether base silica sol prepared according to Example 4.
Figure 5 is a graph showing analysis of the 1,4-butanediol diglycidyl ether base silica sol prepared according to Example 4 using a UV-visible spectrophotometer.

Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the attached drawings. However, the following examples are provided to enable those skilled in the art to fully understand the present invention, and may be modified into various other forms, and the scope of the present invention is limited to the examples described below. It doesn't work.

When it is said that one component "includes" another component in the detailed description or claims of the invention, this shall not be construed as being limited to consisting of only that component, unless specifically stated to the contrary, and other components may not be added. It must be understood that it can be included.

The method for producing silica sol according to a preferred embodiment of the present invention includes the steps of (a) performing primary surface treatment by adding water and an alkoxy silane to acidic silica sol and reacting, (b) treating the primary surface treated silica sol. It includes the step of obtaining an alcohol-based silica sol by replacing the solvent with alcohol, and (c) adding an alkoxy silane to the alcohol-based silica sol and reacting to perform secondary surface treatment.

In step (c), a flame retardant may be added and reacted with the alkoxy silane to increase the flame retardancy of the silica sol.

The flame retardant includes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and ammonium polyphosphate. ), Triethyl Phosphate, Melamine polyphosphate, Triphenyl phosphate, Cresyl diphenyl phosphate, Resorcinol bis( diphenyl phosphate)), Bisphenol A diphosphate, Mg(OH) ₂ , Al(OH) ₃ , melamine monomer (2,4,6-triamino-1,3,5-triazine monomer) ( Melamine Monomer (2,4,6-Triamino-1,3,5-triazine Monomer)), Potassium3-(phenylsulfonyl)benzenesulfonate), 1,3,5-Tris( It may contain one or more substances selected from the group consisting of 2-hydroxyethyl)isocyanurate (1,3,5-Tris(2-hydroxyethyl)isocyanurate) and polytetrafluoroethylene.

In step (c), a water repellent agent may be added and reacted with the alkoxy silane to increase the water repellency of the silica sol.

The water repellent may include fluorine-based silane.

The fluorine-based silane is 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane (1H, 1H, 2H, 2H-Perfluorooctyltrimethoxysilane), 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (1H ,1H,2H,2H-Perfluorooctyltriethoxysilane), 1H,1H,2H,2H-Perfluorodecyltrimethoxysilane (1H,1H,2H,2H-Perfluorodecyltrimethoxysilane) and 1H,1H,2H,2H-Perfluorodecyl It may contain one or more substances selected from the group consisting of triethoxysilane (1H, 1H, 2H, 2H-Perfluorodecyltriethoxysilane).

In step (c), a low dielectric material may be added and reacted with the alkoxy silane to lower the dielectric constant of the silica sol.

The low dielectric material is a material with a lower dielectric constant than silica and may include one or more oligomers selected from the group consisting of hydrogen silsesquioxane (HSSQ) and methyl silsesquioxane (MSSQ). .

The alkoxy silanes include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, phenyldimethylmethoxysilane, chloropropyldimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane. Toxysilane, tetrapropoxysilane, tetrabutoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyl. Liethoxysilane, n-octylmethyldiethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenethyltrimethoxysilane, dodecyltrimethoxysilane, n-octadecyl Triethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(βmethoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane , γ-acryloxypropyltrimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, β-(3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β ( Aminoethyl)γ-(aminopropyl)methyldimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)trimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, It may contain one or more materials selected from the group consisting of n-decyltrimethoxysilane, dimethoxydiethoxysilane, bis(triethoxysilyl)ethane, and hexaethoxydisiloxane.

In the method for producing the silica sol, after step (c), the secondary surface-treated silica sol and an organic solvent are charged into a rotary evaporator and distilled under reduced pressure, and the alcohol contained in the secondary surface-treated silica sol is distilled into other substances. A step of substitution with an organic solvent may be further included.

The organic solvent has a boiling point similar to or higher than that of the alcohol contained in the secondary surface-treated silica sol.

In the method for producing the silica sol, after step (c), the secondary surface-treated silica sol and epoxy monomer are charged into a rotary evaporator and distilled under reduced pressure to convert the alcohol contained in the secondary surface-treated silica sol into epoxy. A step of substitution with a monomer may be further included.

The epoxy monomers include 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, and 2,6-diglycidyl ether. Glycidylphenylglycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4 '-Methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, triglycidyl-p- Aminophenol, tetraglycidylmethoxylenediamine, tetraglycidyldiaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane, bisphenol-A-diglycidyl ether, bisphenol-S -Diglycyldyl ether, pentaerythritol tetraglycidyl ether, resorcinol diglycidyl ether, phthalic acid diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrabromobis. Phenol-A-diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, pentaerythritol diglycidyl ether, hydrogenated bisphenol-A-diglycidyl ether, tris-(2,3-epoxypropyl) ) Isocyanurate, 1-{2,3-di(propionyloxy)}-3,5-bis(2,3-epoxypropyl)-1,3,5-triazine-2,4,6- (1H,3H,5H)-trione, 1,3-bis{2,3-di(propionyloxy)}-5-(2,3-epoxypropyl)-1,3,5-triazine-2 ,4,6-(1H,3H,5H)-trione, monoallyl diglycidyl isocyanurate, diglycerol polydiglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl)cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycy. Dyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tertiary butyl phenyl glycidyl ether, diglycidyl ether adipic acid, o-phthalic acid diglycidyl ether, dibromophenyl glycidyl ether. Sidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylolperfluorohexane diglycidyl ether, 4,4'-bis(2,3-epoxypropoxyperfluoroiso Propyl) diphenyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclo Hexyloxirane, 2-(3,4-epoxycyclohexyl)-3',4'-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxybis(3,4- Epoxycyclohexylmethane), 4',5'-epoxy-2'-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate boxylate), bis-(3,4-epoxycyclohexylmethyl) adipate, and bis(2,3-epoxycyclopentyl) ether.

The silica sol according to a preferred embodiment of the present invention is manufactured using the above silica sol production method, and the silica particles contained in the silica sol have a core made of silica and a shell surrounding the core. is characterized by having a structure composed of soft organic materials.

Below, the method for producing silica sol according to a preferred embodiment of the present invention will be described in more detail.

Prepare the acidic silica sol. The acidic silica sol is an acidic silica sol dispersed in water (H ₂ O). It is preferable to use the acidic silica sol having an average particle size of 5 to 300 nm in consideration of the particle size and physical properties of the silica sol to be finally produced, and the dispersibility, stability and physical properties of the sol. If the average particle diameter of the silica contained in the acidic silica sol is less than 5 nm, the viscosity of the finally produced silica sol is too high and stability is poor, and if it exceeds 300 nm, the dispersibility and storage stability of the sol may be poor. . In addition, the acidic silica sol preferably has a silica content of about 10 to 60% by weight. If the silica content is less than 10% by weight, the amount of solvent increases, making it uneconomical, and if it exceeds 60% by weight, it is uneconomical. If the viscosity is too high, dispersibility may be poor.

The acidic silica sol can be produced directly, for example, by passing an alkaline silica sol through a column filled with a strongly acidic cation exchange resin (e.g., Amberite IR-120). The alkaline silica sol preferably has a SiO ₂ /Na ₂ O molar ratio of about 50 to 300. The acidic silica sol may be used by purchasing a commercially available acidic silica sol.

Water (distilled water) and alkoxy silane are added to the acidic silica sol and reacted to perform primary surface treatment. It is preferable to add 0.001 to 10 parts by weight of the alkoxy silane based on 100 parts by weight of the silica sol.

Alkoxy silanes may have the structure of Formula 1 below.

[Formula 1]

R _n SiX _(4-n)

[Here, R: unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, acrylic group, epoxy group, methacryl group, amino group or CF ₂ group, X: alkoxy group having 1 to 4 carbon atoms, silanol group, halogen or hydrogen, n :integer from 0 to 3]

These alkoxy silanes include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, phenyldimethylmethoxysilane, chloropropyldimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane. Toxysilane, tetrapropoxysilane, tetrabutoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyl. Liethoxysilane, n-octylmethyldiethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenethyltrimethoxysilane, dodecyltrimethoxysilane, n-octadecyl Triethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(βmethoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane , γ-acryloxypropyltrimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, β-(3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β ( Aminoethyl)γ-(aminopropyl)methyldimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)trimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, It is preferably one or more materials selected from the group consisting of n-decyltrimethoxysilane, dimethoxydiethoxysilane, bis(triethoxysilyl)ethane, and hexaethoxydisiloxane.

The primary surface treatment is preferably performed at room temperature (10-30°C) to 90°C for 10 minutes to 48 hours. Agitation during the first surface treatment is preferably performed at about 10 to 1500 rpm.

Through the first surface treatment, the acidic silica sol reacts with the alkoxy silane to cause a hydrolysis reaction, and the silica particles of the acidic silica sol are surface modified and coated with the alkoxy silane component, making the silica sol hydrophobic.

When the acidic silica sol is reacted with an alkoxy silane to perform primary surface treatment, a coupling reaction with Si-OH on the silica surface occurs, resulting in a hydrolysis reaction, and -Si-O-Si-(R ₁ )n on the silica surface. (Here, (R ₁ )n is an alkoxy silane) and is modified and coated with alkoxy silane, forming a network. When the surface is first treated with alkoxy silane, the core is made of silica and the shell surrounding the core is made of alkoxy silane. In this core-shell structure, the shell surrounding the core is mostly composed of organic materials, so the phenomenon of agglomeration of silica sol particles with each other due to the mutual repulsion between organic materials is suppressed, so it has the advantage of excellent stability.

Silica sol that has been first surface treated with alkoxy silane is solvent-substituted with alcohol to obtain alcohol-based silica sol. Below, the method of solvent substitution will be described in more detail.

The first surface treated silica sol is subjected to moisture removal using a UF module (Ultra-filtration module) and the solvent is replaced with alcohol. Figure 1 is a diagram schematically showing a UF module. In Figure 1, '110' represents a thickening tank, '120' represents a thickening pump, '130' represents a pre-treatment filter, '140' represents a filter, '150' represents a backwash tank, '160' represents a backwash pump, and V1 to V9 represent valves. represents.

When the silica sol and alcohol that have undergone primary surface treatment in the UF module are put into the concentration tank (110) and passed through the filter (140), moisture (water and alcohol) is transferred to the backwash tank (150) or to the outside through the pores of the filter. As it is discharged, the silica sol becomes concentrated. The dehydration (substitution) process is repeated until the moisture content in the silica sol is lowered to 5% or less.

Silica sol uses water as a dispersion medium, and the physical properties and stability of the silica sol can be improved by replacing the water contained in the silica sol with alcohol to lower the moisture content. In addition, unreacted alkoxy silane, etc. remaining in the silica sol during the dehydration process is removed along with water by the filter 140, so that a highly purified and highly concentrated silica sol can be obtained.

Alcohols introduced into the UF module include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 1-hexanol, 1- Octanol, 2-ethyl-1-hexanol, allyl alcohol, benzyl alcohol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, 2-methoxyethanol, 2-ethoxyethanol, 2- One or more substances selected from the group consisting of propoxyethanol, 2-(methoxyethoxy)ethanol, 1-methoxy-2-propanol, dipropylene glycol monomethyl ether, diacetone alcohol, ethylcarbitol, and butylcarbitol It is desirable to use . The content of the alcohol introduced into the UF module is preferably used in a volume ratio of 1:1 to 1:3 (content of silica sol:content of alcohol) with respect to the content of silica sol introduced into the UF module. If the alcohol content is more than the above range, too much is used and it is not economical, and if it is less than the above range, there is a limit to sufficiently replacing water with alcohol.

The filter 140 of the UF module used to replace the solvent is a hollow fiber-shaped membrane with many pores of about 1 nm to 10 nm in size, and silica sol with a particle size of about 5 to 300 nm is It does not pass through, but allows water and ions to pass through. The filter 140 of the UF module preferably uses a membrane with a molecular weight of cut-off (MWCO) in the range of 5,000 to 300,000, which indicates the size of the molecular weight that can be separated. If the fractional molecular weight is less than 5,000, it is expensive and the rate of substitution with alcohol is slow, making it uneconomical. If it exceeds 300,000, the pore size is so large that silica particles can escape with water. When filtering moisture using a UF module, it is desirable to apply a pressure of about 2 to 5 kgf/cm2 to the filter 140.

The alcohol and silica sol contained in the concentration tank 110 are pumped and passed through the pre-treatment filter 130 and sent to the filter 140, and in the filter 140, moisture and silica particles are filtered and separated. That is, moisture passes through the pores of the filter 140, but silica particles do not pass through the pores of the filter 140, and the moisture that has passed through the filter 140 is discharged to the backwash tank 150 or to the outside to remove the moisture. The silica sol is concentrated by removing moisture. The silica sol that has passed through the filter (140) passes through V6-1, V6-2, V6-3, V6-4, and V7 and is sent back to the concentration tank (110) to complete the circulation process. The backwash pump 160 is used to unclog the filter 140 by sending the water or organic solvent contained in the backwash tank 150 back to the filter 140 when the filter 140 is blocked by sol particles, etc. .

Alkoxy silane is added to alcohol-based silica sol and reacted to perform secondary surface treatment. The alkoxy silane added during secondary surface treatment is preferably added in a larger amount than during primary surface treatment, for example, 0.01 to 20 parts by weight based on 100 parts by weight of the silica sol. The alkoxy silanes include trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, phenyldimethylmethoxysilane, chloropropyldimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane. Toxysilane, tetrapropoxysilane, tetrabutoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyl. Liethoxysilane, n-octylmethyldiethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenethyltrimethoxysilane, dodecyltrimethoxysilane, n-octadecyl Triethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(βmethoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane , γ-acryloxypropyltrimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, β-(3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β ( Aminoethyl)γ-(aminopropyl)methyldimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)trimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, It is preferably one or more materials selected from the group consisting of n-decyltrimethoxysilane, dimethoxydiethoxysilane, bis(triethoxysilyl)ethane, and hexaethoxydisiloxane.

The secondary surface treatment is preferably performed at room temperature (10-30°C) to 90°C for 10 minutes to 48 hours. Stirring during the secondary surface treatment is preferably performed at about 10 to 1500 rpm.

Through the secondary surface treatment, the alcohol-based silica sol reacts with alkoxy silane to cause a hydrolysis reaction, and the silica particles of the alcohol-based silica sol are surface coated with an alkoxy silane component, which can further stabilize them.

In order to impart flame retardancy to the silica sol or increase the flame retardancy of the silica sol, a flame retardant may be added along with the alkoxy silane during the secondary surface treatment. The flame retardant includes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and ammonium polyphosphate. ), Triethyl Phosphate, Melamine polyphosphate, Triphenyl phosphate, Cresyl diphenyl phosphate, Resorcinol bis( diphenyl phosphate)), Bisphenol A diphosphate, Mg(OH) ₂ , Al(OH) ₃ , melamine monomer (2,4,6-triamino-1,3,5-triazine monomer) ( Melamine Monomer (2,4,6-Triamino-1,3,5-triazine Monomer)), Potassium3-(phenylsulfonyl)benzenesulfonate), 1,3,5-Tris( It is preferable to use at least one material selected from the group consisting of 2-hydroxyethyl)isocyanurate (1,3,5-Tris(2-hydroxyethyl)isocyanurate) and polytetrafluoroethylene, Of course, other materials with flame retardant properties can also be used. By adding the flame retardant, the surface of the silica particles can be coated with a flame retardant component to exhibit flame retardancy. In this case, the core is made of silica, and the shell surrounding the core has a structure composed of an alkoxy silane and a flame retardant component. The flame retardant is preferably added at 0.001 to 10 parts by weight based on 100 parts by weight of the silica sol.

In order to impart water repellency to the silica sol or to increase the water repellency of the silica sol, a water repellent agent may be added along with alkoxy silane during the secondary surface treatment. The water repellent may include fluorine-based silane. The fluorine-based silane is 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane (1H, 1H, 2H, 2H-Perfluorooctyltrimethoxysilane), 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (1H ,1H,2H,2H-Perfluorooctyltriethoxysilane), 1H,1H,2H,2H-Perfluorodecyltrimethoxysilane (1H,1H,2H,2H-Perfluorodecyltrimethoxysilane) and 1H,1H,2H,2H-Perfluorodecyl It is preferable to use at least one material selected from the group consisting of triethoxysilane (1H, 1H, 2H, 2H-Perfluorodecyltriethoxysilane). By adding the water repellent, the surface of the silica particles is coated with a water repellent component (e.g., a fluorinated silane component), and the silica sol coated with the water repellent has a high contact angle and can improve water repellency, making it compatible with non-polar resin (PPO). It improves performance. The water repellent is preferably added from 0.001 to 10 parts by weight based on 100 parts by weight of the silica sol.

In order to impart low dielectric properties to the silica sol or to lower the dielectric constant of the silica sol, a low dielectric material may be added along with alkoxy silane during the secondary surface treatment. The low dielectric material has a lower dielectric constant than silica and may be one or more oligomers selected from the group consisting of hydrogen silsesquioxane (HSSQ) and methyl silsesquioxane (MSSQ). By adding the low dielectric material, the surface of the silica particles is coated with the low dielectric material, thereby lowering the dielectric constant and exhibiting low dielectric properties. The low dielectric material is preferably added in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the silica sol.

The silica sol prepared by secondary surface treatment is an alcohol-based silica sol (containing alcohol as a solvent). Alcohol-based silica sol can also be manufactured into other organic solvent-based silica sol to suit the user's needs. For this purpose, the secondary surface-treated silica sol and an organic solvent that meets the user's needs are charged into a rotary evaporator and distilled under reduced pressure, and the alcohol contained in the secondary surface-treated silica sol is replaced with another organic solvent to produce the desired organic solvent. Solvent-based silica sol can be produced. At this time, it is preferable to use an organic solvent that has a boiling point similar to or higher than that of alcohol (alcohol in alcohol-based silica sol). When reduced-pressure distillation is performed using a rotary evaporator, the boiling point of alcohol is lowered under reduced pressure (vacuum), and alcohol can be removed at a lower temperature than under non-vacuum conditions (e.g., normal pressure). Accordingly, alcohol can be more easily replaced with the desired organic solvent. Even if an organic solvent with a boiling point similar to that of the alcohol is used, the alcohol can be replaced with the desired organic solvent by continuously removing the alcohol while reducing the pressure and continuously replenishing the desired organic solvent. For example, when the silica sol produced through secondary surface treatment is a silica sol based on isopropyl alcohol, the boiling point of isopropyl alcohol is 82.6°C, but when distilled under reduced pressure using a rotary evaporator, the boiling point is lower than that. Isopropyl alcohol can be replaced with other organic solvents at any temperature. More specifically, when the silica sol produced by secondary surface treatment is a silica sol based on isopropyl alcohol, and when isopropyl alcohol is to be replaced with methyl isobutyl ketone (boiling point 117°C), isopropyl alcohol is used. When the base silica sol and methyl isobutyl ketone are charged to a rotary evaporator and distilled under reduced pressure, isopropyl alcohol is removed at a temperature lower than the boiling point of methyl isobutyl ketone (e.g., 60 to 95°C), and thus Accordingly, isopropyl alcohol can be replaced (substituted) with methyl isobutyl ketone.

The organic solvent charged into the rotary evaporator is not particularly limited, but solvents such as alcohol-based, ketone-based, ether-based, ester-based, and hydrocarbon-based solvents can be used.

The alcohol-based solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 1-hexanol, 1-octanol, 2-ethyl-1-hexanol, allyl alcohol, benzyl alcohol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol , 2-(methoxyethoxy)ethanol, 1-methoxy-2-propanol, dipropylene glycol monomethyl ether, diacetone alcohol, ethylcarbitol, butylcarbitol, or mixtures thereof.

The ketone solvents include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, and cyclohexanone. , mixtures thereof, etc. can be given as examples.

Examples of the ether-based solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dioxane, tetrahydrofuran, 1,2-diethoxyethane, or mixtures thereof.

The ester-based solvents include ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and hydroxy Ethyl methacrylate, hydroxyethyl acrylate, γ-butyrolactone, methyl methacrylate, isobutylacrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, trifluoroethyl acrylate, methacrylic acid Examples include glycidyl or mixtures thereof.

Examples of the hydrocarbon-based solvent include n-hexane, cyclohexane, benzene, toluene, xylene, solvent naphtha, styrene, dichloromethane, trichloroethylene, or mixtures thereof.

Epoxy monomer-based silica sol can also be manufactured considering its use in PPG (Prepreg) for forming a copper clad layer (CCL) of a printed circuit board (PCB). For this purpose, the secondary surface treated silica sol and epoxy monomer are charged into a rotary evaporator and distilled under reduced pressure to replace the alcohol contained in the secondary surface treated silica sol with an epoxy monomer to produce the desired epoxy monomer base silica sol. You can.

The epoxy monomers include 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, and 2,6-diglycidyl ether. Glycidylphenylglycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4 '-Methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, triglycidyl-p- Aminophenol, tetraglycidylmethoxylenediamine, tetraglycidyldiaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane, bisphenol-A-diglycidyl ether, bisphenol-S -Diglycyldyl ether, pentaerythritol tetraglycidyl ether, resorcinol diglycidyl ether, phthalic acid diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrabromobis. Phenol-A-diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, pentaerythritol diglycidyl ether, hydrogenated bisphenol-A-diglycidyl ether, tris-(2,3-epoxypropyl) ) Isocyanurate, 1-{2,3-di(propionyloxy)}-3,5-bis(2,3-epoxypropyl)-1,3,5-triazine-2,4,6- (1H,3H,5H)-trione, 1,3-bis{2,3-di(propionyloxy)}-5-(2,3-epoxypropyl)-1,3,5-triazine-2 ,4,6-(1H,3H,5H)-trione, monoallyl diglycidyl isocyanurate, diglycerol polydiglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl)cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycy. Dyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tertiary butyl phenyl glycidyl ether, diglycidyl ether adipic acid, o-phthalic acid diglycidyl ether, dibromophenyl glycidyl ether. Sidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylolperfluorohexane diglycidyl ether, 4,4'-bis(2,3-epoxypropoxyperfluoroiso Propyl) diphenyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclo Hexyloxirane, 2-(3,4-epoxycyclohexyl)-3',4'-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxybis(3,4- Epoxycyclohexylmethane), 4',5'-epoxy-2'-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate boxylate), bis-(3,4-epoxycyclohexylmethyl) adipate, bis(2,3-epoxycyclopentyl) ether, or mixtures thereof can be used.

The silica sol prepared in this way includes silica particles, which have a structure in which the core is made of silica and the shell surrounding the core is made of a soft organic material.

Below, embodiments according to the present invention are presented in detail, but the present invention is not limited to the embodiments presented below.

<Example 1>

5 kg of alkaline silica sol (20 nm, silica content 30 wt%, SiO ₂ /Na ₂ O molar ratio 100) was passed through a column filled with strongly acidic cation exchange resin (Amberite IR-120) to obtain acidic silica sol (pH: 3.20, concentration wt%). ) was prepared. Figure 2 is a diagram showing the results of Fourier transform infrared spectroscopy (FT-IR) analysis of acidic silica sol.

1kg of the acidic silica sol and 2kg of water (ultrapure water) (18MΩ·cm) were added to a 5L four-necked round flask, raised to 50°C with stirring, and then 5g of vinyltrimethoxysilane was added and reacted for 24 hours to form the primary surface. Processing was performed. Figure 3 is a diagram showing the results of FT-IR (Fourier transform infrared spectroscopy) analysis of the first surface-treated silica sol.

While isopropyl alcohol was added to the first surface-treated silica sol, the solvent was replaced with a hollow fiber membrane to obtain an isopropyl alcohol-based silica sol with a SiO ₂ concentration of 30 wt% and a moisture content of 0.7 wt%.

γ-Glycidoxypropyltrimethoxysilane was prepared for secondary surface treatment of the isopropyl alcohol-based silica sol. To impart flame retardancy to silica sol or to increase the flame retardancy of silica sol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene) -10-oxide) was prepared. 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane (1H,1H,2H,2H-Perfluorooctyltrimethoxysilane) was prepared to impart water repellency to the silica sol or to increase the water repellency of the silica sol. To impart low dielectric properties to silica sol or to lower the dielectric constant of silica sol, methyl silsesquioxane (MSSQ) oligomer was prepared.

1kg of the isopropyl alcohol-based silica sol was placed in a 5L 4-neck round flask, the temperature was raised to 50°C while stirring with a magnetic stirrer, and then 20g of γ-glycidoxypropyltrimethoxysilane and 9,10-dihydro-9-oxa were added. -10-Phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) 20g, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (1H 5g of 1H,2H,2H-Perfluorooctyltrimethoxysilane) and 5g of methyl silsesquioxane (MSSQ; methyl silsesquioxane) oligomer were added and reacted for 24 hours.

The silica sol and bisphenol-A-diglycidyl ether obtained in this way were charged into a rotary evaporator and distilled under reduced pressure to obtain bisphenol-A-diglycidyl ether base hybrid silica sol (SiO ₂ 40 wt%, moisture 0.3 wt%, Viscosity 2,200 mPa·s) was obtained.

<Example 2>

5 kg of alkaline silica sol (20 nm, silica content 30 wt%, SiO ₂ /Na ₂ O molar ratio 100) was passed through a column filled with strongly acidic cation exchange resin (Amberite IR-120) to obtain acidic silica sol (pH: 3.20, concentration wt%). ) was prepared.

1kg of the acidic silica sol and 2kg of water (ultrapure water) (18MΩ·cm) were added to a 5L four-necked round flask, raised to 50°C with stirring, and then 5g of vinyltrimethoxysilane was added and reacted for 24 hours to form the primary surface. Processing was performed.

While isopropyl alcohol was added to the first surface-treated silica sol, the solvent was replaced with a hollow fiber membrane to obtain an isopropyl alcohol-based silica sol with a SiO ₂ concentration of 30 wt% and a moisture content of 0.7 wt%.

Epoxycyclohexyltrimethoxysilane was prepared for secondary surface treatment of the isopropyl alcohol-based silica sol. To impart flame retardancy to silica sol or to increase the flame retardancy of silica sol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene) -10-oxide) was prepared. 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane (1H,1H,2H,2H-Perfluorooctyltrimethoxysilane) was prepared to impart water repellency to the silica sol or to increase the water repellency of the silica sol. To impart low dielectric properties to silica sol or to lower the dielectric constant of silica sol, methyl silsesquioxane (MSSQ) oligomer was prepared.

1kg of the isopropyl alcohol-based silica sol was placed in a 5L 4-necked round flask, the temperature was raised to 50°C while stirring with a magnetic stirrer, and then 10g of epoxycyclohexyltrimethoxysilane, 9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) 20g, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (1H,1H, 10 g of 2H,2H-Perfluorooctyltrimethoxysilane) and 10 g of methyl silsesquioxane (MSSQ; methyl silsesquioxane) oligomer were added and reacted for 24 hours.

The silica sol and propylene glycol monomethyl ether acetate thus obtained were charged into a rotary evaporator and distilled under reduced pressure to obtain propylene glycol monomethyl ether acetate base silica sol (SiO ₂ 50 wt%, moisture 0.4 wt%, viscosity 15 mPa·s). .

<Example 3>

5 kg of alkaline silica sol (90 nm, silica content 30 wt%, SiO ₂ /Na ₂ O molar ratio 100) was passed through a column filled with strongly acidic cation exchange resin (Amberite IR-120) to obtain acidic silica sol (pH: 3.50, concentration wt%). ) was prepared.

1kg of the acidic silica sol and 2kg of water (ultrapure water) (18MΩ·cm) were added to a 5L four-necked round flask, raised to 50°C with stirring, and then 5g of vinyltrimethoxysilane was added and reacted for 24 hours to form the primary surface. Processing was performed.

While isopropyl alcohol was added to the first surface-treated silica sol, the solvent was replaced with a hollow fiber membrane to obtain an isopropyl alcohol-based silica sol with a SiO ₂ concentration of 30 wt% and a moisture content of 0.7 wt%.

γ-Glycidoxypropyltrimethoxysilane was prepared for secondary surface treatment of the isopropyl alcohol-based silica sol. Triethyl phosphate was prepared to impart flame retardancy to silica sol or to increase the flame retardancy of silica sol. 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane (1H,1H,2H,2H-Perfluorooctyltrimethoxysilane) was prepared to impart water repellency to the silica sol or to increase the water repellency of the silica sol. Hydrogen silsesquioxane (HSSQ) oligomer was prepared to impart low dielectric properties to silica sol or to lower the dielectric constant of silica sol.

1kg of the isopropyl alcohol-based silica sol was added to a 5L 4-neck round flask, the temperature was raised to 50°C while stirring with a magnetic stirrer, and then 20g of γ-glycidoxypropyltrimethoxysilane, 100g of triethyl phosphate, 1H , 5g of 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane and 5g of hydrogen silsesquioxane (HSSQ) oligomer were added and reacted for 24 hours. .

The silica sol and methyl isobutyl ketone thus obtained were charged into a rotary evaporator and distilled under reduced pressure to obtain methyl isobutyl ketone-based silica sol (SiO ₂ 40 wt%, moisture 0.3 wt%, viscosity 2,200 mPa·s).

<Example 4>

5 kg of alkaline silica sol (10 nm, silica content 30 wt%, SiO ₂ /Na ₂ O molar ratio 200) was passed through a column filled with strongly acidic cation exchange resin (Amberite IR-120) to obtain acidic silica sol (pH: 3.20, concentration wt%). ) was prepared.

1kg of the acidic silica sol and 2kg of water (ultrapure water) (18MΩ·cm) were added to a 5L four-necked round flask, raised to 50°C with stirring, and then 5g of vinyltrimethoxysilane was added and reacted for 24 hours to form the primary surface. Processing was performed.

While isopropyl alcohol was added to the first surface-treated silica sol, the solvent was replaced with a hollow fiber membrane to obtain an isopropyl alcohol-based silica sol with a SiO ₂ concentration of 30 wt% and a moisture content of 0.7 wt%.

Epoxycyclohexyltrimethoxysilane was prepared for secondary surface treatment of the isopropyl alcohol-based silica sol. To impart flame retardancy to silica sol or to increase the flame retardancy of silica sol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene) -10-oxide) was prepared. 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane (1H,1H,2H,2H-Perfluorooctyltrimethoxysilane) was prepared to impart water repellency to the silica sol or to increase the water repellency of the silica sol. To impart low dielectric properties to silica sol or to lower the dielectric constant of silica sol, methyl silsesquioxane (MSSQ) oligomer was prepared.

1kg of the isopropyl alcohol-based silica sol was placed in a 5L 4-necked round flask, the temperature was raised to 50°C while stirring with a magnetic stirrer, and then 10g of epoxycyclohexyltrimethoxysilane, 9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) 20g, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (1H,1H, 10 g of 2H,2H-Perfluorooctyltrimethoxysilane) and 10 g of methyl silsesquioxane (MSSQ; methyl silsesquioxane) oligomer were added and reacted for 24 hours.

The silica sol and 1,4-butanediol diglycidyl ether obtained in this way were charged into a rotary evaporator and distilled under reduced pressure to obtain 1,4-butanediol diglycidyl ether base silica sol (SiO ₂ 50 wt%, moisture 0.4 wt%). , viscosity of 750 mPa·s) was obtained.

Figure 4 is a diagram showing the results of Fourier transform infrared spectroscopy (FT-IR) analysis of the 1,4-butanediol diglycidyl ether base silica sol prepared according to Example 4.

Figure 5 is a graph showing analysis of the 1,4-butanediol diglycidyl ether base silica sol prepared according to Example 4 using a UV-visible spectrophotometer.

The silica (SiO ₂ ) content, moisture content, and viscosity of the silica sol prepared according to Examples 1 to 4 are shown in Table 1 below.

SiO ₂ content (wt%) Moisture content (wt%) Viscosity (mPa·s, 25℃) Example 1 40 0.3 2200 Example 2 50 0.4 15 Example 3 40 0.3 18 Example 4 50 0.4 750

Above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art.

110: enrichment tank 120: enrichment pump
130: pre-treatment filter 140: filter
150: backwash tank 160: backwash pump

Claims (14)

(a) adding water and alkoxy silane to acidic silica sol and reacting to perform primary surface treatment;
(b) solvent-substituting the primary surface-treated silica sol with alcohol to obtain an alcohol-based silica sol; and
(c) A method for producing silica sol comprising the step of adding an alkoxy silane to the alcohol-based silica sol and reacting to perform secondary surface treatment.
The method of claim 1, wherein in step (c),
A method for producing silica sol, characterized in that a flame retardant is added and reacted with the alkoxy silane to increase the flame retardancy of the silica sol.
The method of claim 2, wherein the flame retardant is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, Ammonium polyphosphate, Triethyl Phosphate, Melamine polyphosphate, Triphenyl phosphate, Cresyl diphenyl phosphate, Resorcinol bis(diphenyl) Phosphate) (Resorcinol bis(diphenyl phosphate)), Bisphenol A diphosphate, Mg(OH) ₂ , Al(OH) ₃ , melamine monomer (2,4,6-triamino-1,3,5 -Triazine Monomer) (Melamine Monomer (2,4,6-Triamino-1,3,5-triazine Monomer)), Potassium 3-(phenylsulfonyl)benzenesulfonate), 1, One or more substances selected from the group consisting of 3,5-Tris(2-hydroxyethyl)isocyanurate and polytetrafluoroethylene. A method for producing silica sol, comprising:
The method of claim 1, wherein in step (c),
A method for producing silica sol, characterized in that a water repellent agent is added and reacted with the alkoxy silane to increase the water repellency of the silica sol.
The method of claim 4, wherein the water repellent agent contains a fluorine-based silane.
The method of claim 5, wherein the fluorine-based silane is 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane (1H,1H,2H,2H-Perfluorooctyltrimethoxysilane), 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane 1H,1H,2H,2H-Perfluorooctyltriethoxysilane, 1H,1H,2H,2H-Perfluorodecyltrimethoxysilane (1H,1H,2H,2H-Perfluorodecyltrimethoxysilane) and 1H,1H,2H, A method for producing silica sol, comprising at least one material selected from the group consisting of 2H-perfluorodecyltriethoxysilane (1H, 1H, 2H, 2H-Perfluorodecyltriethoxysilane).
The method of claim 1, wherein in step (c),
A method for producing silica sol, characterized in that a low dielectric material is added and reacted with the alkoxy silane to lower the dielectric constant of the silica sol.
The method of claim 7, wherein the low dielectric material has a lower dielectric constant than silica and is at least one selected from the group consisting of hydrogen silsesquioxane (HSSQ) and methyl silsesquioxane (MSSQ). A method for producing a silica sol comprising an oligomer.
The method of claim 1, wherein the alkoxy silane is trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, phenyldimethylmethoxysilane, chloropropyldimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethylmethoxysilane. Methoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxy Silane, n-octyltriethoxysilane, n-octylmethyldiethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenethyltrimethoxysilane, dodecyltrimethoxy Silane, n-octadecyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(βmethoxyethoxy)silane, γ-methacrylic Oxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxy Silane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxy Silane, N-β(aminoethyl)γ-(aminopropyl)methyldimethoxysilane, N-β(aminoethyl)γ-(aminopropyl)trimethoxysilane, N-β(aminoethyl)γ-(aminopropyl ) Triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-isocyanate Characterized by comprising at least one material selected from the group consisting of propyltriethoxysilane, n-decyltrimethoxysilane, dimethoxydiethoxysilane, bis(triethoxysilyl)ethane, and hexaethoxydisiloxane. Method for producing silica sol.
The method of claim 1, wherein after step (c),
Silica, characterized in that it further comprises the step of charging the secondary surface-treated silica sol and the organic solvent into a rotary evaporator and distilling it under reduced pressure to replace the alcohol contained in the secondary surface-treated silica sol with another organic solvent. Method for producing sol.
The method of claim 10, wherein the organic solvent has a boiling point similar to or higher than that of the alcohol contained in the secondary surface-treated silica sol.
The method of claim 1, wherein after step (c),
Silica sol, characterized in that it further comprises the step of charging the secondary surface-treated silica sol and epoxy monomer into a rotary evaporator and distilling under reduced pressure to replace the alcohol contained in the secondary surface-treated silica sol with an epoxy monomer. Manufacturing method.
The method of claim 12, wherein the epoxy monomer is 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether. , 2,6-diglycidylphenylglycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycy Dyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, Triglycidyl-p-aminophenol, tetraglycidylmetxylenediamine, tetraglycidyldiaminodiphenylmethane, tetraglycidyl-1,3-bisaminomethylcyclohexane, bisphenol-A-diglycy. Diglycidyl ether, bisphenol-S-diglycidyl ether, pentaerythritol tetraglycidyl ether, resorcinol diglycidyl ether, phthalate diglycidyl ester, neopentyl glycol diglycidyl ether, polypropylene glycol diglycy. Diyl ether, tetrabromobisphenol-A-diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, pentaerythritol diglycidyl ether, hydrogenated bisphenol-A-diglycidyl ether, tris-( 2,3-epoxypropyl)isocyanurate, 1-{2,3-di(propionyloxy)}-3,5-bis(2,3-epoxypropyl)-1,3,5-triazine- 2,4,6-(1H,3H,5H)-trione, 1,3-bis{2,3-di(propionyloxy)}-5-(2,3-epoxypropyl)-1,3, 5-triazine-2,4,6-(1H,3H,5H)-trione, monoallyl diglycidyl isocyanurate, diglycerol polydiglycidyl ether, pentaerythritol polyglycidyl ether , 1,4-bis(2,3-epoxypropoxyperfluoroisopropyl)cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, 1,6 -Hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-tertiary butylphenyl glycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether , dibromophenyl glycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylolperfluorohexane diglycidyl ether, 4,4'-bis(2,3-epoxy Propoxyperfluoroisopropyl)diphenyl ether, 2,2-bis(4-glycidyloxyphenyl)propane, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, 2-(3,4-epoxycyclohexyl)-3',4'-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-ethylenedioxy Bis(3,4-epoxycyclohexylmethane), 4',5'-epoxy-2'-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis(3, Characterized by comprising one or more substances selected from the group consisting of 4-epoxycyclohexanecarboxylate), bis-(3,4-epoxycyclohexylmethyl) adipate, and bis(2,3-epoxycyclopentyl) ether. Method for producing silica sol.
It is manufactured using the method for producing silica sol according to claim 1, and the silica particles contained in the silica sol have a structure in which the core is made of silica and the shell surrounding the core is made of a soft organic material. A silica sol characterized by having a.

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