WO2001055030A2 - Method for manufacturing hydrophobic colloidal silica - Google Patents

Method for manufacturing hydrophobic colloidal silica Download PDF

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Publication number
WO2001055030A2
WO2001055030A2 PCT/NL2001/000063 NL0100063W WO0155030A2 WO 2001055030 A2 WO2001055030 A2 WO 2001055030A2 NL 0100063 W NL0100063 W NL 0100063W WO 0155030 A2 WO0155030 A2 WO 0155030A2
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Prior art keywords
colloidal silica
organic solvent
hydrophobic
solvent
hydrophihc
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PCT/NL2001/000063
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French (fr)
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WO2001055030A3 (en
Inventor
Yuichi Eriyama
Atsuya Takahashi
Isao Nishiwaki
Takashi Ukachi
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Dsm N.V.
Jsr Corporation
Japan Fine Coatings Co., Ltd.
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Application filed by Dsm N.V., Jsr Corporation, Japan Fine Coatings Co., Ltd. filed Critical Dsm N.V.
Priority to DE60107049T priority Critical patent/DE60107049T2/en
Priority to AU2001236182A priority patent/AU2001236182A1/en
Priority to EP01908439A priority patent/EP1252095B1/en
Priority to AT01908439T priority patent/ATE282006T1/en
Publication of WO2001055030A2 publication Critical patent/WO2001055030A2/en
Publication of WO2001055030A3 publication Critical patent/WO2001055030A3/en
Priority to US10/205,626 priority patent/US20030035888A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/141—Preparation of hydrosols or aqueous dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/149—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above

Definitions

  • the present invention relates to a method for manufacturing hydrophobic colloidal silica, the silica dispersion in a hydrophobic organic solvent or resin and the use of the colloidal silica in organic hydrophobic solvents and resins
  • a first method (1) describes the manufacturing of colloidal silica dispersed in methanol by removing a metal ion in an aqueous silica sol by an ion exchanging method, mixing the aqueous silica sol with methanol and then dehydrating the mixture by concentration using an ultra filtration method
  • the colloidal silica obtained by this process is unstable in a hydrophobic organic solvent or an organic resin
  • a second method (2) describes the manufacturing of an hydrophobic organosilica sol which comprises neutralizing a dispersion liquid comprising hydrophihc colloidal silica, a silylation reagent, a hydrophobic organic solvent, water, and alcohol, heating and aging the dispersion liquid and replacing the solvent by distillation (Japanese Patent Application Laid-open No 43319/1999)
  • This method requires heating at a high temperature for a long period of time for aging and replacing the solvent
  • an alkaline metal ion which causes corrosion of metal wiring in electronic materials, cannot be removed by replacing the solvent by distillation
  • a third method (3) describes the manufacturing of a silica sol dispersed in an organic solvent which comprises mixing silica sol dispersed in water with an organic solvent and dehydrating the mixture by ultra filtration
  • the silica sol obtained by method (3) does have the desired long-term dispersion stability when using a hydrophobic organic solvent as a dispersion medium
  • an object of the present invention is to provide a method for manufacturing colloidal silica that exhibits good dispersibility in an organic solvent, an organic resin, a paint containing an organic solvent or resin, is stable for a long period of time in a medium containing a hydrophobic organic solvent as a major component and has a small metal ion impurity content under mild conditions
  • the present inventors have conducted extensive studies to achieve the above object As a result, the present inventors have found that the above object can be achieved by preparing hydrophobic colloidal silica by a method comprising the steps
  • an aqueous dispersant refers to a dispersant that contains water as the mam component
  • a hydrophihc organic solvent refers to an organic solvent which is able to contain dissolved water to an amount of at least 12 wt% at 20 °C and preferably can be uniformly mixed with water at 20°C in any optional proportion
  • a hydrophobic organic solvent refers to an organic solvent that is not able to contain dissolved water in an amount of more than 12 wt% at 20°C
  • the organic solvents may comprise one single organic solvent or a mixture of organic solvents
  • colloidal silica is commonly kept as a stable dispersion in an aqueous solution
  • colloidal silica dispersed in an aqueous solvent used in the present invention colloidal silica with a number average particle diameter, determined by a dynamic light scattering method, of 1-100 nm, solid content of 10-40 wt%, and pH of 2 0-6 5 is preferable
  • examples of commercially available products include Snowtex O (manufactured by Nissan Chemical Industries, Ltd , number average particle diameter determined by dynamic light scattering method 7 nm, solid content 20 wt%, pH 2 7), Snowtex OL (manufactured by Nissan Chemical Industries, Ltd , number average particle diameter determined by dynamic light scattering method 15 nm, solid content 20
  • the aqueous dispersant is substantially replaced by a hydrophihc organic solvent
  • 80 to 99 9 % of the aqueous dispersant is replaced by a hydrophihc solvent More preferably 90 to 99 9 %
  • the concentration and dilution may be carried out at the same time (dilute during concentration) or separately depending on the operation method (for example, a batch method or a continuous method) It is preferable to use a method of performing concentration and dilution at the same time, because in that case the amount of the dilution solvent to be used in the process of the invention is small
  • the amount of hydrophihc organic solvent used for dilution is preferably 1-10 kg for 1 kg of water of aqueous colloidal silica
  • the aqueous dispersant is preferably replaced at a temperature lower than the boiling point of the hydrophihc organic solvent
  • the temperature is preferably 40-60°C
  • the circulation flow rate of the solvent converted to the linear velocity in the ultra filter membrane during operation is preferably 2 0-4 5 m/second, and still more preferably 3 0-4 0 m/second, for efficiently replacing the solvent in the ultra filter membrane and for ensuring safety during operation
  • the ultra filter membrane used in this step insofar as the ultra filter membrane does not cause problems due to pressure temperature, and an organic solvent used during the operation It is preferable to use an ultra filter membrane made of ceramics, which is not affected by temperature and pressure and exhibits superior solvent resistance
  • an ultra filter membrane with a pore diameter smaller than the particle diameter of the colloidal silica is used.
  • the fractional molecular weight, which is used as a substitute value for a pore diameter in the art, of the ultra filter membrane is preferably 3,000-1 ,000,000, still more preferably 30,000-500,000, and particularly preferably 100,000-200,000
  • the shape of the ultra filter membrane it is preferable to use a cylindrical ultra filter membrane which exhibits a high permeation flow rate and exhibits almost no clogging
  • hydrophihc organic solvent examples include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and ethylene glycol monomethyl ether, amides such as dimethylformamide and dimethylacetamide Of these, alcohols are preferable, with methanol being particularly preferable
  • alcohols are preferable, with methanol being particularly preferable
  • hydrophobic colloidal silica is prepared by mixing and reacting colloidal silica dispersed in a solvent that contains a hydrophihc organic solvent as a major solvent with a hydrophobizmg agent
  • hydrophobizmg agent used in the present invention comprises a hydrolysable silicon compound having at least one alkoxy group in the molecule or a hydrolyzate thereof
  • the compounds shown by the formula (1) can be given as preferred examples of such a hydrolysable silicon compound (R 1 O) m (R 2 ) 3-m S ⁇ -(-0-S ⁇ Me 2 -) p -(O) q -R 3 (1 )
  • R represents an alkyl group having 1-4 carbon atoms
  • R 2 and R 3 individually represent an alkyl group having 1-12 carbon atoms
  • Me represents a methyl group
  • m is an integer from 0 to 3
  • p is an integer from 0 to 50
  • q is 0 or 1
  • m+q are between 1 and 4
  • Specific examples include trimethylmethoxysilane, t ⁇ butylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methylt ⁇ methoxysilane, butylt ⁇ methoxysilane, octylt ⁇ methoxysilane, dodecylt ⁇ methoxysilane, 1 ,1 ,1- tr ⁇ methoxy-2,2,2-t ⁇ methyl-d ⁇ s ⁇ lane, hexamethyl-1 ,3-d ⁇ s ⁇ loxane, 1 ,1 1-tr ⁇ methoxy- 3,3,3-tr ⁇ methyl-1 ,3-d ⁇ s ⁇ loxane, ⁇ -t ⁇ methylsilyl- ⁇ -dimethylmethoxysilyl- polydimethylsiloxane and ⁇ -t ⁇ methylsilyl- ⁇ -t ⁇ methoxysilyl- polyd ⁇ methyls ⁇ loxanehexamethyl-1 ,3-d ⁇ s ⁇
  • the reaction between the hydrophobizmg agent and the colloidal silica preferably is carried out by mixing the hydrophobizmg agent in an amount of 0 1-100 parts by weight, and preferably 1-10 parts by weight for 100 parts by weight of the silica included in the colloidal silica, and allowing the hydrophobizmg agent to react at a temperature of 20°C or more and equal to or lower than the boiling point of the hydrophihc organic solvent, preferably at 20-60°C for 0 5-24 hours
  • the reaction mechanism in this step is not fully clarified, but it is assumed as follows It is assumed that the polar silanol groups, present on the surface of the colloidal silica dispersed in an aqueous dispersant (such as for example water) or in a hydrophihc organic solvent (that still contains a small amount of water) contribute to the stabilization of the dispersion via hydrogen bonding
  • the hydrophobizmg agent used in the present invention forms a chemical bond with these silanol groups through a condensation reaction, where
  • hydrophobic organic solvent(s) examples include ketones (for example methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone), esters (for example ethyl acetate and butyl acetate), unsaturated acrylic esters (for example butyl acrylate, methyl methacrylate, hexamethylene diacrylate, and t ⁇ methylolpropane triacrylate) aromatic hydrocarbons, (for example toluene and xylene) and ethers (for example dibutyl ether) Of these solvents ketones are preferable, with methyl ethyl ketone and methyl isobutyl ketone being particularly preferable
  • These hydrophobic organic solvents may be used either individually or in combinations of two or more Moreover, a mixture of the hydrophobic organic solvent and the hydrophihc organic solvent can also be used
  • the invention also relates to resin compositions that may comprise radiation curable components These radiation curable components may be either
  • solid content refers to the content of components excluding volatile components such as solvents from the dispersion liquid, specifically, “solid content” refers to the content of a residue (non-volatile components) obtained by drying the dispersion liquid on a hot plate at 175°C for one hour
  • the average particle diameter used in this application refers to an average particle diameter of a sample solution determined by a dynamic light scattering method using the analyser laser particle analyser system PAR-llls manufactured by Otsuka Electronics Co , Ltd Analysis conditions are light source, He-Ne laser 5 mW, measurement angle, 90°)
  • Preparation Example 1 illustrates an example of the preparation of colloidal silica dispersed in a solvent, which contains a hydrophihc organic solvent as a major solvent
  • a tank was charged with 30 kg of colloidal silica dispersed in water ("Snowtex-O” manufactured by Nissan Chemical Industries, Ltd , solid content 20 wt%, pH 2 7, specific surface area measured by BET method 226 m 2 /g, silanol group concentration on silica particles determined by methyl red adsorption method 4 1 x 10 5 mol/g, metal content in solvent determined by atomic absorption method Na, 4 6 ppm, Ca, 0 013 ppm, K, 0 011 ppm)
  • Example 1 illustrates an example of the preparation of hydrophobic colloidal silica
  • the average permeation flow rate of five times of operation was 70 kg/m 2 /hour, which required 4 hours.
  • the specific surface area of the resulting hydrophobic colloidal silica dispersed in MEK measured by the BET method was 230 m 2 /g.
  • the silanol group concentration on the silica particles determined by a methyl red adsorption method was 1.8 x 10 "5 mol/g.
  • the metal content in the solvent of the hydrophobic colloidal silica dispersed in MEK determined by an atomic absorption method was as low as 0.05 ppm of Na and 0.001 ppm of Ca and K, respectively.
  • Comparative Example 1 illustrates an example of the preparation of colloidal silica dispersed in MEK without using a hydrophobizing agent.
  • the specific surface area of the resulting colloidal silica dispersed in MEK measured by the BET method was 230 m 2 /g.
  • the silanol group concentration on the silica particles determined by a methyl red adsorption method was 3.5 x 10 "5 mol/g.
  • Comparative Example 2 illustrates an example of the preparation of colloidal silica dispersed in MEK by distillation. Comparative Example 2
  • the concentration of water and methanol in the Preparation Example 1 was performed by distillation instead of using an ultrafilter membrane. Specifically, colloidal silica dispersed in water with a solid content of 20% was concentrated to a solid content of 30% by distillation at atmospheric pressure The solvent was then replaced by distillation while controlling the amount of methanol added to be the same as the amount of distillate The amount of methanol required until the water content in the colloidal silica was 1 5% as in the Example 1 was 300 kg This was a rather large amount in comparison with the case of using the ultra filter membrane, which required 84 kg Adherence of a large amount of aggregate of silica sol was observed on the inner wall of a distillation container After the addition of 6 kg of trimethylmethoxysilane to 20 kg of the resulting colloidal silica dispersed in methanol, the mixture was hydrophobized while stirring at 60°C for 3 hours The solvent was replaced by distillation while controlling the amount of methanol added to be the same as the amount of distillate The temperature inside the container when
  • hydrophobic acrylate t ⁇ cyclodecanedimethanol diacrylate which is a hydrophobic organic compound (hereinafter may be referred to as "hydrophobic acrylate") was added to 133 g (solid content 40 g) of the resulting hydrophobic colloidal silica dispersed in MEK
  • a solution in which 60 g of t ⁇ cyclodecanedimethanol diacrylate (hydrophobic acrylate) was added to 133 g (solid content 40 g) of colloidal silica dispersed in methanol provided with no hydrophobization was prepared
  • the solutions were concentrated at 40°C and 100 mmHg under reduced pressure using a rotary evaporator until the flowabi ty of the solution disappeared or the solvent was completely removed
  • Dispersion stability was evaluated by wt% of the hydrophobic acrylate in the dispersion medium, flowabihty by naked eye observation (solution which flowed when tilted was evaluated as "Good", solution which
  • Example 1 The preparation steps in Example 1 and Comparative Examples 1 and 2, and the results of evaluation of product characteristics are shown in Table 1
  • Example 1 The hydrophobic colloidal silica dispersed in MEK obtained in Example 1 exhibited good long-term storage stability On the contrary, the dispersion liquid using the colloidal silica dispersed in MEK obtained in Comparative Examples 1 and 2 exhibited inferior long-term storage stability
  • a method of manufacturing colloidal silica which exhibits good dispersibility in an organic solvent, an organic resm, a paint containing an organic solvent or resm, or the like, is stable for a long period of time in a medium containing a hydrophobic organic solvent as a major component, and has a low metal impurity content under mild conditions can be provided

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  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The invention relates to a new method of manufacturing colloidal silica which exhibits good dispersibility in an organic solvent, an organic resin, a paint containing an organic solvent or resin, or the like, is stable for a long period of time in a medium containing a hydrophobic organic solvent as a major component, and has a low metal ion impurity content under mild conditions. The new method comprises the steps of taking a colloidal silica dispersed in an aqueous dispersant; replacing a substantial amount of the aqueous dispersant with one or more hydrophilic organic colvent(s); preparing hydrophobic colloidal silica by reacting the colloidal silica with a hydrophobizing agent; and finally replacing the liquid phase of the dispersion comprising the organic hydrophilic solvent with one or more hydrophobic organic solvent(s) to obtain a hydrophobic colloidal silica dispersed in a hydrophobic organic solvent.

Description

METHOD FOR MANUFACTURING HYDROPHOBIC COLLOIDAL SILICA
The present invention relates to a method for manufacturing hydrophobic colloidal silica, the silica dispersion in a hydrophobic organic solvent or resin and the use of the colloidal silica in organic hydrophobic solvents and resins
Several manufacturing methods are known in the art for preparing colloidal silica in which silica particles are dispersed in an organic solvent For example, the following methods are disclosed
A first method (1) describes the manufacturing of colloidal silica dispersed in methanol by removing a metal ion in an aqueous silica sol by an ion exchanging method, mixing the aqueous silica sol with methanol and then dehydrating the mixture by concentration using an ultra filtration method
(Japanese Patent Application Laid-open No 167813/1990) The colloidal silica obtained by this process is unstable in a hydrophobic organic solvent or an organic resin
A second method (2) describes the manufacturing of an hydrophobic organosilica sol which comprises neutralizing a dispersion liquid comprising hydrophihc colloidal silica, a silylation reagent, a hydrophobic organic solvent, water, and alcohol, heating and aging the dispersion liquid and replacing the solvent by distillation (Japanese Patent Application Laid-open No 43319/1999) This method requires heating at a high temperature for a long period of time for aging and replacing the solvent Moreover an alkaline metal ion which causes corrosion of metal wiring in electronic materials, cannot be removed by replacing the solvent by distillation
A third method (3) describes the manufacturing of a silica sol dispersed in an organic solvent which comprises mixing silica sol dispersed in water with an organic solvent and dehydrating the mixture by ultra filtration
(Japanese Patent Application Laid-open No 8614/1984) The silica sol obtained by method (3) does have the desired long-term dispersion stability when using a hydrophobic organic solvent as a dispersion medium
The present invention has been achieved in view of the above problems in the prior art Specifically, an object of the present invention is to provide a method for manufacturing colloidal silica that exhibits good dispersibility in an organic solvent, an organic resin, a paint containing an organic solvent or resin, is stable for a long period of time in a medium containing a hydrophobic organic solvent as a major component and has a small metal ion impurity content under mild conditions
The present inventors have conducted extensive studies to achieve the above object As a result, the present inventors have found that the above object can be achieved by preparing hydrophobic colloidal silica by a method comprising the steps
(a) taking a colloidal silica dispersed in an aqueous dispersant
(b) replacing a substantial amount of the aqueous dispersant with one or more hydrophihc organic solvent(s)
(c) preparing hydrophobic colloidal silica by reacting the colloidal silica with an hydrophobizmg agent and
(d) replacing the liquid phase of the dispersion comprising the organic hydrophihc solvent with one or more hydrophobic organic solvent(s) to obtain hydrophobic colloidal silica dispersed in a hydrophobic organic solvent
Detailed description of the invention
Preferred embodiments of the present invention will be described in detail below
In the present invention an aqueous dispersant refers to a dispersant that contains water as the mam component A hydrophihc organic solvent refers to an organic solvent which is able to contain dissolved water to an amount of at least 12 wt% at 20 °C and preferably can be uniformly mixed with water at 20°C in any optional proportion A hydrophobic organic solvent refers to an organic solvent that is not able to contain dissolved water in an amount of more than 12 wt% at 20°C The organic solvents may comprise one single organic solvent or a mixture of organic solvents
Colloidal silica is commonly kept as a stable dispersion in an aqueous solution As examples of colloidal silica dispersed in an aqueous solvent used in the present invention, colloidal silica with a number average particle diameter, determined by a dynamic light scattering method, of 1-100 nm, solid content of 10-40 wt%, and pH of 2 0-6 5 is preferable Examples of commercially available products include Snowtex O (manufactured by Nissan Chemical Industries, Ltd , number average particle diameter determined by dynamic light scattering method 7 nm, solid content 20 wt%, pH 2 7), Snowtex OL (manufactured by Nissan Chemical Industries, Ltd , number average particle diameter determined by dynamic light scattering method 15 nm, solid content 20
Figure imgf000004_0001
During the step (b) of the present invention, the aqueous dispersant is substantially replaced by a hydrophihc organic solvent Preferably 80 to 99 9 % of the aqueous dispersant is replaced by a hydrophihc solvent More preferably 90 to 99 9 % of the aqueous dispersant is replaced by a hydrophihc solvent Preferably the replacement of the aqueous dispersant is performed using an ultra filter membrane Specifically, a container equipped with a pressure gauge flow meter, ultra filter membrane, and circulating pump is charged with colloidal silica dispersed in water The dispersant is preferably replaced using the ultra filter membrane while circulating the colloidal silica at a predetermined temperature and a predetermined circulation flow rate (or linear velocity) Preferably a part of the dispersant is removed before replacement with the organic hydrophihc solvent in a batch wise concentration step (by for example filtering or precipitation) The dispersant is replaced by diluting with a predetermined amount of a hydrophihc organic solvent, to prepare colloidal silica dispersed in a hydrophihc organic solvent with a solid content of preferably 20-50-wt% and a water content determined by the Karl Fischer method of preferably 0 1-10 wt% If the water content is less than 0 1 wt%, viscosity may increase during storage If the water content exceeds 10 wt%, a reaction with the hydrophobizmg agent as described later may become nonuniform The dilution step may be carried out batch wise and be repeated as many times as necessary, or it may be carried out continuously together with the removal of solvent
The concentration and dilution may be carried out at the same time (dilute during concentration) or separately depending on the operation method (for example, a batch method or a continuous method) It is preferable to use a method of performing concentration and dilution at the same time, because in that case the amount of the dilution solvent to be used in the process of the invention is small The amount of hydrophihc organic solvent used for dilution is preferably 1-10 kg for 1 kg of water of aqueous colloidal silica
The aqueous dispersant is preferably replaced at a temperature lower than the boiling point of the hydrophihc organic solvent When using methanol, which is the preferable hydrophihc organic solvent, the temperature is preferably 40-60°C The circulation flow rate of the solvent converted to the linear velocity in the ultra filter membrane during operation is preferably 2 0-4 5 m/second, and still more preferably 3 0-4 0 m/second, for efficiently replacing the solvent in the ultra filter membrane and for ensuring safety during operation There are no specific limitations to the ultra filter membrane used in this step insofar as the ultra filter membrane does not cause problems due to pressure temperature, and an organic solvent used during the operation It is preferable to use an ultra filter membrane made of ceramics, which is not affected by temperature and pressure and exhibits superior solvent resistance
In the present invention, preferably an ultra filter membrane with a pore diameter smaller than the particle diameter of the colloidal silica is used The fractional molecular weight, which is used as a substitute value for a pore diameter in the art, of the ultra filter membrane is preferably 3,000-1 ,000,000, still more preferably 30,000-500,000, and particularly preferably 100,000-200,000
Although there are no specific limitations to the shape of the ultra filter membrane, it is preferable to use a cylindrical ultra filter membrane which exhibits a high permeation flow rate and exhibits almost no clogging
Examples of hydrophihc organic solvent are alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and ethylene glycol monomethyl ether, amides such as dimethylformamide and dimethylacetamide Of these, alcohols are preferable, with methanol being particularly preferable These hydrophihc organic solvents may be used either individually or in combinations of two or more The hydrophobic colloidal silica is prepared by mixing and reacting colloidal silica dispersed in a solvent that contains a hydrophihc organic solvent as a major solvent with a hydrophobizmg agent
(2) Hydrophobizmg agent The hydrophobizmg agent used in the present invention comprises a hydrolysable silicon compound having at least one alkoxy group in the molecule or a hydrolyzate thereof
The compounds shown by the formula (1) can be given as preferred examples of such a hydrolysable silicon compound (R1O)m(R2)3-mSι-(-0-SιMe2-)p-(O)q-R3 (1 )
wherein R represents an alkyl group having 1-4 carbon atoms, R2 and R3 individually represent an alkyl group having 1-12 carbon atoms Me represents a methyl group, m is an integer from 0 to 3, p is an integer from 0 to 50, q is 0 or 1 and m+q are between 1 and 4
Specific examples include trimethylmethoxysilane, tπbutylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltπmethoxysilane, butyltπmethoxysilane, octyltπmethoxysilane, dodecyltπmethoxysilane, 1 ,1 ,1- trιmethoxy-2,2,2-tπmethyl-dιsιlane, hexamethyl-1 ,3-dιsιloxane, 1 ,1 1-trιmethoxy- 3,3,3-trιmethyl-1 ,3-dιsιloxane, α-tπmethylsilyl-ω-dimethylmethoxysilyl- polydimethylsiloxane and α-tπmethylsilyl-ω-tπmethoxysilyl- polydιmethylsιloxanehexamethyl-1 ,3-dιsιlazane Of these compounds, silicon compounds containing one alkyl group in the molecule, for example trimethylmethoxysilane, tπbutylmethoxysilane, and α-trιmethylsιlyl-ω- dimethylmethoxysilyl-polydimethylsiloxane are preferable Most preferable are silicon compounds of which the boiling point at ordinary pressure is 150°C or less, for example trimethylmethoxysilane The hydrophobizmg agent used in the present invention may also be a hydrolyzate of the above hydrolysable silicon compound
The reaction between the hydrophobizmg agent and the colloidal silica preferably is carried out by mixing the hydrophobizmg agent in an amount of 0 1-100 parts by weight, and preferably 1-10 parts by weight for 100 parts by weight of the silica included in the colloidal silica, and allowing the hydrophobizmg agent to react at a temperature of 20°C or more and equal to or lower than the boiling point of the hydrophihc organic solvent, preferably at 20-60°C for 0 5-24 hours The reaction mechanism in this step is not fully clarified, but it is assumed as follows It is assumed that the polar silanol groups, present on the surface of the colloidal silica dispersed in an aqueous dispersant (such as for example water) or in a hydrophihc organic solvent (that still contains a small amount of water) contribute to the stabilization of the dispersion via hydrogen bonding The hydrophobizmg agent used in the present invention forms a chemical bond with these silanol groups through a condensation reaction, whereby the surface of the silica is coated with hydrophobic organic groups As a result, the silanol group concentration on the surface of the silica decreases, and the number of hydrophobic groups increases Therefore, silica particles having a hydrophobic surface and exhibiting dispersion stability in the hydrophihc organic solvent and in hydrophobic organic solvents are formed The silanol group concentration on the surface of the colloidal silica dispersed in the hydrophihc organic solvent is preferably from 2 5 x 105 to 5 0 x 105 mol/g Silica dispersions that already contain these amounts of silanol groups at the surface may also be used in the method of the present invention A suitable example of a commercial available product is a methanol silica sol manufactured by Nissan Chemical Industries Ltd The silanol group concentration on the silica particles obtained by the reaction with the hydrophobizmg agent in this step is preferably reduced to a concentration from 1 5 x 10"5 to 2 5 x 105 mol/g by mixing with the hydrophobizmg agent If the silanol group concentration exceeds 2 5 x 10 5 mol/g, stability in the hydrophobic organic solvent may decrease If the concentration is less than 1 5 x 105 mol/g stability in the hydrophihc organic solvent may decrease After reacting the hydrophobic colloidal silica with a hydrophobizmg agent, the mixture containing the hydrophihc organic solvent, aqueous dispersant and reaction components of the hydrophobic colloidal silica dispersion is essentially replaced by one or more hydrophobic organic solvent(s) Preferably the replacement of the hydrophihc organic solvent is carried out by using an ultra filter membrane in the same way as described before The solvent is replaced preferably at the boiling point of the hydrophobic organic solvent or lower, and still more preferably at 40-80°C The final hydrophobic colloidal silica in the hydrophobic organic solvent(s) preferably contains 0 1-10 wt% water and preferably 0 1-10 wt% methanol, and still more preferably 0 1-5-wt% methanol If the methanol content is less than 0 1 wt%, viscosity may increase during preparation or storage If the methanol content exceeds 10 wt%, dispersibihty and uniformity in a hydrophobic organic material may decrease The water content in the hydrophobic colloidal silica dispersed in the hydrophobic organic solvent is preferably 5 wt% or less, and still more preferably 2 wt% or less If the water content exceeds 5 wt%, viscosity may increase during storage
Examples of suitable hydrophobic organic solvent(s) are ketones (for example methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone), esters (for example ethyl acetate and butyl acetate), unsaturated acrylic esters (for example butyl acrylate, methyl methacrylate, hexamethylene diacrylate, and tπmethylolpropane triacrylate) aromatic hydrocarbons, (for example toluene and xylene) and ethers (for example dibutyl ether) Of these solvents ketones are preferable, with methyl ethyl ketone and methyl isobutyl ketone being particularly preferable These hydrophobic organic solvents may be used either individually or in combinations of two or more Moreover, a mixture of the hydrophobic organic solvent and the hydrophihc organic solvent can also be used The invention also relates to resin compositions that may comprise radiation curable components These radiation curable components may be either radically curable or cationically curable components Examples of radically curable components are compounds containing at least one polymerizable unsaturated group Either polyunsaturated organic compounds containing two or more polymerizable unsaturated groups and/or monounsaturated organic compounds containing one polymerizable unsaturated group can be used as the polymerizable unsaturated compound Examples of such components are (meth)acrylates and vinylethers Examples of cationically curable components are epoxy compounds The dispersions may be used in different applications like (hard)coatιngs, as adhesives, in molding and in stereolithography Use of the dispersions of the present invention in resin compositions gives many advantages for example better mechanical properties and improved storage stability of the resm compositions The colloidal silica may also be modified to contain polymerizable groups in order to make the dispersion co reactive with the radiation curable components of the resin compositions Examples of ways to modify the silica particles have been published in WO97/12942, which is incorporated herein by reference
Examples The present invention will be described in more detail by examples, which should not be construed as limiting the present invention In the following examples, "parts" and "%" respectively refer to "parts by weight" and "wt%" unless otherwise indicated
In the present invention, "solid content" refers to the content of components excluding volatile components such as solvents from the dispersion liquid, specifically, "solid content" refers to the content of a residue (non-volatile components) obtained by drying the dispersion liquid on a hot plate at 175°C for one hour
The average particle diameter used in this application refers to an average particle diameter of a sample solution determined by a dynamic light scattering method using the analyser laser particle analyser system PAR-llls manufactured by Otsuka Electronics Co , Ltd Analysis conditions are light source, He-Ne laser 5 mW, measurement angle, 90°)
(1) Preparation of colloidal silica dispersed in a solvent which contains a hydrophihc organic solvent as a major solvent
Preparation Example 1 illustrates an example of the preparation of colloidal silica dispersed in a solvent, which contains a hydrophihc organic solvent as a major solvent
Preparation Example 1
A tank was charged with 30 kg of colloidal silica dispersed in water ("Snowtex-O" manufactured by Nissan Chemical Industries, Ltd , solid content 20 wt%, pH 2 7, specific surface area measured by BET method 226 m2/g, silanol group concentration on silica particles determined by methyl red adsorption method 4 1 x 105 mol/g, metal content in solvent determined by atomic absorption method Na, 4 6 ppm, Ca, 0 013 ppm, K, 0 011 ppm) The colloidal silica was concentrated at 50°C at a circulation flow rate of 50 l/mιnute and pressure of 1 kg/cm2 using an ultra filter membrane module (manufactured by Tπ Tec Corporation) and an ultra filter membrane made of alumina ("Ceramic UF Element" manufactured by NGK Insulators, Ltd , specification 4 mmΦ, 19 pores length, 1 m, fractional molecular weight = 150,000, membrane area = 0 24 m2) After 30 minutes 10 kg of filtrate was discharged to obtain a residue with a solid content of 30-wt% The average permeation flow rate (membrane permeation weight per unit area of ultra filter membrane and unit time) before concentration was 90 kg/m2/hour After concentration, the average permeation flow rate was 55 kg/m2/hour The number average particle diameter determined by a dynamic light scattering method before and after concentration was 11 nm After the addition of 14 kg of methanol to the above colloidal silica, the mixture was then concentrated at 50°C at a circulation flow rate of 50 l/mιnute and pressure of 1 kg/cm2 using the above ultra filter membrane module and ultra filter membrane to discharge 14 kg of filtrate This step was repeated six times to prepare 20 kg of colloidal silica dispersed in methanol with a solid content of 30 wt%, water content determined by the Karl Fischer method of 1 5 wt%, and number average particle diameter determined by a dynamic light scattering method of 11 nm The average permeation flow rate of six times of operation was 60 kg/m2/hour, requiring six hours for the operation to complete The specific surface area of the resulting colloidal silica dispersed in methanol measured by the BET method was 237 m2/g The silently group concentration on the silica particles determined by a methyl red adsorption method was 3 5 x 105 mol/g (2) Preparation of hydrophobic colloidal silica
Example 1 illustrates an example of the preparation of hydrophobic colloidal silica
Example 1
0 6 kg of trimethylmethoxysilane (manufactured by Toray-Dow Corning Siiicone Co Ltd ) was added to 20 kg of the colloidal silica dispersed in methanol prepared in the Preparation Example 1 The mixture was then stirred at 60°C for three hours while heating The number average particle diameter determined by a dynamic light scattering method was 11 nm, which was the same value as that before stirring The specific surface area of the resulting hydrophobic colloidal silica dispersed in methanol measured by a BET method was 240 m2/g The silanol group concentration on the silica particles determined by a methyl red adsorption method was 2 1 x 10"5 mol/g
After the addition of 14 kg of methyl ethyl ketone (MEK) to the above hydrophobic colloidal silica, the mixture was then concentrated at 50°C at a circulation flow rate of 50 l/mιnute and pressure of 1 kg/cm2 using the above ultra filter membrane module and ultra filter membrane to discharge 14 kg of filtrate This step was repeated five times to prepare 20 kg of hydrophobic colloidal silica dispersed in MEK with a solid content of 30 wt%, water content determined by the Karl Fischer method of 0 3 wt%, methanol content determined by gas chromatography (GC) of 3 2 wt%, and number average particle diameter determined by a dynamic light scattering method of 11 nm. The average permeation flow rate of five times of operation was 70 kg/m2/hour, which required 4 hours. The specific surface area of the resulting hydrophobic colloidal silica dispersed in MEK measured by the BET method was 230 m2/g. The silanol group concentration on the silica particles determined by a methyl red adsorption method was 1.8 x 10"5 mol/g. The metal content in the solvent of the hydrophobic colloidal silica dispersed in MEK determined by an atomic absorption method was as low as 0.05 ppm of Na and 0.001 ppm of Ca and K, respectively. (3) Preparation of colloidal silica dispersed in MEK without using hydrophobizing agent
Comparative Example 1 illustrates an example of the preparation of colloidal silica dispersed in MEK without using a hydrophobizing agent.
Comparative Example 1
14 kg of methyl ethyl ketone (MEK) was added to 20 kg of the colloidal silica dispersed in methanol prepared in the Preparation Example 1 without performing hydrophobization. The mixture was concentrated at 50°C at a circulation flow rate of 50 l/minute and pressure of 1 kg/cm2 using the above ultra filter membrane module and ultra filter membrane to discharge 14 kg of filtrate. This step was repeated five times to prepare 20 kg of colloidal silica dispersed in MEK with a solid content of 30 wt%, water content determined by the Karl Fischer method of 0.3 wt%, methanol content determined by gas chromatography (GC) of 3.2 wt%, and number average particle diameter determined by a dynamic light scattering method of 22 nm. The specific surface area of the resulting colloidal silica dispersed in MEK measured by the BET method was 230 m2/g. The silanol group concentration on the silica particles determined by a methyl red adsorption method was 3.5 x 10"5 mol/g.
(4) Preparation of colloidal silica dispersed in MEK by distillation Comparative Example 2 illustrates an example of the preparation of colloidal silica dispersed in MEK by distillation. Comparative Example 2
The concentration of water and methanol in the Preparation Example 1 was performed by distillation instead of using an ultrafilter membrane. Specifically, colloidal silica dispersed in water with a solid content of 20% was concentrated to a solid content of 30% by distillation at atmospheric pressure The solvent was then replaced by distillation while controlling the amount of methanol added to be the same as the amount of distillate The amount of methanol required until the water content in the colloidal silica was 1 5% as in the Example 1 was 300 kg This was a rather large amount in comparison with the case of using the ultra filter membrane, which required 84 kg Adherence of a large amount of aggregate of silica sol was observed on the inner wall of a distillation container After the addition of 6 kg of trimethylmethoxysilane to 20 kg of the resulting colloidal silica dispersed in methanol, the mixture was hydrophobized while stirring at 60°C for 3 hours The solvent was replaced by distillation while controlling the amount of methanol added to be the same as the amount of distillate The temperature inside the container when the methanol content in the colloidal silica was 3 2% as in the Example 1 was 76°C and the amount of MEK added was 33 kg Water content determined by the Karl Fischer method was approximately the same as that in the Example 1 Adherence of a large amount of aggregate of silica sol was observed on the inner wall of the distillation container The resulting solution of the hydrophobic colloidal silica dispersed in MEK was treated using the above ultra filter membrane as in Example 1 The metal content in the permeation liquid determined by an atomic absorption method was approximately the same as that in the raw material colloidal silica dispersed in water (5) Evaluation of product characteristics
A solution in which 60 g of tπcyclodecanedimethanol diacrylate which is a hydrophobic organic compound (hereinafter may be referred to as "hydrophobic acrylate") was added to 133 g (solid content 40 g) of the resulting hydrophobic colloidal silica dispersed in MEK was prepared As a comparative solution, a solution in which 60 g of tπcyclodecanedimethanol diacrylate (hydrophobic acrylate) was added to 133 g (solid content 40 g) of colloidal silica dispersed in methanol provided with no hydrophobization was prepared The solutions were concentrated at 40°C and 100 mmHg under reduced pressure using a rotary evaporator until the flowabi ty of the solution disappeared or the solvent was completely removed Dispersion stability was evaluated by wt% of the hydrophobic acrylate in the dispersion medium, flowabihty by naked eye observation (solution which flowed when tilted was evaluated as "Good", solution which did not flow was evaluated as "Bad"), viscosity at 25°C (measured by using a rotational viscometer B8H manufactured by TOKIMEC Co , Ltd , revolution per minute, 50, rotor, HHM3), and transparency by naked eye observation The resulting hydrophobic colloidal silica dispersed in MEK was allowed to stand in an airtight container at 50°C for one month Long-term storage stability was evaluated by the presence or absence of coloration and precipitation of particles by naked eye observation, the presence or absence of the increase in the particle diameter by a dynamic light scattering method, and the presence or absence of the increase in the viscosity
The preparation steps in Example 1 and Comparative Examples 1 and 2, and the results of evaluation of product characteristics are shown in Table 1
Figure imgf000014_0002
MEK: methyl ethyl ketone
Figure imgf000014_0001
As is clear from Table 1 , the dispersion liquid using the hydrophobic colloidal silica dispersed in MEK obtained in Example 1 and Comparative Example 2 exhibited good dispersibility in a hydrophobic organic medium On the contrary, the dispersion liquid using the colloidal silica dispersed in MEK obtained in Comparative Example 1 that was not hydrophobized exhibited inferior dispersibility
The hydrophobic colloidal silica dispersed in MEK obtained in Example 1 exhibited good long-term storage stability On the contrary, the dispersion liquid using the colloidal silica dispersed in MEK obtained in Comparative Examples 1 and 2 exhibited inferior long-term storage stability
As described above, according to the present invention a method of manufacturing colloidal silica which exhibits good dispersibility in an organic solvent, an organic resm, a paint containing an organic solvent or resm, or the like, is stable for a long period of time in a medium containing a hydrophobic organic solvent as a major component, and has a low metal impurity content under mild conditions can be provided

Claims

A method for manufacturing hydrophobic colloidal silica comprising the following steps
(a) taking a colloidal silica dispersed in an aqueous dispersant
(b) replacing a substantial amount of the aqueous dispersant with one or more hydrophihc organic solvent(s)
(c) preparing hydrophobic colloidal silica by reacting the colloidal silica with an hydrophobizing agent
(d) replacing the liquid phase of the dispersion comprising the organic hydrophihc solvent with one or more hydrophobic organic solvent(s) to obtain hydrophobic colloidal silica dispersed in a hydrophobic organic solvent The method according to claim 1, wherein 90-99 9 % of the aqueous dispersant is replaced by the hydrophihc organic solvent(s) The method for manufacturing hydrophobic colloidal silica according to claim 1 or 2, wherein the hydrophobizing agent comprises a hydrolyzable silicon compound having at least one alkoxy group in the molecule or a hydrolyzate thereof The method according to any one of claims 1 to 3, wherein the hydrophobizing agent comprises a hydrolyzable silicon compound represented by the following formula (1)
(R1O)m(R2)3-mSι-(-0-SιMe2-)p-(0)q-R3 (1)
wherein R1 represents an alkyl group having 1-4 carbon atoms, R2 and R3 individually represent an alkyl group having 1-12 carbon atoms, Me represents a methyl group, m is an integer from 0 to 3, p is an integer from 0 to 50, q is 0 or 1 and m+q is between 1 and 4 The method according to any one of claims 1 to 4, wherein the hydrolyzable silicon compound is trimethylmethoxysilane tπbutylmethoxysilane, or α-tπmethylsilyl-ω-dimethylmethoxysilyl- polydimethylsiloxane The method according to any one of claims 1-5, wherein the hydrophihc organic solvent of the colloidal silica is an alcohol The method according to anyone of claims 1-6, wherein the hydrophihc organic solvent is methanol The method according to any one of claims 1 to 7, wherein the hydrophobic organic solvent contains at least one solvent selected from the following groups ketones, esters, ethers or aromatic hydrocarbons The method according to anyone of claims 1-8, wherein the hydrophobic organic solvent is methyl ethyl ketone and/or methyl isobutyl ketone The method according to any one of claims 1-9, wherein the amount of hydrophihc organic solvent(s) after step (d) is between 0 1 - 10 0 wt % The method according to any one of claims 1 to 10, wherein the solvent replacement under steps b and d is achieved using an ultrafilter membrane Hydrophobic colloidal silica dispersed in a hydrophobic solvent obtain able according to anyone of the method claims 1-11 Use of the hydrophobic colloidal silica as obtainable according to the methods of any of claims 1-11 in resm compositions
PCT/NL2001/000063 2000-01-28 2001-01-29 Method for manufacturing hydrophobic colloidal silica WO2001055030A2 (en)

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JP2001213617A (en) 2001-08-07
JP4631119B2 (en) 2011-02-16
DE60107049D1 (en) 2004-12-16
KR20020074479A (en) 2002-09-30
US20030035888A1 (en) 2003-02-20

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