WO2020179555A1 - コロイダルシリカ及びその製造方法 - Google Patents
コロイダルシリカ及びその製造方法 Download PDFInfo
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- WO2020179555A1 WO2020179555A1 PCT/JP2020/007574 JP2020007574W WO2020179555A1 WO 2020179555 A1 WO2020179555 A1 WO 2020179555A1 JP 2020007574 W JP2020007574 W JP 2020007574W WO 2020179555 A1 WO2020179555 A1 WO 2020179555A1
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- the present invention relates to colloidal silica and a method for producing the same, and particularly to colloidal silica containing modified silica particles and a method for producing the same.
- "atypical” means having a bent structure and / or a branched structure
- the bent structure is a particle formed by connecting three or more particles in a row and is not a straight line.
- the branched structure is a particle in which four or more particles are bonded and is not in a row (has branches).
- Colloidal silica is obtained by dispersing silica fine particles in a medium such as water, and is used as a physical property improving agent in the fields of paper, fiber, steel, etc., and also as an abrasive for electronic materials such as semiconductor wafers. Has been done.
- the silica particles dispersed in the colloidal silica used for such an application are required to have high purity and compactness.
- Patent Document 1 a production method in which a hydrolysis solution obtained by hydrolyzing an alkoxysilane is added to a mother liquor containing an alkali catalyst or the like is disclosed (for example, Patent Document 1). reference).
- Patent Document 2 does not describe that modified silica particles are obtained, and colloidal silica obtained by the manufacturing method described in Patent Document 2 is difficult to obtain high abrasiveness, and thus is difficult to obtain. There is room for consideration for further improvement.
- the present inventors, etc. have colloidal silica produced by the production methods described in Patent Documents 1 and 2, because the number of alkoxy groups per unit area of silica particles is small, so that the polishability is high, but it is an object to be polished. It has been found that there is a problem that defects on the surface of the substrate and the like increase. As a result of diligent studies, the present inventors have succeeded in developing silica having excellent abrasiveness and a high amount of alkoxy groups. Then, he came up with the idea that such colloidal silica can be suitably used as an abrasive and can solve the above-mentioned problems brilliantly, and has reached the present invention.
- the present invention is excellent in compactness, contains a high-purity deformed silica particles having a high amount of alkoxy groups per unit area, colloidal silica excellent in polishability, and the colloidal silica can be easily produced.
- An object of the present invention is to provide a manufacturing method capable of reducing the manufacturing cost.
- the present inventor contains silica particles having a bent structure and/or a branched structure, and the true specific gravity of the silica particles is 1.95 or more.
- the value of the ratio (m / n) of the group content m (ppm) to the average primary particle diameter n (nm) is 200 or more, and it is within an arbitrary field of view at 200,000 times observed by a scanning electron microscope. It has been found that the above object can be achieved by colloidal silica containing 15% or more of silica particles having a bent structure and / or a branched structure in the number of particles, and the present invention has been completed.
- the present invention relates to the following colloidal silica and a method for producing the same.
- the silica particles have a ratio (m/n) of the content m (ppm) of alkoxy groups and the average primary particle diameter n (nm) of 200 or more, Among the number of particles in an arbitrary field of view at 200,000 times observed with a scanning electron microscope, 15% or more of silica particles having a bent structure and / or a branched structure are contained.
- Colloidal silica characterized by that. 2. Item 2.
- the colloidal silica according to Item 1 wherein the true specific gravity of the silica particles is 1.95 or more and 2.20 or less.
- the silica particles contain at least one amine selected from the group consisting of primary amines, secondary amines and tertiary amines (however, hydroxyl groups are excluded as substituents) in an amount of 5 ⁇ mol or more per 1 g of silica particles.
- Item 1 or 2 the colloidal silica. 4.
- the following general formula (1) -(CH 2 ) k- R 5 (1) In formula (1), k represents an arbitrary integer greater than or equal to 0, and R 5 represents an arbitrary functional group.) Item 4.
- Item 2. The colloidal silica according to any one of Items 1 to 4, which has a cationic organic functional group on the surface of the silica particles. 6.
- Item 6. The colloidal silica according to Item 5, which has an amino group on the surface of the silica particles. 7.
- Item 2. The colloidal silica according to any one of Items 1 to 4, which has an anionic organic functional group on the surface of the silica particles.
- Item 8 The colloidal silica according to Item 7, wherein the surface of the silica particles has a sulfo group. 9.
- Step 1 of preparing a mother liquor containing an alkali catalyst and water, (2) Step 2 of preparing a mixed solution by adding alkoxysilane to the mother liquor, and (3) Step 3 of preparing a seed particle dispersion liquid by adding an alkali catalyst to the mixed liquid Is a method for producing colloidal silica having the above in this order.
- the alkaline catalyst is at least one amine selected from the group consisting of primary amine, secondary amine and tertiary amine (provided that a hydroxyl group is excluded as a substituent).
- a method for producing colloidal silica which is characterized by the above. 10. Item 11.
- the production method according to Item 9 or 10 which includes, after Step 3, (4) Step 4 of adding water and alkoxysilane to the seed particle dispersion liquid.
- Any of items 9 to 11, wherein a molar ratio (s2/c1) between the addition amount s2 (mol) of the alkoxysilane and the amount c2 (mol) of the alkali catalyst in the mother liquor in the step 2 is 800 or more.
- the manufacturing method described in Crab. 12 The molar ratio (s2/c3) between the addition amount s2 (mol) of the alkoxysilane in the step 2 and the addition amount c3 (mol) of the alkali catalyst in the step 3 is 185 or less.
- the colloidal silica of the present invention is excellent in denseness, contains deformed silica particles having a high amount of alkoxy groups per unit area with high purity, and can exhibit excellent polishability.
- the method for producing colloidal silica of the present invention can easily produce the colloidal silica, and the production cost can be reduced.
- the colloidal silica of the present invention contains 15% or more of silica particles having a bent structure and / or a branched structure in the number of particles in an arbitrary field of view at 200,000 times observed with a scanning electron microscope, the deformed silica particles. Is contained in high purity and has excellent polishing property. Further, since the colloidal silica of the present invention has a true specific gravity of silica particles of 1.95 or more, it is excellent in denseness and polishing property.
- the value of the ratio (m / n) of the content m (ppm) of the alkoxy group of the silica particles to the average primary particle diameter n (nm) is 200 or more, and the unit area is The amount of alkoxy per unit is high.
- a mother liquor containing an alkali catalyst and water is prepared in step 1, and an alkoxysilane is added to the mother liquor in step 2 to prepare a mixed solution. It is possible to easily produce colloidal silica containing silica particles having a high density of alkoxy groups per unit area, which is not once hydrolyzed with alkoxysilane, and the production cost is reduced due to the small number of steps. ing.
- the alkoxysilane is added in step 2 to the mother liquor containing the alkali catalyst and water prepared in step 1, and then the alkali catalyst is further added in step 3 to prepare seed particles. Therefore, the seed particles are deformed, and colloidal silica containing the deformed silica particles with high purity and excellent in abrasiveness can be easily manufactured, and the manufacturing cost is reduced.
- colloidal Silica The colloidal silica of the present invention is colloidal silica containing silica particles having a bent structure and/or a branched structure, the true specific gravity of the silica particles is 1.95 or more, and the silica particles are alkoxy.
- the value of the ratio (m/n) of the group content m (ppm) to the average primary particle diameter n (nm) is 200 or more, and it is within an arbitrary visual field at 200,000 times observed with a scanning electron microscope. It is characterized by containing 15% or more of silica particles having a bent structure and / or a branched structure in the number of particles of.
- the silica particles preferably contain at least one amine selected from the group consisting of primary amines, secondary amines and tertiary amines.
- the amine is not particularly limited and is represented by the following general formula (X).
- NR a R b R c (X) (In the formula, R a , R b , and R c represent an optionally substituted alkyl group having 1 to 12 carbon atoms or hydrogen. provided that all of R a , R b , and R c are hydrogen, that is, Ammonia is excluded.)
- R a , R b , and R c may be the same or different.
- R a , R b , and R c may be linear, branched, or cyclic.
- the carbon number of the linear or branched alkyl group may be 1 to 12, preferably 1 to 8, and more preferably 1 to 6.
- Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.
- Examples of the branched alkyl group include an isopropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, and a 2,2-dimethylpropyl group.
- Preferred linear or branched alkyl groups are n-propyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group and the like.
- the carbon number of the cyclic alkyl group may be, for example, 3 to 12, and is preferably 3 to 6.
- Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.
- a preferred cyclic alkyl group is a cyclohexyl group.
- Alkyl groups may be substituted in R a , R b , and R c in the above general formula (X).
- the number of substituents may be, for example, 0, 1, 2, 3, 4, etc., preferably 0, 1 or 2, and more preferably 0 or 1. ..
- An alkyl group having 0 substituents is an alkyl group that is not substituted.
- the substituent is, for example, 1 substituted with an alkoxy group having 1 to 3 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, isopropoxy group), amino group, or a linear alkyl group having 1 to 4 carbon atoms.
- Examples thereof include a secondary amino group, an amino group di-substituted with a linear alkyl group having 1 to 4 carbon atoms (for example, a dimethylamino group, a din-butylamino group, etc.), an amino group not substituted, and the like.
- a hydroxyl group is excluded as a substituent.
- the substituents may be the same or different.
- R a , R b and R c in the above general formula (X) are linear or branched alkyl groups having 1 to 8 carbon atoms (preferably 1 to 6 carbon atoms) which may be substituted.
- R a , R b and R c are linear or branched alkyl groups having 1 to 8 carbon atoms (preferably 1 to 6 carbon atoms) which may be substituted with an alkoxy group having 1 to 3 carbon atoms. Is.
- R a , R b , and R c may not be substituted.
- R a , R b and R c are each an unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched carbon atom having 1 to 12 carbon atoms substituted with an alkoxy group. It is an alkyl group of 12.
- the amine in one embodiment include at least one amine selected from the group consisting of 3-ethoxypropylamine, pentylamine, hexylamine, dipropylamine, triethylamine and the like. Of these, 3-ethoxypropylamine, dipropylamine, and triethylamine are more preferable. Further, 3-ethoxypropylamine is preferable in that the content of the deformed silica particles can be further increased.
- the above amine may be used alone or in combination of two or more.
- the content of at least one amine selected from the group consisting of primary amines, secondary amines and tertiary amines (excluding hydroxyl groups as substituents) in the silica particles is 1 particle g of silica. 5 ⁇ mol or more is preferable, and 10 ⁇ mol or more is more preferable.
- the content of the amine is preferably 100 ⁇ mol or less, and more preferably 90 ⁇ mol or less, per 1 g of silica particles.
- the upper limit of the amine content is in the above range, the silica particles are more likely to be deformed.
- the amine content can be measured by the following method. That is, after centrifuging the colloidal silica at 215000 G for 90 minutes, the supernatant is discarded and the solid content is vacuum dried at 60 ° C. for 90 minutes. 0.5 g of the obtained dry silica product is weighed, placed in 50 ml of a 1 M aqueous sodium hydroxide solution, and heated at 50 ° C. for 24 hours with stirring to dissolve the silica. The silica solution is analyzed by ion chromatography to determine the amount of amine. Ion chromatographic analysis is performed according to JIS K0127.
- the boiling point of the amine is preferably 85 ° C. or higher, more preferably 90 ° C. or higher.
- the upper limit of the boiling point of the amine is not particularly limited and is preferably 500°C or lower, more preferably 300°C or lower.
- the true specific gravity of silica particles is preferably 1.95 or more, more preferably 2.00 or more.
- the true specific gravity is preferably 2.20 or less, more preferably 2.16 or less.
- the upper limit of the true specific gravity is within the above range, the occurrence of scratches on the object to be polished is further reduced.
- the true specific gravity shall be measured by a measuring method in which a sample is dried on a hot plate at 150 ° C., held in a furnace at 300 ° C. for 1 hour, and then measured by a liquid phase substitution method using ethanol. You can
- the silanol group density of silica particles in colloidal silica can be determined by the Sears method.
- the Sears method is based on G.I. W. Sears, Jr. , "Determination of Specific Surface Area of Colloidal Silica by Titration with Sodium Hydroxide", Analytical Chemistry, 28(12), 1981 (1956). It was carried out with reference to the description of.
- a 1 wt% silica dispersion is used for the measurement, titration is performed with a 0.1 mol / L sodium hydroxide aqueous solution, and the silanol group density is calculated based on the following formula.
- ⁇ (a ⁇ f ⁇ 6022) ⁇ (c ⁇ S)
- ⁇ silanol group density (pieces / nm 2 )
- a dropping amount (mL) of 0.1 mol / L sodium hydroxide aqueous solution of pH 4-9
- f 0.1 mol / L sodium hydroxide aqueous solution.
- Factor, c mass (g) of silica particles
- S BET specific surface area (m 2 / g), respectively.
- the silica particles have a value of the ratio (m / n) of the alkoxy group content m (ppm) to the average primary particle diameter n (nm) of 200 or more. If the value of m / n is less than 200, defects on the surface of the object to be polished cannot be suppressed.
- the value of m/n is preferably 250 or more, more preferably 300 or more, still more preferably 320 or more.
- the m / n value is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. When the upper limit of the value of m / n is within the above range, the polishability of the colloidal silica of the present invention is further improved.
- the content of the alkoxy group can be obtained by measuring the content m (ppm) of the alkoxy group and the average primary particle diameter n (nm) by the following method, and calculating m/n. it can.
- the colloidal silica of the present invention preferably contains 15% or more of silica particles having a bent structure and/or a branched structure in the number of particles in an arbitrary visual field at 200,000 times observed with a scanning electron microscope, and 20%. It is more preferable to include the above. When the content of the silica particles is within the above range, the polishing property is improved.
- the content of silica particles having the above-mentioned bent structure and / or branched structure can be measured by the following measuring method. That is, particles having a bent structure and a branched structure are counted from the number of particles in an arbitrary field of view at 200,000 times observed with a scanning electron microscope (SEM), and the ratio of these particles is defined as the content (%).
- a bent structure is a particle formed by combining three or more particles in a row and is not a straight line
- a branched structure is a particle formed by combining four or more particles in a row and not in a row (branch). Have).
- the average primary particle diameter of the silica particles in the colloidal silica is preferably 5 nm or more, more preferably 10 nm or more.
- the average primary particle size of the silica particles is preferably 200 nm or less, more preferably 100 nm or less.
- the upper limit of the average primary particle diameter of the silica particles is within the above range, scratches on the object to be polished are further reduced.
- the average secondary particle size of the silica particles in colloidal silica is preferably 8 nm or more, more preferably 15 nm or more.
- the average secondary particle size of the silica particles is preferably 400 nm or less, more preferably 300 nm or less.
- the upper limit of the average secondary particle diameter of the silica particles is within the above range, the scratches on the object to be polished are further reduced.
- the average secondary particle size of the silica particles in the colloidal silica can be measured by the following measuring method. That is, as a sample for measurement of the dynamic light scattering method, colloidal silica is added to a 0.3 wt% citric acid aqueous solution to prepare a homogenized sample. Using the measurement sample, the secondary particle size is measured by the dynamic light scattering method (“ELSZ-2000S” manufactured by Otsuka Electronics Co., Ltd.).
- the association ratio of silica particles in colloidal silica is preferably 1.5 or more, more preferably 1.7 or more.
- the association ratio of the silica particles is preferably 5.5 or less, more preferably 5.0 or less.
- the upper limit of the association ratio of the silica particles is within the above range, the occurrence of scratches on the object to be polished is further reduced.
- the association ratio of the silica particles in the colloidal silica is a value obtained by calculating the average secondary particle diameter / average primary particle diameter of the silica particles in the colloidal silica.
- the silica particles in colloidal silica have the following general formula (1) on the surface. -(CH 2 ) k -R 5 (1) It is preferable to have an organic functional group represented by By having the organic functional group represented by the general formula (1), the aggregation of colloidal silica is further suppressed. Further, by having an organic functional group represented by the above general formula (1), for example, the polishing performance is adjusted by utilizing electrostatic attraction/repulsion with an object to be polished as a polishing agent; It is possible to adjust the interaction with other substances, such as improving the dispersibility when added.
- k indicates an arbitrary integer of 0 or more. k is preferably an arbitrary integer of 1 or more. Further, k is preferably an arbitrary integer of 20 or less, and more preferably an arbitrary integer of 12 or less.
- R 5 represents an arbitrary functional group.
- the R 5 is not particularly limited as long as it is a functional group, and examples thereof include functional groups such as cation, anion, polar, and non-polar.
- the colloidal silica of the present invention preferably has a cationic organic functional group, an anionic organic functional group, a polar organic functional group, a non-polar organic functional group, etc. on the surface of the silica particles, and is preferably a cationic organic functional group or an anionic organic. It is more preferable to have a functional group.
- the cationic organic functional group is not particularly limited, and examples thereof include an amino group.
- the anionic organic functional group is not particularly limited, and examples thereof include a sulfo group and a carboxy group. Among these, a sulfo group is preferable.
- the polar organic functional group or the non-polar organic functional group is not particularly limited, and includes a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, a dodecyl group, an octadecyl group, a vinyl group, an epoxy group, a methacryl group, and acryl. Groups and the like.
- the colloidal silica is centrifuged at 5 ° C. and 77,000 G for 90 minutes.
- the obtained precipitate is dried at 60° C. for 12 hours, ground with a mortar and pestle, and dried under reduced pressure at 60° C. for 2 hours to prepare a dry powder.
- the zeta potential can be measured by an apparatus using measurement principles such as an electrophoretic light scattering method, a colloidal oscillating current method, an electroacoustic method, and an ultrasonic attenuation method.
- the method for producing colloidal silica of the present invention is: (1) Step 1 of preparing a mother liquor containing an alkaline catalyst and water 1. (2) Step 2 of adding alkoxysilane to the mother liquor to prepare a mixed solution, and (3) Step 3 to prepare a seed particle dispersion by adding an alkaline catalyst to the mixed solution. Is a method for producing colloidal silica having the above in this order.
- the alkali catalyst is a production method in which at least one amine selected from the group consisting of primary amines, secondary amines and tertiary amines (however, a hydroxyl group is excluded as a substituent).
- Step 1 is a step of preparing a mother liquor containing an alkaline catalyst and water.
- the alkaline catalyst is at least one amine selected from the group consisting of primary amines, secondary amines and tertiary amines (however, hydroxyl groups are excluded as substituents).
- the amine the same amine as that described in the colloidal silica may be used.
- the amine content in the mother liquor is preferably 0.30 mmol / kg or more, more preferably 0.50 mmol / kg or more.
- the amine content in the mother liquor is preferably 3.00 mmol / kg or less, more preferably 2.50 mmol / kg or less.
- the silica particles in the colloidal silica are further deformed.
- the method for preparing the mother liquor is not particularly limited, and an alkaline catalyst may be added to water by a conventionally known method and stirred.
- the pH of the mother liquor is not particularly limited and is preferably 9.5 or higher, more preferably 10.0 or higher. When the lower limit of the pH of the mother liquor is in the above range, it becomes easier to control the particle size.
- the pH of the mother liquor is preferably 11.5 or less, more preferably 11.0 or less. When the upper limit of the pH of the mother liquor is within the above range, the silica particles in the colloidal silica are further deformed.
- Step 2 is a step of adding alkoxysilane to the mother liquor to prepare a mixed solution.
- the alkoxysilane is not particularly limited, and the following general formula (2) Si(OR 1 ) 4 (2) (In the formula, R 1 represents an alkyl group.)
- R 1 represents an alkyl group.
- R 1 is not particularly limited as long as it is an alkyl group, and is preferably a lower alkyl group having 1 to 8 carbon atoms, and more preferably a lower alkyl group having 1 to 4 carbon atoms.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group and the like.
- Examples of the alkoxysilane represented by the general formula (2) include tetramethoxysilane (tetramethylorthosilicate) in which R 1 is a methyl group, tetraethoxysilane (tetraethylorthosilicate) in which R 1 is an ethyl group, R 1 There tetraisopropoxysilane preferably an isopropyl group, tetramethoxysilane R 1 is a methyl group, tetraethoxysilane is more preferably R 1 is an ethyl group, tetramethoxysilane is more preferable.
- the alkoxysilane represented by the general formula (2) may be used alone or in combination of two or more.
- the addition amount of the alkoxysilane represented by the above general formula (2) in the mixed liquid is not particularly limited, and the addition amount s2 (mol) of the alkoxysilane in step 2 and the amount c1 (mol) of the alkali catalyst in the mother liquor.
- the molar ratio (s2 / c1) of is preferably 800 or more, more preferably 960 or more.
- s2 / c1 is preferably 8500 or less, more preferably 8000 or less.
- the upper limit of s2 / c1 is within the above range, the formation of new nuclear particles during the reaction is suppressed, the growth of the main particles is further promoted, and the gelation during the reaction is further suppressed. ..
- the addition time of the alkoxysilane is preferably 5 minutes or more, more preferably 10 minutes or more. Since the lower limit of the addition time is within the above range, it is difficult to gel during the reaction.
- the addition time of the alkoxysilane is preferably 1000 minutes or less, more preferably 600 minutes or less. When the upper limit of the addition time is within the above range, the productivity can be further improved and the manufacturing cost can be further suppressed.
- the pH of the mixed solution is preferably 7.0 or less, more preferably 6.5 or less.
- the pH of the mixed solution is preferably 4.5 or higher, more preferably 4.9 or higher.
- the lower limit of the pH of the mixed solution is in the above range, gelation is further suppressed.
- the temperature of the mixed solution in step 2 is preferably 70 ° C. or higher, more preferably 75 ° C. or higher. When the lower limit of the temperature of the mixed solution is within the above range, gelation during the reaction is further suppressed.
- the temperature of the mixed solution is preferably 95 ° C. or lower, more preferably 90 ° C. or lower. When the upper limit of the temperature of the mixed liquid is within the above range, vaporization of alkoxysilane is further suppressed.
- Step 3 is a step of adding an alkaline catalyst to the mixed solution to prepare a seed particle dispersion.
- the time from the end of addition of the alkoxysilane to the start of addition of the alkaline catalyst in step 3 (hereinafter referred to as "aging time") is preferably 0 minutes or more and 1500 minutes or less.
- the degree of irregularity can be controlled by the aging time, and when the aging time is within the above range, it is possible to obtain the particles having the desired degree of irregularity while ensuring the productivity.
- the alkaline catalyst is at least one amine selected from the group consisting of primary amines, secondary amines and tertiary amines (however, the hydroxyl group is excluded as a substituent).
- the amine the same amine as that described in the colloidal silica may be used.
- the alkaline catalyst used in step 3 may be the same as or different from the alkaline catalyst used in step 1.
- the addition amount of the alkali catalyst in step 3 is not particularly limited, and the molar ratio of the addition amount s2 (mol) of the alkoxysilane in step 2 and the addition amount c3 (mol) of the alkali catalyst in step 3 (s2/c3). Is preferably 185 or less, more preferably 105 or less.
- s2 / c3 is preferably 30 or more, and more preferably 35 or more.
- gelation is further suppressed.
- the pH of the seed particle dispersion is preferably 8.0 or higher, more preferably 8.5 or higher.
- the pH of the seed particle dispersion is preferably 12.0 or less, more preferably 11.0 or less.
- the upper limit of the pH of the seed particle dispersion is in the above range, the dissolution of silica particles is further suppressed.
- the temperature of the seed particle dispersion in step 3 is preferably 70 ° C. or higher, more preferably 75 ° C. or higher.
- the temperature of the seed particle dispersion is preferably 95 ° C. or lower, more preferably 90 ° C. or lower.
- the upper limit of the temperature of the seed particle dispersion liquid is within the above range, gelation is further suppressed.
- the production method of the present invention may include a step 4 of adding water and an alkoxysilane to the seed particle dispersion (4) after the step 3.
- the alkoxysilane the same one as the alkoxysilane described in the above step 2 may be used. Further, the alkoxysilane used in the step 4 may be the same as or different from the alkoxysilane used in the step 2.
- the alkoxysilane in step 4 may be used alone or in combination of two or more.
- the alkoxysilane used in step 4 has an organic functional group in addition to the alkoxysilane represented by the general formula (2), which is the tetraalkoxysilane having no organic functional group described in step 2 above. Alkoxysilane may be used.
- alkoxysilane having an organic functional group examples include alkoxysilanes represented by the following general formula (3) and the following general formula (4).
- R 1 is a group defined in the same manner as R 1 in the general formula (2), and R 5 and R 6 are the same as R 5 in the general formula (1). It is a similarly defined group.
- alkoxysilane represented by the general formula (3) or (4) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and trimethylethoxysilane.
- alkoxysilanes having an organic functional group may be used alone or in combination of two or more.
- the amount of the alkoxysilane having an organic functional group added is preferably 0.0004 to 0.03 mol times, and 0.001 to 0.03 times the amount of the alkoxysilane represented by the general formula (2). More preferably, it is a molar ratio. If the ratio of the addition amount of the alkoxysilane represented by the general formula (2) is too small, the number of organic functional groups introduced into the particles is small, and there is a possibility that desired properties cannot be imparted. If the proportion of the amount of alkoxysilane having an organic functional group added is too large, an increase in secondary particle size, formation of agglomerates, and gelation may occur.
- the alkoxysilane may be diluted with an organic solvent in advance and then added.
- an organic solvent in step 4 for example, a hydrophilic organic solvent is used, and specifically, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, and 1,4-butanediol. Ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate can be exemplified.
- the organic solvent may be used alone or in combination of two or more.
- alcohols are preferably used from the viewpoint of being easily available industrially, methanol and ethanol are more preferable, and methanol is even more preferable. This is because alcohols are easily replaced with water by heating distillation when replacing water. Furthermore, it is even more preferable to use the same alcohol as the alcohol produced by the hydrolysis of alkoxysilane as the organic solvent. For example, when tetramethyl orthosilicate is used as the alkoxysilane, methanol is generated in the reaction system by hydrolysis of the silicate, so the same methanol is used as the organic solvent. By doing so, the solvent can be easily recovered and reused.
- the amount of the organic solvent added in step 4 is preferably 0 to 3 times the total amount of the alkoxysilane added, and more preferably 0 to 1.5 times the mass.
- the upper limit of the amount of the organic solvent added is in the above range, it becomes easy to suppress the decrease in the true specific gravity.
- the amount of alkoxysilane added in step 4 is not particularly limited, and the molar ratio (s4 / sp4) of the amount of alkoxysilane added in step 4 s4 (mol) to the amount of seed particles sp4 (mol) in the seed particle dispersion is 0. It is preferably 30 or more and 30 or less. When the upper limit of s4/sp4 is within the above range, it is difficult to generate new core particles during the reaction, and the growth of the main particles is further promoted.
- the molar ratio is a value defined by setting the molecular weight of the seed particles to 60.08 g / mol.
- the amount of water added in step 4 is preferably 0 part by mass or more and 55.0 parts by mass or less with respect to 1 part by mass of the seed particles.
- the upper limit of the amount of water added is within the above range, colloidal silica can be obtained even more efficiently.
- the pH of the colloidal silica in step 4 is preferably 11.0 or less, more preferably 10.0 or less.
- the pH of colloidal silica is preferably 6.5 or higher, more preferably 7.0 or higher.
- the lower limit of the pH of colloidal silicia is within the above range, gelation is further suppressed.
- the temperature of colloidal silica in step 4 is preferably 70 ° C. or higher, more preferably 75 ° C. or higher.
- the temperature of colloidal silica is preferably 90 ° C. or lower, more preferably 85 ° C. or lower.
- the upper limit of the temperature of colloidal silica is in the above range, the vaporization of alkoxysilane is further suppressed.
- the addition time of alkoxysilane in step 4 is preferably 0 minutes or more and 1000 minutes or less. When the addition time is in the above range, it is difficult to generate new core particles during the reaction and the growth of the main particles is promoted.
- the method for producing colloidal silica of the present invention may further have a step of concentrating the colloidal silica after the above step 3 or step 4.
- the method of concentration is not particularly limited, and the concentration can be performed by a conventionally known method. Examples of such a concentration method include a method of heating and concentrating at a temperature of about 65 to 100 ° C. and a method of concentrating by ultrafiltration.
- the concentration of the silica particles of the colloidal silica after concentration is not particularly limited, and is preferably about 1 to 50% by mass based on 100% by mass of the colloidal silica.
- the method for producing colloidal silica of the present invention may further include a step of distilling off methanol produced as a by-product during the reaction after the above-mentioned step 3 or step 4.
- the method for distilling off methanol is not particularly limited, and examples thereof include a method in which pure water is added dropwise while heating colloidal silica to keep the volume constant, thereby replacing the dispersion medium with pure water.
- a method of separating colloidal silica from a solvent by precipitation / separation, centrifugation or the like and then redispersing it in water, or a method of replacing the solvent with water by ultrafiltration can be exemplified.
- the method for producing colloidal silica of the present invention further comprises adding an alkoxysilane having an organic functional group after the above step 4. It may have step 5.
- step 5 as the alkoxysilane having an organic functional group, an alkoxysilane having an organic functional group represented by the above general formula (3) or (4) can be used.
- examples of the alkoxysilane having a cationic functional group include alkoxysilanes having an organic functional group represented by the above general formula (3) or (4).
- examples of the silane coupling agent include aminopropyltrimethoxysilane, (aminoethyl)aminopropyltrimethoxysilane, (aminoethyl)aminopropyltriethoxysilane, and aminopropyltriethoxy.
- examples thereof include silane, aminopropyldimethylethoxysilane, aminopropylmethyldiethoxysilane, and aminobutyltriethoxysilane.
- the addition amount of the alkoxysilane having an organic functional group in step 5 is not particularly limited, and is 0 relative to 1 g of the solid content of the colloidal silica before the addition of the silane coupling agent. It is preferably 5.5 to 350 ⁇ mol, more preferably 5.5 to 170 ⁇ mol.
- the lower limit of the addition amount of the silane coupling agent is within the above range, the degree of modification of the colloidal silica becomes more sufficient, and a modified colloidal silica that can be stably dispersed for a longer period of time can be obtained.
- the electrostatic attraction and repulsion with the object to be polished can be further increased.
- the upper limit of the addition amount of the alkoxysilane having an organic functional group is within the above range, the increase in secondary particle size, the formation of aggregates, and the gelation are further suppressed.
- step 5 when the organic functional group is an anionic organic functional group, particularly a sulfo group, for example, as an alkoxysilane having an organic functional group, an organic functional group having a functional group that can be chemically converted to a sulfonic acid group is used. Alkoxysilanes with are preferred.
- the alkoxysilane having such an organic functional group for example, 1) an alkoxysilane having an organic functional group having a sulfonic acid ester group which can be converted into a sulfonic acid group by hydrolysis, and 2) can be converted into a sulfonic acid group by oxidation.
- alkoxysilanes having an organic functional group having a mercapto group and / or a sulfide group examples thereof include alkoxysilanes having an organic functional group having a mercapto group and / or a sulfide group. Since the sulfonic acid modification of the colloidal silica surface is carried out in a solution, it is preferable to use the latter alkoxysilane having an organic functional group having a mercapto group and/or a sulfide group in order to improve the modification efficiency.
- alkoxysilane having an organic functional group having a mercapto group examples include 3-mercaptopropyltrimethoxysilane, 2-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane and 2-mercaptoethyltriethoxysilane.
- alkoxysilane having an organic functional group having a sulfide group examples include bis (3-triethoxysilylpropyl) disulfide.
- the amount of the silane coupling agent used in step 5 is not particularly limited, and the solid content of colloidal silica before the addition of the silane coupling agent is 1 g. On the other hand, 0.5 to 350 ⁇ mol is preferable, and 5.5 to 170 ⁇ mol is more preferable.
- the lower limit of the addition amount of the alkoxysilane having an organic functional group is within the above range, the zeta potential in acid is further stabilized.
- the upper limit of the addition amount of the alkoxysilane having an organic functional group is within the above range, the increase in secondary particle size, the formation of aggregates, and the gelation are further suppressed.
- Examples of the method for oxidizing the modified mercapto group and sulfide group include a method using an oxidizing agent.
- examples thereof include nitric acid, hydrogen peroxide, oxygen, ozone, organic peracid (percarboxylic acid), bromine, hypochlorite, potassium permanganate, and chromic acid.
- oxidizing agents hydrogen peroxide and organic peracids (peracetic acid, perbenzoic acids) are preferable because they are relatively easy to handle and the oxidation yield is good. It is most preferable to use hydrogen peroxide in consideration of the substances by-produced in the reaction.
- the amount of the oxidizing agent added is preferably 3 to 100 times the molar amount of the alkoxysilane having an organic functional group.
- the upper limit of the amount of the oxidizing agent added is not particularly limited, and is more preferably about 50 times the molar amount.
- colloidal silica and alkoxysilane having an organic functional group have a stable structure in the oxidation reaction except for the functional group which is oxidized (converted) to a sulfonic acid group, so that by-products are suppressed.
- the temperature at which the silane coupling agent is added is not limited, but the boiling point is preferably from room temperature (about 20 ° C.).
- the reaction time is also not limited, but is preferably 10 minutes to 10 hours, more preferably 30 minutes to 2 hours.
- the pH at the time of addition is not limited, but is preferably 3 or more and 11 or less. When the pH is within the above range, the reaction between the silane coupling agent and the silica surface is further promoted, and the self-condensation between the silane coupling agents is further suppressed. Further, the addition amount of the acidic/basic substance for adjusting the pH is small, and the silica particles are stably held.
- the alkoxysilane having an organic functional group is diluted with an organic solvent and added to the colloidal silica.
- the dilution ratio of the alkoxysilane having an organic functional group is not particularly limited, but the proportion of the alkoxysilane having an organic functional group is 0.1 to 100% by mass, preferably 1 to 100% by mass. It may be diluted with an organic solvent so that the concentration becomes %.
- the organic solvent is not particularly limited and is preferably a hydrophilic organic solvent, and examples thereof include lower alcohols such as methanol, ethanol, isopropanol and butanol.
- the colloidal silica of the present invention has a content of metal impurities such as sodium, potassium, iron, aluminum, calcium, magnesium, titanium, nickel, chromium, copper, zinc, lead, silver, manganese, and cobalt of 1 ppm or less. Is preferred. When the content of metal impurities is 1 ppm or less, it can be suitably used for polishing electronic materials and the like.
- the colloidal silica of the present invention and the colloidal silica produced by the production method of the present invention can be used for various purposes such as an abrasive and a paper coating agent.
- An abrasive containing the above colloidal silica is also one aspect of the present invention. Since the colloidal silica of the present invention can have a high purity of 1 ppm or less of metal impurities such as sodium, it can be particularly suitably used as an abrasive for chemical mechanical polishing of semiconductor wafers.
- Example 1 7500 g of pure water as a solvent was placed in a flask, and 1.93 g of 3-ethoxypropylamine (3-EOPA) was added as an alkali catalyst to prepare a mother liquor. The pH of the mother liquor was 10.5.
- Step 2 After heating the mother liquor to an internal temperature of 85° C., 2740 g of tetramethyl orthosilicate was added dropwise to the mother liquor at a constant rate over 60 minutes while controlling the temperature so that the internal temperature did not change.
- Step 3 After stirring for 15 minutes, 50.14 g of 3-ethoxypropylamine (3-EOPA) was added to the mixed solution to prepare a seed particle dispersion. The pH of the seed particle dispersion was 10.3.
- Step 4 2452 g of seed particle dispersion and 5537 g of pure water were placed in a flask. Then, the internal temperature is heated to 80° C., 1762.7 g of tetramethyl orthosilicate is added dropwise at a constant rate over 360 minutes while adjusting the internal temperature so that the internal temperature does not fluctuate. A containing liquid was prepared. Next, 800 mL of the deformed silica-containing liquid was collected as a base amount under normal pressure, colloidal silica was fed while keeping the volume constant, and the mixture was heated and concentrated until the silica concentration became 20 wt%.
- the colloidal silica was prepared by replacing the dispersion medium with 500 mL of pure water while keeping the volume constant. Table 1 shows the physical properties of the obtained colloidal silica.
- Example 2 7500 g of pure water as a solvent was put in a flask, and 0.580 g of 3-ethoxypropylamine (3-EOPA) was added as an alkali catalyst to prepare a mother liquor.
- the pH of the mother liquor was 10.2.
- Step 2 After the mother liquor was heated to an inner temperature of 85° C., 2740 g of tetramethyl orthosilicate was added dropwise to the mother liquor at a constant rate over 120 minutes while controlling the inner temperature so that the inner temperature did not fluctuate.
- Step 3 After stirring for 420 minutes, 50.12 g of 3-ethoxypropylamine (3-EOPA) was added to the mixed solution to prepare a seed particle dispersion.
- the pH of the seed particle dispersion was 10.3.
- Step 4 2331 g of seed particle dispersion and 5265 g of pure water were placed in a flask. Next, while heating the inner temperature to 80° C. and adjusting the temperature so that the inner temperature does not fluctuate, 1957 g of tetramethyl orthosilicate was added dropwise at a constant rate over 360 minutes, and after the addition was completed, the mixture was stirred for 15 minutes to obtain a modified silica-containing liquid.
- 800 mL of the deformed silica-containing liquid was collected as a base amount under normal pressure, colloidal silica was fed while keeping the volume constant, and the mixture was heated and concentrated until the silica concentration reached 20 wt%.
- the colloidal silica was prepared by replacing the dispersion medium with 500 mL of pure water while keeping the volume constant. Table 1 shows the physical properties of the obtained colloidal silica.
- Example 3 Colloidal silica (silica concentration 20% by mass) was prepared in the same manner as in Example 2. (Process 5) To 10085 g of the prepared colloidal silica, 9.2 g of 3-ethoxypropylamine (3-EOPA) was added to adjust the pH to 9. Then, the mixture was heated to 50 ° C., and a mixed solution of 10.2 g of 3-aminopropyltrimethoxysilane and 331.5 g of methanol was added. Then, the dispersion medium was replaced with 5,000 mL of pure water while maintaining the volume constant in order to distill off the methanol in the liquid out of the system, to prepare colloidal silica in which silica organic particles were surface-modified with a cationic organic functional group. .. The zeta potential of the obtained colloidal silica is shown in FIG.
- Example 4 Colloidal silica (silica concentration: 20% by mass) was prepared in the same manner as in Example 2. (Process 5) To 830 g of the prepared colloidal silica, 0.8 g of 3-ethoxypropylamine (3-EOPA) was added to adjust the pH to 9. Then, 10.0 g of 3-mercaptopropyltrimethoxysilane and 21.3 g of 30% hydrogen peroxide solution were added at room temperature. Then, while keeping the volume constant in order to distill off the methanol in the liquid out of the system, the dispersion medium is replaced with 600 mL of pure water, and the mixture is heated under reflux for 3 hours, and the silica particles are surface-modified with anionic organic functional groups. The colloidal silica was adjusted. The zeta potential of the obtained colloidal silica is shown in FIG.
- Example 5 7500 g of pure water as a solvent was placed in a flask, and 0.774 g of 3-ethoxypropylamine (3-EOPA) was added as an alkali catalyst to prepare a mother liquor. The pH of the mother liquor was 10.2.
- Step 2 After heating the mother liquor to an internal temperature of 85° C., 2740 g of tetramethyl orthosilicate was added dropwise to the mother liquor at a constant rate over 60 minutes while controlling the temperature so that the internal temperature did not change.
- Step 3 After stirring for 60 minutes, 28.00 g of 3-ethoxypropylamine (3-EOPA) was added to the mixed solution to prepare a seed particle dispersion. The pH of the seed particle dispersion was 9.5.
- Example 6 A mother liquor was prepared by adding 7500 g of pure water as a solvent and 1.328 g of dipropylamine (DPA) as an alkali catalyst to a flask. The pH of the mother liquor was 10.9.
- Step 2 After heating the mother liquor to an internal temperature of 85° C., 2740 g of tetramethyl orthosilicate was added dropwise to the mother liquor at a constant rate over 60 minutes while controlling the temperature so that the internal temperature did not change.
- Step 3 After stirring for 15 minutes, 49.18 g of dipropylamine (DPA) was added to the mixed solution to prepare a seed particle dispersion. The pH of the seed particle dispersion was 10.4.
- colloidal silica was prepared.
- the silica concentration of colloidal silica was 10 wt%. Table 1 shows the physical properties of the obtained colloidal silica.
- Example 7 A mother liquor was prepared by adding 7500 g of pure water as a solvent and 1.328 g of triethylamine (TEA) as an alkali catalyst to a flask. The pH of the mother liquor was 10.8.
- Step 2 After heating the mother liquor to an internal temperature of 85° C., 2740 g of tetramethyl orthosilicate was added dropwise to the mother liquor at a constant rate over 60 minutes while controlling the temperature so that the internal temperature did not change.
- Step 3 After stirring for 15 minutes, 49.18 g of triethylamine (TEA) was added to the mixed solution to prepare a seed particle dispersion. The pH of the seed particle dispersion was 10.1.
- colloidal silica was prepared.
- the silica concentration of colloidal silica was 10 wt%. Table 1 shows the physical properties of the obtained colloidal silica.
- Comparative example 2 To 2000 g of water, 0.365 g of a 25% aqueous solution of tetramethylammonium hydroxide (TMAH) was added and stirred to prepare a mother liquor, which was heated to 80 ° C. While maintaining the temperature of the mother liquor at 80 ° C., 228 g of tetramethyl orthosilicate was added dropwise over 3 hours. Then, immediately, 2.92 g of a 25% aqueous solution of tetramethylammonium hydroxide (TMAH) was added.
- TMAH tetramethylammonium hydroxide
- Average secondary particle size As a sample for measurement of the dynamic light scattering method, colloidal silica was added to a 0.3 wt% citric acid aqueous solution to prepare a homogenized sample. Using the measurement sample, the average secondary particle size was measured by a dynamic light scattering method (“ELSZ-2000S” manufactured by Otsuka Electronics Co., Ltd.).
- a bent structure is a particle formed by combining three or more particles in a row and is not a straight line
- a branched structure is a particle formed by combining four or more particles in a row and not in a row (branch). (Has).
- the colloidal silica was centrifuged at 215000 G for 90 minutes, the supernatant was discarded, and the solid content was vacuum dried at 60 ° C. for 90 minutes.
- 0.5 g of the obtained dried silica product was weighed and put into 50 ml of a 1 M aqueous sodium hydroxide solution, and the silica was dissolved by heating at 50° C. for 24 hours while stirring.
- the amount of amine was determined by analyzing with a silica solution ion chromatograph. The ion chromatographic analysis complied with JIS K0127.
- silanol group density The silanol group density of silica particles in colloidal silica can be determined by the Sears method.
- the Sears method is based on G.I. W. Sears, Jr. , "Determination of Specific Surface Area of Colloidal Silica by Titration with Sodium Hydroxide", Analytical Chemistry, 28(12), 1981 (1956). It was carried out with reference to the description of.
- a 1 wt% silica dispersion is used for the measurement, titration is performed with a 0.1 mol / L sodium hydroxide aqueous solution, and the silanol group density is calculated based on the following formula.
- ⁇ (a ⁇ f ⁇ 6022) ⁇ (c ⁇ S)
- ⁇ silanol group density (pieces / nm 2 )
- a dropping amount (mL) of 0.1 mol / L sodium hydroxide aqueous solution of pH 4-9
- f 0.1 mol / L sodium hydroxide aqueous solution.
- Factor, c mass (g) of silica particles
- S BET specific surface area (m 2 / g), respectively.
- the particle size distribution of the colloidal silica obtained in Example 2 was measured by the following method. That is, a diluting solution was prepared by diluting colloidal silica with a 0.5 mass% sodium dodecyl sulfate aqueous solution so that the silica concentration was 2 mass %. Using the prepared solution, the particle size distribution of colloidal silica was measured by a disk centrifugal particle size distribution analyzer (“DC24000UHR” manufactured by CPS Instruments). The measurement was performed in a density gradient solution of 8% to 24% sucrose under the condition of a rotation speed of 18,000 rpm, with the true specific gravity of silica being 2.1. The measurement results of the particle size distribution are shown in Table 2 and FIG.
- the zeta potential of colloidal silica was measured using a measuring device using an ultrasonic attenuation method.
- the prepared dry powder was measured by XPS, and a peak derived from an organic functional group on the particle surface was confirmed.
- FIG. 2 is a diagram showing an XPS spectrum of the 1s orbital of the N element forming an amino group.
- FIG. 3 is a diagram showing an XPS spectrum of a 2s orbital of an S element forming a sulfo group.
- Example 3 the zeta potential of the colloidal silica obtained in Example 3 was positively shifted with respect to the zeta potential of the colloidal silica obtained in Example 2.
- the isoelectric point of Example 3 was 5 or more.
- the surface of the silica particle was provided with an amino group which is a cationic functional group.
- the zeta potential of the colloidal silica obtained in Example 4 was shifted to the minus with respect to the zeta potential of the colloidal silica obtained in Example 2.
- the zeta potential of Example 4 was negative in all regions of pH 3-9.
- the S atom was detected in the XPS measurement result of FIG. 3, it was found that the sulfo group, which is an anionic functional group, was added to the surface of the silica particle.
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Abstract
Description
1.屈曲構造及び/又は分岐構造を持つシリカ粒子を含有するコロイダルシリカであって、
前記シリカ粒子の真比重は、1.95以上であり、
前記シリカ粒子は、アルコキシ基の含有量m(ppm)と、平均一次粒子径n(nm)との比(m/n)の値が200以上であり、
走査型電子顕微鏡で観察した20万倍での任意の視野内の粒子個数中、屈曲構造及び/又は分岐構造を持つシリカ粒子を15%以上含む、
ことを特徴とするコロイダルシリカ。
2.前記シリカ粒子の真比重は、1.95以上2.20以下である、項1に記載のコロイダルシリカ。
3.前記シリカ粒子は、1級アミン、2級アミン及び3級アミンからなる群より選択される少なくとも1種のアミン(ただし、置換基として、ヒドロキシル基は除外する)をシリカ粒子1g当たり5μmol以上含有する、項1又は2に記載のコロイダルシリカ。
4.前記シリカ粒子の表面に、下記一般式(1)
-(CH2)k-R5 (1)
(式(1)中、kは0以上の任意の整数を示し、R5は任意の官能基を示す。)
で表される有機官能基を有する、項1~3のいずれかに記載のコロイダルシリカ。
5.前記シリカ粒子の表面に、カチオン性有機官能基を有する、項1~4のいずれかに記載のコロイダルシリカ。
6.前記シリカ粒子の表面に、アミノ基を有する、項5に記載のコロイダルシリカ。
7.前記シリカ粒子の表面に、アニオン性有機官能基を有する、項1~4のいずれかに記載のコロイダルシリカ。
8.前記シリカ粒子の表面に、スルホ基を有する、項7に記載のコロイダルシリカ。
9.(1)アルカリ触媒及び水を含む母液を調製する工程1、
(2)アルコキシシランを前記母液に添加して混合液を調製する工程2、及び、
(3)前記混合液にアルカリ触媒を添加して、種粒子分散液を調製する工程3
をこの順に有するコロイダルシリカの製造方法であって、
前記アルカリ触媒は、1級アミン、2級アミン及び3級アミンからなる群より選択される少なくとも1種のアミン(ただし、置換基として、ヒドロキシル基は除外する)である、
ことを特徴とするコロイダルシリカの製造方法。
10.前記工程3の後に、(4)前記種粒子分散液に、水及びアルコキシシランを添加する工程4を有する、項9又は10に記載の製造方法。
11.前記工程2における前記アルコキシシランの添加量s2(mol)と、前記母液中の前記アルカリ触媒の量c2(mol)のモル比(s2/c1)は、800以上である、項9~11のいずれかに記載の製造方法。
12.前記工程2における前記アルコキシシランの添加量s2(mol)と、前記工程3におけるアルカリ触媒の添加量c3(mol)とのモル比(s2/c3)は、185以下である、項9~11のいずれかに記載の製造方法。
本発明のコロイダルシリカは、屈曲構造及び/又は分岐構造を持つシリカ粒子を含有するコロイダルシリカであって、前記シリカ粒子の真比重は、1.95以上であり、前記シリカ粒子は、アルコキシ基の含有量m(ppm)と、平均一次粒子径n(nm)との比(m/n)の値が200以上であり、走査型電子顕微鏡で観察した20万倍での任意の視野内の粒子個数中、屈曲構造及び/又は分岐構造を持つシリカ粒子を15%以上含むことを特徴とする。
NRaRbRc (X)
(式中、Ra、Rb、Rcは置換されてもよい炭素数1~12のアルキル基、又は水素を示す。ただし、Ra、Rb、Rcのすべてが水素の場合、つまりアンモニアは除外する。)
Ra、Rb、Rcは、同一でも異なっていてもよい。Ra、Rb、Rcは直鎖状、分岐状、環状のいずれであってもよい。
ρ=(a×f×6022)÷(c×S)
上記式中、ρ:シラノール基密度(個/nm2)、a:pH4-9の0.1mol/L水酸化ナトリウム水溶液の滴下量(mL)、f: 0.1mol/L水酸化ナトリウム水溶液のファクター、c:シリカ粒子の質量(g)、S:BET比表面積(m2/g)をそれぞれ表す。
コロイダルシリカを215000G、90分の条件で遠心分離後、上澄みを廃棄して、固形分を60℃、90分の条件で真空乾燥させる。得られたシリカ乾固物0.5gを秤量し、1M水酸化ナトリウム水溶液50mlに入れ、撹拌させながら50℃で24時間加熱することでシリカを溶解させる。前記シリカ溶解液をガスクロマトグラフにより分析し、アルコール含有量を求め、アルコキシ基の含有量とする。ガスクロマトグラフの検出器は水素炎イオン化検出器(FID)を用いる。ガスクロマトグラフ分析は、JIS K0114に従って行う。
コロイダルシリカをホットプレートの上で予備乾燥後、800℃で1時間熱処理して測定用サンプルを調製する。調製した測定用サンプルを用いて、BET比表面積を測定する。シリカの真比重を2.2として、2727/BET比表面積(m2/g)の値を換算して、コロイダルシリカ中のシリカ粒子の平均一次粒子径(nm)とする。
-(CH2)k-R5 (1)
で表される有機官能基を有することが好ましい。上記一般式(1)で表わされる有機官能基を有することにより、コロイダルシリカの凝集がより一層抑制される。また、上記一般式(1)で表わされる有機官能基を有することにより、例えば、研磨剤として研磨対象物との静電気的引力・斥力を利用して研磨性能を調整する;フィラーとしてポリマー樹脂内に添加した際に分散性を向上させる等の、他物質との相互作用を調整することができる。
コロイダルシリカを5℃、77,000Gで、90分間遠心分離する。得られた沈殿物を60℃で12時間乾燥させた後、乳鉢と乳棒を使用してすりつぶし、60℃で2時間減圧乾燥して、乾燥粉を調製する。
ゼータ電位は、電気泳動光散乱法、コロイド振動電流法、電気音響法、超音波減衰法等の測定原理を使用した装置により測定できる。
本発明のコロイダルシリカの製造方法は、
(1)アルカリ触媒及び水を含む母液を調製する工程1、
(2)アルコキシシランを前記母液に添加して混合液を調製する工程2、及び、
(3)前記混合液にアルカリ触媒を添加して、種粒子分散液を調製する工程3
をこの順に有するコロイダルシリカの製造方法であって、
前記アルカリ触媒は、1級アミン、2級アミン及び3級アミンからなる群より選択される少なくとも1種のアミン(ただし、置換基として、ヒドロキシル基は除外する)である製造方法である。
工程1は、アルカリ触媒及び水を含む母液を調製する工程である。
工程2は、アルコキシシランを上記母液に添加して混合液を調製する工程である。
Si(OR1)4 (2)
(式中、R1はアルキル基を示す。)
で表されるアルコキシシランが挙げられる。
工程3は、混合液にアルカリ触媒を添加して、種粒子分散液を調製する工程である。
本発明の製造方法は、上記工程3の後に、(4)種粒子分散液に、水及びアルコキシシランを添加する工程4を有してもよい。
(OR1)3Si[(CH2)k-R5] (3)
(OR1)2Si[(CH2)k-R5][(CH2)k-R6] (4)
本発明のコロイダルシリカが上記一般式(1)で表わされる有機官能基を有する場合、本発明のコロイダルシリカの製造方法は、上記工程4の後に、更に、有機官能基を有するアルコキシシランを添加する工程5を有していてもよい。
(工程1)フラスコに、溶媒として純水7500gを入れ、アルカリ触媒として3-エトキシプロピルアミン (3-EOPA) 1.93gを添加し、母液を調製した。母液のpHは10.5であった。
(工程2)母液を内温85℃まで加熱した後、当該母液にテトラメチルオルトシリケート2740gを内温変動しないよう温調しつつ、60分かけて定速滴下し、混合液を調製した。
(工程3)15分撹拌後、混合液に3-エトキシプロピルアミン(3-EOPA)50.14gを添加して、種粒子分散液を調製した。種粒子分散液のpHは10.3であった。
(工程4)フラスコに、種粒子分散液2452g、及び、純水5537gを入れた。次いで、内温80℃まで加熱し、内温変動しないように温調しながら、360分かけてテトラメチルオルトシリケート1762.7gを定速滴下し、滴下終了後15分間撹拌して、異形化シリカ含有液を調製した。次いで、異形化シリカ含有液を常圧下ベース量として800mL採取し、容量を一定に保ちながらコロイダルシリカをフィードして、シリカ濃度が20wt%なるまで加熱濃縮した。次いで、反応時に副生したメタノールを系外留去するために、容量を一定に保ちながら、純水500mLにて分散媒を置換して、コロイダルシリカを調製した。得られたコロイダルシリカの物性を表1に示す。
(工程1)フラスコに、溶媒として純水7500gを入れ、アルカリ触媒として3-エトキシプロピルアミン(3-EOPA)0.580gを添加し、母液を調製した。母液のpHは10.2であった。
(工程2)母液を内温85℃まで加熱した後、当該母液にテトラメチルオルトシリケート2740gを内温変動しないよう温調しつつ、120分かけて定速滴下し、混合液を調製した。
(工程3)420分撹拌後、混合液に3-エトキシプロピルアミン(3-EOPA)50.12gを添加して、種粒子分散液を調製した。種粒子分散液のpHは10.3であった。
(工程4)フラスコに、種粒子分散液2331g、及び、純水5265gを入れた。次いで、内温80℃まで加熱し、内温変動しないように温調しながら、360分かけてテトラメチルオルトシリケート1957gを定速滴下し、滴下終了後15分間撹拌して、異形化シリカ含有液を調製した。次いで、異形化シリカ含有液を常圧下ベース量として800mL採取し、容量を一定に保ちながらコロイダルシリカをフィードして、シリカ濃度が20wt%になるまで加熱濃縮した。次いで、反応時に副生したメタノールを系外留去するために、容量を一定に保ちながら、純水500mLにて分散媒を置換して、コロイダルシリカを調製した。得られたコロイダルシリカの物性を表1に示す。
実施例2と同様にして、コロイダルシリカ(シリカ濃度20質量%)を調製した。
(工程5)
調製されたコロイダルシリカ10085gに、3-エトキシプロピルアミン(3-EOPA)9.2gを添加し、pH9に調整した。次いで、50℃まで加熱し、3-アミノプロピルトリメトキシシラン10.2gおよびメタノール331.5gの混合液を添加した。次いで、液中のメタノールを系外留去するために容量を一定に保ちつつ、純水5000mLで分散媒を置換して、シリカ粒子にカチオン性有機官能基が表面修飾されたコロイダルシリカを調整した。得られたコロイダルシリカのゼータ電位を図1に示す。
実施例2と同様にして、コロイダルシリカ(シリカ濃度20質量%)を調製した。
(工程5)
調製されたコロイダルシリカ830gに、3-エトキシプロピルアミン(3-EOPA)0.8gを添加し、pH9に調整した。次いで、室温で3-メルカプトプロピルトリメトキシシラン10.0g及び30%過酸化水素水21.3gを添加した。次いで、液中のメタノールを系外留去するために容量を一定に保ちつつ、純水600mLで分散媒を置換して、3時間加熱還流し、シリカ粒子にアニオン性有機官能基が表面修飾されたコロイダルシリカを調整した。得られたコロイダルシリカのゼータ電位を図1に示す。
(工程1)フラスコに、溶媒として純水7500gを入れ、アルカリ触媒として3-エトキシプロピルアミン(3-EOPA)0.774gを添加し、母液を調製した。母液のpHは10.2であった。
(工程2)母液を内温85℃まで加熱した後、当該母液にテトラメチルオルトシリケート2740gを内温変動しないよう温調しつつ、60分かけて定速滴下し、混合液を調製した。
(工程3)60分撹拌後、混合液に3-エトキシプロピルアミン(3-EOPA)28.00gを添加して、種粒子分散液を調製した。種粒子分散液のpHは9.5であった。次いで、種粒子分散液を常圧下ベース量として800mL採取し、容量を一定に保ちながらコロイダルシリカをフィードして、シリカ濃度が20wt%なるまで加熱濃縮した。次いで、反応時に副生したメタノールを系外留去するために、容量を一定に保ちながら、純水400mLにて分散媒を置換して、コロイダルシリカを調製した。得られたコロイダルシリカの物性を表1に示す。
(工程1)フラスコに、溶媒として純水7500gを入れ、アルカリ触媒としてジプロピルアミン(DPA)1.328gを添加し、母液を調製した。母液のpHは10.9であった。
(工程2)母液を内温85℃まで加熱した後、当該母液にテトラメチルオルトシリケート2740gを内温変動しないよう温調しつつ、60分かけて定速滴下し、混合液を調製した。
(工程3)15分撹拌後、混合液にジプロピルアミン(DPA)49.18gを添加して、種粒子分散液を調製した。種粒子分散液のpHは10.4であった。次いで、種粒子分散液を常圧下ベース量として800mL採取し、反応時に副生したメタノールを系外留去するために、容量を一定に保ちながら、純水1400mLにて分散媒を置換して、コロイダルシリカを調製した。コロイダルシリカのシリカ濃度は10wt%であった。得られたコロイダルシリカの物性を表1に示す。
(工程1)フラスコに、溶媒として純水7500gを入れ、アルカリ触媒としてトリエチルアミン(TEA)1.328gを添加し、母液を調製した。母液のpHは10.8であった。
(工程2)母液を内温85℃まで加熱した後、当該母液にテトラメチルオルトシリケート2740gを内温変動しないよう温調しつつ、60分かけて定速滴下し、混合液を調製した。
(工程3)15分撹拌後、混合液にトリエチルアミン(TEA)49.18gを添加して、種粒子分散液を調製した。種粒子分散液のpHは10.1であった。次いで、種粒子分散液を常圧下ベース量として800mL採取し、次いで、反応時に副生したメタノールを系外留去するために、容量を一定に保ちながら、純水650mLにて分散媒を置換して、コロイダルシリカを調製した。コロイダルシリカのシリカ濃度は10wt%であった。得られたコロイダルシリカの物性を表1に示す。
水1732gに25%水酸化テトラメチルアンモニウム(TMAH)水溶液0.151gを加え撹拌して母液を調製し、還流するまで加熱した。また、テトラメチルオルトシリケートを加水分解して、9%のケイ酸水溶液を調製した。還流下で、母液にケイ酸水溶液346.5gを3時間かけて滴下した後、30分間還流した。次いで、25%水酸化テトラメチルアンモニウム(TMAH)水溶液を1.26g滴下して種粒子分散液を調製した。次いで、種粒子分散液に水2910gを加え、撹拌して加熱還流した。次いで、9%ケイ酸水溶液500gと、25%水酸化テトラメチルアンモニウム(TMAH)水溶液1.21gとを2.5時間かけて滴下しながら、水とメタノールとの混合物を600g抽出した。この操作を26回行うことで、コロイダルシリカを調製した。得られたコロイダルシリカの物性を表1に示す。比較例1で得られたコロイダルシリカは、m/nの値が実施例1及び2と比較して少ないことが分かった。
水2000gに25%水酸化テトラメチルアンモニウム(TMAH)水溶液0.365gを加え撹拌して母液を調製し、80℃まで加熱した。母液の温度を80℃に保ちながら、テトラメチルオルトシリケート228gを3時間かけて滴下した。次いで、直ちに25%水酸化テトラメチルアンモニウム(TMAH)水溶液2.92gを添加した。温度を80℃に保ちながら、テトラメチルオルトシリケート228gと25%水酸化テトラメチルアンモニウム(TMAH)水溶液3.19gを3時間かけて滴下した。この操作を4回行うことで、コロイダルシリカを調製した。得られたコロイダルシリカの物性を表1に示す。比較例2で得られたコロイダルシリカは、屈曲分岐粒子含有量が低いことが分かった。
コロイダルシリカをホットプレートの上で予備乾燥後、800℃で1時間熱処理して測定用サンプルを調製した。調製した測定用サンプルを用いて、BET比表面積を測定した。シリカの真比重を2.2として、2727/BET比表面積(m2/g)の値を換算して、コロイダルシリカ中のシリカ粒子の平均一次粒子径n(nm)とした。
動的光散乱法の測定用サンプルとして、コロイダルシリカを0.3重量%クエン酸水溶液に加えて均一化したものを調製した。当該測定用サンプルを用いて、動的光散乱法(大塚電子株式会社製「ELSZ-2000S」)により平均二次粒子径を測定した。
平均二次粒子径/平均一次粒子径により算出される値を会合比とした。
走査型電子顕微鏡(SEM)で観察した20万倍での任意の視野内の粒子個数中から屈曲構造と分岐構造を有する粒子を数え、それら粒子の割合を屈曲分岐粒子含有量(%)とした。屈曲構造とは、3つ以上の粒子が一列に結合してできた粒子で直線ではないものであり、また、分岐構造とは、4つ以上の粒子が結合した粒子であって一列でない(枝を有する)ものである。
コロイダルシリカを215000G、90分の条件で遠心分離後、上澄みを廃棄して、固形分を60℃、90分の条件で真空乾燥させた。得られたシリカ乾固物0.5gを秤量し、1M水酸化ナトリウム水溶液50mlに入れ、撹拌させながら50℃で24時間加熱することでシリカを溶解させた。シリカ溶解液イオンクロマトグラフにより分析し、アミン量を求めた。イオンクロマトグラフ分析は、JIS K0127に従った。
コロイダルシリカを215000G、90分の条件で遠心分離後、上澄みを廃棄して、固形分を60℃、90分の条件で真空乾燥させた。得られたシリカ乾固物0.5gを秤量し、1M水酸化ナトリウム水溶液50mlに入れ、撹拌させながら50℃で24時間加熱することでシリカを溶解させた。前記シリカ溶解液をガスクロマトグラフにより分析し、アルコール含有量を求め、アルコキシ基の含有量とした。ガスクロマトグラフの検出器は水素炎イオン化検出器(FID)を用いた。ガスクロマトグラフ分析は、JIS K0114に従った。
アルコキシ基の含有量m(ppm)/平均一次粒子径n(nm)から算出される値をm/nとした。
試料を150℃のホットプレート上で乾固後、300℃炉内で1時間保持した後、エタノールを用いた液相置換法で測定する測定方法により、真比重を測定した。
コロイダルシリカ中のシリカ粒子のシラノール基密度はシアーズ法により求めることができる。シアーズ法は、G.W.Sears,Jr.,“Determination of Specific Surface Area of Colloidal Silica by Titration with Sodium Hydroxide”,Analytical Chemistry,28(12),1981(1956).の記載を参照して実施した。測定には1wt%シリカ分散液を使用し、0.1mol/Lの水酸化ナトリウム水溶液で滴定を行い、下記式に基づき、シラノール基密度を算出する。
ρ=(a×f×6022)÷(c×S)
上記式中、ρ:シラノール基密度(個/nm2)、a:pH4-9の0.1mol/L水酸化ナトリウム水溶液の滴下量(mL)、f: 0.1mol/L水酸化ナトリウム水溶液のファクター、c:シリカ粒子の質量(g)、S:BET比表面積(m2/g)をそれぞれ表す。
コロイダルシリカのゼータ電位を超音波減衰法を利用した測定装置を用いて測定した。
コロイダルシリカを5℃、77,000Gで、90分間遠心分離した。得られた沈殿物を60℃で12時間乾燥させた後、乳鉢と乳棒を使用してすりつぶし、60℃で2時間減圧乾燥して、乾燥粉を調製した。
Claims (12)
- 屈曲構造及び/又は分岐構造を持つシリカ粒子を含有するコロイダルシリカであって、
前記シリカ粒子の真比重は、1.95以上であり、
前記シリカ粒子は、アルコキシ基の含有量m(ppm)と、平均一次粒子径n(nm)との比(m/n)の値が200以上であり、
走査型電子顕微鏡で観察した20万倍での任意の視野内の粒子個数中、屈曲構造及び/又は分岐構造を持つシリカ粒子を15%以上含む、
ことを特徴とするコロイダルシリカ。 - 前記シリカ粒子の真比重は、1.95以上2.20以下である、請求項1に記載のコロイダルシリカ。
- 前記シリカ粒子は、1級アミン、2級アミン及び3級アミンからなる群より選択される少なくとも1種のアミン (ただし、置換基として、ヒドロキシル基は除外する)をシリカ粒子1g当たり5μmol以上以上含有する、請求項1又は2に記載のコロイダルシリカ。
- 前記シリカ粒子の表面に、下記一般式(1)
-(CH2)k-R5 (1)
(式(1)中、kは0以上の任意の整数を示し、R5は任意の官能基を示す。)
で表される有機官能基を有する、請求項1~3のいずれかに記載のコロイダルシリカ。 - 前記シリカ粒子の表面に、カチオン性有機官能基を有する、請求項1~4のいずれかに記載のコロイダルシリカ。
- 前記シリカ粒子の表面に、アミノ基を有する、請求項5に記載のコロイダルシリカ。
- 前記シリカ粒子の表面に、アニオン性有機官能基を有する、請求項1~4のいずれかに記載のコロイダルシリカ。
- 前記シリカ粒子の表面に、スルホ基を有する、請求項7に記載のコロイダルシリカ。
- (1)アルカリ触媒及び水を含む母液を調製する工程1、
(2)アルコキシシランを前記母液に添加して混合液を調製する工程2、及び、
(3)前記混合液にアルカリ触媒を添加して、種粒子分散液を調製する工程3
をこの順に有するコロイダルシリカの製造方法であって、
前記アルカリ触媒は、1級アミン、2級アミン及び3級アミンからなる群より選択される少なくとも1種のアミン(ただし、置換基として、ヒドロキシル基は除外する)である、
ことを特徴とするコロイダルシリカの製造方法。 - 前記工程3の後に、(4)前記種粒子分散液に、水及びアルコキシシランを添加する工程4を有する、請求項9に記載の製造方法。
- 前記工程2における前記アルコキシシランの添加量s2(mol)と、前記母液中の前記アルカリ触媒の量c1(mol)のモル比(s2/c1)は、800以上である、請求項9又は10に記載の製造方法。
- 前記工程2における前記アルコキシシランの添加量s2(mol)と、前記工程3におけるアルカリ触媒の添加量c3(mol)とのモル比(s2/c3)は、185以下である、請求項9~11のいずれかに記載の製造方法。
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JP7119208B2 (ja) | 2022-08-16 |
KR20210132177A (ko) | 2021-11-03 |
CN113544093A (zh) | 2021-10-22 |
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CN113544093B (zh) | 2024-07-26 |
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