CN117730055A - Low dielectric loss tangent silica sol and method for producing low dielectric loss tangent silica sol - Google Patents
Low dielectric loss tangent silica sol and method for producing low dielectric loss tangent silica sol Download PDFInfo
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- CN117730055A CN117730055A CN202380012875.0A CN202380012875A CN117730055A CN 117730055 A CN117730055 A CN 117730055A CN 202380012875 A CN202380012875 A CN 202380012875A CN 117730055 A CN117730055 A CN 117730055A
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- silica particles
- silica
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- silica sol
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims description 116
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 325
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000001179 sorption measurement Methods 0.000 claims abstract description 52
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- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
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- 238000000034 method Methods 0.000 claims description 59
- 125000001424 substituent group Chemical group 0.000 claims description 54
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 37
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 34
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- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
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- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- JFJRLGIMKOMFAZ-UHFFFAOYSA-N phenyl(dipropoxy)silane Chemical compound CCCO[SiH](OCCC)C1=CC=CC=C1 JFJRLGIMKOMFAZ-UHFFFAOYSA-N 0.000 description 1
- FABOKLHQXVRECE-UHFFFAOYSA-N phenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=CC=C1 FABOKLHQXVRECE-UHFFFAOYSA-N 0.000 description 1
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention provides silica particles having a dielectric loss tangent of 0.01 or less at 1GHz and a dispersion thereof. The solution is that the medium at 1GHz satisfies the following matters (i), (ii) and (iii)Silica particles having a mass loss tangent of 0.01 or less, and a dispersion thereof, (i) an average primary particle diameter of 5 to 120nm, (ii) a specific surface area (S) measured by steam adsorption H2O ) And the specific surface area measured by nitrogen adsorption (S N2 ) Ratio (S) H2O /S N2 ) Is 0.6 or less, (iii) has a total silanol group ratio of 5% or less represented by the following formula (1), all silanol group ratio (%) = (q2×2/4+q3×1 +. 4+Q4X0/4) formula (1) [ in formula (1), Q2, Q3, Q4 represent the content ratio of the Q2 structure, the Q3 structure, and the Q4 structure in the silicon atoms of the silica particles.]。
Description
Technical Field
The present invention relates to silica particles having a low dielectric loss tangent, a dispersion thereof, and a method for producing the same.
Background
In recent years, with an increase in information traffic in the field of 5G and the like, efficient use of a high frequency band in electronic devices, communication devices and the like has been expanding.
As a problem of increasing transmission loss of a circuit signal occurs with the application of a high frequency band, a material having a low dielectric loss tangent is generally used for an insulator constituting an electric and electronic component such as an antenna, a circuit, or a substrate. The polymer material used for the insulator material is generally a material having a low dielectric constant but a high dielectric loss tangent. On the other hand, ceramic materials are often materials having their opposite properties. Therefore, a ceramic filler-filled polymer material that combines these materials to have both low dielectric constant and low dielectric loss tangent characteristics has been widely used (patent documents 1 and 2).
As the ceramic filler (inorganic filler), fused silica having a micron size is generally widely used, but coarse particles generated during production have a large influence on the performance of molded articles, and separation and removal of coarse particles are a problem (non-patent document 1, patent document 2, patent document 3, and patent document 4).
On the other hand, since the silica particles having an average particle diameter of nano-scale are not easily produced as coarse particles in production, and can be filtered and centrifugally separated, it is considered that the separation/removal is easy even if coarse particles are produced. It is also considered that the nano-sized particles have various advantages such as being applicable to transparent polymer materials and having a large recombination effect as compared with the micro-sized filler (patent documents 5 and 6).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2014-24916
Patent document 2: japanese patent No. 6793282
Patent document 3: japanese patent application laid-open No. 2004-269636
Patent document 4: japanese patent No. 6546386
Patent document 5: japanese patent No. 5862886
Patent document 6: japanese patent No. 6813815
Non-patent literature
Non-patent document 1: fuji mountain , month 12 of 2019, no.831906736, in 2020-2030, the back of the child is cut off, the size of the new child is reduced by , and the back of the child is explored (the full exploration of the new low dielectric material of the next generation targeting 2020-2030)
Disclosure of Invention
Problems to be solved by the invention
As described above, although nano-sized particles have various advantages in ceramic fillers, conventional nano-sized particles have a high dielectric loss tangent, and thus are difficult to apply to materials for electronic devices and the like operating in a high frequency band.
The present invention has been made in view of the above circumstances, and an object thereof is to provide nanoscale particles having a low dielectric loss tangent, specifically, silica particles having a dielectric loss tangent of 0.01 or less at 1GHz and a dispersion thereof.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that silica particles having an average primary particle diameter of 5nm to 120nm, a specific surface area measured by water vapor adsorption and a specific surface area measured by nitrogen adsorption of 0.6 or less, and a total silanol group ratio of 5% or less exhibit low dielectric characteristics such that the dielectric loss tangent at 1GHz is 0.01 or less, and completed the present invention.
Further, the present inventors have found that silica particles (surface-modified silica particles) obtained by modifying at least a part of the surface of the silica particles with an organosilicon compound having an alkyl group and/or a substituent having an unsaturated bond are also particles exhibiting low dielectric characteristics such that the dielectric loss tangent at 1GHz is 0.01 or less, and have completed the present invention.
That is, in the present invention, as the 1 st aspect, there is provided silica particles having a dielectric loss tangent of 0.01 or less at 1GHz, which satisfy the following items (i), (ii) and (iii).
(i) The average primary particle diameter is 5nm to 120nm,
(ii) Specific surface area measured by vapor adsorption (S H2O ) And the specific surface area measured by nitrogen adsorption (S N2 ) Ratio (S) H2O /S N2 ) Is not more than 0.6 and is preferably used,
(iii) The total silanol groups represented by the following formula (1) are 5% or less,
all silanol group ratio (%) = (q2×2 +. 4+Q3×1/4+Q4×0 +. 4) formula (1)
[ in formula (1), Q2, Q3, Q4 are each represented by 29 The ratio (%) of the peak area of the structure derived from each silicon atom obtained by Si NMR measurement to the total (100%) of the peak areas of the structures derived from silicon atoms, Q2 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 2 oxygen atoms and 2 hydroxyl groups, and Q3 represents the ratio derived from the structures bonded with 3 oxygen atoms and 1 hydroxyl groupThe ratio of peak areas of the structures of silicon atoms, Q4 represents the ratio of peak areas of the structures derived from silicon atoms to which 4 oxygen atoms are bonded.]
The silica particles according to item 2, which are characterized in that at least a part of the surface of the silica particles is coated with an organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond.
The silica particles according to the aspect 3 are, as described in the aspect 1, obtained by bonding at least a part of an organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond to the surface of at least a part of the silica particles.
The silica particles according to the aspect 4 are the silica particles according to the aspect 2 or the aspect 3, wherein the substituent of the organosilicon compound is at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a phenyl group, a phenylmethyl group, and a vinyl group.
The silica particles according to any one of the aspects 2 to 4, wherein the organosilicon compound has the substituent and a hydrolyzable group.
The silica particles according to the aspect 6 are the silica particles according to the aspect 2 or the aspect 3, wherein the organic silicon compound is at least one compound selected from the group consisting of compounds represented by the following formulas (a) to (g).
The silica particles according to any one of the aspects 2 to 6, wherein the organosilicon compound is present at a concentration of 1nm per silica particle 2 The silica particles have a surface area of 0.5 to 6, and are coated or bonded to the surface.
As an aspect 8, there is provided a silica dispersion liquid obtained by dispersing the silica particles described in the aspect 1 in water or an organic solvent.
As a 9 th aspect, the silica dispersion according to any one of the 2 nd to 7 th aspects is a silica dispersion obtained by dispersing silica particles in at least 1 organic solvent selected from alcohols, ketones, hydrocarbons, amides, ethers, esters and amines.
As a 10 th aspect, there is provided a composite material comprising the silica particles according to any one of the 2 nd to 7 th aspects and an organic resin material.
The 11 th aspect relates to the composite material according to the 10 th aspect, wherein the organic resin material is at least 1 selected from the group consisting of epoxy resin, phenol resin, acrylic resin, maleimide resin, polyurethane, polyimide, polytetrafluoroethylene, cycloolefin polymer, unsaturated polyester, vinyl triazine, crosslinkable polyphenylene ether, and curable polyphenylene ether.
As a 12 th aspect, the composite material of the 10 th or 11 th aspect is directed to a use selected from the group consisting of a semiconductor device material, a copper clad laminate, a flexible wiring material, a flexible display material, an antenna material, an optical wiring material, and a sensor material.
As a 13 th aspect, there is provided a method for producing surface-modified silica particles, comprising the steps of: a step of mixing silica particles, which are described below, with an organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond in an organic solvent,
the silica particles have an average primary particle diameter of 5 to 120nm and a specific surface area (S H2O ) And the specific surface area measured by nitrogen adsorption (S N2 ) Ratio (S) H2O /S N2 ) 0.6 or less, and the total silanol group ratio represented by the following formula (1) is 5% or less:
all silanol group ratio (%) = (q2×2 +. 4+Q3×1/4+Q4×0 +. 4) formula (1)
[ in formula (1), Q2, Q3, Q4 are each represented by 29 Obtained by Si NMR measurementThe ratio (%) of the peak area of the structure derived from each silicon atom to the total (100%) of the peak areas of the structures derived from the silicon atoms, Q2 represents the ratio of the peak areas of the structures derived from the silicon atoms to which 2 oxygen atoms and 2 hydroxyl groups are bonded, Q3 represents the ratio of the peak areas of the structures derived from the silicon atoms to which 3 oxygen atoms and 1 hydroxyl group are bonded, and Q4 represents the ratio of the peak areas of the structures derived from the silicon atoms to which 4 oxygen atoms are bonded.]。
As a 14 th aspect, there is provided a method for producing surface-modified silica particles, comprising the following steps (a) to (C):
(A) The working procedure comprises the following steps: a step of preparing a silica sol containing silica particles having an average primary particle diameter of 5 to 120nm and an alcohol having 1 to 4 carbon atoms as a dispersion medium, the silica sol having a specific surface area (S H2O ) And the specific surface area measured by nitrogen adsorption (S N2 ) Ratio (S) H2O /S N2 ) 0.6 or less, and the total silanol groups ratio represented by the following formula (1) is 5% or less,
all silanol group ratio (%) = (q2×2 +. 4+Q3×1/4+Q4×0 +. 4) formula (1)
[ in formula (1), Q2, Q3, Q4 are each represented by 29 The ratio (%) of the peak area of the structure derived from each silicon atom obtained by Si NMR measurement to the total (100%) of the peak areas of the structures derived from silicon atoms, Q2 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 2 oxygen atoms and 2 hydroxyl groups, Q3 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 3 oxygen atoms and 1 hydroxyl group, and Q4 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 4 oxygen atoms.]
(B) The working procedure comprises the following steps: a step of heating and stirring an organosilicon compound having at least 1 substituent selected from an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond, with the silica sol obtained in the step (A) at 40 to 100 ℃ for 0.1 to 10 hours,
(C) The working procedure comprises the following steps: and (c) removing the alcohol solvent from the silica sol obtained in the step (B).
As the 15 th aspect, the method for producing surface-modified silica particles according to the 14 th aspect is one wherein either one or both of the (B) step and the (C) step are performed under reduced pressure.
In the 16 th aspect, the method for producing surface-modified silica particles according to the 14 th aspect is characterized in that the silica sol prepared in the step (a) is a silica sol having a moisture content of 0.1 to 2 mass%.
In the 17 th aspect, the method for producing surface-modified silica particles according to the 14 th aspect is characterized in that the silica sol prepared in the step (a) is a silica sol obtained by replacing an aqueous silica sol solvent obtained by hydrothermal synthesis at 200 to 380 ℃ and 2 to 22MPa with an alcohol having 1 to 4 carbon atoms.
As an 18 th aspect, there is provided a method for producing a surface-modified silica dispersion, comprising the following steps (a) and (B):
(A) The working procedure comprises the following steps: a step of preparing a silica sol containing silica particles as a dispersoid and an alcohol having 1 to 4 carbon atoms as a dispersion medium,
the silica particles have an average primary particle diameter of 5 to 120nm and a specific surface area (S H2O ) And the specific surface area measured by nitrogen adsorption (S N2 ) Ratio (S) H2O /S N2 ) 0.6 or less, and the total silanol groups ratio represented by the following formula (1) is 5% or less,
all silanol group ratio (%) = (q2×2 +. 4+Q3×1/4+Q4×0 +. 4) formula (1)
[ in formula (1), Q2, Q3, Q4 are each represented by 29 The ratio (%) of the peak area of the structure derived from each silicon atom obtained by Si NMR measurement to the total (100%) of the peak areas of the structures derived from silicon atoms, Q2 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 2 oxygen atoms and 2 hydroxyl groups, Q3 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 3 oxygen atoms and 1 hydroxyl group, and Q4 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 4 oxygen atoms.]
(B) The working procedure comprises the following steps: and (b) a step of heating and stirring the silica sol obtained in the step (A) at 40 to 100 ℃ for 0.1 to 10 hours, the organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond.
As a 19 th aspect, the method for producing a surface-modified silica dispersion according to the 18 th aspect further comprises the following step (D):
(D) The working procedure comprises the following steps: and (c) replacing the silica sol solvent obtained in the step (B) with at least 1 solvent selected from the group consisting of alcohols, ketones, hydrocarbons, amides, esters, ethers and amines.
ADVANTAGEOUS EFFECTS OF INVENTION
The silica particles and the surface-modified silica of the present invention exhibit the effect of exhibiting low dielectric characteristics. In addition, the dispersion in an organic solvent is satisfactory. Further, the silica particles according to the present invention can form a composite material with an organic resin material, and thus can be expected to be used for the production of semiconductor device materials and the like.
Detailed Description
< silica particle >)
The silica particles of the present invention satisfy the following items (i), (ii) and (iii) and have a dielectric loss tangent at 1GHz of 0.01 or less.
(i) The average primary particle diameter is 5nm to 120nm,
(ii) Specific surface area measured by vapor adsorption (S H2O ) And the specific surface area measured by nitrogen adsorption (S N2 ) Ratio (S) H2O /S N2 ) Is not more than 0.6 and is preferably used,
(iii) The total silanol groups represented by the following formula (1) are 5% or less,
all silanol group ratio (%) = (q2×2 +. 4+Q3×1/4+Q4×0 +. 4) formula (1)
[ in formula (1), Q2, Q3, Q4 are each represented by 29 The peak area of the structure derived from each silicon atom obtained by Si NMR measurement is relative to the peak area of the structure derived from the silicon atomThe ratio (%), Q2 represents the ratio of the peak areas derived from the structure of the silicon atom having 2 oxygen atoms and 2 hydroxyl groups, Q3 represents the ratio of the peak areas derived from the structure of the silicon atom having 3 oxygen atoms and 1 hydroxyl group, and Q4 represents the ratio of the peak areas derived from the structure of the silicon atom having 4 oxygen atoms. ]
< average primary particle diameter >)
The average primary particle diameter of the silica particles according to the present invention can be determined by the BET method using nitrogen as an adsorption molecule to the particle surface, and the specific surface area (S N2 ) The calculated specific surface area diameter.
The specific surface area diameter (average primary particle diameter: D (nm)) is the specific surface area S measured by the nitrogen adsorption method (BET method) N2 (m 2 The primary particle diameter calculated by the formula D (nm) =2720/S means the particle diameter converted into spherical silica particles.
The silica particles according to the present invention may have an average primary particle diameter in the range of 5nm to 120nm, for example, in the range of 5nm to 100 nm.
Silica particles having an average primary particle diameter of 5 to 100nm exhibit a low dielectric loss tangent and can be well dispersed in an organic solvent. In addition, when a composite material using the silica particles is molded, defects can be suppressed and high transparency can be exhibited.
Specific surface area measured by Nitrogen adsorption (S N2 )＞
The silica particles according to the present invention can have a specific surface area (S N2 ) 25-550 m 2 Per gram, or 25-300 m 2 Per gram, or 25-250 m 2 Substances in the range of/g.
By making the specific surface area (S N2 ) 25 to 250m 2 And/g, thereby efficiently performing surface modification with an organosilicon compound while maintaining a low dielectric loss tangent.
Specific surface area measured by steam adsorption (S H2O )＞
Specific surface area of silica particles measured by vapor adsorption (S H2O ) The measurement can be performed by a BET method using water vapor as an adsorption molecule to the particle surface.
The silica particles according to the present invention can have a specific surface area (S H2O ) Is 5 to 500m 2 Per gram, or 5-300 m 2 Per gram, or 5-100 m 2 Substances in the range of/g.
By making the specific surface area (S H2O ) In the above numerical range, the silica particles can be well dispersed in an organic solvent, and the surface modification with an organosilicon compound can be efficiently performed. Further, by making the specific surface area (S H2O ) Is 5 to 100m 2 And/g, whereby the decrease in dielectric loss tangent due to moisture absorption can also be suppressed.
Specific surface area ratio (S) H2O /S N2 )＞
Specific surface area measured by vapor adsorption (S H2O ) And the specific surface area measured by nitrogen adsorption (S N2 ) Ratio (S) H2O /S N2 ) The larger the value, the more active sites are present on the silica surface, which is an index of the presence amount of active sites (surface silanol) per unit surface area of the particles.
The silica particles according to the present invention can use the specific surface area ratio (S H2O /S N2 ) Is 0.6 or less. By using a compound having such S H2O /S N2 The silica particles of (3) can be used to improve dispersibility in an organic solvent without increasing the dielectric loss tangent, and can be efficiently surface-modified with an organosilicon compound.
< all silanol groups Rate >)
Silicon (Q4) not bonded to hydroxyl groups, and silicon bonded to 1 (Q3), 2 (Q2), or 3 (Q1) hydroxyl groups are present in silicon atoms in the silicon dioxide.
That is, in the silica of the present invention, the silicon atoms mainly have 3 structures, i.e., a silicon atom (Q2) having 2 oxygen atoms and 2 hydroxyl groups bonded thereto, a silicon atom (Q3) having 3 oxygen atoms and 1 hydroxyl group bonded thereto, and a silicon atom (Q4) having 4 oxygen atoms bonded thereto, as shown in the following formula.
Further, by determining the ratio of Q2, Q3, and Q4 in the silicon atoms in the silica, the silanol (si—oh) group amount of the silica can be estimated.
In the present specification, the total silanol group ratio means the existence ratio of silanol groups in all silicon atoms of Q2 to Q4 structures of the silica particles.
The existence rate of silanol groups in the silicon atoms having the above-mentioned Q2 to Q4 structures can be determined, for example, by using a water-dispersible silica sol containing silica particles as a target of investigation of the existence rate 29 Si NMR method.
Specifically, will pass through 29 The spectrum obtained by the Si NMR method was subjected to waveform separation, and peaks observed between-80 ppm and-105 ppm in chemical shift were identified as originating from Q2 structure, peaks observed between-90 ppm and-115 ppm were identified as originating from Q3 structure, and peaks observed between-95 ppm and-130 ppm were identified as originating from Q4 structure. At this time, the ratio (%) of the area value of each peak of Q2 to Q4 to the total (100%) of the area values of each peak becomes the content ratio (mol%) of each structure (Q2 to Q4) in the silica particles to be measured. Further, the total silanol group ratio (%) can be calculated according to the following formula using the value and the content ratio of hydroxyl groups in each of the structures Q2 to Q4 relative to the total mole number of oxygen atoms and hydroxyl groups.
All silanol group ratio (%) = (q2×2 +. 4+Q3×1/4+Q4×0 +. 4) formula (1)
In the above formula, Q2, Q3 and Q4 respectively represent a group represented by 29 The sum of the peak areas of the structures derived from the silicon atoms obtained by Si NMR measurement and the peak areas of the structures derived from the silicon atoms (100%)The ratio (%) of each structure obtained from the above NMR measurement result.
In the silica particles according to the present invention, the total silanol group ratio is 5% or less, and if it is more than 5%, the dielectric characteristics of low dielectric constant/dielectric loss tangent cannot be exhibited.
The silica particles of the present invention are not particularly limited in their production method, but are preferably those which have been heat-treated in water at 200 to 380 ℃. The heat treatment may be performed using a pressure-resistant vessel (autoclave).
< organosilicon Compound >)
The silica particles of the present invention also include a case where at least a part of the surface of the silica particles is covered with an organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond (these are collectively referred to simply as "substituents"), or a case where at least a part of an organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond is bonded to the surface of at least a part of the silica particles, that is, a case where the surface of the particles is modified with an organosilicon compound (these cases are collectively referred to as "surface-modified silica particles"). In the present specification, the term "surface modification" also includes both of a case where the surface of the silica particles is coated with the organosilicon compound and a case where the organosilicon compound is bonded to the surface of the silica particles.
In the present invention, the term "at least a part of the surface of the silica particles is covered with the organosilicon compound" may be any one as long as the organosilicon compound described later covers at least a part of the surface of the silica particles, that is, the organosilicon compound covers a part of the surface of the silica particles and the organosilicon compound covers the entire surface of the silica particles. This scheme is whether or not the organosilicon compound is bonded to the surface of the silica particles.
In the present invention, the term "bonding at least a part of the organosilicon compound to at least a part of the surface of the silica particles" may be any one as long as the organosilicon compound to be described later is bonded to at least a part of the surface of the silica particles, that is, the organosilicon compound to be described later is bonded to a part of the surface of the silica particles and covers at least a part of the surface, the organosilicon compound to be described later is bonded to the entire surface of the silica particles and covers the entire surface, and the like.
The organosilicon compound may be any compound having the substituent, and examples thereof include a silicon compound having the substituent and a hydrolyzable group described later, an organosilicon compound having the substituent and a Si-O-Si bond, and an organosilicon compound having the substituent and a Si-N-Si bond. The surface-modified silica particles can be obtained by surface-modifying the silica particles with these organosilicon compounds.
Among the substituents of the organosilicon compound, the alkyl group, the aryl group having 6 to 12 carbon atoms, and the substituent having an unsaturated bond are preferably an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, decyl), phenyl, phenylmethyl, or vinyl group, and if a plurality of the substituents are present, the alkyl group, the aryl group, and the substituent may be the same or different from each other.
The hydrolyzable groups are preferably the same or different in number. The alkoxy group is preferably an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a methoxy group.
In the case where the organosilicon compound is a silicon compound having the substituent and the hydrolyzable group, the number of substituents and the number of hydrolyzable groups are not particularly limited, but it is preferable that the organosilicon compound has 1 to 3 substituents and 1 to 3 hydrolyzable groups per silicon atom (however, the sum of both groups is not more than 4).
Specific examples of the organosilicon compound having a substituent and a hydrolyzable group include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, methyltripropoxysilane, dimethyldipropoxysilane, trimethylpropoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, phenyltripropoxysilane, diphenyldipropoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyldipropoxysilane, vinyltrimethoxysilane, divinyldimethoxysilane, vinyltriethoxysilane, divinyldiethoxysilane, vinyltripropoxysilane, divinyldipropoxysilane, decyltrimethoxysilane, hexamethyldisiloxane, and the like.
Among them, organosilicon compounds represented by the following formulas (a) to (g) are preferable.
Among the substituents of the organosilicon compound having a substituent and a Si-O-Si bond, the alkyl group (for example, an alkyl group having 1 to 10 carbon atoms), the aryl group having 6 to 12 carbon atoms, and the substituent having an unsaturated bond are preferably methyl, decyl, phenyl, phenylmethyl, or vinyl groups, and if a plurality of the substituents are present, they may be the same or different from each other. Methyl is particularly preferred, and specific examples of the organosilicon compound include hexamethyldisiloxane.
Among the substituents of the organosilicon compound having a substituent and an Si-N-Si bond, the alkyl group (for example, an alkyl group having 1 to 10 carbon atoms), the aryl group having 6 to 12 carbon atoms, and the substituent having an unsaturated bond are preferably methyl, decyl, phenyl, phenylmethyl, or vinyl groups, and if a plurality of the substituents are present, they may be the same or different from each other. Methyl is particularly preferred, and specific examples of the organosilicon compound include hexamethyldisilazane.
Surface treatment (repair) using the above organosilicon compoundDecoration), i.e., the surface of the coated silica particles or the organosilicon compound bonded to the surface, may be 1nm per silica particle 2 The surface area is, for example, about 0.5 to 6.
The method for producing the surface-modified silica particles, that is, the method for coating (surface treatment) the surfaces of the silica particles using the above-mentioned organosilicon compound is not particularly limited, and for example, the silica particles may be surface-modified by adding at least one of the organosilicon compounds represented by the above-mentioned formulas (a) to (g) to an organic solvent dispersion of the silica particles and mixing them, so that hydrolysis and condensation of the organosilicon compound occur.
As for the addition amount of the organosilicon compound, it is possible to add silica particles per 1nm 2 The surface area, for example, the organosilicon compound is added in a range of about 0.5 to 6.0 to modify the surface. For example, silica particles can be used at a concentration of 1nm 2 The surface area is 0.5 to 10.0, or 1.0 to 8.0, or 1.0 to 6.0. The remaining organosilicon compound which does not contribute to surface modification may be present in the system, but the preferable organosilicon compound is added in an amount of 1nm per 1nm of the silica particles 2 The surface area is 1.0 to 6.0.
The hydrolysis of the organosilicon compound may be carried out completely or partially, but water is necessary, and it is preferable to add about 1 mol or more of water to 1 mol of the hydrolyzable group of the organosilicon compound, the [ Si-O-Si ] bond or the [ Si-N-Si ] bond. In addition, moisture contained in the organic solvent may be used.
In the case of using an organosilicon compound having a hydrolyzable group, the hydrolysis may be performed completely or partially, but water is necessary, and preferably about 1 mol or more of water is added to 1 mol of the hydrolyzable group of the organosilicon compound. In addition, moisture contained in the organic solvent may be used.
In the case of hydrolyzing and condensing, a catalyst may be used. As the hydrolysis catalyst, a chelate compound, an organic acid, an inorganic acid, an organic base, or an inorganic base may be used alone or in combination. More specifically, for example, an aqueous hydrochloric acid solution, acetic acid, an aqueous ammonia solution, or the like can be used.
< determination of dielectric Properties >)
The dielectric constant and dielectric loss tangent of the silica particles can be measured using a special apparatus using a dry powder of silica particles. Examples of the dedicated device include a vector network analyzer (trade name: fieldFox N6626A, manufactured by KEYSIGHT TECHNOLOGIES).
When the silica particles are compounded with an organic resin material and are suitable for use as an insulator, the silica particles preferably have a dielectric loss tangent of 0.01 or less, particularly 0.009 or less at a frequency of 1 GHz. The lower limit value of the dielectric loss tangent is 0.00001, 0.00005, 0.0001, or 0.0005.
Silicon dioxide dispersion (1) >, a process for producing the same
The silica dispersion of the present invention is a dispersion obtained by dispersing the silica particles in water or an organic solvent. The silica particles as the dispersoids of the present dispersion liquid are surface-modified (coated/bonded) by the above-mentioned organosilicon compound, regardless of the particle surfaces.
Examples of the organic solvent include alcohols, ketones, ethers, and amides.
Examples of the alcohols include alcohols having 1 to 5 carbon atoms, and specifically, methanol, ethanol, isopropanol, n-butanol, and the like.
Examples of the ketones include ketones having 1 to 5 carbon atoms, and specifically methyl ethyl ketone, methyl isobutyl ketone, γ -butyl lactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and the like.
Examples of the ethers include ethylene glycol monomethyl ether and propylene glycol monomethyl ether.
Examples of the amides include dimethylacetamide, N-dimethylformamide, dimethylacrylamide, acryloylmorpholine, diethylacrylamide, and the like.
< surface-modified silica Dispersion [ silica Dispersion (2) ] >
The silica dispersion of the present invention also includes a dispersion of silica particles (surface-modified silica particles) whose particle surfaces are surface-modified (coated/bonded) with the above-mentioned organosilicon compound, and the dispersion of this dispersion is hereinafter referred to as "surface-modified silica dispersion" (also referred to as "surface-modified silica particle dispersion").
The surface-modified silica dispersion of the present invention is a dispersion in which the surface-modified silica particles are dispersed in at least 1 organic solvent selected from alcohols, ketones, hydrocarbons, amides, ethers, esters and amines.
Examples of the alcohols include alcohols having 1 to 5 carbon atoms, and specifically, methanol, ethanol, isopropanol, n-butanol, and the like.
Examples of the ketones include ketones having 1 to 5 carbon atoms, and specifically methyl ethyl ketone, methyl isobutyl ketone, γ -butyl lactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and the like.
Examples of the hydrocarbon include toluene, xylene, n-pentane, n-hexane, and cyclohexane.
Examples of the amides include dimethylacetamide, N-dimethylformamide, dimethylacrylamide, acryloylmorpholine, diethylacrylamide, and the like.
Examples of the ethers include ethylene glycol monomethyl ether and propylene glycol monomethyl ether.
Examples of the esters include ethyl acetate and butyl acetate.
Examples of the amines include triethylamine, tributylamine, N-dimethylaniline, pyridine, picoline and the like.
The content of the surface-modified silica particles in the surface-modified silica dispersion may be expressed as a (surface-modified) silica concentration. The surface-modified silica concentration can be calculated by measuring the firing residual component obtained by firing the surface-modified silica dispersion at 1000 ℃. The concentration of the surface-modified silica in the surface-modified silica dispersion may be, for example, 1 to 60 mass%, or 10 to 40 mass%.
The water content of the surface-modified silica dispersion is preferably 5 mass% or less. By setting the water content to this level, the stability of the dispersion may be improved, and a composite material with an organic resin material may be easily obtained.
< composite Material >)
The composite material according to the present invention is a composite material comprising the silica particles according to the present invention and an organic resin material. The silica particles to be blended in the composite material are preferably surface-modified silica particles, regardless of whether or not the particle surfaces thereof are surface-modified (coated/bonded) with the above-mentioned organosilicon compound.
The organic resin material may be selected from at least 1 selected from epoxy resins, phenolic resins, acrylic resins, maleimide resins, polyurethanes, polyimides, polytetrafluoroethylene, cyclic olefin polymers, unsaturated polyesters, vinyl triazines, crosslinkable polyphenylene ethers, and curable polyphenylene ethers.
The method for producing the composite material is not particularly limited, and for example, a composite material can be obtained by mixing a dispersion of silica particles or surface-modified silica particles with a monomer or polymer solution of an organic resin material to prepare a polymerizable composition, removing the remaining solvent, and then subjecting the resultant to light or heat curing. Further, the polymerizable composition may be prepared by directly adding silica particles or a powder of surface-modified silica particles to a monomer or polymer solution of an organic resin material, removing the remaining solvent, and then subjecting the resulting solution to light or heat curing to obtain a composite material.
The mixing ratio of the silica particles or the surface-modified silica particles in the polymerizable composition to the monomer or polymer solution of the organic resin material may be calculated as the mass ratio of the (surface-modified) silica particles to the monomer or polymer of the organic resin material: monomer or polymer of organic resin material = 1:100 to 0.1, for example 1:20 to 0.1.
The polymerizable composition can be cured by using a polymerization initiator with light or heat. The photopolymerization initiator may be a photo radical polymerization initiator or a photo cation polymerization initiator, and the thermal polymerization initiator may be a thermal radical polymerization initiator or a thermal cation polymerization initiator. The polymerization initiator may be used in the range of 0.01 to 50 parts by mass based on 100 parts by mass of the polymerizable composition.
Further, as optional components, conventional additives used in conventional polymerizable compositions (composite materials) may be used by mixing various additives used in the technical field, such as a catalyst for curing acceleration, a pigment, a radical scavenger (quencher), a leveling agent, a viscosity regulator, an antioxidant, an ultraviolet absorber, a stabilizer, a plasticizer, and a surfactant.
The composite material of the present invention can be used as a semiconductor device material, a copper clad laminate, a flexible wiring material, a flexible display material, an antenna material, an optical wiring material, or a sensor material by selecting an appropriate organic resin material according to the use.
Method for producing surface-modified silica particles
The surface-modified silica particles according to an embodiment of the present invention can be produced by a process comprising: a step of mixing silica particles having an average primary particle diameter of 5 to 120nm, a specific surface area (S H2O ) And the specific surface area measured by nitrogen adsorption (S N2 ) Ratio (S) H2O /S N2 ) 0.6 or less and the total silanol groups ratio is 5% or less.
The silica particles and the organosilicon compound may be used as the silica particles and the organosilicon compound, respectively.
In the mixing step, the amount of the organosilicon compound may be as followsEvery 1nm of silica particles 2 The surface area is 0.5 to 6. Specifically, silica particles can be used per 1nm 2 The organosilicon compound is added so that the surface area is 0.5 to 10.0, or 1.0 to 8.0, or 1.5 to 6.0. The remaining organosilicon compound that does not contribute to the surface modification may be present in the reaction system.
The organic solvent used in the mixing step may be an organic solvent containing an alcohol and/or a ketone solvent.
The alcohol may be an alcohol having 1 to 5 carbon atoms, and specifically, methanol, ethanol, isopropanol, n-butanol, and the like.
The ketone solvent includes those having 1 to 5 carbon atoms, and specifically, methyl ethyl ketone, methyl isobutyl ketone, gamma-butyrolactone, and the like.
The mixing step is not particularly limited as long as it is a temperature at which the hydrolysis and condensation reaction of the organosilicon compound proceeds, and may be performed at a temperature of 20 ℃ or more and less than 120 ℃.
In terms of reaction efficiency, it is preferable to conduct the mixing step around the boiling point of the organic solvent, for example, 65℃if the organic solvent containing methanol is used. The reaction may be carried out by a device having a reflux device or the like as needed in order to suppress the variation in the silica concentration and the organosilicon compound concentration in the mixing step. The mixing step may be performed at the same temperature a plurality of times, or may be performed at different temperatures a plurality of times.
The mixing step may be performed for 30 minutes to 24 hours, and is desirably performed within 24 hours from the industrial point of view.
The mixing step may further include a step of adjusting the pH using an organic amine. The pH adjustment step may be performed 1 or more times before the mixing step, during the mixing step, or after the mixing step.
As the organic amine, a secondary amine or a tertiary amine can be used. As the secondary or tertiary amine, alkylamine, allylamine, aralkylamine, alicyclic amine, alkanolamine, cyclic amine, and the like can be used.
Specifically, diethylamine, triethylamine, diisopropylamine, tri-isopropylamine, di-N-propylamine, tri-N-propylamine, diisobutylamine, di-N-butylamine, tri-N-butylamine, dipentylamine, tripentylamine, di-2-ethylhexyl amine, di-N-octylamine, tri-N-octylamine, N-ethyldiisopropylamine, dicyclohexylamine, N-dimethylbutylamine, N-dimethylhexylamine, N, N-dimethyloctylamine, N-dimethylbenzylamine, piperidine, N-methylpiperidine, quinuclidine, triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-diethylethanolamine, N, N-dibutylethanolamine, triisopropanolamine, imidazole derivatives, 1, 8-diaza-bicyclo (5, 4, 0) undec-7-ene, 1, 5-diaza-bicyclo (4, 3, 0) non-5-ene, 1, 4-diaza-bicyclo (2, 2) octane, diallylamine, and the like. These organic amines may be used singly or in combination of 1 or more than 2.
The amount of the organic amine to be added may be 0.001 to 5% by mass and 0.01 to 1% by mass based on the mass of the silica particles. The pH of the mixed solution may be adjusted to 4.0 to 11.0, preferably pH7.5 to 9.5, by adding an organic amine.
The liquid obtained after the mixing step, that is, the liquid containing the surface-modified silica particles can be used for producing the composite material as a surface-modified silica dispersion.
Further, from the viewpoint of ease of manufacturing the composite material, at least a part of the organic solvent contained in the mixed solution obtained in the above-described mixing step may be replaced with another organic solvent. As the other organic solvent, at least one or two or more selected from alcohols, ketones, ethers, esters, hydrocarbons and nitrogen-containing organic compounds can be used. The solvent to be replaced is not particularly limited as long as it is different from the organic solvent of the mixed solution, and may be selected from the viewpoint of solubility of the organic resin material to be compounded.
Examples of the other organic solvents include alcohols such as methanol, ethanol, isopropanol, and N-butanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, γ -butyl lactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, esters such as ethyl acetate and butyl acetate, hydrocarbons such as toluene, xylene, N-pentane, N-hexane, and cyclohexane, amides such as dimethylacetamide, N-dimethylformamide, dimethylacrylamide, acryloylmorpholine, diethylacrylamide, and amines such as triethylamine, tributylamine, N-dimethylaniline, pyridine, and picoline.
The substitution method may be any known method, and for example, the substitution method may be replaced with another organic solvent by an evaporation method using a rotary evaporator or the like, or an ultrafiltration method using an ultrafiltration membrane.
As a specific example of the method for producing the surface-modified silica particles, there is a production method including the following steps (a) to (C), but the method is not limited to these steps.
(A) The working procedure comprises the following steps: a step of preparing a silica sol containing silica particles having an average primary particle diameter of 5 to 120nm and an alcohol having 1 to 4 carbon atoms as a dispersion medium, the silica sol having a specific surface area (S H2O ) And the specific surface area measured by nitrogen adsorption (S N2 ) Ratio (S) H2O /S N2 ) 0.6 or less, and the total silanol groups ratio represented by the following formula (1) is 5% or less,
all silanol group ratio (%) = (q2×2 +. 4+Q3×1/4+Q4×0 +. 4) formula (1)
[ in formula (1), Q2, Q3, Q4 are each represented by 29 The ratio (%) of the peak area of the structure derived from each silicon atom obtained by Si NMR measurement to the total (100%) of the peak areas of the structures derived from silicon atoms, Q2 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 2 oxygen atoms and 2 hydroxyl groups, Q3 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 3 oxygen atoms and 1 hydroxyl group, and Q4 represents the source Ratio of peak area of structure of silicon atom bonded with 4 oxygen atoms.]
(B) The working procedure comprises the following steps: a step of heating and stirring an organosilicon compound having at least 1 substituent selected from an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond, with the silica sol obtained in the step (A) at 40 to 100 ℃ for 0.1 to 10 hours,
(C) The working procedure comprises the following steps: and (c) removing the alcohol solvent from the silica sol obtained in the step (B).
The amount of the organosilicon compound to be added in the present production method, the hydrolysis conditions in the step (B), and the like may be as described above.
The silica sol prepared in the step (a) may be a silica sol having a moisture content of 0.1 to 2 mass%.
The silica sol prepared in the step (a) may be a silica sol obtained by replacing an aqueous silica sol solvent obtained by hydrothermal synthesis at 200 to 380 ℃ and 2 to 22MPa with an alcohol having 1 to 4 carbon atoms.
Either or both of the steps (B) and (C) may be performed under reduced pressure, for example.
The step of adjusting the pH using the organic amine may be included in any one or more of the step (B), and the step (B) before, during, and after the step (B), as necessary.
The silica sol obtained in the step (B) may be used for the production of the composite material as a surface-modified silica dispersion, and for example, the solvent substitution may be performed in the step (D) described below.
Specifically, specific examples of the method for producing the surface-modified silica dispersion include a method comprising the following steps (a) and (B), and a method further comprising the step (D) in addition to the step (a) and the step (B), but the method is not limited to these methods (steps).
(A) The working procedure comprises the following steps: preparing a silica sol containing silica particles having an average primary particle diameter of 5 to 120nm as a dispersoid and an alcohol having 1 to 4 carbon atoms as a dispersion medium.
(B) The working procedure comprises the following steps: and (b) a step of heating and stirring the silica sol obtained in the step (A) at 40 to 100 ℃ for 0.1 to 10 hours, the organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond.
(D) And (c) replacing the silica sol solvent obtained in the step (B) with at least 1 solvent selected from the group consisting of alcohols, ketones, hydrocarbons, amides, esters, ethers and amines.
Specific examples of the alcohols, ketones, hydrocarbons, amides and amines (nitrogen-containing organic compounds), esters and ethers in the present production method, and the method for replacing the solvent may be as described above.
Examples
Hereinafter, the present invention will be described in more detail by showing examples and comparative examples, but the present invention is not limited to the following examples.
[ silica Sol ]
Silica sols used in examples and comparative examples are described below. The properties of the silica particles in the water-dispersible silica sols a to E are shown in table 1.
Water-dispersible silica sol A (manufactured by Nissan chemical Co., ltd., pH3, silica concentration 20% by mass)
Water-dispersible silica sol B (manufactured by Nissan chemical Co., ltd., pH3, silica concentration 20% by mass)
Water-dispersible silica sol C (manufactured by Nissan chemical Co., ltd., pH3, silica concentration 34% by mass)
Water-dispersible silica sol D (manufactured by Nissan chemical Co., ltd., pH3, silica concentration 20% by mass)
Water-dispersible silica sol E (manufactured by Nissan chemical Co., ltd., pH3, silica concentration 20% by mass)
The water-dispersible silica sol E was produced by the procedure of examples 1 to 8 described below.
TABLE 1
In addition, the organosilicon compounds used are as follows.
PTMS: phenyltrimethoxysilane (trade name: KBM-103, manufactured by Xinyue chemical industries, ltd.)
MTMS: methyltrimethoxysilane (trade name: KBM-13, manufactured by Xinyue chemical industries, ltd.)
VTMS: vinyl trimethoxy silane (trade name: KBM-1003, manufactured by Xinyue chemical industries, ltd.)
DMDPS: dimethoxydiphenylsilane (trade name: KBM-202SS, manufactured by Xinyue chemical industries, ltd.)
DMMPS: dimethoxymethylphenyl silane (trade name: LS-2720, manufactured by Xinyue chemical industries, ltd.)
DTMS: decyl trimethoxysilane (trade name: KBM-3103C, manufactured by Xinyue chemical industries, ltd.)
HMDS: hexamethyldisiloxane (trade name: KF-96L-0.65CS, manufactured by Xinyue chemical industry Co., ltd.)
The physical properties of the aqueous dispersion silica sols a to E, the surface-modified silica particle dispersions prepared in examples and comparative examples, and the silica sols and dispersions in the dispersion production process were measured and evaluated in the following manner.
[ measurement of silica concentration ]
The silica concentration of the aqueous dispersion silica sol, the dispersion of the surface-modified silica particles, and the silica sol in the step of producing the dispersion was calculated by taking the silica sol or dispersion into a crucible, heating the crucible to remove the solvent, then firing the crucible at 1000 ℃.
[ method for measuring pH of Water-dispersible silica Sol ]
The pH of the aqueous dispersion silica sol was measured using a pH meter (manufactured by Miq Site, inc., MM-43X).
[ method for measuring pH of organic solvent-dispersed silica sol ]
Regarding the pH of the methanol-dispersed silica sol, the mass ratio of the methanol-dispersed silica sol to methanol to pure water was 1:1:1, MM-43X) was measured by a pH meter. The pH measured by the present measurement method is expressed as pH (1+1+1).
[ measurement of specific surface area, specific surface area ratio and average Primary particle diameter ]
Specific surface area of steam adsorption method (S H2O ) Measurement of (3)
Specific surface area of silica particles in the water-dispersible silica sol by vapor adsorption (S H2O ) The water-soluble cations and anions in the water-dispersible silica sol were prepared in accordance with cation exchange resins (manufactured by dow chemical company, trade name: the "doctor" includes one-touch IR-120B), an anion exchange resin (manufactured by dow chemical company, trade name: the "rakan" type IRA 400J), cation exchange resin (manufactured by dow chemical company, trade name: the sample was prepared by drying the silica sol at 290 ℃ after the removal of the notch IR-120B) in this order, and the sample was measured by using a specific surface area measuring device (Q5000 SA, manufactured by tataron er company) using a vapor adsorption method.
Specific surface area of nitrogen adsorption method (S N2 ) Measurement of (3)
Specific surface area of silica particles in the water-dispersible silica sol by nitrogen adsorption (S N2 ) Cation exchange resin (trade name: the metal oxide sol was dried at 290 ℃ after the metal oxide sol was removed to prepare a measurement sample, and the measurement was performed using a nitrogen adsorption specific surface area measurement device Monosorb (manufactured by metal oxide co).
[ ratio of specific surface area of Water vapor adsorption to specific surface area of Nitrogen adsorption (S) H2O /S N2 )〕
The specific surface area ratio was calculated from the following formula using the values of the specific surface area of the steam adsorption method and the specific surface area of the nitrogen adsorption method obtained by the above measurement.
Specific surface area ratio of water vapor/nitrogen adsorption (S H2O /S N2 ) Specific surface area by steam adsorption/specific surface area by nitrogen adsorption
[ average primary particle diameter ]
Regarding the average primary particle diameter, the specific surface area S obtained by the nitrogen adsorption method described above N2 (m 2 And/g) is calculated by converting the following formula into spherical particles.
Average primary particle diameter (nm) =2720/S (m) 2 /g)
[ measurement of moisture content ]
The water content of the silica sol in the surface-modified silica particle dispersion and the production process thereof was measured by the Karl Fischer titration method using a Karl Fischer moisture meter (trade name: MKA-610, manufactured by Kyoto electronic industries, ltd.).
[ organic solvent content ]
The organic solvent content of the dispersion of the surface-modified silica particles was determined by gas chromatography (GC-2014 s, shimadzu corporation).
Gas chromatography conditions:
column: 3mm x 1m glass column
Filler: one-way tap Q
Column temperature: 130-230 ℃ (heating 8 ℃/min)
And (3) a carrier: n (N) 2 40 mL/min
A detector: FID (FID)
Sample injection amount: 1 mu L
Internal standard: acetonitrile was used.
[ measurement of viscosity ]
The viscosity of the dispersion in the surface-modified silica particle production process was measured using an ostwald viscometer (manufactured by chai field science).
[ measurement of NMR and calculation of the total silanol groups ratio ]
〈 29 Si NMR spectraDetermination of the above-mentioned diseases
To 2mL of the aqueous dispersion silica sol was added 0.5. 0.5mLD 2 O was prepared as a measurement sample, and the measurement sample was added to a sample tube made of Polytetrafluoroethylene (PTFE) having a diameter of 10 mm. A nuclear magnetic resonance device (model name "ECA 500", manufactured by Nippon Denshoku Co., ltd.) having a diameter of 10mm was used 29 Si free probe, the observation core is set as 29 Si, 1-dimensional NMR spectrum was measured. The measurement conditions are that 29 The Si resonance frequency was 99.36MHz, the spectral width was 37.4kHz, the X_pulse was 90 °, the correlation_Delay was 120 seconds, and the measurement temperature was room temperature. The data analysis was performed by using the japanese electronic < Model > software "Delta 5.3.1", and waveform separation analysis was performed using the center position, height, and half width of the peak shape produced by gaussian waveform (gaussian Model) as variable parameters for each peak of the spectrum after fourier transformation. After waveform separation, peaks observed between-80 ppm and-105 ppm of chemical shifts were identified as originating from Q2 structure, peaks observed between-90 ppm and-115 ppm were identified as originating from Q3 structure, and peaks observed between-95 ppm and-130 ppm were identified as originating from Q4 structure.
All silanol group ratio
The total silanol group ratio of the silica particles in the water-dispersible silica sol is determined from the above 29 The area value of each peak obtained from the Si NMR spectrum data was calculated.
The ratio (%) of the area value of each peak after waveform separation to the total (100%) of the area values of each peak (Q2, Q3, Q4) was set as the content ratio of each structure, and the total silanol group ratio was calculated from the following formula (1). Wherein Q2, Q3 and Q4 represent the content ratio of each structure obtained from the NMR measurement result.
All silanol group ratio (%) = (q2×2 +. 4+Q3×1/4+Q4×0 +. 4) formula (1)
[ measurement of dielectric constant and dielectric loss tangent ]
The dielectric constant and dielectric loss tangent of the sample were measured by a vector network analyzer (trade name: fieldFox N6626A, KEYSIGHT TECHNOLOGIES) after filling a powder sample (silica powder obtained in examples 2-1 to 2-9 and comparative examples 2-1 to 2-4 described later) into a sample tube (length: 30mm, inner diameter: 3 mm) made of PTFE using a cavity resonator holder (manufactured by Kunststo コ Co., ltd.) for measuring frequency 1 GHz.
The low dielectric characteristics "OK" were evaluated when the measured value of the dielectric loss tangent was 0.01 or less, and the low dielectric characteristics "NG" were evaluated when the measured value of the dielectric loss tangent was more than 0.01.
Examples 1 to 1
(a) The working procedure comprises the following steps: the aqueous dispersion silica sol A2,500 g was charged into a glass reactor having an internal volume of 3L and comprising a stirrer, a condenser, a thermometer and 2 injection ports, and heated to boil the silica sol. In a state where the silica sol in the reactor is boiled, the vapor of methanol generated in another boiler is continuously blown into the silica sol in the reactor, and water as a dispersion medium is replaced with methanol. When the water content of the methanol dispersion became 3.0 mass% or less, the substitution was completed, and 1,250g of a methanol-dispersed silica sol was obtained.
The obtained methanol-dispersed silica sol had a silica concentration of 40.5 mass%, a water content of 1.5 mass% and a viscosity of 2.0 mPas.
(b) The working procedure comprises the following steps: the obtained methanol-dispersed silica sol (1,000 g) was charged into a 2L eggplant-type flask, and stirred with an electromagnetic stirrer while using silica particles obtained by a nitrogen adsorption method for every 1nm 2 PTMS was added in an amount to provide a surface area of 2.0, and the mixture was heated to 60℃for 1 hour. Then, diisopropylamine was added so that the pH (1+1+1) became 8 to 9, and the mixture was heated to 60℃for 1 hour. Then, further at each 1nm of the silica particles 2 PTMS was added in an amount to set the surface area to 1.0, and the mixture was heated to 60℃and held for 1 hour to prepare a methanol dispersion of surface-modified silica particles. The total amount of PTMS added is 1nm per silica particle in the sol 2 Surface area 3.0.
(c) The working procedure comprises the following steps: then, the eggplant-type flask to which the methanol dispersion liquid of the surface-modified silica particles was added was placed in a rotary evaporator, and methyl ethyl ketone was supplied to the flask at a bath temperature of 80℃and a reduced pressure of 500 to 350 Torr, and distilled, whereby the dispersion medium was replaced with methyl ethyl ketone, to obtain a methyl ethyl ketone dispersion liquid of the surface-modified silica particles.
The obtained surface-modified silica particles had a methyl ethyl ketone dispersion having a silica concentration of 30.5 mass%, a water content of 0.1 mass% or less, and a methanol content of 0.1 mass% or less.
Examples 1 to 2
Instead of PTMS in the step (b) of example 1-1, the silica particles contained in the silica sol were used at a concentration of 1nm 2 A methanol-dispersed silica sol, a methanol dispersion of surface-modified silica particles, and a methyl ethyl ketone dispersion of surface-modified silica particles were prepared in the same manner as in steps (a) to (c) of example 1-1, except that VTMS (total amount) was added so that the surface area became 3.0.
Examples 1 to 3
Instead of PTMS in the step (b) of example 1-1, the silica particles contained in the silica sol were used at a concentration of 1nm 2 A methanol-dispersed silica sol, a methanol dispersion of surface-modified silica particles, and a methyl ethyl ketone dispersion of surface-modified silica particles were prepared in the same manner as in steps (a) to (c) of example 1-1, except that DMDPS (total amount) was added so that the surface area became 3.0.
Examples 1 to 4
Instead of PTMS in the step (b) of example 1-1, the silica particles contained in the silica sol were used at a concentration of 1nm 2 DMMPS (total amount) was added so that the surface area became 3.0, and the procedure was carried out in the same manner as in steps (a) to (c) of example 1-1, except that a methanol-dispersed silica sol, a methanol dispersion of surface-modified silica particles, and a methyl ethyl ketone dispersion of surface-modified silica particles were prepared.
Examples 1 to 5
In place of PTMS in step (b) of example 1-1, a silica sol was usedEvery 1nm of the silica particles contained 2 A methanol-dispersed silica sol, a methanol dispersion of surface-modified silica particles, and a methyl ethyl ketone dispersion of surface-modified silica particles were prepared in the same manner as in steps (a) to (c) of example 1-1, except that MTMS (total amount) was added so that the surface area became 3.0.
Examples 1 to 6
(a) The working procedure comprises the following steps: 660g of the water-dispersible silica sol B was diluted with 1,000g of methanol, and the diluted solution was put into a 2L evaporator equipped with an eggplant-type flask, and then water was distilled off at 600 Torr while slowly adding methanol, whereby water as a dispersion medium was replaced with methanol. After the completion of the substitution when the water content of the methanol dispersion became 3.0 mass% or less, 1,000g of a methanol-dispersed silica sol was obtained.
The obtained methanol-dispersed silica sol had a silica concentration of 13.2 mass%, a water content of 1.6 mass% and a viscosity of 0.9 mPas.
Further, the same operations as in the steps (b) to (c) of example 1-1 were carried out to prepare a methanol dispersion of surface-modified silica particles, and further a methyl ethyl ketone dispersion of surface-modified silica particles.
Examples 1 to 7
Instead of PTMS in step (b) of examples 1 to 6, the silica particles contained in the silica sol were used at a concentration of 1nm 2 Except that DMMPS (total amount) was added so that the surface area became 3.0, the same operations as in steps (a) to (c) of examples 1 to 6 were performed to prepare a methanol-dispersed silica sol, a methanol dispersion of surface-modified silica particles, and a methyl ethyl ketone dispersion of surface-modified silica particles.
Examples 1 to 8/preparation of Water-dispersible silica Sol E
129g of a water-dispersible silica sol (30 mass% of silica concentration, pH11, average primary particle diameter: 46nm, manufactured by Nissan chemical Co., ltd.) and 121g of a water-dispersible silica sol (32 mass% of silica concentration, pH3, average primary particle diameter: 9nm, manufactured by Nissan chemical Co., ltd.) were charged into a SUS autoclave reactor having an inner volume of 300mL, and a hydrothermal treatment was performed at 300.+ -. 20 ℃ for 1 hour. 100g of the obtained sol was mixed with 30g of a hydrogen form strongly acidic cation exchange resin (registered trademark) IR-120B, and stirred for 30 minutes and then filtered to obtain 100g of a water-dispersible silica sol E (pH 3, silica concentration 20 mass%, average primary particle diameter 74 nm).
Examples 1 to 9
(a) The working procedure comprises the following steps: the aqueous dispersion silica sol E62 g obtained in examples 1 to 8 was diluted with methanol to 130g, and the diluted solution was charged into a 1L evaporator equipped with an eggplant-type flask, and then water was distilled off at 550 Torr while slowly adding methanol, whereby water as a dispersion medium was replaced with methanol. When the water content of the methanol dispersion became 1.0 mass% or less, the substitution was completed, and 155g of a methanol-dispersed silica sol was obtained.
The obtained methanol-dispersed silica sol had a silica concentration of 8 mass% and a moisture content of 0.5 mass%.
(b) The working procedure comprises the following steps: 66g of the obtained methanol-dispersed silica sol was charged into a 200mL eggplant-type flask, and stirred with an electromagnetic stirrer while using 1nm per silica particle (obtained by nitrogen adsorption) contained in the silica sol 2 DMMPS (total amount) was added so that the surface area became 3.0, and the mixture was heated to 60 ℃ and held for 8 hours, to prepare a methanol dispersion of surface-modified silica particles.
(c) The working procedure comprises the following steps: then, the eggplant-type flask to which the methanol dispersion liquid of the surface-modified silica particles was added was placed in a rotary evaporator, and the methyl ethyl ketone was supplied under reduced pressure of 600 to 400 torr at a bath temperature of 80 ℃ and distilled until the water content of the methyl ethyl ketone dispersion liquid became 1.0 mass% or less, and the dispersion medium was replaced with methyl ethyl ketone, whereby a methyl ethyl ketone dispersion liquid of the surface-modified silica particles was obtained.
The methyl ethyl ketone dispersion of the surface-modified silica particles thus obtained had a silica concentration of 11 mass%, a water content of 0.03 mass% and a methanol content of 1.3 mass%.
Examples 1 to 10
(a) The working procedure comprises the following steps: the aqueous dispersion silica sol A2,500 g was charged into a glass reactor having an internal volume of 3L and comprising a stirrer, a condenser, a thermometer and 2 injection ports, and heated to boil the silica sol. In a state where the silica sol in the reactor is boiled, the vapor of methanol generated in another boiler is continuously blown into the silica sol in the reactor, and water as a dispersion medium is replaced with methanol. When the water content of the methanol dispersion became 3.0 mass% or less, the substitution was completed, and 1,250g of a methanol-dispersed silica sol was obtained.
The obtained methanol-dispersed silica sol had a silica concentration of 40.5 mass%, a water content of 1.5 mass% and a viscosity of 2.5 mPas.
(b) The working procedure comprises the following steps: 1,000g of the obtained methanol-dispersed silica sol was charged into a 2L eggplant-type flask, 150g of Methyl Ethyl Ketone (MEK) was added thereto while stirring with an electromagnetic stirrer, and the silica particles were obtained for every 1nm by the nitrogen adsorption method 2 DMMPS was added in an amount to provide a surface area of 3, and heated to 60 ℃ for 3 hours. Then, further at each 1nm of the silica particles 2 HMDS was added in an amount to give a surface area of 5, and the mixture was heated to 60℃for 3 hours. Then, diisopropylamine was added so that the pH (1+1+1) became 8.0 to 10.0, and the mixture was heated to 60 ℃ and kept for 1 hour, to prepare a methanol/MEK dispersion of surface-modified silica particles.
(c) The working procedure comprises the following steps: then, the eggplant-type flask to which the methanol/MEK dispersion liquid of the surface-modified silica particles was added was placed in a rotary evaporator, and methyl ethyl ketone was supplied under reduced pressure of 550 to 350 torr at a bath temperature of 80 ℃ and distilled, whereby the entire dispersion medium was replaced with methyl ethyl ketone, and a methyl ethyl ketone dispersion liquid of the surface-modified silica particles was obtained.
The obtained surface-modified silica particles had a methyl ethyl ketone dispersion having a silica concentration of 42.7 mass%, a water content of 0.1 mass% or less and a methanol content of 0.1 mass% or less.
Examples 1 to 11
Instead of DMMPS in step (b) of examples 1-10, silica particles contained in the silica sol were used at a concentration of 1nm 2 A methanol-dispersed silica sol, a methanol/MEK dispersion of surface-modified silica particles, and a methyl ethyl ketone dispersion of surface-modified silica particles were prepared in the same manner as in steps (a) to (c) of examples 1 to 10, except that DTMS were added so that the surface area became 1.0, and the mixture was kept at 60 ℃ for 3 hours.
Examples 1 to 12
After DMMPS was added in the step (b) of examples 1 to 10, the silica particles contained in the silica sol were added at a concentration of 1nm 2 DTMS was added so that the surface area became 1.0, and the mixture was kept at 60℃for 3 hours, followed by adding silica particles at a concentration of 1nm 2 Except that HMDS was added in an amount of 5 surface areas, the same operations as in steps (a) to (c) of examples 1 to 10 were performed to prepare a methanol-dispersed silica sol, a methanol/MEK dispersion of surface-modified silica particles, and a methyl ethyl ketone dispersion of surface-modified silica particles.
Examples 1 to 13
Instead of DMMPS as in examples 1-10, every 1nm of silica particles contained in the silica sol was used 2 A methyl ethyl ketone dispersion of surface-modified silica particles was prepared in the same manner as in examples 1 to 10, except that HMDS was added so that the surface area became 5.
Comparative examples 1 to 1
(a) The working procedure comprises the following steps: the water-dispersible silica sol c1,029.4g was charged into a 2L evaporator with an eggplant-type flask, and then water was distilled off at 600 torr while slowly adding methanol, whereby water as a dispersion medium was replaced with methanol. After the completion of the substitution when the water content of the methanol dispersion became 3.0 mass% or less, 1,000g of a methanol-dispersed silica sol was obtained.
The obtained methanol-dispersed silica sol had a silica concentration of 35% by mass, a water content of 1.5% by mass and a viscosity of 1.3 mPas.
Further, the procedure was carried out in the same manner as in steps (b) to (c) of example 1-1, to prepare a methanol dispersion of surface-modified silica particles, and further a methyl ethyl ketone dispersion of surface-modified silica particles.
Comparative examples 1 to 2
(a) The working procedure comprises the following steps: the water-dispersible silica sol d1,525g was charged into a 2L evaporator with an eggplant-type flask, and then water was distilled off at 600 torr while slowly adding methanol, whereby water as a dispersion medium was replaced with methanol. After the completion of the substitution when the water content of the methanol dispersion became 3.0 mass% or less, 1,000g of a methanol-dispersed silica sol was obtained.
The obtained methanol-dispersed silica sol had a silica concentration of 30.5 mass%, a water content of 1.7 mass% and a viscosity of 1.6 mPas.
Further, the procedure was carried out in the same manner as in steps (b) to (c) of example 1-1, to prepare a methanol dispersion of surface-modified silica particles, and further a methyl ethyl ketone dispersion of surface-modified silica particles.
Comparative examples 1 to 3 and comparative examples 1 to 4
As comparative examples 1 to 3, water-dispersible silica sol C was used, and as comparative examples 1 to 4, water-dispersible silica sol D was used.
Examples 2 to 1
The surface-modified silica particles obtained in example 1-1 were dried in a vacuum drier at 100℃to prepare silica powder by pulverizing the silica gel obtained in the above manner in a mortar and then further drying the silica gel at 150℃for 1 hour.
The dielectric constant and dielectric loss tangent of the obtained silica powder were measured at 23℃and a frequency of 1 GHz. The dielectric properties of the surface-modified silica particles are shown in table 2.
[ examples 2-2 to 2-7, comparative examples 2-1, and comparative examples 2-2]
Regarding the methyl ethyl ketone dispersion liquid of the surface-modified silica particles obtained in examples 1-2 to 1-7, comparative examples 1-1 and comparative examples 1-2, silica powder was prepared in the same manner as in example 2-1, and dielectric constant and dielectric loss tangent were measured. The dielectric properties of the surface-modified silica particles are shown in table 2.
Examples 2 to 8
Regarding the water-dispersible silica sol E obtained in example 1-8, a silica powder was prepared in the same manner as in example 2-1, and the dielectric constant and dielectric loss tangent were measured. The dielectric properties of the silica particles are shown in table 2.
Examples 2 to 9
Regarding the methyl ethyl ketone dispersion of the surface-modified silica particles obtained in example 1-9, a silica powder was prepared in the same manner as in example 2-1, and the dielectric constant and dielectric loss tangent were measured. The dielectric properties of the surface-modified silica particles are shown in table 2.
Examples 2 to 10 to 2 to 13
Regarding the methyl ethyl ketone dispersion liquid of the surface-modified silica particles obtained in examples 1-10 to 1-13, a silica powder was prepared in the same manner as in example 2-1, and the dielectric constant and dielectric loss tangent were measured. The dielectric properties of the surface-modified silica particles are shown in table 2.
Comparative examples 2 to 3 and comparative examples 2 to 4
Regarding comparative examples 1 to 3 (water-dispersible silica sol C) and comparative examples 1 to 4 (water-dispersible silica sol D), silica powders were produced in the same manner as in example 2 to 1, and dielectric constants and dielectric loss tangents were measured. The dielectric properties of the silica particles are shown in table 2.
TABLE 2
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As shown in Table 2, it was confirmed that the average primary particle diameter was 5nm to 120nm, and the water vapor adsorption surface area/nitrogen adsorption surface area (S H2O /S N2 ) Silica particles having a silanol group ratio of 0.6 or less and a total silanol group ratio of 5% or less, examples 1-1 to 1-13 being the frequencies The dielectric loss tangent at 1GHz shows a value of 0.01 or less, and a silica particle exhibiting very excellent low dielectric characteristics.
On the other hand, the average primary particle diameter is 5nm to 120nm, but the water vapor adsorption surface area/nitrogen adsorption surface area (S H2O /S N2 ) The silica particles of comparative examples 1-1 to 1-4 having a dielectric loss tangent of more than 0.6 and/or a silanol group ratio of more than 5% were silica particles having a dielectric loss tangent of more than 0.01 and poor low dielectric characteristics.
Further, it was confirmed that the average primary particle diameter was 5nm to 120nm, and the water vapor adsorption surface area/nitrogen adsorption surface area (S H2O /S N2 ) The silica particles of examples 1-1 to 1-7 and examples 1-13, in which the surface-modified silica particles were coated with an organosilicon compound and the silanol group ratio was not more than 0.6 and not more than 5%, exhibited dielectric loss tangent at 1GHz at a frequency of 0.01 or less, and exhibited very excellent low dielectric characteristics.
The present invention reduces the dielectric loss tangent of the conventional hydrophobized silica sol to half or less, and is expected to be applied to high-frequency applications.
Claims (19)
1. A silica particle satisfying the following matters (i), (ii) and (iii) and having a dielectric loss tangent at 1GHz of 0.01 or less,
(i) The average primary particle diameter is 5nm to 120nm,
(ii) Specific surface area S measured by vapor adsorption H2O And specific surface area S measured by nitrogen adsorption N2 The ratio is S H2O /S N2 Is not more than 0.6 and is preferably used,
(iii) The total silanol groups represented by the following formula (1) are 5% or less,
all silanol group ratio (%) = (q2×2/4+q3×1/4+q4×0/4) formula (1)
In the formula (1), Q2, Q3 and Q4 are respectively represented by 29 The ratio of the peak area of the structure derived from each silicon atom obtained by Si NMR measurement to the total 100% of the peak areas of the structures derived from silicon atoms is singleThe position is%, Q2 represents the ratio of the peak areas derived from the structure of the silicon atom to which 2 oxygen atoms and 2 hydroxyl groups are bonded, Q3 represents the ratio of the peak areas derived from the structure of the silicon atom to which 3 oxygen atoms and 1 hydroxyl group are bonded, and Q4 represents the ratio of the peak areas derived from the structure of the silicon atom to which 4 oxygen atoms are bonded.
2. The silica particle according to claim 1, wherein at least a part of the surface of the silica particle is coated with an organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond.
3. The silica particles according to claim 1, wherein at least a part of the organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond is bonded to the surface of at least a part of the silica particles.
4. The silica particles according to claim 2 or 3, wherein the substituent of the organosilicon compound is at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a phenyl group, a phenylmethyl group, and a vinyl group.
5. The silica particles according to any one of claims 2 to 4, wherein the organosilicon compound is a compound having a hydrolyzable group together with the substituent.
6. The silica particles according to claim 2 or 3, wherein the organosilicon compound is at least one compound selected from the group consisting of compounds represented by the following formulas (a) to (g),
7. according to claimThe silica particles according to any one of claims 2 to 6, wherein the organosilicon compound is present at a concentration of 1nm per silica particle 2 The silica particles have a surface area of 0.5 to 6, and are coated or bonded to the surface.
8. A silica dispersion comprising the silica particles according to claim 1 dispersed in water or an organic solvent.
9. A silica dispersion comprising the silica particles according to any one of claims 2 to 7 dispersed in at least 1 organic solvent selected from the group consisting of alcohols, ketones, hydrocarbons, amides, ethers, esters and amines.
10. A composite material comprising the silica particles according to any one of claims 2 to 7, and an organic resin material.
11. The composite material according to claim 10, wherein the organic resin material is at least 1 selected from the group consisting of epoxy resin, phenolic resin, acrylic resin, maleimide resin, polyurethane, polyimide, polytetrafluoroethylene, cyclic olefin polymer, unsaturated polyester, vinyl triazine, crosslinkable polyphenylene ether, and curable polyphenylene ether.
12. The composite material according to claim 10 or 11, having a use selected from the group consisting of semiconductor device materials, copper clad laminates, flexible wiring materials, flexible display materials, antenna materials, optical wiring materials and sensing materials.
13. A method for producing surface-modified silica particles, comprising the steps of: a step of mixing silica particles, which are described below, with an organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond in an organic solvent,
The dioxygenThe average primary particle diameter of the silicon carbide particles is 5-120 nm, and the specific surface area S is measured by water vapor adsorption H2O And specific surface area S measured by nitrogen adsorption N2 The ratio is S H2O /S N2 0.6 or less, and the total silanol groups ratio represented by the following formula (1) is 5% or less,
all silanol group ratio (%) = (q2×2/4+q3×1/4+q4×0/4) formula (1)
In the formula (1), Q2, Q3 and Q4 are respectively represented by 29 The ratio of the peak area of the structure derived from each silicon atom obtained by Si NMR measurement to the total 100% of the peak areas of the structures derived from the silicon atoms is expressed in terms of the unit, Q2 represents the ratio of the peak areas of the structures derived from the silicon atoms to which 2 oxygen atoms and 2 hydroxyl groups are bonded, Q3 represents the ratio of the peak areas of the structures derived from the silicon atoms to which 3 oxygen atoms and 1 hydroxyl group are bonded, and Q4 represents the ratio of the peak areas of the structures derived from the silicon atoms to which 4 oxygen atoms are bonded.
14. A method for producing surface-modified silica particles, which comprises the following steps (A) to (C):
(A) The working procedure comprises the following steps: a step of preparing a silica sol containing silica particles having an average primary particle diameter of 5 to 120nm and a specific surface area S measured by vapor adsorption, as a dispersoid and an alcohol having 1 to 4 carbon atoms as a dispersion medium H2O And specific surface area S measured by nitrogen adsorption N2 The ratio is S H2O /S N2 0.6 or less, and the total silanol groups ratio represented by the following formula (1) is 5% or less,
all silanol group ratio (%) = (q2×2/4+q3×1/4+q4×0/4) formula (1)
In the formula (1), Q2, Q3 and Q4 are respectively represented by 29 The ratio of the peak area of the structure derived from each silicon atom obtained by Si NMR measurement to the total 100% of the peak areas of the structures derived from silicon atoms is expressed in terms of unit, Q2 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 2 oxygen atoms and 2 hydroxyl groups, and Q3 represents the ratio derived from the structures bonded with 3 oxygen atoms and 1 hydroxyl groupThe ratio of the peak areas of the structures of the silicon atoms of the radicals, Q4 represents the ratio of the peak areas of the structures derived from the silicon atoms to which 4 oxygen atoms are bonded,
(B) The working procedure comprises the following steps: a step of heating and stirring an organosilicon compound having at least 1 substituent selected from an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond, with the silica sol obtained in the step (A) at 40 to 100 ℃ for 0.1 to 10 hours,
(C) The working procedure comprises the following steps: and (c) removing the alcohol solvent from the silica sol obtained in the step (B).
15. The method for producing surface-modified silica particles according to claim 14, wherein either one or both of the step (B) and the step (C) are performed under reduced pressure.
16. The method for producing surface-modified silica particles according to claim 14, wherein the silica sol prepared in the step (a) is a silica sol having a moisture content of 0.1 to 2% by mass.
17. The method for producing surface-modified silica particles according to claim 14, wherein the silica sol prepared in the step (a) is a silica sol obtained by replacing an aqueous silica sol solvent obtained by hydrothermal synthesis at 200 to 380 ℃ and 2 to 22MPa with an alcohol having 1 to 4 carbon atoms.
18. A method for producing a surface-modified silica dispersion, which comprises the following steps (A) and (B):
(A) The working procedure comprises the following steps: a step of preparing a silica sol containing silica particles having an average primary particle diameter of 5 to 120nm and a specific surface area S measured by vapor adsorption, as a dispersoid and an alcohol having 1 to 4 carbon atoms as a dispersion medium H2O And specific surface area S measured by nitrogen adsorption N2 The ratio is S H2O /S N2 0.6 or less, and the total silanol groups ratio represented by the following formula (1) is 5% or less,
all silanol group ratio (%) = (q2×2/4+q3×1/4+q4×0/4) formula (1)
In the formula (1), Q2, Q3 and Q4 are respectively represented by 29 The ratio of the peak area of the structure derived from each silicon atom obtained by Si NMR measurement to the total 100% of the peak areas of the structures derived from silicon atoms is expressed in terms of the unit, Q2 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 2 oxygen atoms and 2 hydroxyl groups, Q3 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 3 oxygen atoms and 1 hydroxyl group, Q4 represents the ratio of the peak areas of the structures derived from silicon atoms bonded with 4 oxygen atoms,
(B) The working procedure comprises the following steps: and (b) a step of heating and stirring the silica sol obtained in the step (A) at 40 to 100 ℃ for 0.1 to 10 hours, the organosilicon compound having at least 1 substituent selected from the group consisting of an alkyl group, an aryl group having 6 to 12 carbon atoms, and a substituent having an unsaturated bond.
19. The method for producing a surface-modified silica dispersion according to claim 18, further comprising the following step (D):
(D) The working procedure comprises the following steps: and (c) replacing the silica sol solvent obtained in the step (B) with at least 1 solvent selected from the group consisting of alcohols, ketones, hydrocarbons, amides, esters, ethers and amines.
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| CN105813977A (en) * | 2013-12-12 | 2016-07-27 | 日产化学工业株式会社 | Silica particles, manufacturing method for same, and silica sol |
| CN106414328A (en) * | 2014-06-03 | 2017-02-15 | Az电子材料（卢森堡）有限公司 | Method for producing surface-modified silica nanoparticles, and surface-modified silica nanoparticles |
| CN113474288A (en) * | 2019-02-25 | 2021-10-01 | 日产化学株式会社 | Inorganic oxide particles, inorganic oxide particle dispersion liquid, method for producing inorganic oxide particle dispersion liquid, and method for producing surface modifier |
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