WO2020144923A1

WO2020144923A1 - Particulate silica material and particulate silica material dispersion

Info

Publication number: WO2020144923A1
Application number: PCT/JP2019/043369
Authority: WO
Inventors: 雄己新井; 冨田　亘孝
Original assignee: 株式会社アドマテックス
Priority date: 2019-01-08
Filing date: 2019-11-06
Publication date: 2020-07-16
Also published as: JP2020111474A; JP7208022B2; TW202026242A

Abstract

Provided is a particulate silica material dispersion which is capable of achieving a high packing factor.　The present invention comprises a particulate silica material that has a median size of 150 nm or less and a dispersion medium which disperses the particulate silica material, wherein I100/half width of a small angle X-ray scattering spectrum thereof is 300 or less. "I100" is the peak top of the largest peak in the small angle X-ray scattering spectrum. The small angle X-ray scattering spectrum is measured for the particulate silica material dispersion. Specifically, intensity values are standardized with a sum total of values being 100, wherein values are obtained by multiplying, by 0.01, intensity values (arbitrary unit) measured in 0.001° increments from 0.001 to 1.0° in the small angle X-ray scattering spectrum. The largest value from among the intensities is I100 and half the intensity value I100 is I50. The peak width at the intensity of I50 in a peak to which I100 belongs is defined as the half width (unit°) of I100.

Description

Silica particle material and silica particle material dispersion

The present invention relates to a silica particle material and a silica particle material dispersion liquid that can increase the filling rate.

Silica particle materials are widely used as fillers for electronic materials. The silica particle material is used as a resin composition dispersed in a resin material or the like (Patent Document 1, etc.). Comparing the physical properties of the silica particle material and the resin material, it is desirable to increase the filling amount of the silica particle material. Therefore, technical development has been carried out aiming at providing a silica particle material having a higher filling rate than ever before.

Japanese Patent Laid-Open No. 2007-51187

The present invention has been completed in view of the above circumstances, and it is an object to be solved to provide a silica particle material and a silica particle material dispersion liquid that can realize a high filling rate.

(1) The silica particle material of the present invention for solving the above problems has a specific surface area of 10 to 150 m ² /g, an oil absorption amount per unit area (m ² ) of the surface area of 0.0003 to 0.01 mL, and a total mass. The amount of carbon is 0.5% or more, the particle size is 5 nm to 250 nm, and the surface treatment is performed.

(2) The silica particle material dispersion liquid of the present invention which solves the above-mentioned problems comprises a silica particle material having a median diameter (D50) of 150 nm or less and a dispersion medium in which the silica particle material is dispersed. I100/half-value width is 300 or less.

In particular, the silica particle material of the present invention described above can also be adopted. Here, the term “I100/half-width” in the present specification will be described. “I100” is the peak top of the largest peak in the X-ray small angle scattering spectrum. The X-ray small angle scattering spectrum is measured for a silica particle material dispersion liquid.

Specifically, in the X-ray small angle scattering spectrum, the total value of the intensity values (arbitrary units) measured in 0.001° increments from 0.001° to 1.0° multiplied by 0.01 is 100. The strength value is standardized as. The largest value among the intensities is I100, and half of the intensity value of I100 is I50. The peak width at the intensity of I50 in the peak to which I100 belongs is defined as the full width at half maximum of I100 (unit: °).

(3) The silica particle material of the present invention for solving the above-mentioned problems has an I100/half width of 300 or less of an X-ray small angle scattering spectrum in a dispersion liquid in which cyclohexanone is dispersed at a mass ratio of 1:1. , And the median diameter is 150 nm or less.

The silica particle material having the above structure can realize a high filling rate. In addition, the silica particle material dispersion liquid having the above structure contains the silica particle material contained therein at a high filling rate.

3 is a small angle X-ray scattering spectrum of the silica particle material dispersions of Test Examples 1 to 4. 9 is an X-ray small angle scattering spectrum of the silica particle material dispersion liquids of Test Examples 5 to 8. 3 is an X-ray small angle scattering spectrum of the silica particle material dispersion liquids of Test Examples 9 to 11.

The silica particle material and the silica particle material dispersion liquid of the present invention will be described in detail below based on the embodiments. The silica particle material of the present embodiment can be suitably used as a filler for electronic materials. The silica particle material dispersion liquid of the present embodiment can be suitably used when preparing a resin composition produced using a silica particle material as a filler.

The silica particle material of the present embodiment has at least one of "Part 1" and "Part 2" described below. In addition, the silica particle material means a material in which the contained inorganic material contains 80% by mass or more of SiO ₂ (silica), preferably 90% by mass or more of silica, and more preferably silica except for inevitable impurities. It is composed of.

(Silica particle material: Part 1)
The silica particle material of the present embodiment has a specific surface area of 10 to 150 m ² /g. The specific surface area is a value measured by the BET method using nitrogen. The upper limit of the specific surface area may be 150 m ² /g, 130 m ² /g, 100 m ² /g, and the lower limit may be 10 m ² /g, 20 m ² /g, 30 m ² /g. As for the specific surface area, these upper limit values and lower limit values can be arbitrarily combined.

The oil absorption amount per unit area (m ² ) of the surface area is 0.0003 to 0.01 mL. The measurement of the oil absorption amount in the present specification is as follows. When 2 g of powder to be measured was dropped and mixed with flaxseed oil, the oil absorption was calculated from the amount of flaxseed oil added when the powder was changed into a paste by the following conversion formula. The dripping near the end point was performed while letting the flaxseed oil drop in one by one. The dropping and mixing were repeated, and the point where the silica changed from powder to paste was taken as the end point. Then, using the following formula, the flaxseed oil absorption per 1 g of the measurement target was calculated, and the obtained oil absorption per 1 g was divided by the specific surface area of the measurement target to determine the surface area per unit area (m ² ). Calculate the oil absorption of.
(Oil absorption amount per 1 g) = flaxseed oil droplet amount (mL) / mass of powder to be measured (g)

The silica particle material has a particle size of 5 nm to 250 nm. The particle size may have an upper limit of 230 nm, 200 nm, and 130 nm, and a lower limit of 10 nm. The upper limit value and the lower limit value of the particle size can be arbitrarily combined. The particles of the silica particle material are preferably a mixture of particles having a plurality of kinds of particle diameters, and in particular, the particles of the particle material having a substantially monodisperse particle size distribution are combined in three or more particle diameters. desirable. Examples of the particle material to be combined include 10 nm, 50 nm and 100 nm.

The surface treatment is performed on the silica particle material of the present embodiment. The surface treatment is not particularly limited, but is performed using a surface treatment agent containing carbon. Examples of the surface treatment agent include silane compounds and silazanes. Examples thereof include vinylsilane, phenylsilane, aminophenylsilane, methacrylsilane, alkylsilane, epoxysilane, aminosilane, and hexamethyldisilazane.

The reaction amount of the surface treatment agent is selected such that the carbon content is 0.5% or more, preferably the carbon content is 1.0% or more, based on the total mass of the silica particle material. .. The upper limit of the reaction amount of the surface treatment agent is not particularly limited, but it is necessary that the particle size is increased by the surface treatment and does not deviate from the particle size range described later.

The silica particle material of the present embodiment is obtained by preparing a silica particle raw material having the above-mentioned specific surface area and particle size distribution after the surface treatment and performing the surface treatment. The silica particle raw material may be produced by any method, and examples thereof include a sol-gel method, an alkoxide method, a VMC method (deflagration method), and a melting method. From the beginning, there is a manufacturing method in which the values of the particle size distribution and the specific surface area are within the required range, and a manufacturing method in which the values are out of the range, and any method can be adopted. If it is out of the required range, it is adjusted to the required range by an appropriate classification means (centrifugal type in the gas phase, sieving, difference in sedimentation speed, etc.).

(Silica particle material: Part 2)
The silica particle material has an I100/half-value width of 300 or less of the X-ray small angle scattering spectrum in a dispersion liquid in which cyclohexanone is dispersed at a mass ratio of 1:1. As a result of measuring "I100/half-width of X-ray small angle scattering spectrum" under the above conditions by preparing some silica particle materials having a high filling rate and a few silica particle materials having a low filling rate, it was confirmed that high filling properties were obtained in the range of 300 or less. It turned out to be possible. The upper limit of the value of "I100 of X-ray small-angle scattering spectrum/half-width" may be 250, 100, or 85.

"I100/half-width of X-ray small angle scattering spectrum" is as described above. The X-ray small angle scattering spectrum was measured using synchrotron synchrotron radiation (Aichi Synchrotron Center BL8S3: X-ray energy 12 keV) as an X-ray source and R-AXIS as a detector. The camera length from the X-ray source was 4 m, and the measurement sample was stored in a quartz tube having a diameter of 1 mm for measurement.

The silica particle material has a median diameter of 150 nm or less, and particularly 130 nm or less and 110 nm or less. As the method for producing the silica particle material, the method described in “Part 1” and the like can be adopted. Further, the surface treatment can be performed as described in "Part 1".

(Silica particle material dispersion liquid)
The silica particle material dispersion liquid of the present embodiment is a dispersion liquid in which the above-described silica particle material (No. 2) is dispersed in a dispersion medium. The silica particle material may have all of the features of the silica particle material (1) described above.

The dispersion medium is not particularly limited as long as it is a liquid. An organic solvent such as cyclohexanone or a thermosetting resin before curing (epoxy resin, phenol resin, urea resin, polyester, etc.) may be used.

The mixing ratio of the dispersion medium and the silica particle material is not particularly limited. It is desirable to increase the content of silica particulate material as long as the viscosity is acceptable. For example, it is desirable to contain 50% or more, 55% or more, and 60% or more of the silica particle material on the basis of the total mass.

(Other)
The silica particle material of the present embodiment and the silica particle material contained in the silica particle material dispersion liquid can be prepared by mixing silica having a plurality of particle sizes. For example, silica having a D50 of about 10 nm to 200 nm can be mixed in an appropriate ratio. As a specific example, when silica having D50 of 10 nm, 50 nm, and 100 nm is 100 parts by mass as a whole, 10 nm silica is about 0 to 30 parts by mass, 50 nm silica is about 0 to 90 parts by mass, and 100 nm is about 100 nm. About 0 to 95 parts by mass of silica can be mixed.

The silica particle material and the silica particle material dispersion liquid of the present invention will be described below in detail based on examples.

As silica particle raw materials, Admanano YC100C-SM1 (median diameter 100 nm, Admatex nanosilica, specific surface area 30 m ² /g, hereinafter referred to as “100 nm particles”), YA050C-SM1 (median diameter 50 nm, Admatex nanosilica, specific surface area) 60 m ² /g, hereinafter referred to as “50 nm particle”), YA010C-SM1 (median diameter 10 nm, nano silica manufactured by Admatex, specific surface area 300 m ² /g, hereinafter referred to as “10 nm particle”) were used. All of these silica particle raw materials have been surface-treated with 3-methacryloxypropyltrimethoxysilane.

(Test 1)
・Test example 1
A silica particle material produced by uniformly mixing with 95 parts by mass of 100 nm particles, 0 parts by mass of 50 nm particles and 5 parts by mass of 10 nm particles was used as a test sample of this test example. The oil absorption, the specific surface area, and the amount of carbon were measured. The oil absorption was measured by the method described above. The specific surface area was measured by the BET method using nitrogen. The amount of carbon was measured with a carbon analyzer. The blending amount and the measurement result are shown in Table 1. Further, the same operation was performed with the compounding amounts shown in Table 1 to prepare test samples of Test Examples 2 to 11, and the measurement results are shown in Table 1 in the same manner. Here, since the test samples of these test examples are mixed with particles having median diameters of 10 nm, 50 nm, and 100 nm, the median diameter falls within the range of 10 nm to 100 nm.

A dispersion liquid (silica particle material dispersion liquid) was produced using cyclohexanone as a dispersion medium for the silica particle material of each test example (Table 2). The X-ray small angle scattering spectra of the obtained dispersions of each test example were measured, and the value of I100/half-value width was calculated by the above method (FIGS. 1 to 3). In addition, the viscosity and the particle size (D50) of the dispersed silica particle material were measured for the dispersion liquid of each test example (Table 2). The viscosity was measured in a state where 40 mL of the dispersion was set in a vibration type viscometer (Viscomate VM-1G, manufactured by Yamaichi Denki Co., Ltd.). The content of the silica particle material is the maximum value examined in 1 mass% increments so that the viscosity of the produced dispersion is 200 mPa·s or less (eg, 56 mass% is 400 mPa·s and 55 mass% is 200 mPa·s. -If it was s, it was set to 55% by mass).

As is clear from Tables 1 and 2, in Test Examples 1 to 9 and 11, the oil absorption amount per unit area (m ² ) was in the range of 0.0003 to 0.01 mL. The magnitude of the oil absorption amount per unit area was inversely correlated with the carbon amount.

Further, in Test Examples 1 to 9 in which the value of I100/half-value width was 300 or less, the viscosity did not increase even when the filling rate was increased as compared with Test Examples 10 and 11 in which the value was more than 300. Although the viscosity of the dispersion liquid of Test Example 10 was smaller than that of Test Examples 5, 7, and 8, the filling rate of Test Examples 5, 7, and 8 was higher than that of Test Example 10. In addition, Test Example 11 could not increase the filling rate as compared with the other Test Examples.

(Test 2)
Test samples of Test Examples 2, 3, 5, 9, 10, and 11 and resin materials: Liquid BPA type/BPF type high-purity epoxy resin ZX-1059 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. A silica particle material dispersion liquid (resin composition) in which the dispersion medium is a resin material was prepared by mixing and dispersing so as to have the described content. The viscosity of the obtained resin composition was measured at a share rate of 1 s ⁻¹ and the maximum value of the measuring device. The viscosity was measured using a rheometer viscometer (TARES ARES-G2). The results are shown in Table 3.

As is clear from Table 3, in Test Examples 2, 3, 5, and 9 in which the dilatancy index exceeds 1, the values of I100/half-width are compared with those in Test Examples 10 and 11 in which the dilatancy index is less than 1. It was as small as 300 or less, and it became clear that the value of I100/half-width is related to the dilatancy index. The dilatancy index exceeding 1 means that the packing efficiency of the silica particles is high.

Claims

The specific surface area is 10 to 150 m 2 /g, the oil absorption amount per unit surface area (m 2 ) is 0.0003 to 0.01 mL, the carbon amount is 0.5% or more based on the total mass, and the particle size is Having a particle size of 5 nm to 250 nm and a median diameter of 150 nm or less and a surface-treated silica particle material and a dispersion medium in which the silica particle material is dispersed, and having an I100/half width of 300 or less of an X-ray small angle scattering spectrum. Dispersion.
A silica particle material dispersion liquid comprising a silica particle material having a median diameter of 150 nm or less and a dispersion medium in which the silica particle material is dispersed, and having an I100/half-width of the X-ray small angle scattering spectrum of 300 or less.
The specific surface area is 10 to 150 m 2 /g, the oil absorption amount per unit surface area (m 2 ) is 0.0003 to 0.01 mL, the carbon amount is 0.5% or more based on the total mass, and the particle size is A surface-treated silica particle material having a particle size of 5 nm to 250 nm.
A silica particle material having an I100/half width of the X-ray small angle scattering spectrum of 300 or less and a median diameter of 150 nm or less in a dispersion liquid in which a mass ratio of cyclohexanone is 1:1.