JP6046903B2 - Filler-containing liquid composition and method for producing the same - Google Patents

Description

The present invention relates to a liquid composition in which a filler is dispersed and a method for producing the same .

  Conventionally, a cured product of a resin composition in which a filler such as a silica particle material is dispersed in a resin such as a thermosetting resin is known. By including a silica particle material in the resin, heat resistance can be improved, and physical strength can be improved. In order to obtain a cured product of the resin composition, a fluid prepolymer that can be cured by reaction is molded into a necessary shape and cured (see Patent Document 1, etc.).

JP 2011-256243 A

  By the way, since the specific gravity is often different between the filler and the resin material in which the filler is dispersed, the distribution of the filler may be biased due to the influence of gravity. Then, after filling the liquid resin composition containing the filler when used as an underfill material of a semiconductor element, the filler settles or the resin composition is actually used until the resin composition is cured. There was a possibility that the filler content assumed during the storage until the filler settled could not be ensured. In order to suppress such sedimentation of the filler, it is necessary to immediately cure after filling the liquid resin composition or to keep stirring the stored liquid resin composition.

This invention is made | formed in view of the said situation, and makes it the subject which should be solved to provide the filler containing liquid composition with a slow sedimentation rate of a filler, and its manufacturing method .

As a result of intensive studies by the present inventors to solve the above problems, the following invention has been completed.
(I) That is, the filler-containing liquid composition that solves the above problems has a surface treated with a silane compound and an organosilazane with respect to a raw material silica having a volume average particle diameter of 1 nm to 100 nm. Ultrasound is applied for 5 minutes to 100 mL of a dispersion in which 10% by mass is dispersed in one or more dispersion media selected from the group consisting of PMG, MEK, ethyl acetate, and toluene based on the total mass. After that, a silica particle material through which 95% or more passes when suction filtered with 5 types C filter paper of JISP3801 standard,
A filler composed of an inorganic material having a volume average particle size of 0.5 μm or more;
A liquid composition in which the silica particle material and the filler are dispersed;
It is characterized by having.
The silane compound is at least one compound selected from a silane coupling agent and a compound having three alkoxy groups and a phenyl group.

  Since the terminal velocity of sedimentation in a liquid is proportional to the square of the particle size, the sedimentation velocity of a silica particle material having a particle size relatively smaller than that of the filler is small. In addition, since the filler is disturbed by the presence of the silica particle material, the sedimentation rate thereof is also slowed. Therefore, the filler is stably present in the liquid composition as compared with the case where no silica particle material is present.

  The “particle diameter” in this specification is a volume sphere equivalent diameter. Moreover, the particle size in this specification is the diameter of the smallest unit when moving together without separation. That is, it is the particle size of the primary particles when dispersed as primary particles, and the particle size of the secondary particles when formed as secondary particles and dispersed as secondary particles.

Furthermore, as a configuration of (iii), the filler-containing liquid composition that solves the above-described problems has a surface treated with a silane compound and an organosilazane with respect to raw silica having a particle diameter of 1 nm to 100 nm, 5 ultrasonic waves are applied to 100 mL of a dispersion in which 10 mass% is dispersed in one or more dispersion media selected from the group consisting of isopropanol, PMG, MEK, ethyl acetate and toluene based on the total mass. After irradiating for 5 minutes, a silica particle material through which 95% or more passes when suction filtered with 5 types C filter paper of JISP3801 standard,
A filler composed of an inorganic material having a particle size of 0.5 μm or more;
A liquid composition in which the silica particle material and the filler are dispersed;
Have
The mixing ratio of the silica particle material is more than 15% and less than 50% based on the total mass of the filler and the silica particle material.
The silane compound is at least one compound selected from a silane coupling agent and a compound having three alkoxy groups and a phenyl group.

  In addition to the configuration (i) above, at least one of the following configurations (ii), (iv), and (viii) can be added. When the configuration (iv) is adopted, at least one of the configurations (v), (vi), and (vii) described below can be added. Furthermore, when the configuration (viii) is adopted, at least one of the configurations (ix) and (x) described below can be added.

(Ii) The mixing ratio of the silica particle material is more than 15% and less than 50% based on the total mass of the filler and the silica particle material.
(Iv) The silica particle material includes a functional group represented by the formula (1): -OSiX ¹ X ² X ³ and a functional group represented by the formula (2): -OSiY ¹ Y ² Y ³ and both functionalities. It consists of silica particles with groups bonded to the surface. In the above formulas (1) and (2); X ¹ is a phenyl group, vinyl group, epoxy group, methacryl group, amino group, ureido group, mercapto group, isocyanate group, or acrylic group; X ² and X ³ are -OSiR ₃ and -OSiY ⁴ Y ⁵ Y ⁶ are each independently selected from; ^{Y 1} is an ^{R; Y} 2, Y ³ are each selected from R and -OSiY ⁴ Y ⁵ Y ⁶ independently. Y ⁴ is R; Y ⁵ and Y ⁶ are each independently selected from R and —OSiR ₃ ; R is independently selected from an alkyl group having 1 to 3 carbon atoms. X ² , X ³ , Y ² , Y ³ , Y ⁵ , and Y ⁶ are any of X ² , X ³ , Y ² , Y ³ , Y ⁵ , and Y ⁶ of the adjacent functional group. You may combine with heel -O-.
(V) The abundance ratio between the functional group represented by the formula (1) and the functional group represented by the formula (2) is 1:12 to 1:60.
(Vi) X ¹ is 0.5 to 2.5 per unit surface area (nm ² ) of the silica particle material.
(Vii) R is 1 to 10 per unit surface area (nm ² ) of the silica particle material.
(Viii) The silica material is treated by a surface treatment method having a surface treatment step of treating the silica particles with a silane compound and organosilazane in a liquid medium containing water,
The silane compound has three alkoxy groups, phenyl group, vinyl group, epoxy group, methacryl group, amino group, ureido group, mercapto group, isocyanate group, or acrylic group,
The molar ratio between the organo silazane and the silane compound, the silane compound: The organosilazane = 1: 2 to 1: 10.
(Ix) The surface treatment step includes
A first treatment step of treating the silica particles with the silane compound ;
A second treatment step of treating the silica particles with the organosilazane,
The second processing step is performed after the first processing step.
(X) In the second treatment step, a part of the organosilazane is replaced with a second silane compound having three alkoxy groups and an alkyl group having 1 to 3 carbon atoms,
After the second treatment step, the method further comprises a third treatment step of treating the silica particles with the organosilazane.

  In this invention, since it has the said structure, the sedimentation rate of a filler becomes smaller than the speed considered from the particle size of a filler, and can improve the stability of dispersion | distribution of the filler in a liquid composition.

  The filler-containing liquid composition of the present invention will be described in detail below based on the embodiment. Since the filler-containing liquid composition of the present embodiment contains a filler, it can have high physical properties such as high strength, and the contained filler can be stably dispersed.

  The filler-containing liquid composition of this embodiment has a silica particle material, a filler, and a liquid composition (resin material, solvent, etc.) in which they are dispersed. The liquid composition is not particularly limited except that it is liquid. The necessary amount of filler and the total amount of filler and silica particle material are contained. The content of the silica particle material is preferably more than 15%, more preferably 20% or more, based on the total mass of the filler and silica particles combined. And it is preferable that it is less than 50%, and it is more preferable that it is 40% or less. The mixing method of the filler, the silica particle material, and the liquid composition is not particularly limited, and can be mixed and dispersed by a known stirrer / kneader. Further, the order of mixing is not particularly limited.

  Moreover, when employ | adopting resin produced | generated by reaction from a smaller molecular weight compound as a liquid composition, it can also carry out in the state which mixed the silica particle material and the filler during the reaction. Furthermore, it is possible to introduce a functional group that can be bonded by the reaction into the surface of the silica particle material or the surface of the filler, and to chemically bond it to the liquid composition by the reaction.

Silica particle material The silica particle material has the following “first form” or “second form” configuration. Note that there is no difference between the first embodiment and the second embodiment as the idea of the invention that a silica particle material having a particle size smaller than that of the filler is added.
(First form)
The silica particle material is a material obtained by subjecting raw material silica, which is a particle made of silica having a volume average particle diameter of 1 nm to 100 nm, to surface treatment. The particle diameter of the raw material silica is desirably 2 nm or more, particularly desirably 5 nm or more, and more desirably 10 nm or more. Moreover, 80 nm or less is desirable and 50 nm or less is more desirable.
(Second form)
The silica particle material has a particle size of 100 nm or less. In this case, the mixing ratio of the silica particle material is more than 15% and less than 50% based on the total mass of the filler and the silica particle material. The particle size is specified because it is difficult to distinguish when a filler made of silica is used, so that the particle size can be simply distinguished only by the particle size.
(Common features of the first form and the second form 2)
The surface of the silica particle material is treated with a silane compound and an organosilazane. The silane compound is at least one compound selected from a silane coupling agent and a compound having three alkoxy groups and a phenyl group.

A silica particle material with higher sphericity is desirable because the fluidity is improved. The sphericity is preferably 0.8 or more, and more preferably 0.9 or more. The sphericity is measured by taking a photograph with an SEM, and calculating from (Sphericality) = {4π × (Area) ÷ (Ambient Length) ² } from the area and circumference of the observed particle. calculate. The closer to 1, the closer to a true sphere. Specifically, an average value measured for 100 particles randomly extracted using an image processing apparatus (Sysmex Corporation: FPIA-3000) is employed.

  The silica particle material is used for 100 mL of a dispersion in which 10% by mass is dispersed in one or more dispersion media selected from the group consisting of isopropanol, PMG, MEK, ethyl acetate, and toluene based on the total mass. After irradiating with ultrasonic waves for 5 minutes, 95% or more passes when suction filtration is performed with 5 kinds C filter paper of JISP3801 standard. By this test, the dispersibility in the dispersion can be evaluated. Type 5 C filter paper is a filter paper for fine precipitation, and does not pass through unless it is highly dispersed.

The method for imparting such dispersibility to the silica particle material is not particularly limited except that the silane compound and organosilazane are used in combination. For example, the method described later in Part 1 and Part 2 (even if used together) Good).

(Part 1)
The silica particle material is a silica in which a functional group represented by the formula (1): -OSiX ¹ X ² X ³ and a functional group represented by the formula (2): -OSiY ¹ Y ² Y ³ are bonded to the surface. It is a particulate material. Hereinafter, it referred to functional group represented by the formula (1) and the first functional group, referred to as functional group represented by the formula (2) and the second functional group.

X ¹ in the first functional group is a phenyl group, vinyl group, epoxy group, methacryl group, amino group, ureido group, mercapto group, isocyanate group, or acrylic group. X ² and X ³ are —OSiR ₃ or —OSiY ⁴ Y ⁵ Y ⁶ , respectively. Y ⁴ is R. Y ⁵ and Y ⁶ are each R or —OSiR ₃ .

Y ¹ in the second functional group is R. Y ² and Y ³ are each —OSiR ₃ or —OSiY ⁴ Y ⁵ Y ⁶ .

The more —OSiR ₃ contained in the first functional group and the second functional group, the more R on the surface of the silica particle material. The more R (alkyl group having 1 to 3 carbon atoms) contained in the first functional group and the second functional group, the less the silica particle material is aggregated.

Regarding the first functional group, when X ² and X ³ are each —OSiR ₃ , the number of R is minimized. Further, ^{X 2} and ^{X 3} is -OSiY ⁴ Y ⁵ Y ^6, respectively, ^and, if Y 5, ^{Y 6} is -OSiR ₃ respectively, the number of R is maximized.

Regarding the second functional group, when Y ² and Y ³ are each —OSiR ₃ , the number of R is minimized. Further, ^{Y 2} and ^{Y 3} are each a -OSiY ⁴ Y ⁵ Y ^{6, and,} if Y 5, ^{Y 6} is -OSiR ₃ respectively, the number of R is maximized.

The number of X ¹ contained in the first functional group, the number of R contained in the first functional group, and the number of R contained in the second functional group are the abundance ratio of R and X ¹ , silica What is necessary is just to set suitably according to the particle size and use of a particulate material.

^{Incidentally, X 2, X 3, Y} 2, Y 3, Y 5, and any of ^{Y 6, X} 2 of the adjacent ^{functionality, X 3, Y 2, Y} 3, Y 5, and any ^{Y 6} You may combine with heel -O-. For example, any one of the first functional group X ² , X ³ , Y ⁵ , and Y ⁶ is the first functional group adjacent to the first functional group X ² , X ³ , Y ⁵ , and It may be bonded to any of Y ⁶ by —O—. Similarly, any of Y ² , Y ³ , Y ⁵ , and Y ⁶ of the second functional group is replaced with Y ² , Y ³ , Y ⁵ , Y ² of the second functional group adjacent to the second functional group. And Y ⁶ may be bonded to each other by —O—. Furthermore, any one of the first functional groups X ² , X ³ , Y ⁵ , and Y ⁶ is the second functional group adjacent to the first functional group, Y ² , Y ³ , Y ⁵ , And Y ⁶ may be bonded to each other by —O—.

Presence ratio of the first functional groups and second functional groups is 1: 12-1: if 60, the surface of the silica particulate material with X ¹ and R are present good balance. For this reason, the silica particle material whose abundance ratio between the first functional group and the second functional group is 1:12 to 1:60 is particularly excellent in the affinity for the resin and the aggregation suppressing effect. Further, if X ¹ is 0.5 to 2.5 per unit surface area (nm ² ) of the silica particle material, a sufficient number of first functional groups are bonded to the surface of the silica particle material, and the first There are also a sufficient number of R derived from the functional group and the second functional group. Accordingly, also in this case, the affinity for the resin and the aggregation suppressing effect of the silica particle material are sufficiently exhibited.

In any case, R per unit surface area (nm ² ) of the silica particle material is preferably 1 to 10. In this case, the balance between the number of X ¹ present on the surface of the silica particle material and the number of R is improved, and both the affinity for the resin and the aggregation suppressing effect of the silica particle material are exhibited in a well-balanced manner.

It is preferable that all of the hydroxyl groups present on the surface of the silica particles are substituted with the first functional group or the second functional group. If the sum of the first functional group and the second functional group is 2.0 or more per unit surface area (nm ² ) of the silica particle material, the silica particle material is present on the surface of the silica particle. It can be said that almost all of the hydroxyl groups are substituted with the first functional group or the second functional group.

The silica particle material has R on the surface. This can be confirmed by an infrared absorption spectrum. Specifically, when the infrared absorption spectrum of the silica particle material is measured by the solid diffuse reflection method, there is a maximum absorption of C—H stretching vibration at 2962 ± 2 cm ⁻¹ . For this reason, whether or not the inorganic powder mixture of the present embodiment is a silica particle material can be confirmed by an infrared absorption spectrum.

  Further, as described above, the silica particle material of the inorganic powder mixture of the present invention is difficult to agglomerate. Therefore, it can employ | adopt as a silica particle material with a small particle size. For example, the silica particle material can have an average particle size of about 3 nm to 5000 nm. It is preferable to apply to a silica particle material having an average particle diameter of 3 to 200 nm.

  Note that the silica particle material can be dispersed again by ultrasonic treatment even if it is slightly agglomerated. Specifically, the silica particle material can be substantially dispersed into primary particles by irradiating an ultrasonic wave having an oscillation frequency of 39 kHz and an output of 500 W on a silica particle material dispersed in methyl ethyl ketone. The ultrasonic irradiation time at this time may be 10 minutes or less. Whether or not the silica particle material is dispersed into the primary particles can be confirmed by measuring the particle size distribution. Specifically, when the methyl ethyl ketone dispersion material of the silica particle material is measured with a particle size distribution measuring device such as a microtrack device, and the particle size distribution of the silica particle material is present, it can be said that the silica particle material is dispersed into primary particles.

  Since this silica particle material hardly aggregates, it can be provided as a silica particle material that is not dispersed in a liquid medium such as water or alcohol. In addition, since the silica particle material hardly aggregates, it can be easily washed with water.

(Part 2)
It can replace with the silica particle material shown in the 1 and can also adopt the silica particle material which performed the surface treatment shown below. In addition, since the silica particle material (the 1) can also be obtained with the following method, the 1 and the 2 are not exclusive.

The surface treatment method of a silica particle material has a step (surface treatment step) of surface-treating silica particles with a silane compound and organosilazane in a liquid medium containing water. The silane compound has three alkoxy groups and a phenyl group, a vinyl group, an epoxy group, a methacryl group, an amino group, a ureido group, a mercapto group, an isocyanate group, or an acrylic group (that is, X ¹ described above).

By surface treatment with a silane compound, a hydroxyl group present on the surface of the silica particles are substituted with a functional group derived from the silane compound. The amount of the silane compound to be subjected to the surface treatment is not particularly limited, but can be an amount capable of reacting 80% or more with respect to the silanol group on the surface of the silica particle material before the treatment. Especially when about 2.5 silanol groups / nm ² are present on the surface of the silica particle material before the reaction, the remaining silanol groups can be reduced to 0.5 / nm ² or less by reacting at least 80%. The amount of water generated by the reaction can be sufficiently suppressed. The functional group derived from the silane compound is represented by the formula (3); —OSiX ¹ X ⁴ X ⁵ . The functional group represented by the formula (3) is referred to as a third functional group. X ¹ in the third functional group is the same as X ¹ in the functional group represented by the formula (1). X ⁴ and X ⁵ are each an alkoxy group. By surface-treating with organosilazane, the third functional group X ⁴ and X ⁵ are derived from organosilazane —OSiY ¹ Y ² Y ³ (the functional group represented by the formula (2), the second functional group ). When all of the hydroxyl groups present on the surface of the silica particles are not substituted with the third functional group, the hydroxyl groups remaining on the surface of the silica particles are substituted with the second functional group. Therefore, the surface of the surface-treated silica particle material has a functional group represented by the formula (1): —OSiX ¹ X ² X ³ (that is, the first functional group) and a formula (2): —OSiY. ^The functional group represented by ¹ Y ² Y ³ is bonded to the functional group (that is, the second functional group). Incidentally, the silane compound and the molar ratio of organosilazane, silane compound: organosilazane = 1: 2 to 1: for a 10, a first functional group in the obtained silica particles material and the second functional group The abundance ratio is theoretically from 1:12 to 1:60.

In the surface treatment step, the silica particles may be simultaneously surface treated with a silane compound and an organosilazane. Alternatively, the silica particles may be first surface treated with a silane compound and then surface treated with organosilazane. Alternatively, the silica particles may be first surface treated with organosilazane, then surface treated with a silane compound , and then surface treated with organosilazane. In any case, the amount of organosilazane may be adjusted so that all the hydroxyl groups present on the surface of the silica particles are not substituted with the second functional group. The hydroxyl groups present on the surface of the silica particles may all be substituted with the third functional group, or only a part may be substituted with the third functional group, and the other part may be substituted with the second functional group. It may be replaced. All of X ⁴ and X ⁵ contained in the third functional group may be substituted with the second functional group.

A part of the organosilazane may be replaced with the second silane compound . The second silane compound, and three alkoxy groups, Ru der those with one alkyl group. In this case, X ⁴ and X ⁵ contained in the third functional group are substituted with the fourth functional group derived from the second silane compound . The fourth functional group has the formula (4); - represented by OSiY ¹ X ⁶ X ^7. Y ¹ is the same R as ^{Y 1} in the second functional ^{group, X 6,} X ⁷ is an alkoxy group or a hydroxyl group, respectively. X ⁶ and X ⁷ contained in the fourth functional group are substituted with the second functional group derived from organosilazane, or are substituted with another fourth functional group. In this case, the amount of R present on the surface of the silica particle material can be further increased. Incidentally, a part of organosilazane, to replace the second silane compound, after surface-treated with a second silane compound, it is necessary to surface treatment with an organosilazane again. This is because X ⁶ and X ⁷ contained in the fourth functional group are finally substituted with the second functional group derived from organosilazane.

When a part of the organosilazane is replaced with the second silane compound, X ⁴ and X ⁵ contained in the first functional group described above are replaced with the second functional group derived from the organosilazane or the second functional group. The fourth functional group derived from the silane compound is substituted. When X ⁴ and X ⁵ are substituted with the fourth functional group, X ⁶ and X ⁷ contained in the fourth functional group are substituted with the second functional group or another fourth functional group. Is replaced by If X ^6, X ⁷ contained in the fourth functional group has been replaced by another fourth functional group, X ^6, X ⁷ contained in the fourth functional groups is substituted with the second functional group The Therefore the second silane compound, the amount of organosilazane set when (if the organosilazane was replaced with a second silane compound) to a surface treatment of only the first silane compound and organosilazanes (a) mol In contrast, a maximum of 5a / 3 mol can be replaced. The amount of organosilazane required in this case is 8a / 3 mol.

Silane compound and the alkoxy group of the second silane compound is not particularly limited, relatively small is preferable number of carbon atoms is preferably 1 to 12 carbon atoms. Considering the hydrolyzability of the alkoxy group, the alkoxy group is more preferably any one of a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

Specific examples of the silane compound include phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-amino trimethoxysilane like et be.

The organosilazane is not particularly limited as long as it can replace the hydroxyl group, the silane compound and the alkoxy group derived from the second silane compound present on the surface of the silica particles with the above-mentioned second functional group. Is preferably used. Specific examples include tetramethyldisilazane, hexamethyldisilazane, pentamethyldisilazane, and the like.

Examples of the second silane compound include methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, and hexyltriethoxysilane.

Incidentally, in the surface treatment step, for suppressing the polymerization of the polymerization or the second silane compound of the silane compound may be added a polymerization inhibitor. As the polymerization inhibitor, common ones such as 3,5-dibutyl-4-hydroxytoluene (BHT) and p-methoxyphenol (methoquinone) can be used.

  The surface treatment for obtaining the silica particle material will be described. The surface treatment method may include a solidification step after the surface treatment step. The solidification step is a step of precipitating the surface-treated silica particle material with a mineral acid and washing and drying the precipitate with water to obtain a solid of the silica particle material. As described above, since a general silica particle material is very likely to aggregate, it is very difficult to disperse the once solidified silica particle material. However, since the silica particle material is difficult to aggregate, it is difficult to aggregate even if solidified, and it is easy to redisperse even if aggregated. In addition, as mentioned above, the silica particle material used for uses, such as an electronic component, can be easily manufactured by wash | cleaning a silica particle material with water. In the cleaning step, it is preferable to repeat the cleaning until the electric conductivity of the water extracted from the silica particle material (specifically, the water in which the silica particle material is immersed at 121 ° C. for 24 hours) is 50 μS / cm or less. .

  Examples of the mineral acid used in the solidification step include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and hydrochloric acid is particularly desirable. The mineral acid may be used as it is, but is preferably used as a mineral acid aqueous solution. The concentration of the mineral acid in the aqueous mineral acid solution is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The amount of the mineral acid aqueous solution can be about 6 to 12 times based on the mass of the silica particle material to be cleaned.

  The cleaning with the mineral acid aqueous solution can be performed a plurality of times. The washing with the mineral acid aqueous solution is preferably performed after the silica particle material is immersed in the mineral acid aqueous solution. Further, it can be left in the immersed state for 1 to 24 hours, and further for about 72 hours. When it is allowed to stand, stirring can be continued or not stirred. When washing in the mineral acid-containing liquid, it can be heated to room temperature or higher.

  Thereafter, the washed and suspended silica particle material is collected by filtration and then washed with water. It is desirable that the water used does not contain ions such as alkali metals (for example, 1 ppm or less on a mass basis). For example, ion exchange water, distilled water, pure water and the like. Washing with water is the same as washing with an aqueous mineral acid solution, after the silica particle material is dispersed and suspended, it can be filtered, or by continuously passing water through the filtered silica particle material. Is possible. The end time of washing with water may be determined by the electric conductivity of the extracted water described above, or may be the time when the alkali metal concentration in the waste water after washing the silica particle material becomes 1 ppm or less, It is good also as the time of the alkali metal concentration of extraction water becoming 5 ppm or less. When washing with water, it can be heated to a room temperature or higher.

The silica particle material can be dried by a conventional method. For example, heating or leaving under reduced pressure (vacuum).
-The filler has a volume average particle diameter of 0.5 μm or more (in the case of the first form of silica particle material) or a particle diameter of 0.5 μm or more (in the case of the second form of silica particle material) ). The material constituting the filler is not limited except that it is made of an inorganic material. For example, as a filler, silica, alumina (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), zeolite, titanium oxide (TiO ₂ ), aluminum nitride (AlN), silicon carbide (SiC), silicon nitride (Si ₃ N ₄ ) , Barium titanate (BaTiO ₃ ), strontium titanate (SrTiO ₃ ), calcium titanate (CaTiO ₃ ), aluminum borate, boronite, calcium carbonate, lead oxide, tin oxide, cerium oxide, calcium oxide, trimanganese tetraoxide Magnesium oxide, cerium zirconate, calcium silicate, zirconium silicate, ITO, titanium silicate can be used alone or in combination.

  The form of the filler is not particularly limited, but the sphericity of the filler is preferably 0.8 or more, and more preferably 0.9 or more. Furthermore, the surface of the filler is also appropriately selected (a surface treatment agent that can be reacted or can be attached is selected. And for the purpose of improving the affinity with the liquid composition) Done.)

Liquid resin material The liquid resin material may be any material that has fluidity at the operating temperature. For example, a case where a low molecular weight substance (such as a solvent) or a thermoplastic resin is employed and the use at a temperature higher than the melting point of the thermoplastic resin is considered. Moreover, the material which hardens | cures by the hardening reaction performed later may be used.

  Specifically, it can have a polymer material and / or a precursor of the polymer material. The polymer material precursor is a polymer or a low-molecular material, and is a material that can form a cured product by further increasing the molecular weight or proceeding cross-linking as the reaction proceeds. Examples of the cured material formed from the polymer material and the polymer material precursor may include general resin materials such as a thermoplastic resin, a thermosetting resin, and a photocurable resin. The polymer material precursor may have an epoxy group, an oxetane group, a hydroxyl group, a blocked isocyanate group, an amino group, a half ester group, an amic group, a carboxy group, and a carbon-carbon double bond group in the chemical structure. desirable. These functional groups are functional groups (polymerizable functional groups) that can be bonded to each other by setting suitable reaction conditions, and the molecular weight of the mixed material can be improved. Suitable reaction conditions include simple heating and light irradiation, generation of reactive species such as radicals and ions (anions and cations) by heat and light irradiation, and a reaction initiator that binds between these functional groups. (Polymerization initiator) is added and heating or light irradiation is performed. A compound necessary for the polymerization reaction can be added as a curing agent, or a catalyst for the reaction can be added.

  Preferred examples of the polymer material precursor include a monomer that forms a polymer material by polymerization and a polymer material modified with a polymerizable functional group as described above. For example, a prepolymer such as an epoxy resin, an acrylic resin, or a urethane resin before curing is suitable.

The silane compound or organosilazane for surface treatment of the silica particle material or filler is preferably selected according to the material selected as the resin material. For example, a functional group having affinity for the resin material can be imparted to the surface of the silica particle material.

  Hereinafter, the filler-containing liquid composition of the present invention will be described in detail based on examples.

(Preparation of filler-containing liquid composition)
-Preparation of silica particle material Nano-sized colloidal silica (volume average particle diameter 10 nm, dispersed in water and having a solid content concentration of 20%) synthesized from water glass was prepared as a raw material silica.
Isopropanol was prepared as the alcohol.
Methacrylic silane was prepared as a silane compound .
Hexamethyldisilazane (HMDS, manufactured by Shin-Etsu Chemical Co., Ltd., HDMS-1) was prepared as organosilazane.

(Surface treatment process)
(1) Preparatory process By adding 60 parts by mass of isopropanol to 100 parts by mass of slurry in which silica particles are dispersed in water at a concentration of 20% by mass, and mixing at room temperature (about 25 ° C.), the raw material silica is dispersed in the liquid medium. A dispersion was obtained.

(2) First Step 2.0 parts by mass of vinylsilane was added to this dispersion and mixed at 40 ° C. for 72 hours. By this step, the hydroxyl group present on the surface of the raw material silica was surface-treated with the silane compound . At this time, vinylsilane was calculated and added so that a necessary amount of hydroxyl groups (partially) remained without being surface-treated.

(3) Second Step Next, 4.3 parts by mass of hexamethyldisilazane was added to this mixture and left at 40 ° C. for 72 hours. Through this step, the silica particles were surface-treated to obtain a silica particle material. As the surface treatment progressed, the silica particles that became hydrophobic could no longer exist stably in water and isopropanol, and agglomerated and precipitated. The molar ratio of vinylsilane to hexamethyldisilazane was 1: 2.

(Solidification process)
5 parts by mass of 35% aqueous hydrochloric acid solution was added to the total amount of the mixture obtained in the surface treatment step to precipitate the silica particle material. The precipitate was filtered with a filter paper (5A manufactured by Advantech). The filtration residue (solid content) was washed with pure water and then vacuum-dried at 200 ° C. for 2 hours to obtain a silica particle material solid (silica particle material). The surface of the silica particle material had 2.5 / nm ² of silanol groups before treatment, and about 70% of the silanol groups were consumed by these treatments.

Filler Titanium oxide having a volume average particle diameter of primary particles of 0.25 μm and a volume average particle diameter of secondary particles of 1 μm was used as a filler.

-Preparation of sample for sedimentation test Methyl ethyl ketone (MEK) was used as a liquid composition. Titanium oxide is dispersed so as to be 5% with respect to the total mass, and the silica particle material described above is further added to 0% (Test Example 1: filler and silica particle material based on the mass of the filler (titanium oxide)). 0%), 15% (Test Example 2: about 13% based on the total mass of filler and silica particle material), 30% (Test Example 3: filler and silica particles) About 23.1% based on the total mass of the material and 50% (Test Example 4: about 33.3% based on the total mass of the filler and the silica particle material), and uniformly Stir. As a result of leaving these test samples for 4 days, test samples 1 and 2 were separated into two layers, and precipitation of filler was observed, whereas in test samples 3 and 4, a single layer in a uniform state was observed. The precipitation prevention effect was recognized.

  Viscosity was measured for each of test samples 1 to 4 (rotary viscometer). The results are shown as relative values when the test sample 1 (concentration 0%) is 1. Test sample 2 was 1.1, test sample 3 was 1.1, and test sample 4 was 1.7.

・ Reference test (Reference Test Example 1)
(material)
As a silica particle, Snowtex OS (manufactured by Nissan Chemical Industries, Ltd., average particle size of 10 nm, solid concentration 20% dispersed in water) was prepared as a kind of colloidal silica.
Isopropanol was prepared as the alcohol.
As the silane compound , phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-103) was prepared.
Hexamethyldisilazane (HMDS, manufactured by Shin-Etsu Chemical Co., Ltd., HDMS-1) was prepared as organosilazane.

(Surface treatment process)
(1) Preparation Step Silica particles are dispersed in a liquid medium by adding 60 parts by mass of isopropanol to 100 parts by mass of slurry in which silica particles are dispersed in water at a concentration of 20% by mass, and mixing at room temperature (about 25 ° C.). A dispersion was obtained.

(2) First Step 1.8 parts by mass of phenyltrimethoxysilane was added to this dispersion and mixed at 40 ° C. for 72 hours. By this step, the hydroxyl group present on the surface of the silica particles was surface-treated with the silane compound . At this time, phenyltrimethoxysilane was calculated and added so that a necessary amount of hydroxyl groups (partially) remained without being surface-treated.

(3) Second Step Next, 3.7 parts by mass of hexamethyldisilazane was added to this mixture and left at 40 ° C. for 72 hours. Through this step, the silica particles were surface-treated to obtain a silica particle material. As the surface treatment progressed, the silica particles that became hydrophobic could no longer exist stably in water and isopropanol, and agglomerated and precipitated. The molar ratio of phenyltrimethoxysilane to hexamethyldisilazane was 2: 5.

(Solidification process)
5 parts by mass of 35% aqueous hydrochloric acid solution was added to the total amount of the mixture obtained in the surface treatment step to precipitate the silica particle material. The precipitate was filtered with a filter paper (5A manufactured by Advantech). The filtration residue (solid content) was washed with pure water and then vacuum dried at 100 ° C. to obtain a solid of silica particle material.

(Reference Test Example 2)
The silica particle surface treatment method of Reference Test Example 2 uses vinyltrimethoxysilane instead of phenyltrimethoxysilane, except that the molar ratio of vinyltrimethoxysilane to hexamethyldisilazane was 2: 5. This is the same as the silica particle surface treatment method of Test Example 5. In the first step, 1.36 parts by mass of vinyltrimethoxysilane was added, and in the second step, 3.7 parts by mass of hexamethyldisilazane was added.

  As vinyltrimethoxysilane, KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

(Reference Test Example 3)
The surface treatment method of the silica particles of Reference Test Example 3 uses vinyltrimethoxysilane instead of phenyltrimethoxysilane, except that the molar ratio of vinyltrimethoxysilane to hexamethyldisilazane was 1: 5. This is the same as the surface treatment method for silica particles of Reference Test Example 1. In the first step, 1.36 parts by mass of vinyltrimethoxysilane was added, and in the second step, 7.41 parts by mass of hexamethyldisilazane was added.

(Reference Test Example 4)
In the surface treatment method of silica particles of Reference Test Example 4, as a silica particle, Snowtex OL (manufactured by Nissan Chemical Industries, Ltd., average particle size 50 nm, dispersed in water and having a solid content concentration of 20) is used as a silica particle. %) Was used. In the first step, 0.48 parts by mass of 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503) was added as a silane compound . Furthermore, in addition to this silane compound , 0.01 mass parts of polymerization inhibitors (3,5-dibutyl-4-hydroxytoluene (BHT), manufactured by Kanto Chemical Co., Inc.) were added. In the second step, 0.78 parts by mass of hexamethyldisilazane was added. Furthermore, in the solidification step, 2.6 parts by mass of a 35% aqueous hydrochloric acid solution was added to the total amount of the mixture obtained in the surface treatment step to precipitate the silica particle material. Except this, the silica particle surface treatment method of Test Example 8 was the same as the silica particle surface treatment method of Reference Test Example 1. The molar ratio of 3-methacryloxypropyltrimethoxysilane to hexamethyldisilazane was 2: 5.

(Reference Test Example 5)
The silica particle surface treatment method of Reference Test Example 5 is the same as the silica particle surface treatment method of Reference Test Example 1 except that the molar ratio of phenyltrimethoxysilane and hexamethyldisilazane was 1: 1. It is. In the first step, 4.5 parts by mass of phenyltrimethoxysilane was added, and in the second step, 3.7 parts by mass of hexamethyldisilazane was added.

(Reference Test Example 6)
The surface treatment method of the silica particles of Reference Test Example 6 is the surface of the silica particles of Reference Test Example 4 except that the molar ratio of 3-methacryloxypropyltrimethoxysilane to hexamethyldisilazane was 2: 1. It is the same as the processing method. In the first step, 0.48 parts by mass of 3-methacryloxypropyltrimethoxysilane was added, and in the second step, 0.16 parts by mass of hexamethyldisilazane was added.

(Reference Test Example 7)
The surface treatment method of the silica particles of Reference Test Example 7 is the surface of the silica particles of Reference Test Example 4 except that the molar ratio of 3-methacryloxypropyltrimethoxysilane to hexamethyldisilazane was 1: 1. It is the same as the processing method. In the first step, 0.48 parts by mass of 3-methacryloxypropyltrimethoxysilane was added, and in the second step, 0.31 parts by mass of hexamethyldisilazane was added.

(Cohesiveness evaluation test)
About the silica particle material of the reference test examples 1-7, the cohesiveness in a liquid medium was measured.

  Specifically, for Reference Test Examples 1 to 3 and Reference Test Example 5, a mixture of 10 g of silica particle material and 40 g of methyl ethyl ketone was stirred to obtain a dispersion sample of silica particle material.

  In Reference Test Examples 4, 6, and 7, a mixture of 10 g of silica particle material and 10 g of methyl ethyl ketone was stirred to obtain a dispersion sample of silica particle material. The particle size distribution of the silica particle material contained in each of the obtained dispersion samples was measured by a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., Microtrack).

As a result, it was found that the silica particle materials of Reference Test Examples 1 to 4 were dispersed in a primary particle state without aggregation. This is supported by the fact that only one particle size distribution (peak) of each silica particle material of Reference Test Examples 1 to 4 appears at a position having a particle diameter of about 10 nm to 50 nm. If the silica particle material is a secondary particle (that is, if there is even agglomeration), at least one peak appears at a position having a particle diameter of 100 nm or more. For this reason, although the silica particle material of Test Examples 5-8 was once solidified, it turns out that most are primary particles and hardly aggregated. On the other hand, the silica particle materials of Test Examples 9 to 11 are not dispersed only by stirring, and even after ultrasonic stirring at an oscillation frequency of 39 kHz and an output of 500 W for 1 hour or more, aggregation can be confirmed with the naked eye. It did not disperse to primary particles. From this result, it can be seen that by making the molar ratio of the silane compound and the organosilazane within the range of 1: 2 to 1:10, it is possible to produce a silica particle material that hardly aggregates even when solidified. The average particle size of the silica particle material of Test Example 5 is 10 nm, the average particle size of the silica particle material of Test Example 6 is 10 nm, the average particle size of the silica particle material of Test Example 7 is 10 nm, and the silica particles of Test Example 8 The average particle size of the material was 50 nm. From this result, it can be seen that the molar ratio of the silane compound to the organosilazane is preferably in the range of 1: 5 to 2: 5 in order to suppress aggregation.

(Maximum absorption measurement test)
The silica particle material of Reference Test Examples 1 to 7 was prepared, and the infrared absorption spectrum of this sample was measured by a powder diffusion reflection method using FT-IR Avatar manufactured by Thermo Nicolet. The measurement conditions at this time were a resolution of 4 and a scan count of 64. As a result, the infrared absorption spectra of the silica particle materials of Test Examples 5 to 11 all have a maximum absorption (peak) of C—H stretching vibration at 2962 cm ⁻¹ . For this reason, it can be seen that these silica particle materials have an alkyl group (that is, are surface-treated with an organosilazane having an alkyl group). In addition, the peak height of the silica particle material of Reference Test Examples 5 to 7 was lower than the peak height of the silica particle material of Reference Test Examples 1 to 4. This result suggests that the silica particle materials of Reference Test Examples 5 to 7 do not have a sufficient amount of alkyl groups. Specifically, in the infrared absorption spectra of the silica particle materials of Test Examples 5 to 8, the methyl group (2962 cm ⁻¹⁾ derived from organosilazane with respect to the peak height of C—H specific to each functional group derived from the silane compound. ) Was 3 times or more. In the infrared absorption spectra of the silica particle materials of Reference Test Examples 5 to 7, the methyl group (2962 cm ⁻¹ ) derived from organosilazane with respect to the peak height of C—H specific to each functional group derived from the silane compound. The peak height was 2 times or less. As described above, the silica particle materials of Reference Test Examples 1 to 4 were hardly aggregated, and the silica particle materials of Reference Test Examples 5 to 7 were easily aggregated. From these results, the silica particle material in which the peak height of the methyl group (2962 cm ⁻¹ ) derived from the organosilazane is three times or more the C—H peak height specific to each functional group derived from the silane compound. Can hardly be agglomerated.

(Carbon content measurement test)
About the silica particle material of the reference test examples 1-7, the quantity (mass%) of the carbon which exists per mass of a silica particle material was measured. For the measurement, an organic carbon measuring device (HORIBA, EMIA-320V) was used.

  As a result, the carbon amount of the silica particle material of Reference Test Example 1 was 3.5% by mass, the carbon amount of the silica particle material of Reference Test Example 2 was 2.6% by mass, and the silica particles of Reference Test Example 3 The carbon content of the material was 2.8% by mass, and the carbon content of the silica particle material of Reference Test Example 4 was 0.96% by mass. The carbon content of the silica particle material of Reference Test Example 5 is 4.0% by mass, the carbon content of the silica particle material of Reference Test Example 6 is 1.8% by mass, and the carbon of the silica particle material of Reference Test Example 7 The amount was 1.0% by mass.

(X ¹ number measurement test)
For the silica particle materials of Reference Test Examples 1 to 7, the number of X ¹ present per unit surface area (nm ² ) of the silica particle material was measured. X ¹ in the silica particle material of Reference Test Example 1 and Reference Test Example 5 is a phenyl group, X ¹ in the silica particle material of Reference Test Examples 2 and 3 is a vinyl radical, the Reference Test Examples 4, 6 and 7 X ¹ in the silica particle material was a methacryloxy group. The surface area (specific surface area) of the silica particle material was measured by the BET method using nitrogen. The number of X ¹ was calculated based on the carbon content of the silica particle material. Specifically, the silica particles after the first step were washed with water, centrifuged and then dried to obtain a silica particle sample after the silane compound treatment. The carbon content of this sample was measured using an organic carbon measuring device, and the number of X ¹ was calculated based on the measured value.

As a result, the number of X ¹ in the silica particle material of Reference Test Example 1 was about 1.2 / nm ² . The number of X ¹ in the silica particle material of Reference Test Example 2 was about 1.1 pieces / nm ² . The number of X ¹ in the silica particle material of Reference Test Example 3 was about 1.1 pieces / nm ² . The number of X ¹ in the silica particle material of Reference Test Example 4 was about 2.0 / nm ² . The number of X ¹ in the silica particle material of Reference Test Example 5 was about 1.7 pieces / nm ² . The number of X ¹ in the silica particle material of Reference Test Example 6 was about 2.0 / nm ² . The number of X ¹ in the silica particle material of Reference Test Example 7 was about 2.0 / nm ² . For reference, the carbon content of the silica particle sample after the silane compound treatment was 3.6% by mass for the silica particle material of Reference Test Example 1, 1.1% by mass for the silica particle material of Reference Test Example 2, and Reference Test Example The silica particle material of No. 3 was 1.1 mass%, and the silica particle material of Reference Test Example 4 was 1.5 mass%. Further, the silica particle material of Reference Test Example 5 was 5.0% by mass, the silica particle material of Reference Test Example 6 was 1.5% by mass, and the silica particle material of Reference Test Example 7 was 1.5% by mass.

As mentioned above, the affinity to the resin material of the silica particulate material depends on the number and type of X ^1, silica particulate material of the silica particulate material and Reference Test Example 4 of Reference Test Example 1 is excellent in affinity to a resin material It was. From this result, in order to exhibit excellent affinity for the resin material, X ¹ per unit surface area (nm ² ) of the silica particle material is preferably 0.5 to 2.5, It can be said that 1.0 to 2.0 is more preferable.

Claims (9)

A raw material silica having a volume average particle diameter of 1 nm to 100 nm has a surface treated with a silane compound and an organosilazane, and is selected from the group consisting of isopropanol, PMG, MEK, ethyl acetate, and toluene. When 100 mL of a dispersion liquid of 10% by mass based on the total mass of a seed or two or more kinds of dispersion media is irradiated with ultrasonic waves for 5 minutes, and then suction filtered with 5 kinds C filter paper of JISP3801 standard. Silica particle material through which 95% or more passes;
A filler composed of an inorganic material having a volume average particle size of 0.5 μm or more;
A liquid composition in which the silica particle material and the filler are dispersed;
I have a,
The silane compound is a silane coupling agent and one or more compounds selected from compounds having three alkoxy groups and a phenyl group,
The filler-containing liquid composition in which the mixing ratio of the silica particle material is more than 15% and less than 50% based on the total mass of the filler and the silica particle material . One type selected from the group consisting of isopropanol, PMG, MEK, ethyl acetate, and toluene, the surface of which is treated with a silane compound and an organosilazane with respect to a raw material silica having a particle size of 1 nm to 100 nm After irradiating ultrasonic waves for 5 minutes to 100 mL of a dispersion in which 10% by mass of the total mass is dispersed in two or more types of dispersion media as a reference, it is 95% when suction filtered with 5C filter paper of JISP3801 standard. Silica particle material through which the above passes,
A filler composed of an inorganic material having a particle size of 0.5 μm or more;
A liquid composition in which the silica particle material and the filler are dispersed;
Have
The silane compound is a silane coupling agent and one or more compounds selected from compounds having three alkoxy groups and a phenyl group,
The filler-containing liquid composition, wherein the mixing ratio of the silica particle material is more than 15% and less than 50% based on the total mass of the filler and the silica particle material. The silica particle material has a functional group represented by the formula (1): -OSiX ¹ X ² X ³ and a functional group represented by the formula (2): -OSiY ¹ Y ² Y ³ , and both functional groups are on the surface. filler-containing liquid composition according to claim 1 or 2 consisting of silica particles to bind to. (In the above formulas (1) and (2); X ¹ is a phenyl group, a vinyl group, an epoxy group, a methacryl group, an amino group, a ureido group, a mercapto group, an isocyanate group, or an acrylic group; X ² , X ³ Are independently selected from —OSiR ₃ and —OSiY ⁴ Y ⁵ Y ⁶ ; Y ¹ is R; Y ² and Y ³ are each independently selected from R and —OSiY ⁴ Y ⁵ Y ⁶ .Y ⁴ is an R; ^{Y 5} and ^{Y 6} is selected from R and -OSiR ₃ independently;. R is independently selected from alkyl groups of 1 to 3 carbon atoms Incidentally, ^{X 2} , X ³ , Y ² , Y ³ , Y ⁵ , and Y ⁶ are any of the adjacent functional groups X ² , X ³ , Y ² , Y ³ , Y ⁵ , and Y ⁶ , and —O—. May be combined with each other.) The filler-containing liquid composition according to claim 3 , wherein the ratio of the number of the functional group represented by the formula (1) and the functional group represented by the formula (2) is 1:12 to 1:60. Wherein ^{X 1} is unit surface area (nm ²⁾ 0.5 to 2.5 or a is claim 3 or filler-containing liquid composition according to 4 per the silica particles material. Wherein R is unit surface area (nm ²⁾ filler-containing liquid composition according to any one of claims 3 to 5, which is a 1-10 around the silica particles material. A method for producing a filler-containing liquid composition for producing the filler-containing liquid composition according to any one of claims 1 to 6,
The silica material is treated by a surface treatment method having a surface treatment step of surface-treating the raw silica particles with the silane compound and organosilazane in a liquid medium containing water,
The silane compound has three alkoxy groups, phenyl group, vinyl group, epoxy group, methacryl group, amino group, ureido group, mercapto group, isocyanate group, or acrylic group,
The molar ratio between the organo silazane and the silane compound, the silane compound: The organosilazane = 1: 2 to 1: Ru 10 der,
A method for producing a filler-containing liquid composition . 80% or more of the silanol groups present on the surface of the raw silica particles are bonded to the silane compound, and
The method for producing a filler-containing liquid composition according to claim 7, wherein the organosilazane is bonded to the remainder of the silanol groups present on the surface of the raw silica particles and the silane compound. The filler-containing liquid composition according to claim 7 or 8, wherein a part of the bonded organosilazane is replaced with a second silane compound having three alkoxy groups and an alkyl group having 1 to 3 carbon atoms. Manufacturing method .