JPWO2019194321A1 - Filler for resin composition, slurry composition containing filler, resin composition containing filler, and method for producing filler for resin composition - Google Patents

Abstract

It is an object to be solved to provide a filler for a resin composition that can reduce the coefficient of thermal expansion by containing the filler. Among the siliceous materials, the crystalline siliceous material having a crystal structure of FAU type, FER type, LTA type, MFI type, CHA type, and / or MWW type has a negative thermal expansion coefficient, It has been revealed that dispersion in a resin material promotes yellowing of the resin material. Therefore, by making the crystalline siliceous material exhibit no activity in the NH3-TPD method, it becomes possible to deactivate the active sites derived from the aluminum element, which is one of the causes of yellowing of the resin material. It was found that yellowing can be suppressed. The crystalline siliceous material has an alkali metal content of 0.1% by mass or less, and Li, Na, and K extracted in water under the conditions of being immersed in water at 120 ° C., 2 atm, and 24 hours, respectively. It is 5 ppm or less.

Description

  The present invention is a resin composition filler used by being contained in a resin composition, a filler-containing slurry containing the resin composition filler, and a filler-containing resin composition containing the resin composition filler, and a resin. The present invention relates to a method for producing a filler for a composition.

  Conventionally, inorganic particles are blended as a filler in a resin composition used for a mounting material such as a printed wiring board or a sealing material for the purpose of adjusting a thermal expansion coefficient. Amorphous silica particles are mainly widely used as a filler because of their low thermal expansion coefficient and excellent insulating properties.

  2. Description of the Related Art In recent years, along with the demand for higher functionality of electronic devices, semiconductor packages have become thinner and more dense, and thermal expansion and warpage of semiconductor packages have a greater influence on reliability. Therefore, studies have been conducted to reduce the thermal expansion coefficient and the thermal expansion coefficient of the cured product of the resin composition used for the printed wiring board and the sealing material. (Patent Document 1, etc.)

Japanese Patent No. 5192259 JP, 2005-214440, A Japanese Patent No. 4766852 JP, 2015-24945, A JP, 2003-292806, A JP-A-59-133265 JP, 2016-118679, A JP, 2000-26108, A

Journal of Computer Chemistry, Japan, 2015, Vol.14, No.14, p.105-110

  In view of the above situation, it is an object of the present invention to provide a filler for a resin composition, which can reduce the coefficient of thermal expansion by being contained in the resin composition.

In order to solve the above problems, the present inventors have conducted research on applying a material having a negative coefficient of thermal expansion, which has a coefficient of thermal expansion lower than that of amorphous silica and shrinks when heat is applied, to a filler material. Examples of materials having a negative coefficient of thermal expansion include particles made of β-eucryptite (LiAlSiO ₄ ) and zirconium tungstate (ZrW ₂ O ₈ ) (Patent Documents 2 and 3). However, β-eucryptite contains Li as a main constituent element, and since Li ions diffuse to lower the insulating property, there is a problem that electrical characteristics are not sufficient.

  As a conventional technique for solving the problem of the diffusion of Li ions, Patent Document 4 discloses an inorganic filler in which a shell made of silica formed by a sol-gel method from tetraethylorthosilicate (TEOS) is formed on the surface. There is. That is, Patent Document 4 is a technique characterized by coating the surface of the filler with a shell in order to suppress the elution of ions from the filler, and is not a technique applied to fillers without elution of ions.

  Although various studies have been conducted on zirconium tungstate, it takes a long time and cost to synthesize it, and many reports have been produced at a laboratory level, but an industrial production method has not been established.

  Next, among the siliceous materials, a crystalline siliceous material having a crystal structure of FAU type, FER type, LTA type, MFI type, CHA type, and / or MWW type has a negative thermal expansion coefficient. . Among such crystalline siliceous materials, it has been proposed that faujasite be contained in a resin material to provide a composite material (claim 6 of Patent Document 5). It should be noted that it is well known that faujasite contains Na, and elution of Na becomes a problem as it is, but when Patent Document 5 is disclosed, the required level for elution of ions is still low, and there is a problem. It wasn't.

  In recent years, regarding crystalline siliceous materials containing faujasite, we have studied to reduce the content of alkali metals in order to suppress the elution amount of ions, and have demonstrated sufficient practicality (mechanical properties, electrical properties, etc.). It is possible to reduce the content of the alkali metal while keeping it.

  Therefore, it is common general knowledge that the crystalline siliceous material can be used as it is by being mixed with the resin material.

  Under such circumstances, the inventors of the present application have earnestly studied crystalline silica materials. As a result, it has been clarified that when the crystalline siliceous material is dispersed in the resin material, yellowing or curing of the resin material is promoted. The occurrence of this yellowing or curing does not become a problem immediately after the crystalline siliceous material is dispersed in the resin material, but becomes a problem after a while, so it has not been noticed in the past, or Although not a problem, it became a problem when the inventors of the present application aimed to provide a resin composition having high performance.

  As a result of examining the promotion of yellowing and the like, the present inventors have found that the hydroxy group derived from the aluminum element contained in these crystalline siliceous materials acts as an active point on the resin. This active site was evaluated by the NH3-TPD method, and it was revealed that yellowing occurred when it was active. It was also possible to keep the coefficient of thermal expansion in the negative range even if the activity was lost and yellowing was suppressed until it was not observed by the NH3-TPD method.

  Here, the crystalline siliceous material has an alkali metal content of 0.1% by mass or less, and Li, Na, and Li extracted into water under the condition of being immersed in water under the conditions of 120 ° C., 2 atm, and 24 hours. K is 5 ppm or less. This is for suppressing the influence of the eluted ions.

  The "NH3-TPD method" defined in this specification is judged to be active when desorbed gas is generated when the temperature is continuously raised after adsorbing ammonia (NH3) as a probe molecule on a measurement target. To do. The specific measurement conditions are as follows. About 50 mg of the measurement sample is weighed and subjected to degassing treatment in a He atmosphere at 500 ° C. for 1 hour, and then 1 atm of 0.5% ammonia gas is adsorbed on the measurement target at 100 ° C. for 1 hour. After that, when the temperature was raised to 600 ° C. at a rate of 10 ° C./min, the peak temperature could be confirmed in the chart of the amount of desorbed ammonia with respect to the temperature, and the desorbed gas of ammonia generated up to 500 ° C. was 2 μmol / g or more. When it is, it is determined that there is activity in the NH3-TPD method.

The following inventions have been completed based on this finding. That is, the first resin composition filler that solves the above problems has a crystalline siliceous material having a crystal structure of FAU type, FER type, LTA type, MFI type, CHA type, and / or MWW type. Is a filler material,
No activity by NH3-TPD method,
The amount of the crystalline siliceous material is used by being contained in the resin material that constitutes the mounting material for electronic equipment, in which the filler material has a negative thermal expansion coefficient.

A second resin composition filler that solves the above problems is a filler material having a crystalline siliceous material having a crystal structure of FAU type, FER type, LTA type, MFI type, CHA type, and / or MWW type. And
Amount of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, cobalt, and nickel not exposed on the surface and inactive by NH3-TPD method, and the amount of the crystalline siliceous material Is used by being contained in the resin composition, which is a range in which the filler material exhibits a negative coefficient of thermal expansion.

  These resin composition fillers are preferably used by being contained in a resin composition used as a mounting material for electronic components. If the thermal expansion coefficient of the resin composition is large, cracks may occur in the solder connection due to thermal expansion in the surface direction, or conduction failure may occur between layers of the printed wiring board due to thermal expansion in the thickness direction. Further, since the difference in the coefficient of thermal expansion of each member is large, the semiconductor package is likely to warp. By lowering the coefficient of thermal expansion, it is possible to suppress the occurrence of these problems. Further, when the resin composition filler of the present invention is used, the desired thermal expansion coefficient can be achieved with a smaller filler blending ratio than when using only a conventional filler having a positive thermal expansion coefficient, so that the resin content ratio is It can be expected to obtain a resin composition having high adhesiveness and good machinability after curing or semi-curing.

  Then, the resin composition filler of the present invention is used as a filler-containing slurry composition in combination with a solvent for dispersing the resin composition filler, or in combination with a resin material for dispersing the resin composition filler. It can also be used as a filler-containing resin composition.

A method for producing a filler for a resin composition that solves the above problems is a raw material particle having a crystalline siliceous material having a crystal structure of FAU type, FER type, LTA type, MFI type, CHA type, and / or MWW type. A coating step of producing a silicone-coated particle material by coating the surface of the material with a silicone material,
A conversion step of producing a filler material by heating the silicone-coated particle material to convert the silicone material to silica;
Have
The amount of crystalline siliceous material is in the range where the filler material exhibits a negative coefficient of thermal expansion.

  Since the filler for resin composition of the present invention has the above-mentioned constitution, it has an effect that it has a negative coefficient of thermal expansion and has little adverse effect on the resin.

It is a figure which shows the crystal skeleton structure of the crystalline siliceous material of this invention. It is a figure which shows the thermal expansion measured about the siliceous particle A in an Example. It is a figure which shows the thermal expansion measured about the siliceous particle B in an Example. It is a figure which shows the thermal expansion measured about the siliceous particle C in an Example. It is a figure which shows the thermal expansion measured about the siliceous particle D in an Example. It is a figure which shows the thermal expansion measured about the siliceous particle E in an Example. It is the figure which measured the thermal expansion of the resin composition which mixed the filler for resin compositions of test examples 1, 3, 5, and 7 in the example. It is the figure which measured the activity by the NH3-TPD method of Test Examples 3 and 7 and the siliceous particle A in an Example.

  The filler for resin composition of the present invention is intended to make the thermal expansion coefficient as small as possible, and it becomes possible to make the thermal expansion coefficient of the resin composition obtained by containing the filler in the resin composition small. Hereinafter, the filler for resin composition of the present invention will be described in detail based on embodiments.

(Filler for resin composition)
The resin composition filler of the present embodiment is used to disperse in a resin material to form a resin composition. The particle size distribution is not particularly limited, but the upper limit value may be 50 μm, 30 μm, 20 μm, 10 μm, 5 μm, 3 μm, 1 μm. In particular, it is preferable not to have particles (coarse particles) having a particle size larger than these upper limits.

  The resin material to be combined is not particularly limited, but examples thereof include thermosetting resins (including those before curing) such as epoxy resin and phenol resin, and thermoplastic resins such as polyester, acrylic resin, and polyolefin. Further, a filler other than the filler for resin composition of the present embodiment (regardless of the form such as powder or granules or fibrous form) may be contained. For example, inorganic materials such as amorphous silica, alumina, aluminum hydroxide, boehmite, aluminum nitride, boron nitride, and carbon materials, and resin materials other than resin materials as a matrix in which a filler is dispersed (fiber-shaped or particle-shaped It is also possible to include an organic material (which does not need to be strictly distinguished from the resin material as the matrix, and is difficult to distinguish it). Regarding the resin composition produced by the resin material or the other filler having a positive coefficient of thermal expansion, the resin composition filler of the present embodiment has a negative coefficient of thermal expansion. The coefficient of thermal expansion can be made small, zero, or negative.

  The proportion of the resin composition filler of the present embodiment to be contained is not particularly limited, but by increasing the proportion, the thermal expansion coefficient of the resin composition finally obtained can be reduced. For example, the content may be about 5% to 85% based on the mass of the entire resin composition.

  The method for dispersing the resin composition filler of the present embodiment in the resin material is not particularly limited, and the resin composition filler is mixed in a dry state, or some solvent is dispersed as a dispersion medium in the slurry. After that, they may be mixed with the resin material.

The resin composition filler of the present embodiment is (1) used by being contained in a resin material that constitutes a mounting material for electronic devices, or (2) silver, copper, zinc, mercury, tin, lead. , Bismuth, cadmium, chromium, cobalt, and nickel are not exposed on the surface.
By adopting the constitution of (1) and adopting it as a mounting material for electronic equipment, it is possible to improve the reliability of a precision electronic equipment, and since it has the constitution of (2) and these elements are not exposed. Diffusion and elution of these elements to the outside of the filler can be suppressed.

  Furthermore, the filler for resin composition of the present embodiment, in addition to at least one of the above (1) or (2), FAU type, FER type, LTA type, MFI type, CHA type, and / or It is a filler material having a crystalline siliceous material having a MWW type crystalline structure, is inactive by the NH3-TPD method, and the amount of the crystalline siliceous material is in a range where the filler material exhibits a negative thermal expansion coefficient. . A crystalline siliceous material having these crystal structures has a negative coefficient of thermal expansion. Particularly, the FAU type is preferable. The crystalline siliceous material does not necessarily have to have these crystal structures, and 50% or more (preferably 80% or more) based on the total mass may have these crystal structures. Here, the crystal skeleton structure of the type represented by three alphabets is shown in FIG. Furthermore, the crystalline siliceous material has an alkali metal content of 0.1% by mass or less, and Li, Na, and K extracted in water under the conditions of immersion in water at 120 ° C., 2 atm, and 24 hours. Is 5 ppm or less.

  The particle size distribution and particle shape of the filler material are set to such an extent that when the filler material is contained in the resin composition, necessary properties can be exhibited. For example, when the obtained resin composition is used as a semiconductor encapsulating material, it is preferable not to include a resin composition having a particle size larger than the gap into which the semiconductor encapsulating material penetrates. Specifically, it is preferably about 0.5 μm to 50 μm, and it is preferable that coarse particles of 100 μm or more are not substantially contained. Further, when the resin composition is used for, for example, a printed wiring board, it is preferable not to include a resin composition having a particle size larger than the thickness of the insulating layer. Specifically, it is preferably about 0.2 μm to 5 μm, and it is preferable that coarse particles of 10 μm or more are not substantially contained. The particle shape is preferably low in aspect ratio, and more preferably spherical.

  The filler material can be manufactured by using a crystalline siliceous material having a corresponding crystal structure as a raw material and performing operations such as pulverization, classification, granulation, and mixing individually or in combination. By adopting appropriate conditions in each operation and performing an appropriate number of times, it is possible to obtain particles having a required particle size distribution and particle shape. The crystalline siliceous material itself as a raw material can be synthesized by a usual method (for example, a hydrothermal synthesis method).

  The content of the aluminum element in the crystalline siliceous material is preferably 12% or less, and more preferably 8% or less and 4% or less, based on the total mass. It is presumed that aluminum contained in the crystalline siliceous material is preferably close to 0%, but at present, it is often unavoidably contained.

  The filler material can have a core part made of a crystalline siliceous material and a shell part made of an amorphous silica material to cover the core part. It is preferable to cover the core portion with the shell portion. It is preferable that the crystalline siliceous material forming the core portion and the amorphous silica material forming the shell portion are combined. The method of forming the core portion and the shell portion will be described later.

  The abundance ratio of the crystalline siliceous material and the amorphous silica material is not particularly limited as long as the overall coefficient of thermal expansion is negative. For example, the coefficient of thermal expansion is negative, and the crystallinity as a whole is preferably in the range of 0.3 to 0.9, and more preferably 0.4 to 0.8. In the form having the core portion and the shell portion, the higher the crystallinity, the larger the negative thermal expansion coefficient. Here, the crystallinity of 1.0 is based on the crystallinity (X-ray intensity) of only the crystalline siliceous material contained in the core portion.

  The filler for resin composition of the present embodiment and the filler material constituting the filler for resin composition can be surface-treated with a surface treatment agent. The surface treatment agent is not particularly limited, but is preferably made of an organic silicon compound. It is possible to further prevent the active points that promote yellowing from coming into contact with the resin due to the reaction or adhesion of the surface treatment agent made of an organosilicon compound on the surface. In particular, a silane compound is preferable, and a silane coupling agent among the silane compounds and a silazane can be firmly bonded to the surface of the treatment object made of the filler for the resin composition or the filler material. It will be possible. As the silane compound, in addition to being able to shield the yellowing active points of the crystalline siliceous material, in order to improve the affinity with the resin material to be mixed, a functional compound with a high affinity for the resin material is used. Those having a group can be adopted.

  The silane compound is preferably a compound having a phenyl group, a vinyl group, an epoxy group, a methacrylic group, an amino group, a ureido group, a mercapto group, an isocyanate group, an acryl group or an alkyl group. Among the silane compounds, examples of silazanes include 1,1,1,3,3,3-hexamethyldisilazane.

  The conditions for performing the treatment with the surface treatment agent are not particularly limited. For example, based on the surface area calculated from the average particle size assuming that the object to be treated is an ideal sphere, the area covered by the surface treatment agent (a value calculated from the molecular size of the surface treatment agent and the treatment amount. The agent can be 50% or more (further, 60% or more, 80% or more), assuming that the agent adheres or reacts in a single layer on the surface to be treated. Furthermore, if the amount of the surface treatment agent is too large, the filler for the resin composition of the present embodiment may not exhibit a negative coefficient of thermal expansion, so the upper limit of the amount of the surface treatment agent is the resin composition of the present embodiment. The range is such that the material filler exhibits a negative coefficient of thermal expansion.

  Any surface treatment may be performed on the object to be treated. The surface treatment agent can be attached to the surface by contacting the surface treatment agent as it is or by contacting a solution in which the surface treatment agent is dissolved in some solvent. The attached surface treatment agent can be heated to accelerate the reaction.

(Method for producing filler for resin composition)
The method for producing the filler for resin composition of the present embodiment is a method suitable for producing one of the above-described fillers for resin composition having a core portion and a shell portion. The manufacturing method of the filler for resin composition of this embodiment has a coating process and a conversion process.

  The coating step is a step of producing a silicone-coated particle material by coating the raw material particle material with a silicone material. The raw material particle material has a crystalline siliceous material having a crystal structure of FAU type, FER type, LTA type, MFI type, CHA type, and / or MWW type. FAU type is particularly preferable. The matters described above for the filler for resin composition can be applied as they are.

  The silicone material is a material that can be converted to silica in the conversion step described later, and is not particularly limited as long as it can be converted to silica by selecting any material.

  Preferred silicone materials include silicone and silane compounds. Silicone is a siloxane polymer in which siloxane bonds are continuous, and those having an alkyl group or the like as a side chain are widely used. Further, the silicone may have a highly reactive functional group such as SiH group or an alkoxy group. Examples of the silane compound include silane coupling agents and silazanes.

The silicone material can be selected to facilitate coating of the raw particle material. For example, by selecting a material having high fluidity, uniform coating can be facilitated. Examples of the silicone material having high fluidity include low molecular weight compounds and siloxane polymers having a kinematic viscosity at 25 ° C. of 200 mm ² / s or less (preferably 150 mm ² / s or less). Examples include those that adhere to the surface of the raw material particle material by physical action (adsorption, entanglement, etc.) during coating, and those that form new chemical bonds. Examples of the new chemical bond include reaction with the surface of the raw material particle material through SiH groups and alkoxy groups.

  The amount of the silicone material to be coated in the coating step can be arbitrarily determined within the limit that the finally manufactured filler for resin composition exhibits a negative coefficient of thermal expansion. Further, it is preferable that the surface of the raw material particle material can be covered without a gap.

  The method of coating the surface of the raw material particle material with the silicone material in the coating step is not particularly limited. For example, a method in which a silicone material and a raw material particle material are mixed and coated by applying a shearing force by a crushing operation or the like, a surface of the raw material particle material in a state where the silicone material is dissolved or dispersed in an appropriate solvent or dispersion medium. A method of removing the solvent or the dispersion medium after contacting with the surface of the silicone or the dispersion medium, and dissolving the silicone material in an appropriate solvent or dispersion medium or dispersing the raw material particle material in a liquid Examples include a method of depositing the raw material particle material on the surface.

  The conversion step is a step of converting the coated silicone material into silica by heating. The heating condition is not particularly limited as long as it can be converted to silica. For example, 600 ° C. or higher, 700 ° C. or higher, 800 ° C. or higher can be exemplified as the lower limit, and 1100 ° C. or lower, 1200 ° C. or lower, 1300 ° C. or lower can be exemplified as the upper limit. These upper and lower limits can be arbitrarily combined. An oxidizing atmosphere (air, oxygen) can be exemplified as the heating atmosphere. The heating time is sufficient if the silicone material can be converted to silica, and the conversion to silica may be a part of the silicone material. For example, it is sufficient if 80% or more and 90% or more of the silicone material can be converted.

  Since the filler material obtained after the conversion step may partially or entirely aggregate, it may have a crushing step, a classification step, a coarse particle removing step, and the like.

-Evaluation of crystalline siliceous material About siliceous particles A to D (crystalline siliceous material) and siliceous particle E (amorphous silica material) shown in Table 1 at 800 ° C in a discharge plasma sintering machine. A test piece was obtained by heating and sintering for 1 hour. The thermal expansion coefficient of each test piece was measured with a measuring device (TMA: Q-400EM manufactured by TA Instruments). The measurement temperature was -50 ° C to 250 ° C. Table 1 shows the average value of the measured values, and FIGS. 2 to 6 (corresponding to the siliceous particles A to E) show how the temperature changes.

  In addition, for the siliceous particles A to E, a mixture with linseed oil was prepared so that the siliceous particles were 40% by mass, and the mixture was stored at 40 ° C. for 24 hours. After that, the degree of discoloration of the mixture was confirmed. Those with light discoloration were marked with "△", those with deep discoloration were marked with "X", and those with almost no discoloration were marked with "○". The higher the degree of discoloration, the more the linseed oil is oxidized, indicating that the mixed particulate material is more active.

  Furthermore, when the content of the alkali metal is measured for each of the siliceous particles A to D, it is 0.1% by mass or less, and the content of the alkali metal is extracted in water under the conditions of immersion in water at 120 ° C., 2 atm, and 24 hours. And Li, Na, and K were each 5 ppm or less.

  As is clear from Table 1, the discoloration of linseed oil was not observed in the siliceous particles E which is an amorphous silica material, but all the siliceous particles A to D which are made of the crystalline siliceous material showed a deep discoloration. Admitted. Further, as is clear from FIGS. 2 to 6, the siliceous particles A to D made of the crystalline siliceous material show a negative coefficient of thermal expansion (CTE), whereas the siliceous particles are amorphous silica materials. It was found that the siliceous particles E have a positive coefficient of thermal expansion. It was also found that the FAU type siliceous particles A to C have a larger absolute value of the negative thermal expansion coefficient than the MFI type siliceous particles D. It was also found that in the same FAU type, the smaller the Al content, the larger the absolute value of the negative thermal expansion coefficient.

By mixing the siliceous particles A and the silicone material at a mass ratio shown in Table 2 with a mixer for powder, the surface of the siliceous material A was coated with the silicone material to obtain a silicone-coated particle material ( Coating process). By heating the silicone-coated particle material at 1050 ° C. for 1 hour to convert it into an amorphous silica material, a composite particle (filler material) having a siliceous particle A as a core part and an amorphous silica material as a shell part is obtained. Manufactured (conversion process). Here, kinematic viscosity at 25 ° C. of the silicone material A~D using a silicone material A 25 mm ² / s, the silicone material B is 110 mm ² / s, the silicone material C is 100 mm ² / s, the silicone material D is 7mm It was ² / s. The siliceous particles E were also evaluated by heating at 1050 ° C. for 1 hour.

  The following evaluation was performed on the obtained composite particles of each test example.

-Measurement of Crystallinity When the XRD diffraction evaluation was performed on the composite particles of each of Test Examples 1 to 6, the crystal peak of the siliceous particles A and the halo of the amorphous silica material existing on the surface overlapped with each other. Was observed. For Test Example 7, only the halo derived from the amorphous silica material was observed. The crystallinity of Test Examples 1 to 7 is calculated as a relative value when the crystallinity of the siliceous particles A alone is 1, and is shown in Table 2.

Evaluation of linseed oil discoloration The linseed oil discoloration was evaluated for the composite particles of Test Examples 1 to 7 by the method described above. The results are shown in Table 2.
As is clear from Table 2, discoloration was hardly observed in Test Examples 2 to 7, and it was found that discoloration could be suppressed by coating the surface with the amorphous silica material. In Test Example 1, a slight discoloration was observed, but a great improvement was observed with respect to the raw material siliceous particles A. It can be considered that in Test Example 1, the crystallinity was high and the ratio of the amorphous silica material was lower than in other Test Examples, so that the catalytic activity of the siliceous particles A could not be completely suppressed.

-Evaluation of thermal expansion coefficient of resin composition 35 parts by mass of composite particles of Test Examples 1 to 5, 5 and 7 are composed of a liquid epoxy resin (bisphenol A: bisphenol F = 50: 50) and an amine curing agent. After being mixed with 65 parts by mass of a resin material and then cured, a resin composition (cured product) was used as a test piece to evaluate the thermal expansion coefficient (average value at temperatures from 0 ° C to 50 ° C). The results are shown in Table 2. The thermal expansion coefficient of the solidified resin material alone was 70.0 ppm / K.

  As is clear from Table 2, all of Test Examples 1 to 5 containing the crystalline siliceous material showed a lower CTE than Test Example 7 containing only the amorphous silica material, and the thermal expansion of the resin material alone. The thermal expansion coefficients of the composite particles of Test Examples 1 to 3 and 5 calculated from the coefficients were all negative values. FIG. 7 shows changes in thermal expansion due to temperature changes in Test Examples 1, 3, 5, and 7.

-Evaluation of activity by NH3-TPD method The composite particles of Test Example 3 and Test Example 7 and the siliceous particles A are ammonia warming desorption, which is a widely used method for evaluating the activity of a powder catalyst. Evaluation was performed by the separation method (NH3-TPD method). As pretreatment, ammonia was adsorbed to the particles at 100 ° C for 1 hour, and the sample was continuously heated to 600 ° C to measure desorbed ammonia gas. The results are shown in Fig. 8.

  In the siliceous particles A, ammonia desorbed at 200 ° C. to 300 ° C. was detected (desorption peak temperature 271 ° C., desorption amount: ammonia gas 5.5 μmol / g), but in Test Examples 3 and 7. No desorption of ammonia gas was observed (desorption amount: less than 0.6 μmol / g of ammonia gas).

  In other words, in the siliceous particles A made of the FAU type crystalline siliceous material, while the high activity derived from the material was observed by the NH3-TPD method, the surface of the siliceous particles A was changed to the amorphous silica material. It was found that the composite particles of Test Example 3 coated by the above method could completely suppress the activity of the FAU type crystalline siliceous material present in the core part. In addition, no activity was observed for the siliceous particles E (Test Example 7) which consisted of the amorphous silica material alone.

-Evaluation of dielectric constant The dielectric constants of the test pieces of Test Examples 3 and 7 used for measuring the coefficient of thermal expansion were measured. The measurement conditions were a perturbation method using a network analyzer, and the dielectric constant at a frequency of 1 GHz was measured (an average value measured three times). As a result, the relative permittivity of each test piece was 3.0 in Test Example 3, 3.3 in Test Example 7, and 3.2 in the resin alone, and the siliceous particles A as the crystalline siliceous material were By using the core portion, the dielectric constant can be made lower than that in the case of using the siliceous particles E which is an amorphous silica material.

  The filler for resin composition of the present invention has a negative thermal expansion coefficient. Therefore, by mixing with a resin material having a positive coefficient of thermal expansion, the positive coefficient of thermal expansion of the resin material can be offset or reduced. As a result, a resin composition having a small coefficient of thermal expansion and excellent thermal characteristics can be obtained.

Claims (10)

A filler material having a crystalline siliceous material having a crystal structure of FAU type, FER type, LTA type, MFI type, CHA type, and / or MWW type,
No activity by NH3-TPD method,
The amount of the crystalline siliceous material is in the range where the filler material exhibits a negative coefficient of thermal expansion,
The crystalline siliceous material,
The content of the alkali metal is 0.1% by mass or less,
Li, Na, and K extracted in water under the conditions of being immersed in water at 120 ° C., 2 atm, and 24 hours are 5 ppm or less, respectively.
A filler for a resin composition, which is used by being contained in a resin material constituting a mounting material for electronic equipment. A filler material having a crystalline siliceous material having a crystal structure of FAU type, FER type, LTA type, MFI type, CHA type, and / or MWW type,
Amount of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, cobalt, and nickel not exposed on the surface and inactive by NH3-TPD method, and the amount of the crystalline siliceous material Is a range in which the filler material exhibits a negative coefficient of thermal expansion,
The crystalline siliceous material,
The content of the alkali metal is 0.1% by mass or less,
Li, Na, and K extracted in water under the conditions of being immersed in water at 120 ° C., 2 atm, and 24 hours are 5 ppm or less, respectively.
A filler for a resin composition, which is used by being contained in the resin composition.   The filler material has a core portion made of the crystalline siliceous material, and a shell portion made of an amorphous silica material to cover the core portion, and the crystalline siliceous material and the amorphous silica material. The filler for a resin composition according to claim 1, wherein is a composite.   The resin composition filler according to any one of claims 1 to 3, further comprising a surface treatment agent composed of an organosilicon compound that reacts with or adheres to the surface of the filler material.   The filler for resin composition according to claim 4, wherein the organosilicon compound is at least one selected from silazanes and / or silane coupling agents.   The filler for resin composition according to any one of claims 1 to 5, wherein the content of the aluminum element is 12% or less based on the total mass.   The filler for resin composition according to any one of claims 1 to 6, wherein the crystal structure is a FAU type.   A filler-containing slurry composition comprising the filler for resin composition according to any one of claims 1 to 7 and a solvent for dispersing the filler for resin composition.   A filler-containing resin composition comprising the resin composition filler according to any one of claims 1 to 7 and a resin material in which the resin composition filler is dispersed. Silicone-coated particles obtained by coating the surface of a raw material particle having a crystalline siliceous material having a crystal structure of FAU type, FER type, LTA type, MFI type, CHA type, and / or MWW type with a silicone material. A coating process for producing the material,
A conversion step of producing a filler material by heating the silicone-coated particle material to convert the silicone material to silica;
Have
The amount of crystalline siliceous material is in the range where the filler material exhibits a negative coefficient of thermal expansion,
The manufacturing method of the filler for resin compositions.

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