JP5281250B2 - Inorganic powder for resin composition addition and resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having both of fluidity and moldability in high levels. <P>SOLUTION: The resin composition is obtained by dispersing in a resin an inorganic powder having two or more local maximum values in the volume-based size distribution wherein the first local maximum value of one of the local maximum values is &ge;0.1 &mu;m and &le;2 &mu;m, and the second local maximum value of one of the local maximum value except the first maximum value is &ge;20 &mu;m and &le;70 &mu;m, and further having &ge;6 &mu;m and &lt;50 &mu;m of each of the volume average particle diameter and d50, and &ge;0.950 of the average roundness of particles having &ge;15 &mu;m and &le;70 &mu;m particle diameters. Especially, it is preferable that the particles constituting the local maximum value of the size distribution formed in a &ge;0.1 &mu;m and &le;2 &mu;m range occupies 5-15 vol.% of the whole particles, and the particles constituting the local maximum value of the size distribution formed in a &ge;20 &mu;m and &le;70 &mu;m range occupies &ge;50 vol.% of the whole particles. More preferably, the local maximum value is not present in a 2-20 &mu;m range. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to an inorganic powder for adding a resin composition to be added to an inorganic powder used in a resin composition in which an inorganic powder is dispersed and used as a semiconductor sealing material, and a resin composition using the inorganic powder. About.

  As electronic devices have higher performance, higher functionality, and smaller and lighter weight, the form of semiconductor packages to be mounted is becoming more highly integrated, smaller, and thinner. For practical use of such a semiconductor package, development of a sealing material is indispensable together with development of an IC chip. As a current sealing material, a resin composition in which a thermosetting resin such as an epoxy resin is used as a matrix and an inorganic powder is blended therein has been developed. Such a sealing material is required to have high performance for the purpose of ensuring various reliability of the semiconductor element.

  For example, as a result of requiring high adhesiveness, heat resistance, moisture resistance, etc., a large amount of inorganic powder is filled in the sealing material. Filling with a large amount of inorganic powder causes a problem that the fluidity of the sealing material decreases, so the fluidity of the sealing material has been improved. Inconvenience may occur in moldability, such as.

  As a conventional technique proposed for the purpose of solving such inconveniences, the kurtosis of the frequency particle size distribution is 2.9 or less, the minimum diameter is 15 μm or more and less than 30 μm, and the minimum diameter is 3 μm or more and less than 15 μm and 30 μm or more and less than 70 μm. There is an inorganic powder characterized by having a maximum diameter and an average particle diameter of 7 to 40 μm (Patent Document 1). In particular, it is disclosed that it is preferable to further have a maximum diameter in a region of 0.2 μm or more and less than 1.5 μm.

The skewness of the frequency particle size distribution is 0.6 to 1.8, at least 3 to 10 [mu] m and 30 to 70 [mu] m, and the mode diameter is 30 to 70 [mu] m and the median diameter is 5 A spherical inorganic powder characterized by a thickness of ˜40 μm is disclosed (Patent Document 2). In particular, it is preferable to have a maximum diameter in the region of 0.2 to 1.2, and the ratio between the specific surface area S _B measured by the BET method and the theoretical specific surface area S _C calculated by the particle size distribution (S _B / S _C ). Is preferably 2.5 or less. It is stated that it is preferable not to substantially contain particles of less than 50 nm, and that the spherical inorganic powder is preferably amorphous silica.

Further, it has a multimodal frequency particle size distribution showing a maximum value in a particle size range of at least 2 to 10 μm and 20 to 50 μm, an average particle size of 5 to 35 μm, a maximum particle size of 60 μm or less, and (d99 / mode) A spherical inorganic powder characterized in that the diameter is 2.2 or less is disclosed (Patent Document 3). In particular, the ratio (S _B / S _C ) between the BET specific surface area S _B and the theoretical specific surface area S _C calculated from the particle size distribution is preferably 2.5 or less, and substantially contains no particles less than 50 nm. Is preferred. Further, it is disclosed that the average sphericity of particles having a particle diameter of less than d75 is preferably 0.90 or more, and the average sphericity of particles having a particle diameter of d75 or more is preferably 0.85 or more.

And also, 0.3 [mu] m area of the ultra 0.85 .mu.m, has a frequency particle size distribution showing the maximum value in the region of the area and 20~70μm of 3 to 10 [mu] m, calculated by the specific surface area S _B and the particle size distribution measured by the BET method A spherical inorganic powder characterized in that the ratio (S _B / S _C ) to the theoretical specific surface area S _C is 2.5 or less and substantially contains no particles less than 50 nm (patent document) 4).

Furthermore, in the frequency particle size distribution, a spherical inorganic powder characterized by having a maximum value in a region of 20 to 70 μm, a region of 3.0 to 10 μm, and a region of 0.20 to 1.0 μm. And an epoxy resin, an epoxy resin curing agent, and a spherical inorganic powder, and a semiconductor sealing resin composition is disclosed (Patent Document 5).
JP 2004-59343 A JP 2003-146648 A JP 2003-110065 A Japanese Patent No. 3557109 JP 2001-158614 A

  However, with the recent development of technology, a resin composition having higher performance than the resin composition used in the sealing material of the prior art has been demanded. As described above, a resin composition having high fluidity and moldability is often capable of exhibiting high performance other than as a semiconductor sealing material.

  The present invention has been made in view of such a situation, and an inorganic powder for adding a resin composition capable of realizing a resin composition capable of achieving both high fluidity and moldability and an inorganic for adding the resin composition. Providing a resin composition using powder is a problem to be solved.

Means for Solving the Problems and Effects of the Invention

(1) As a result of intensive investigations for the purpose of solving the above-mentioned problems, the present inventors have obtained fluidity and moldability by adopting an inorganic powder having a specific particle size distribution as an inorganic powder to be added to a resin composition. I found that I can achieve both. Specifically, it has been found that high performance can be achieved by employing an inorganic powder having two or more maximum values within a predetermined range in a volume-based particle size distribution, and the following invention has been completed.

(1-1) That is, the inorganic powder for resin composition addition of the present invention that solves the above-mentioned problems has a maximum value of 2 or more in the volume-based particle size distribution,
A first maximum value that is one of the maximum values is not less than 0.1 μm and not more than 2 μm;
The second maximum value, which is one other than the first maximum value, is 20 μm or more and 70 μm or less,
The volume average particle size and d50 based on the whole are 6 μm or more and less than 50 μm,
The average circularity of particles having a particle size of 15 μm or more and 70 μm or less is 0.950 or more.

  In particular, the particles constituting the maximum value of the particle size distribution formed at 0.1 μm or more and 2 μm or less are 5 to 15% by volume of the whole, and the particles constituting the maximum value of the particle size distribution formed at 20 μm or more and 70 μm or less are It is desirable that it is 50 volume% or more of the whole.

  Here, the determination as to whether or not it is included in the “particles constituting the maximum value of the particle size distribution formed to be 0.1 μm or more and 2 μm or less” is performed as follows. First, basically, particles belonging to a peak having a maximum value in the range of 0.1 μm to 2 μm are included in “particles constituting the maximum value of the particle size distribution formed to be 0.1 μm to 2 μm”. And

  Whether or not it is included in this peak includes all particles from the maximum value in the particle size distribution to the minimum value in both the small and large particle sizes. That is, even if the minimum value is out of the range of “0.1 μm or more and 2 μm or less”, particles having the particle diameter are included.

  When the minimum value does not appear, all the particles on the side where the minimum value does not appear are included in the peak (for example, when there is no minimum value in the direction in which the particle size increases (decreases) from the maximum value). (All particles with a particle size greater than or equal to the maximum value are included in the peak.) Further, when there are two or more maximum values in the range of “0.1 μm or more and 2 μm or less”, “the particles constituting the maximum value of the particle size distribution formed to be 0.1 μm or more and 2 μm or less” by the method described above for each. It is judged whether it is included in "."

  The above description is valid for the range of “20 μm to 70 μm” and the range of “15 μm to 70 μm” described in (1-2).

  Furthermore, it is desirable that there is no maximum value in the range of 2 to 20 μm.

(1-2) In addition, the other inorganic powder for resin composition addition of the present invention that solves the above problems has a maximum value of 2 or more in the volume-based particle size distribution,
The first maximum value and the second maximum value which are two of the maximum values are 15 μm or more and 70 μm or less,
The volume average particle size and d50 based on the whole are 6 μm or more and less than 50 μm,
The average circularity of particles having a particle size of 15 μm or more and 70 μm or less is 0.950 or more.

  In particular, it is desirable that the particles constituting the maximum value of the particle size distribution formed to be 15 μm or more and 70 μm or less occupy 60% or more based on the entire volume.

(1-3) As the inorganic powder for resin composition addition described in the above (1-1) and (1-2), it is desirable that the particle size distribution has two maximum values.

Furthermore, the specific surface area measured by the BET method is desirably 1.5 to 3.5 m ² / g.

  And it is desirable that it is a silica powder whose crystallization rate is less than 2%.

(2) The resin composition of the present invention that solves the above problems has a filler composed of the inorganic powder for resin composition addition described in (1), and a resin composition for dispersion that disperses the filler. It is characterized by. By adopting the inorganic powder having the above particle size distribution, both fluidity and moldability can be achieved.

  The resin composition of the present invention can be prepared by dispersing and adding the resin composition-added inorganic powder of the present invention in a resin. The prepared resin composition can be used for sealing semiconductor elements, and can also be used for substrate materials, inorganic pastes, adhesives, coating agents, precision molding resins, prepregs, and the like. Details will be described later.

<Inorganic powder for resin composition addition>
Hereinafter, the inorganic powder for resin composition addition of the present invention will be described in detail based on embodiments. The inorganic powder for adding a resin composition of the present embodiment is characterized by a particle size distribution. First, the particle size distribution has a maximum value of 2 or more. By having two or more local maximum values as shown below, both fluidity and moldability can be achieved.

  There is no particular limitation on the method of having a maximum value of 2 or more in a predetermined range described later. For example, a method in which particles having a target maximum value and a narrow particle size range are selected by the number of necessary maximum values by sieving and then mixed, a particle manufacturing method (VMC method) in which particles having a narrow particle size range are obtained And the like, and a method of mixing the particles having a predetermined maximum value after producing the required number of maximum values.

  The number of maximum values may be any number as long as it is two or more, but is preferably two. It is required that the particle size indicated by two of the plurality of maximum values (the first maximum value and the second maximum value) be in a range described later. In addition, although called the 1st maximum value and the 2nd maximum value for convenience, the magnitude of the peak height is not limited between the 1st maximum value and the 2nd maximum value.

  Here, the particle size distribution is measured on a volume basis. As a specific measuring method, it is measured by a laser diffraction light scattering method. The measurement was performed using a laser diffraction scattering particle size distribution measuring device (model number: LS 13 320) manufactured by Beckman Coulter. The measurement conditions are such that water is used as the solvent, the dispersion medium refractive index is 1.33, the sample refractive index is 1.5 (in the case of silica), the PIDS (Polarizatuon Intensity Differential Scattering) concentration is 45 to 55%, and the relative concentration is It was 5 to 15%, and was measured after dispersing with an ultrasonic homogenizer as a pretreatment. The presence or absence of a maximal value is judged when this measurement result is used for evaluation.

  There are two types of inorganic powder for resin composition addition of the present embodiment.

(A) First, the first maximum value, which is one of two or more maximum values, is 0.1 μm or more and 2 μm or less, and the second maximum value is one other than the first maximum value. The value is required to be 20 μm or more and 70 μm or less. In particular, the first maximum value is preferably 0.1 μm or more and 1 μm or less. The second maximum value is desirably 20 μm or more and 60 μm or less.

  The volume average particle diameter and d50 (particle diameter at which the cumulative volume becomes 50%) based on the whole are 6 μm or more and less than 50 μm. And the average circularity of the particle | grains with a particle size of 15 micrometers or more and 70 micrometers or less is 0.950 or more. The volume average particle diameter and d50 are preferably 10 μm or more and 40 μm or less. The average circularity of particles having a particle size of 15 μm or more and 70 μm or less is preferably 0.970 or more.

The volume average particle diameter and d50 are values measured simultaneously with the measurement of the particle size distribution described above. The average circularity is a value of circularity measured by using an image analyzer (manufactured by Sysmex Corporation: flow type particle image analyzer: FPIA3000) and using a sheath liquid (PSE-900A, manufactured by Sysmex Corporation) as a solvent (hereinafter referred to as “circular particle image analyzer”). the same). Specifically, it is calculated as a value calculated by (circularity) = {4π × (area) ÷ (peripheral length) ² }. The closer to 1, the closer to a true sphere. The average value measured for 100 particles is adopted as the average circularity.

  In particular, particles having a particle size of 0.1 μm or more and 2 μm or less are 5 to 15% by volume based on the whole volume, and particles having a particle size of 20 μm or more and 70 μm or less are 50% by volume or more based on the whole volume. It is desirable that The particle size and volume are values that can be measured simultaneously with the particle size distribution described above.

  Furthermore, it is desirable that the particle size distribution does not have a maximum value in the range of 2 to 20 μm.

(B) Secondly, each of the first maximum value which is one of two or more maximum values and the second maximum value which is one other than the first maximum value is 15 μm or more and 70 μm or less. It is required to be. In particular, the first maximum value is preferably 15 μm or more and 30 μm or less. The second maximum value is preferably 30 μm or more and 60 μm or less.

  The volume average particle diameter and d50 (particle diameter at which the cumulative volume becomes 50%) based on the whole are 6 μm or more and less than 50 μm. And the average circularity of the particle | grains with a particle size of 15 micrometers or more and 70 micrometers or less is 0.950 or more. The volume average particle diameter and d50 are preferably 10 μm or more and 40 μm or less. The average circularity of particles having a particle size of 15 μm or more and 70 μm or less is preferably 0.970 or more.

  In particular, it is desirable that particles having a particle diameter of 15 μm or more and 70 μm or less be 60% or more based on the total volume. The particle size and volume are values that can be measured simultaneously with the particle size distribution described above.

In any of (a) and (b) described above, the specific surface area measured by the BET method is preferably 1.5 to 3.5 m ² / g.

  The composition of the inorganic powder for adding a resin composition of the present embodiment is not particularly limited except that the inorganic substance is mainly used. Here, “mainly composed of an inorganic substance” is intended to include those in which a film made of an organic substance is formed on the surface of particles made of an inorganic substance. For example, what processed the surface of the powder which consists of inorganic substances with the silane coupling agent is mentioned.

  Examples of the inorganic material that can be used to form the inorganic powder for adding a resin composition of the present embodiment include silica, alumina, titania, zirconia, and composite oxides thereof, aluminum nitride, and carbon nitride. In particular, it is desirable to employ an inorganic substance (particularly silica) having a crystallization rate of less than 2%.

  It does not specifically limit as a method of obtaining the inorganic powder for resin composition addition. A method of producing amorphous silica fine particles, such as a method of reacting a metal corresponding to an inorganic substance with oxygen to form oxide fine particles, a method of melting a corresponding inorganic substance by heat to form oxide fine particles, and a method of producing silica by crushing silica The method of using fine particles is mentioned.

<Resin composition>
The resin composition of this embodiment is composed of the above-described inorganic powder for adding a resin composition of this embodiment and a dispersing resin composition in which the inorganic powder for adding the resin composition is dispersed. Since the inorganic powder for resin composition addition is as above-mentioned, description is abbreviate | omitted. The inorganic powder for adding a resin composition is desirably contained in an amount of 70% by mass or more based on the total mass. Furthermore, a mold release agent (such as carnauba wax) can be added as another additive.

  The resin composition for dispersion is not particularly limited, but it is desirable to employ a thermosetting resin (precursor thereof). For example, a cationic polymerizable compound can be employed. Examples of the cationic polymerizable compound include epoxy resins, oxirane resins, oxetane compounds, cyclic ether compounds, cyclic lactone compounds, thiirane compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds, vinyl compounds, and the like. Can be used alone or in combination.

  In particular, an epoxy resin is preferable from the viewpoints of availability, handleability and the like. Although an epoxy resin is not specifically limited, The monomer, oligomer, and polymer which have two or more epoxy groups in 1 molecule are mentioned. For example, biphenyl type epoxy resin, stilbene type epoxy resin, bisphenol type epoxy resin, triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, naphthol type epoxy resin, triazine core containing An epoxy resin is mentioned.

  Specific examples other than the epoxy resin include oxirane compounds such as phenylglycidyl ether, ethylene oxide and epichlorohydrin; oxetane compounds such as trimethylene oxide, 3,3-dimethyloxetane and 3,3-dichloromethyloxetane; tetrahydrofuran, 2 Cyclic ether compounds such as 1,3-dimethyltetrahydrofuran, trioxane, 1,3-dioxofuran, 1,3,6-trioxacyclooctane; cyclic lactone compounds such as β-propiolactone and ε-caprolactone; ethylene sulfide, 3, Thiane compounds such as 3-dimethylthiirane; Thiane compounds such as 1,3-propyne sulfide and 3,3-dimethyl thietane; Cyclic thioether compounds such as tetrahydrothiophene derivatives; Spiro ortho ester compounds obtained by reaction with kuton; spiro ortho carbonate compounds; cyclic carbonate compounds; vinyl compounds such as ethylene glycol divinyl ether, alkyl vinyl ether, triethylene glycol divinyl ether; styrene, vinyl cyclohexene, isobutylene, polybutadiene, etc. An ethylenically unsaturated compound can be illustrated. As a cationically polymerizable compound, an epoxy resin and these compounds can be used alone or in combination.

  Further, a curing agent and a curing catalyst can be mixed in order to cure the cationic polymerizable compound. As the curing agent, primary amine, secondary amine, phenol resin, and acid anhydride can be used. As the curing catalyst, a phosphorus-based imidazole compound, a tertiary amine, or the like is used. In addition, a Lewis acid can be complexed with a tertiary amine, an onium salt, or the like and used as a latent heating catalyst. Specific examples of the curing agent include diaminodiphenylmethane, hexahydrophthalic anhydride, and phenol resin (novolak). Examples of the curing catalyst include 2-methylimidazole, triphenylphosphine, and 1,8-diazabicycloundecene.

<Preparation of test sample>
After pulverizing natural silica, amorphous silica powder was obtained by a so-called melting method in which it was introduced into a high-temperature flame together with a carrier gas. It prepared so that it might become the particle size distribution shown in Table 1 and 2 by the particle size distribution before flame injection, flame conditions, classification operation, and mixing | blending, and it was set as the test sample (inorganic powder for resin composition addition) of each test example. All the silica powders had a crystallization rate of less than 1% (amorphous rate of 99% or more) and an average circularity of 0.9 or more.

  Each test sample was tested for each test sample. With respect to 160 parts by mass of each test sample of each test example, 33 parts by mass of a cresol novolac type epoxy resin having a softening point of 70 ° C., 17 parts by mass of a phenol novolac type epoxy resin having a softening point of 80 ° C., and 1 part by mass of triphenylphosphine , 1 part by weight of a hydrophilic silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 1 part by weight of carnauba wax that acts as a release agent from the mold, silica powder (Admafine) After mixing 40 parts by mass of SO-25R, volume average particle size 0.5 μm, manufactured by Admatechs) and 40 parts by mass of silica powder (Admafine SO-32R, volume average particle diameter 1.5 μm, manufactured by Admatex), Henschel Premixed with a mixer. The resulting mixture was heated and kneaded with a twin-screw extrusion kneader. (Paddle rotation speed 120 rpm, discharge rate 15 kg / h, kneader internal temperature 70 ° C.). The obtained kneaded material was pulverized using a mortar to obtain a resin composition corresponding to each test example.

<test>
A fluidity test and a moldability test were performed using the resin composition of each test example.

The fluidity test was performed by using a spiral flow measurement mold in accordance with EMMI 1-66 and applying a temperature and pressure with a transfer molding machine to perform a spiral flow measurement test. The molding conditions were a temperature of 175 ° C., a pressure of 1.96 MPa (20 kgf / cm ² ), and a molding time of 180 seconds.

  The moldability test was performed by measuring the degree of formation of burrs generated under predetermined molding conditions. The resin composition of each test example was molded using an evaluation die having slits with a vent depth of 5 μm, 10 μm, 20 μm, 30 μm, and 50 μm. The length of the resin composition that flowed to a vent depth of 5 μm was measured as a value related to the length at which burrs that cause problems in moldability were formed, and used as an index of moldability.

  As is clear from the table, the resin compositions of Test Examples 1 to 6 have both fluidity exceeding 100 cm and the burr length is as short as 1.0 mm or less, and both fluidity and moldability are compatible. It became clear that

  In Test Examples 7 and 8, since there is only one of the two maximum values required, it is considered that the fluidity is low. In particular, in Test Example 7, the moldability was not sufficient.

In Test Example 9, the burr length was 3.5 mm and a relatively long burr was generated. This is because the specific surface area is 0.9 m ² / g, which is smaller than the test samples of other test examples, and it can be assumed that the content of the relatively fine powder is reduced. That is, it was found that the cause of burr formation is the high fluidity in the gap, but the presence of fine powder has the effect of suppressing the fluidity in the gap.

  Although Test Examples 10 to 12 had both of the required maximum values, since the average circularity was less than 0.950, the fluidity of less than 100 cm was not sufficient.

Claims (8)

Has a maximum value of 2 or more in the volume-based particle size distribution,
A first maximum value that is one of the maximum values is 0.1 μm or more and less than 2 μm;
The second maximum value, which is one other than the first maximum value, is 50.2 μm or more and 70 μm or less,
The volume average particle size and d50 based on the whole are 6 μm or more and less than 50 μm,
Ri Der average circularity of 0.950 or more particles having 70μm or less particle size than 15 [mu] m,
An inorganic powder for adding a resin composition, which is an amorphous silica powder having a crystallization rate of less than 1% , wherein no maximum value exists in the range of 2 to 20 μm . The particles constituting the maximum value of the particle size distribution formed to be 0.1 μm or more and less than 2 μm are 5 to 15% by volume of the whole,
2. The inorganic powder for resin composition addition according to claim 1, wherein particles constituting the maximum value of the particle size distribution formed to be 20 μm or more and 70 μm or less are 50% by volume or more of the whole. Has a maximum value of 2 or more in the volume-based particle size distribution,
The first maximum value and the second maximum value which are two of the maximum values are 15 μm or more and 70 μm or less,
The volume average particle size and d50 based on the whole are 6 μm or more and less than 50 μm,
Ri Der average circularity of 0.950 or more particles having 70μm or less particle size than 15 [mu] m,
Resin composition which is an amorphous silica powder having a crystallization rate of less than 1%, wherein particles constituting two maximum values existing in 15 μm or more and 70 μm or less occupy 60% or more based on the total volume Inorganic powder for product addition. Has two local maxima in the volume-based particle size distribution,
The first maximum value and the second maximum value which are two of the maximum values are 15 μm or more and 70 μm or less,
The volume average particle size and d50 based on the whole are 6 μm or more and less than 50 μm,
An inorganic powder for resin composition addition, which is an amorphous silica powder having a crystallization rate of less than 1%, wherein the average circularity of particles having a particle size of 15 μm or more and 70 μm or less is 0.950 or more.   The inorganic powder for resin composition addition according to claim 4, wherein particles constituting two maximum values existing in 15 µm or more and 70 µm or less occupy 60% or more based on the total volume. The inorganic powder for resin composition addition according to any one of claims 1 to 3 , wherein the particle size distribution has two maximum values. The inorganic powder for adding a resin composition according to any one of claims 1 to 6, wherein the specific surface area measured by the BET method is 1.5 to 3.5 m ² / g. A filler made of claims 1-7 added inorganic powder resin composition according to any one of the resin composition; and a dispersion resin composition for dispersing the fillers.