JP2018138634A - Resin composition and semiconductor device using the resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which easily flows out from an application nozzle when an interlayer filler composition layer is formed, exhibits such high fluidity as to sufficiently spread on a narrow gap between a solder bump and a semiconductor substrate and to thereby form an interlayer filler composition layer with no gap (void), and exhibits such low fluidity or non-fluidity as to prevent flowing out from the substrate after formation of a composition layer, and to provide a semiconductor device using the resin composition.SOLUTION: A resin composition contains an inorganic filler and an epoxy resin. In frequency distribution of a particle diameter based on the volume of particles of the inorganic filler measured by a laser diffraction scattering type particle size distribution measurement apparatus, at least a range of 0.01 μm or more and less than 3.0 μm of the particle diameter and a range of 3.0 μm or more and less than 10.0 μm each have a maximum value, and a maximum particle size is less than 45 μm. A semiconductor device has a layer formed of the resin composition as a layer adjacent to a semiconductor substrate between a plurality of semiconductor substrates.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a resin composition having excellent flow characteristics suitable as an interlayer filler composition for a semiconductor device, and a semiconductor device using the resin composition.

  In recent years, in order to further improve the performance of semiconductor devices, in addition to miniaturization of transistors and wiring, a plurality of substrates such as a semiconductor substrate on which a semiconductor device layer is formed and an organic substrate are placed perpendicular to the substrate surface. Research and development of stacked semiconductor devices stacked and stacked is underway. Multilayer semiconductor devices are known in which a semiconductor substrate and an organic substrate are stacked. More specifically, semiconductor substrates are connected to each other with electrical signal terminals such as solder bumps between the substrates. In addition, a three-dimensional stacked semiconductor device having a structure in which an interlayer filler composition is filled between substrates and the substrates are bonded to each other by an interlayer filler composition layer is known.

  As a method for manufacturing a stacked semiconductor device, a layer made of an interlayer filler composition (ICF: Inter Chip Fill) is formed on a wafer on which a semiconductor device layer is formed, and heated to perform a B-stage. Next, a process by a pre-applied method is proposed in which chips are cut out by dicing, a plurality of obtained semiconductor substrates are stacked, temporary bonding by pressure heating is repeated, and finally final bonding is performed under pressure heating conditions. (For example, refer nonpatent literature 1).

  FIG. 1 is a perspective view showing a method of manufacturing a semiconductor device by a pre-apply method, and a coating nozzle is formed on a semiconductor substrate (semiconductor chip) 2 on which a plurality of solder bumps 1 composed of land terminals 1A and solder 1B are formed. After supplying the interlayer filler composition 3 from FIG. 4 (FIG. 1 (a)) and forming the interlayer filler composition layer 5 (FIG. 1 (b)), if necessary, performing B-stage, The semiconductor chip 2 on which the interlayer filler composition layer 5 is formed is inverted and placed on the semiconductor substrate 7 on which the electrode pads 6 are formed, which is placed on the stage (not shown) of the thermocompression bonding apparatus. The filler composition layer 5 side is opposed and pressed by a head (not shown) (FIG. 1C). By heating and pressurizing the semiconductor substrate 7 and the semiconductor chip 2 between the head and the stage of the thermocompression bonding apparatus, the interlayer filler composition is cured, and the semiconductor is interposed through the cured adhesive layer 8 of the interlayer filler composition. A semiconductor device 10 in which the chip 2 and the semiconductor substrate 7 are bonded can be obtained (FIG. 1D).

  The stacked semiconductor device repeats such a process, and an electrode pad is provided on the surface of the semiconductor device 10 shown in FIG. 1D on the side opposite to the cured adhesive layer 8 of the semiconductor chip 2. 1) is further manufactured by repeating the step of bonding the semiconductor chip 2 on which the interlayer filler composition layer 5 shown in FIG. 1B is formed.

The interlayer filler composition of such a stacked semiconductor device is required to have the following opposite flow characteristics (1) and (2).
(1) An interlayer filler composition layer can be easily extruded (flowed out) from a coating nozzle, and an interlayer filler composition layer after extrusion can be easily formed between solder bumps or between semiconductor substrates. High fluidity that flows smoothly in a narrow area and can be sufficiently filled without forming voids between the solder bumps and between the substrates.
(2) After forming the interlayer filler composition layer, it has low fluidity or non-fluidity so that it does not flow out from the edge of the substrate during handling before bonding or during bonding.

  If the interlayer filler composition does not reach the narrow gaps between the solder bumps and between the substrates, and voids are formed in this area, the difference in shrinkage of the substrate due to temperature changes, etc. will increase, and the adhesive surface may peel off. Although the performance as a semiconductor device is impaired by cracking, the recent high integration has further narrowed the gaps between the semiconductor substrates and between the solder bumps. The demand for liquidity is increasing.

  On the other hand, if it flows out of the edge of the substrate during handling before bonding or during bonding, it becomes difficult to manufacture the semiconductor device. The demand for is also increasing.

  These requirements are conspicuous in the stacked semiconductor device, but the packaging material that embeds the entire semiconductor has the same requirement for both high fluidity and non-fluidity.

Conventionally, as an inorganic powder that can provide a semiconductor encapsulating material that is excellent in fluidity and moldability and has few burrs, Patent Document 1 discloses a multimodal particle size distribution having at least two peaks in the frequency particle size distribution. It has been proposed that the first peak has a maximum value of 3 to 10 μm, and the second peak has a maximum value of 20 to 70 μm.
Further, in Patent Document 2, a ceramic powder capable of preparing a semiconductor sealing material excellent in filling rate, moldability, heat resistance, and flame retardancy was measured with a laser diffraction scattering particle size distribution measuring machine. The particle size has a multimodal frequency particle size distribution with at least two peaks, and the maximum particle size of the first peak is in the range of 40 to 80 μm and the maximum particle size of the second peak is in the range of 3 to 8 μm. Ceramic powders have been proposed.
Furthermore, Patent Document 3 discloses a frequency particle size as an amorphous siliceous powder that can reduce the viscosity at the time of sealing of the resin composition and improve the moldability even when highly filled with an inorganic filler. The distribution has a multimodal particle size distribution with at least two peaks, the maximum value of the first peak is in the particle size range of 15-70 μm, the maximum value of the second peak is in the particle size range of 3-10 μm, The thing with an average particle diameter of 5-50 micrometers is proposed.

JP 2009-184843 A International Publication WO2007 / 132771 Pamphlet International Publication WO2009 / 154186 Pamphlet

Proceedings of the Japan Institute of Electronics Packaging (61, 23, 2009)

  However, even when the inorganic powders proposed in Patent Documents 1 to 3 are used as the inorganic filler of the interlayer filler composition, the above-described (1) high fluidity and (2) low fluidity or non-fluidity are obtained. It cannot be made into the resin composition which has the fluidity | liquidity satisfy | filled together.

  In the present invention, when used as a resin composition satisfying the flow characteristics (1) and (2) described above, that is, as an interlayer filler composition of a laminated semiconductor device, for example, it can be easily applied from an application nozzle during interlayer filling operations. It flows out and reaches the narrow gap between the solder bumps and the semiconductor substrate sufficiently, so that it shows high fluidity that can form an interlayer filler composition layer without voids, and after filling, the substrate It is an object of the present invention to provide a resin composition exhibiting low fluidity or non-fluidity that does not flow out from above, and a semiconductor device using the resin composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that the resin composition has a viscosity when shear stress is applied to the resin composition, such as when protruding from the coating nozzle. High fluidity by lowering, and imparting thixotropic properties, that is, thixotropic properties, that is, low viscosity and non-fluidity by increasing viscosity after filling without applying shear stress. Thickotropic properties are imparted by using a filler with a specific profile (distribution of two peaks having a peak in a specific range) in the frequency distribution of particle size as an inorganic filler to be blended in the product, and the interlayer of the stacked semiconductor device It has been found that the filler composition can have particularly suitable flow characteristics.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] A resin composition containing an inorganic filler and an epoxy resin, wherein the inorganic filler has a volume-based particle size frequency distribution measured with a laser diffraction / scattering particle size distribution analyzer, and has a particle size of at least 0. A resin composition having a maximum value in a range of 0.01 μm or more and less than 3.0 μm and a particle size in a range of 3.0 μm or more and less than 10.0 μm and a maximum particle size of less than 45 μm.

[2] The resin composition according to [1], wherein the inorganic filler has a thermal conductivity of 2 W / (m · K) or more.

[3] The resin composition according to [1] or [2], further containing a flux.

[4] The resin composition according to any one of [1] to [3], further including a release agent.

[5] A semiconductor device having a layer made of the resin composition according to any one of [1] to [4] as a layer adjacent to a semiconductor substrate between a plurality of semiconductor substrates.

When the resin composition of the present invention is used, for example, as an interlayer filler composition in a laminated semiconductor device, the resin composition easily flows out from a coating nozzle when forming an interlayer filler composition layer. By sufficiently reaching the narrow gap between the substrates, an inter-layer filler composition layer having no voids can be formed, showing high fluidity, and during the bonding operation after forming the composition layer, Low fluidity or non-fluidity that does not flow out of
For this reason, an interlayer filler composition layer having no voids is formed between the semiconductor substrates, and a cured adhesive layer excellent in bondability and electrical conductivity is formed with good workability with good yield. It is possible to manufacture high-quality and highly reliable semiconductor devices with high productivity even when manufacturing semiconductor devices that embed the entire semiconductor, as well as when manufacturing stacked semiconductor devices. It becomes possible.

It is a perspective view which shows the manufacturing method of the semiconductor device by a pre-applied method. It is a chart which shows the frequency distribution measurement result of the volume particle size of the inorganic filler used for the resin composition of Example 1. It is a chart which shows the frequency distribution measurement result of the volume particle size of the inorganic filler used for the resin composition of Example 2. It is a chart which shows the frequency distribution measurement result of the volume particle size of the inorganic filler used for the resin composition of Example 3. It is a chart which shows the frequency distribution measurement result of the volume particle size of the inorganic filler used for the resin composition of Example 4. It is a chart which shows the frequency distribution measurement result of the volume particle size of the inorganic filler used for the resin composition of Example 5. It is a chart which shows the frequency distribution measurement result of the volume particle size of the inorganic filler used for the resin composition of Example 6. It is a chart which shows the frequency distribution measurement result of the volume particle size of the inorganic filler used for the resin composition of Example 7. It is a chart which shows the frequency distribution measurement result of the volume particle size of the inorganic filler used for the resin composition of the comparative example 1. It is a chart which shows the frequency distribution measurement result of the volume particle size of the inorganic filler used for the resin composition of the comparative example 2. It is a chart which shows the frequency distribution measurement result of the volume particle size of the inorganic filler used for the resin composition of the comparative example 3.

  Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

[Resin composition]
The resin composition of the present invention is a resin composition containing an inorganic filler and an epoxy resin, and is a volume-based particle size (hereinafter, “ In the frequency distribution of “volume particle size”, there is a maximum value in a range of at least a particle size of 0.01 μm or more and less than 3.0 μm and a particle size of 3.0 μm or more and less than 10.0 μm, The maximum particle size is less than 45 μm.

<Volume particle size>
The volume particle size in the present invention is a particle size based on the volume particle size measured with a laser diffraction / scattering particle size distribution analyzer. Although there is no special restriction | limiting in the model of a laser diffraction scattering type particle size distribution measuring device, Specifically, it can measure by "Shimadzu SALD-2200" by Shimadzu Corporation.

  For example, the maximum value in the frequency distribution of the volume particle size is measured by measuring the frequency distribution of the total volume of the particles under the following conditions using the following laser diffraction / scattering particle size distribution measuring device, and the frequency (% ) Higher than the frequency of the volume particle size larger than the specific volume particle size and adjacent to it, and higher than the frequency of the volume particle size smaller than the specific volume particle size In this case, it is determined by determining that the specific volume particle size has a maximum value.

  The inorganic filler contained in the resin composition of the present invention (hereinafter sometimes referred to as “the inorganic filler of the present invention”) has a volume particle size frequency distribution of at least 0.01 μm to less than 3.0 μm. It has a maximum value in the range and a range of particle size of 3.0 μm or more and less than 10.0 μm, and the maximum particle size is less than 45 μm.

Device used: “Shimadzu SALD-2200” manufactured by Shimadzu Corporation
Pretreatment: Put a sample in a beaker, dilute with cyclohexanone, and then disperse with an ultrasonic disperser for 2 minutes to obtain a sample solution.
Number of measurements: 2 times Particle permeability: transmission Particle refractive index: 1.60
Solvent: Cyclohexanone Solvent refractive index: 1.85

<Inorganic filler>
The inorganic filler is added for the purpose of improving the thermal conductivity and controlling the linear expansion coefficient, and is mainly intended to improve the thermal conductivity.
For this reason, the inorganic filler used in the present invention preferably has a thermal conductivity of 2 W / (m · K) or more.

  The thermal conductivity of the inorganic filler can be measured by a steady method or a non-stationary method after forming a thin plate by sintering or the like. In the unsteady method, the thermal conductivity λ is proportional to the thermal diffusivity (α), the specific heat capacity (Cp), and the density (ρ). Therefore, for example, α, Cp, and ρ are obtained according to the method specified in JIS R1611. Then, the thermal conductivity λ can be measured by these products.

  Examples of the inorganic filler used in the present invention include at least one selected from the group consisting of metals, carbon, metal carbides, metal oxides, and metal nitrides. Examples of carbon include carbon black, carbon fiber, graphite, fullerene and diamond. Examples of metal carbides include silicon carbide, titanium carbide, tungsten carbide and the like. Examples of metal oxides include magnesium oxide, aluminum oxide, silicon oxide, calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, sialon (ceramics composed of silicon, aluminum, oxygen, and nitrogen). Can be mentioned. Examples of metal nitrides include boron nitride, aluminum nitride, silicon nitride and the like.

  There is no restriction | limiting about the shape of an inorganic filler, A particulate form, a whisker form, a fiber form, plate shape, or those aggregates may be sufficient.

  Moreover, you may use the inorganic filler surface-treated beforehand with the below-mentioned coupling agent.

In an interlayer filler composition for a semiconductor device, since insulation is often required, the inorganic filler is excellent in insulation having a volume resistivity of 10 ¹³ Ω · cm or more, particularly 10 ¹⁴ Ω · cm or more. In particular, metal oxides and metal nitrides are preferable since the electrical insulation of the cured product is sufficient.

As such an inorganic filler, more specifically, alumina (Al ₂ O ₃ , thermal conductivity 30 W / (m · K), volume resistivity 10 ¹⁴ Ω · cm), aluminum nitride (AlN, thermal conductivity 285 W) / (M · K), volume resistivity 10 ¹⁴ Ω · cm), boron nitride (BN, thermal conductivity 410/2 W / (m · K), volume resistivity 10 ¹⁴ Ω · cm), silicon nitride (Si ₃ N ₄ , thermal conductivity 28 W / (m · K), volume resistivity 10 ¹⁴ Ω · cm), silica (SiO ₂ , thermal conductivity 1 W / (m · K), volume resistivity 10 ¹⁴ Ω · cm), etc. Among them, Al ₂ O ₃ , AlN, BN, and SiO ₂ are preferable, and Al ₂ O ₃ , BN, and SiO ₂ are particularly preferable.
As the BN filler, those disclosed in JP2013-241321A are preferably used.

  In the present invention, as the inorganic filler, in the frequency distribution of the volume particle size measured with a laser diffraction / scattering particle size distribution analyzer, at least within the range of 0.01 μm or more and less than 3.0 μm and the particle size of 3.0 μm or more and 10 Those having a maximum value within a range of less than 0.0 μm and a maximum particle size of less than 45 μm are used.

  The particle size is 0.01 μm or more and less than 3.0 μm, preferably 0.3 to 2.0 μm, and the particle size is 3.0 μm or more and less than 10.0 μm, preferably 3.0 to 7.0 μm. If it is an inorganic filler having a maximum value, the above-mentioned (1) high fluidity required for the interlayer filler composition of the laminated semiconductor device and (2) low fluidity or non-fluidity fluidity And an interlayer filler composition layer having no voids and a cured layer thereof can be formed with good yield.

  The inorganic filler of the present invention is not particularly limited as long as it has a maximum value within the above range, and the frequency (%) of the maximum value is not particularly limited, but is within a range of a particle size of 0.01 μm or more and less than 3.0 μm. Frequency (%) of a local maximum value (hereinafter may be referred to as “first local maximum value”) and a local maximum value within a range of 3.0 μm or more and less than 10.0 μm (hereinafter referred to as “second maximum value”). The frequency (%) of the second maximum value is about 2.0 to 8.0 times the frequency (%) of the first maximum value. In addition, the difference in particle diameter between the first maximum value and the second maximum value is preferably about 3.0 to 6.0 μm.

Thus, an inorganic filler having a maximum value within a predetermined range can be prepared by, for example, mixing and using two types of inorganic fillers having different average particle diameters.
More specifically, the first inorganic filler having an average particle size of 0.01 μm or more and less than 3.0 μm, preferably 0.3 to 1.0 μm and the average particle size of 3.0 μm or more and less than 10.0 μm, preferably A method in which 3.0 to 6.0 μm of the second inorganic filler is mixed and used at a ratio of the first inorganic filler: second inorganic filler = 2.0 to 5.0 (weight ratio) is used. .

In the present invention, the reason for using an inorganic filler having a maximum particle size of less than 45 μm is as follows.
That is, in recent years, the distance between chips has been reduced to about 10 to 50 μm between chips in order to improve performance such as higher speed and higher capacity. In the filler composition layer, the maximum particle size of the inorganic filler to be blended is smaller than the thickness of the interlayer filler composition layer, preferably 1/3 or less of the thickness of the interlayer filler composition layer, and less than 45 μm, preferably Is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less.

  If the maximum particle size of the inorganic filler exceeds 45 μm, the inorganic filler protrudes from the surface of the interlayer filler composition layer after curing, and the surface shape of the interlayer filler composition layer tends to deteriorate.

  The average particle size of the inorganic filler is not particularly limited as long as it satisfies the above-mentioned maximum value and maximum particle size, but the average particle size is excessively small, and the viscosity of the resin composition of the present invention is controlled. The average particle size of the inorganic filler is preferably about 0.3 to 6.0 μm.

  The content of the inorganic filler in the resin composition of the present invention is preferably from 50% by weight to 76% by weight, and more preferably from 60% by weight to 76% by weight, based on the entire resin composition. When described in terms of volume filling rate, the content of the inorganic filler in the resin composition of the present invention is preferably 30% by volume to 55% by volume, more preferably 35% by volume to 50% by volume with respect to the entire resin composition. Preferably, it is more preferably 45% by volume or more and 50% by volume or less. Further, the content of the inorganic filler per 100 parts by weight of the total of the epoxy resin and the curing agent described later is preferably 10 parts by weight or more and 500 parts by weight or less, more preferably 20 parts by weight or more and 400 parts by weight or less. Moreover, when describing by volume filling rate, 10 volume part or more and 300 volume part or less are preferable, and, as for content of the inorganic filler per 100 volume part of sum total of an epoxy resin and the below-mentioned hardening | curing agent, 20 volume part or more and 240 volume part or less are more. preferable. When the content of the inorganic filler is less than the above lower limit, the effect of adding the inorganic filler is reduced, and the target linear expansion coefficient and thermal conductivity may not be obtained. When the content is larger than the upper limit, the presence of the inorganic filler is present. May interfere with conjugation.

<Epoxy resin>
The epoxy resin used in the present invention is preferably a compound having two or more epoxy groups in order to improve the glass transition temperature of the resin composition of the present invention. Further, in order to increase the fracture toughness value K1c value of the cured product obtained by thermosetting the resin composition of the present invention, the number of epoxy groups contained in one molecule is preferably 1 or more and 8 or less, More preferably, it is 2 or more and 3 or less.

  In order to improve the thermal conductivity of the resin composition of the present invention, it is preferable to use an epoxy compound having an aromatic ring such as a bisphenol A skeleton, a bisphenol F skeleton, or a biphenyl skeleton as the epoxy resin used in the present invention.

  More specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene ring-containing epoxy resin, epoxy resin having a dicyclopentadiene skeleton, phenol novolac type resin, cresol Examples include novolak type epoxy resins, triphenylmethane type epoxy resins, aliphatic epoxy resins, aliphatic epoxy resins and copolymer epoxy resins of aromatic epoxy resins, among which bisphenol A type epoxy resins and bisphenols F-type epoxy resins, bisphenol S-type epoxy resins, biphenyl-type epoxy resins, and naphthalene ring-containing epoxy resins are preferable, and bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, Futaren ring-containing epoxy resins, biphenyl type epoxy resin is used.

Moreover, in order to improve the fracture toughness of the hardened | cured material which heat-cured the resin composition, you may use a polyfunctional epoxy resin as an epoxy resin.
Polyfunctional epoxy resins include phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolac resin, biphenyl novolac resin, terpene phenol resin, heavy oil modified phenol resin, etc. Manufactured from various phenolic compounds such as polyphenolic resins obtained by condensation reaction of various phenols, various phenols and various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal, and epihalohydrin A glycidyl ether type polyfunctional epoxy resin such as an epoxy resin is preferable.

From the viewpoint of fluidity, the epoxy resin used in the present invention preferably contains one having a shear viscosity at 25 ° C. of 15 Pa · s or less, for example, 5 to 10 Pa · s.
Here, the shear viscosity at 25 ° C. is a value measured according to JIS Z 8803: 2011, and is a value measured by a viscosity measurement method using a cone-plate rotational viscometer. More specifically, it is measured by an E-type viscometer defined by JIS K 7117-2: 1999. Moreover, even if it is the low molecular weight epoxy resin which shows crystallinity, the state when it cools to 25 degreeC within 12 hours in the environment of 5 degreeC or more after warming more than crystal melting temperature is a liquid state, 25 degreeC The epoxy resin having a viscosity of 10 Pa · s or less is treated as an epoxy resin having a viscosity at 25 ° C. of 10 Pa · s or less. The shear viscosity at 25 ° C. of the epoxy resin is preferably 5.0 to 7.0 Pa · s.

  In addition, the epoxy resin preferably has an epoxy equivalent of 50 g / equivalent to 500 g / equivalent, more preferably 150 g / equivalent to 200 g / equivalent from the viewpoint of viscosity control. When the epoxy equivalent is less than 50 g / equivalent, the heat resistance tends to be inferior. When the epoxy equivalent is greater than 500 g / equivalent, the melting point of the epoxy resin is increased and the melt viscosity of the resin composition is increased. May cause problems.

  These epoxy resins may be used individually by 1 type, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.

  The content of the epoxy resin in the resin composition of the present invention is preferably 10 to 50% by weight, particularly 10 to 25% by weight, more preferably 10 to 15% by weight, based on the entire composition. Moreover, it is preferable that content of an epoxy resin is 10-65 volume% with respect to the whole composition, 20-40 volume% especially, More preferably, it is 24-30 volume%. If the content of the epoxy resin in the resin composition is too small, sufficient adhesiveness cannot be obtained, and kneading or the like at the time of producing the resin composition may be difficult. Moreover, when too much, content, such as an inorganic filler, will decrease relatively and it exists in the tendency for thermal conductivity etc. to fall.

<Curing agent>
The resin composition of the present invention preferably further contains a curing agent. A hardening | curing agent shows the substance which contributes to the crosslinking reaction between the crosslinking groups of an epoxy resin.

  There is no restriction | limiting in particular as a hardening | curing agent, The thing generally known as an epoxy resin hardening | curing agent can be used. For example, phenolic curing agents, aliphatic amines, polyether amines, alicyclic amines, aromatic amines and other amine curing agents, acid anhydride curing agents, amide curing agents, tertiary amines, imidazoles and the like Derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan curing agents, isocyanate curing agents, blocked isocyanate curing agents, and the like. From the viewpoint of imparting fluidity and rapid curability, the curing agent is preferably an acid anhydride curing agent.

  Specific examples of the phenolic curing agent include bisphenol A, bisphenol F, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, 1,3-bis. (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cle All novolak, xylenol novolak, poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2 , 4-Benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2, -Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol, etc. The

  Specific examples of the amine curing agent include aliphatic diamines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, Examples include diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine, and the like. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ethylamine , Diaminodiethyl Examples include rudimethyldiphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene.

  Specific examples of acid anhydride curing agents include dodecenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) Anhydride, Methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Hexahydrophthalic anhydride, Methylhymic anhydride, Tetrahydrophthalic anhydride, Trialkyltetrahydrophthalic anhydride, Methylcyclohexene dicarboxylic anhydride, Methylcyclohexene tetracarboxylic Acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic dianhydride, het anhydride, nadic anhydride, methyl nadic anhydride, 5- ( 2, -Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexene-1 , 2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro Examples include -1-naphthalene succinic dianhydride.

  Examples of the amide type curing agent include dicyandiamide and polyamide resin.

  Examples of the tertiary amine include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. .

  Examples of imidazole and derivatives thereof include 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazo Lithium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-di Mino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole and adducts of an epoxy resin and the imidazoles.

  Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like, and phosphonium salts include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, Examples include tetrabutylphosphonium / tetrabutylborate, and examples of the tetraphenylboron salt include 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and the like.

  These curing agents may be used alone or in a combination of two or more in any combination and ratio.

  The content of the curing agent in the resin composition of the present invention is such that when the curing agent is a phenol curing agent, an amine curing agent, or an acid anhydride curing agent, the epoxy group in the epoxy resin and the functionality in the curing agent. It is preferable to use so that it may become the range of 0.8-1.5 by equivalent ratio with group. Outside this range, unreacted epoxy groups and functional groups of the curing agent may remain, and desired physical properties may not be obtained.

  Curing agents are amide-based curing agents, tertiary amines, imidazoles and their derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents. In the case of a curing agent, a blocked isocyanate curing agent, and the like, it is preferably used in a range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Moreover, in the case of a dicyandiamine compound, it is preferable to use in the range of 0.1-10 weight part with respect to 100 weight part of epoxy resins, and 0.5-6 weight part is more preferable.

[Curing accelerator]
The resin composition of the present invention may contain a curing accelerator together with a curing agent in order to lower the curing temperature and shorten the curing time.

  Examples of curing accelerators include compounds containing tertiary amino groups, imidazoles and their derivatives, organic phosphines, dimethylurea, microcapsules of the above compounds using coating agents such as organic polymers and inorganic compounds, etc. Is mentioned.

  Examples of the compound containing a tertiary amino group include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, etc. Is exemplified.

  Examples of imidazole and derivatives thereof include 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl -(1 ')]-ethyl-s-triazine, 2,4-di Mino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resin and the above imidazoles, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. Is exemplified.

  Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like, and phosphonium salts include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, Examples include tetrabutylphosphonium / tetrabutylborate, and examples of the tetraphenylboron salt include 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and the like.

  Of these, imidazole compounds (imidazole and its derivatives) and coatings made of organic polymers and inorganic compounds are used because of their relatively long pot life, high curability in the middle temperature range, and high heat resistance of the cured resin. It is preferable to use a microencapsulated product of the above compound.

  These curing accelerators may be used alone or in a combination of two or more in any combination and ratio.

  When the resin composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.001 to 15 parts by weight per 100 parts by weight of the total of the epoxy resin and the curing agent. More preferably, it is 0.01 parts by weight or more and 10 parts by weight or less. If the content of the curing accelerator is less than 0.001 part by weight per 100 parts by weight of the total of the epoxy resin and the curing agent, the curing acceleration effect may be insufficient, and if it exceeds 15 parts by weight, the catalyst curing reaction may occur. It becomes dominant and void reduction may not be achieved.

[flux]
The resin composition of the present invention may further contain a flux as necessary. For example, flux means, for example, when soldering metal terminals, the metal electric signal terminals such as solder bumps and the surface oxide film of the land are dissolved and removed, the wet spread of the solder bumps on the land surface is improved, and further the solder bumps It is a compound having functions such as prevention of reoxidation of the metal terminal surface.

  Examples of the flux used in the present invention include aliphatic carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, citric acid, lactic acid, acetic acid, propionic acid, butyric acid, oleic acid, and stearic acid. Organic carboxylic acids such as benzoic acid, salicylic acid, phthalic acid, trimellitic acid, trimellitic anhydride, aromatic carboxylic acids such as trimesic acid, benzenetetracarboxylic acid, and terpene carboxylic acids such as abietic acid and rosin Organic carboxylic acid esters, glutamic acid hydrochlorides, aniline hydrochlorides, hydrazine hydrochlorides, cetylpyridine bromides, phenylhydrazine hydrochlorides, tetrachlors, which are hemiacetal esters converted by reacting acids and organic carboxylic acids with alkyl vinyl ethers Naphthalene, methylhydrazine hydrochloride, Organic halogen compounds such as tilamine hydrochloride, ethylamine hydrochloride, diethylamine hydrochloride and butylamine hydrochloride, amines such as urea and diethylenetriamine hydrazine, polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and glycerin , Inorganic acids such as hydrochloric acid, hydrofluoric acid, phosphoric acid, borohydrofluoric acid, fluorides such as potassium fluoride, sodium fluoride, ammonium fluoride, copper fluoride, nickel fluoride, zinc fluoride, potassium chloride, sodium chloride , Chlorides such as cuprous chloride, nickel chloride, ammonium chloride, zinc chloride, stannous chloride, bromides such as potassium bromide, sodium bromide, ammonium bromide, tin bromide, zinc bromide, etc. . These compounds may be used as they are or may be microencapsulated using a coating agent made of an organic polymer or an inorganic compound.

  Especially, organic carboxylic acid derivatives, such as polyhydric alcohols, organic carboxylic acid, and carboxylic acid ester, are preferable from the solubility to an epoxy resin. In addition, organic carboxylic acids are particularly preferable because they are less foamable when heated than epoxy resins. Among these, organic carboxylic acids having two or more carboxyl groups are particularly preferable because of reactivity as a flux.

The organic carboxylic acid ester can be obtained by reacting an organic carboxylic acid and an alkyl vinyl ether according to the following formula (2) at room temperature, normal pressure, or if necessary, heated.
In addition, since the reaction of formula (2) is also an equilibrium reaction, in order to increase the proportion of the organic carboxylic acid converted to the organic carboxylic acid ester, an equal amount or more of alkyl vinyl ether is added to the carboxyl group in the organic carboxylic acid It is preferable to make it react.

(In formula (2), R ₁ represents the remaining molecular chain excluding one carboxyl group in the carboxylic acid. R ₂ represents an alkyl group having 1 to 6 carbon atoms.)

  The organic carboxylic acid ester is decomposed by heating in the resin composition to produce an organic carboxylic acid and vinyl ether. The organic carboxylic acid produced by the decomposition exhibits a surface activation action (flux action) on the solder balls.

  In addition, some organic carboxylic acids generated by decomposition may exhibit a curing action on epoxy resins. This is because in the carboxyl group, hydrogen ions released by the dissociation may exhibit a curing action on the epoxy resin. In order to suppress the generation of hydrogen ions due to the dissociation of the carboxyl group, an organic carboxylic acid ester obtained by protecting an organic carboxylic acid with an alkyl vinyl ether is preferably used.

Even when an organic carboxylic acid ester is used, if the decomposition temperature is too low, the epoxy resin may be hardened at the time of temporary bonding by pressurization and heating during production.
Therefore, the decomposition temperature of the organic carboxylic acid ester as the flux is preferably 130 ° C. or higher, more preferably 140 ° C. or higher, more preferably 160 ° C. or higher, in order to avoid or suppress decomposition at the time of temporary bonding. Most preferably, it is 180 ° C. or higher. The upper limit of the decomposition temperature is 220 ° C.

  Organic carboxylic acids used as raw materials for organic carboxylic acid esters include monocarboxylic acids such as lactic acid, acetic acid, propionic acid, butyric acid, oleic acid, stearic acid, benzoic acid, abietic acid, and rosin; succinic acid, malonic acid, succinic acid, Dicarboxylic acids such as glutaric acid, adipic acid, malic acid, tartaric acid, isophthalic acid, pyromellitic acid, maleic acid, fumaric acid, itaconic acid; citric acid, 1,2,4-trimellitic acid, tris (2-carboxyethyl) ) Tricarboxylic acids such as isocyanurate; tetracarboxylic acids such as pyromellitic acid and butanetetracarboxylic acid can be used. Among these, organic carboxylic acids having two or more carboxyl groups are preferable in terms of reactivity as flux.

Moreover, as alkyl vinyl ethers used as a raw material for the organic carboxylic acid ester, R ₂ in the above formula (2) is preferably an alkyl group having 1 to 6 carbon atoms, among which R ₂ is a methyl group, an ethyl group, a propyl group. Group is preferably a butyl group. Among these alkyl groups, the lower the electron donating property, the higher the temperature dissociation property, so the alkyl group is preferably secondary or primary.

  As organic carboxylic acid esters, commercially available products such as Santacid G (dialkyl vinyl ether block bifunctional polymer carboxylic acid), Santacid H (monoalkyl vinyl ether block bifunctional low molecular weight carboxylic acid) manufactured by NOF Corporation, Santacid I (mono) Alkyl vinyl ether block bifunctional carboxylic acid) and the like can be preferably used.

  These fluxes may be used alone or in a combination of two or more in any combination and ratio.

  When the resin composition of the present invention contains a flux, the content of the flux in the resin composition is 100 parts by weight in total of the epoxy resin in the resin composition, the curing agent, and a curing accelerator used as necessary. On the other hand, it is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. If the flux content is less than the lower limit, there is a risk of poor solder connection due to a decrease in oxide film removability, and if it exceeds the upper limit, there is a risk of poor connection due to an increase in the viscosity of the resin composition.

<Release agent>
The resin composition of the present invention further contains a release agent in order to enhance the releasability so that it can be easily removed from the mold when it is cured and molded in a mold intended to make a certain shape. It may be.

  Any mold release agent may be used without particular limitation as long as it is a wax that has been conventionally blended into a resin for mold release. Specific examples thereof include natural carnauba wax, montanic acid wax, paraffin wax, Fischer-Tropsch wax, linear / branched polyethylene wax, ethylene / propylene copolymer wax, microcrystalline wax, and the like. Among these, natural carnauba wax and montanic acid wax are preferable because they have a relatively high melting point and are unlikely to adversely affect the contacts and the like when a reflow process is performed on a wiring board on which a semiconductor device is mounted.

  When the resin composition of the present invention contains a release agent, the content of the release agent in the resin composition is the sum of the epoxy resin, the curing agent, and the curing accelerator used as necessary in the resin composition. Preferably they are 0.01 weight part or more and 10 weight part or less with respect to 100 weight part, More preferably, they are 0.05 weight part or more and 5 weight part or less. If the content of the release agent is less than the above lower limit, a sufficient release effect cannot be obtained, and if it exceeds the above upper limit, the effect becomes insufficient and a cured product having sufficient strength cannot be obtained. There is a risk that the durability of the device with respect to changes in the operating environment temperature may be reduced.

<Dispersant>
The resin composition of the present invention may contain a dispersant in order to improve the dispersibility of the inorganic filler.

  As the dispersant, it is preferable to use a dispersant having an amine value (mg-KOH / g) of 10 or more and 300 or less in order to improve the dispersibility of the inorganic filler. Moreover, when using the resin composition of this invention as a compound using a dispersing agent, since it is excellent in the improvement of the applicability | paintability of a compound and the coating-film property, what has a tertiary amino group as a functional group is preferable. As an example of such a dispersant, for example, an acrylic dispersant and / or a urethane dispersant may be mentioned.

  The content of the dispersant appropriately contained in the resin composition of the present invention may be any content as long as it does not impair the object of the present invention, but the content of the dispersant contained in the resin composition of the present invention. When the inorganic filler is 100 parts by weight, the dispersant is preferably 0.1 parts by weight or more and 4 parts by weight or less, and more preferably 0.1 parts by weight or more and 2 parts by weight or less. If the content of the dispersant is less than the above lower limit, it may be difficult to uniformly disperse the inorganic filler in the resin composition of the present invention. If the upper limit is exceeded, phase separation or aggregation of the inorganic filler with the epoxy resin may occur. May cause.

<Other additives>
The resin composition of the present invention may contain various additives other than those described above within a range not impairing the effects of the present invention for the purpose of further improving the functionality.

  Examples of additives include coupling agents for improving bondability and bondability between epoxy resins and inorganic fillers, UV inhibitors for improving storage stability, antioxidants, plasticizers, flame retardants, and colorants. , Fluidity improvers, and adhesion improvers with substrates, such as thermoplastic oligomers.

  Any of these may be used alone or in a combination of two or more in any combination and ratio.

  The amount of other additives is not particularly limited, and is used in the usual amount of the resin composition to the extent that the required functionality is obtained. The amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, per 100 parts by weight of the total amount of the curing agent.

≪Coupling agent≫
The resin composition of this invention may contain coupling agents, such as a silane coupling agent and a titanate coupling agent, from a viewpoint of improving the adhesiveness of an epoxy resin and an inorganic filler.

  Here, as the silane coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ, -Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltri Aminosilane such as ethoxysilane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysila And vinyl silanes such as γ-methacryloxypropyltrimethoxysilane, and epoxy, amino and vinyl polymer type silanes.

  On the other hand, titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate It is done.

  These coupling agents may be used alone or in a combination of two or more in any combination and ratio.

When the resin composition of this invention contains a coupling agent, it is preferable that the content shall be about 0.1-2.0 weight% with respect to the total solid in a resin composition. If the amount of the coupling agent is small, the effect of improving the adhesion between the epoxy resin, which is a matrix resin, and the inorganic filler due to the incorporation of the coupling agent cannot be sufficiently obtained. There is a problem that the coupling agent bleeds out.
In addition, a coupling agent may be previously used for the surface treatment of an inorganic filler, and may be contained in the resin composition of this invention as a surface treatment agent of an inorganic filler.

≪Thermoplastic oligomers≫
The resin composition of the present invention may contain thermoplastic oligomers in order to improve fluidity during molding and to improve adhesion to the substrate. Thermoplastic oligomers include C5 and C9 petroleum resins, styrene resins, indene resins, indene / styrene copolymer resins, indene / styrene / phenol copolymer resins, indene / coumarone copolymer resins, indene / benzothiophene. Examples thereof include copolymer resins. These may be used alone or in combination of two or more.

  When the resin composition of the present invention contains these thermoplastic oligomers, the content thereof is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin.

≪Other additives≫
The resin composition of the present invention may further contain a surfactant, an emulsifier, a low elasticity agent, a diluent, an antifoaming agent, an ion trapping agent and the like.

As the surfactant, any of conventionally known anionic surfactants, nonionic surfactants, and cationic surfactants can be used.
For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl Examples include sulfonates, sulfosuccinate esters, alkylbetaines, amino acids, and the like.
In these dispersants, a fluorosurfactant in which a part or all of the C—H bonds are C—F bonds can also be preferably used.
When the resin composition of the present invention contains these surfactants, the content thereof is usually in the range of 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the total of the epoxy resin and the curing agent. .

In addition, an organic solvent can also be added to the resin composition of the present invention.
Examples of the organic solvent include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and other ketones, ethyl acetate and other esters, ethylene glycol monomethyl ether and other ethers, N, N-dimethylformamide, Examples thereof include amides such as N, N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, and aromatics such as toluene and xylene.

Among these, considering the solubility of the resin and the boiling point of the solvent, ketones such as methyl ethyl ketone and cyclohexanone, esters and ethers are preferable, and ketones such as methyl ethyl ketone and cyclohexanone are particularly preferable.
These organic solvents may be used alone or in a combination of two or more in any combination and ratio.

  However, when a solvent is used, the solvent volatilizes in the joining step, and voids are easily formed in the cured adhesive layer. Therefore, the resin composition of the present invention preferably does not contain a solvent.

<Method for producing resin composition>
The resin composition of the present invention is usually uniformly mixed with an epoxy resin, an inorganic filler, a curing agent used as necessary, a curing accelerator, a flux, a release agent, a dispersant, and other additive components using a mixer or the like. And then kneaded with a heating roll, a kneader or the like. There is no restriction | limiting in particular in the mixing | blending order of these components. It is also possible to form a film using a press after kneading. Further, after kneading, the melt-kneaded product can be pulverized to be powdered or tableted.

<Method of molding resin composition>
The resin composition of the present invention can be molded by heating and molding. This shaping | molding can be suitably performed according to the compounding component composition etc. of a resin composition using the method used generally.

  For example, the resin composition having plasticity and fluidity can be molded by curing the resin composition in a desired shape, for example, in a state of being accommodated in a mold. In the production of such a molded body, injection molding, injection compression molding, extrusion molding, or compression molding can be used. Moreover, shaping | molding of a molded object, ie, hardening, can be performed on each hardening temperature conditions. Moreover, the said molded object can be obtained also by shaving the hardened | cured material of a resin composition into a desired shape.

  The resin composition of the present invention is particularly effective as an interlayer filler composition for laminated semiconductor devices because it has superior flow characteristics than the inorganic filler of the present invention, but in addition, an inorganic filler with high thermal conductivity is used. Therefore, it can be used for a heat radiating substrate, a heat radiating sheet, a heat conductive paste, a heat conductive adhesive, a semiconductor package, a heat sink, a heat pipe, a casing of an electric / electronic device, and the like that require thermal conductivity.

[Stacked semiconductor devices]
The semiconductor device of the present invention has a layer made of the resin composition of the present invention as a layer adjacent to the semiconductor substrate. In particular, the semiconductor device of the present invention is suitable for a stacked semiconductor device. A stacked semiconductor device has a plurality of substrates, and the substrate is typically an organic substrate typified by an organic interposer or the like, or a silicon substrate on which a semiconductor device layer such as a memory circuit or a logic circuit is formed. The interlayer filler composition layer containing the resin composition of the present invention can be formed between any substrates selected from these substrates.

  The semiconductor device of the present invention is suitable for the process of laminating the substrate and the stacked semiconductor device due to the thixotropic property of the resin composition of the present invention, and the electrical bonding of the stacked semiconductor device is stable even under various environmental changes. An interlayer filler composition layer can be formed that is maintained at

<Board>
More specifically, the substrate in the semiconductor device of the present invention includes an organic substrate made of epoxy resin or polyimide resin, or a semiconductor substrate on which a wiring circuit, a through electrode (TSV), a semiconductor element circuit, or the like is formed. The layer formed by curing the resin composition of the present invention may be provided between the organic substrate and the semiconductor substrate, may be provided between the semiconductor substrate and the semiconductor substrate, It may be provided between the organic substrate. By using the resin composition of the present invention, even in a laminated semiconductor device composed of an organic substrate and a semiconductor substrate, a void in bonding of a thin semiconductor substrate or a large semiconductor substrate is smaller than in conventional interlayer filling by underfill after reflow. Therefore, it is possible to achieve bonding with low resistance between terminals. In addition, the semiconductor substrate has higher surface smoothness than the organic substrate, enables circuit transfer by finer lithography, and enables the formation of smaller connection terminals such as copper posts and solder bumps. By forming the narrow connection terminals between them, it is possible to realize a high performance stacked semiconductor device with higher wiring density.

<Semiconductor substrate>
As the semiconductor substrate in the present invention, any material that can be used as a substrate in the manufacture of an integrated circuit can be used, but a silicon substrate is preferably used. The silicon substrate may be used as it is, depending on the aperture, or may be used after being thinned to 100 μm or less by backside polishing such as backside etching or backgrinding.

  Examples of the semiconductor substrate in the present invention include a semiconductor substrate on which a wiring circuit is formed, a semiconductor substrate on which a through electrode (TSV) is formed, a semiconductor substrate on which a semiconductor element circuit such as a transistor is formed, silicon, germanium, A substrate in which germanium silicide, silicon carbide, gallium arsenide, gallium phosphide, gallium nitride or the like is doped with phosphorus or boron as required by an ion implantation method, more specifically, an N-type silicon substrate, A P-type silicon substrate may be used.

  Examples of the semiconductor element circuit formed on the surface of the semiconductor substrate include storage elements such as a nonvolatile memory and a dynamic random access memory in addition to arithmetic elements such as a DSP and MPU. The linear expansion coefficient of the semiconductor substrate is usually 1 to 10 ppm / K, although it varies depending on the material.

  The semiconductor substrate usually has solder bumps and land terminals. As solder bumps, fine solder balls may be used, and after forming an opening by lithography, a solder plating is applied directly on the base of the opening or after a nickel or copper post is formed, and a resist material After removing, solder bumps may be formed by heat treatment. The solder composition is not particularly limited, but a solder containing tin as a main component is preferably used in consideration of electrical bondability and low-temperature bondability.

  The land terminal can be formed by forming a thin film on a semiconductor substrate using PVD (Physical Vapor Deposition) or the like and then removing an unnecessary portion by forming a resist film by lithography and dry or wet etching. . The material of the land terminal is not particularly limited as long as it can be bonded to the solder bump, but gold or copper can be preferably used in consideration of the bondability with solder and the reliability.

<Organic substrate>
The organic substrate has a conductive wiring circuit, and more specifically, a thermosetting resin such as an epoxy resin or a polyimide resin is formed into a plate shape with glass fibers or the like interposed therebetween. The organic substrate is a pattern conversion substrate (interposer) for high-density mounting that connects an array of electrodes with solder balls as external electrodes and a semiconductor substrate, and an epoxy resin or the like as a resin component that constitutes the organic substrate is a wiring layer As copper, Cu (Cu) is preferably used. Terminals for connection are provided on the surface of the organic substrate and are usually formed by a combination of a photolithography method and a plating method or a printing method, and the interval between the terminals is usually 50 μm to 300 μm. The linear expansion coefficient of the organic substrate varies depending on the material, but is usually 5 to 50 ppm / K in the case of the organic interposer substrate. The semiconductor substrate laminated body mounted on the printed board may be connected to the organic substrate through solder bumps or the like, and the organic substrate may be electrically connected to terminals of the printed board through arrayed electrodes.

<Lamination>
The interlayer filler composition layer made of the resin composition of the present invention is formed between any substrates selected from an organic substrate and a semiconductor substrate. In order to take advantage of the flow characteristics of the resin composition of the present invention, a semiconductor substrate is used. The interlayer filler composition layer made of the resin composition of the present invention is preferably formed between the semiconductor substrate and the semiconductor substrate.

<Method for Manufacturing Multilayer Semiconductor Device>
The laminated semiconductor device of the present invention is preferably formed by forming an interlayer filler composition layer made of the resin composition of the present invention on the surface of a semiconductor substrate by a pre-apply method and pressurizing and bonding the semiconductor substrate and another substrate. Can be manufactured by a manufacturing method including a process in a temperature range of 120 ° C. or higher and 180 ° C. or lower.

≪Formation of interlayer filler composition layer by pre-apply method≫
In the formation of the interlayer filler composition layer by the pre-apply method, it is formed by a conventionally known formation method, more specifically, for example, a dip method, a spin coat method, a spray coat method, a blade method, or any other method. Can do. The interlayer filler composition layer may be formed on any surface of the semiconductor substrate, but is preferably formed on the surface having solder bumps or the surface having lands.

≪Pressure bonding≫
In order to remove the low molecular weight component and the like contained in the resin composition, the interlayer filler composition layer comprising the resin composition of the present invention has an arbitrary temperature of 50 to 150 ° C., preferably 60 to 130 ° C. It is preferable to perform a baking process at a temperature of B-Stage.
At this time, the baking treatment may be performed at a constant temperature, but in order to smoothly remove the volatile components in the composition, the baking treatment may be performed under reduced pressure conditions. Moreover, you may perform the baking process by stepwise temperature rise in the range in which hardening of resin does not advance. For example, baking can be performed at 60 ° C., then 80 ° C., and 120 ° C. for about 5 to 90 minutes each.

After forming the interlayer filler composition layer, temporary bonding is performed with the substrates to be bonded. The temporary bonding is preferably performed at a temperature of 80 to 150 ° C. When the semiconductor substrate is bonded to a plurality of layers, the temporary bonding may be repeated for the number of layers of the substrate, or the substrates may be stacked and then temporarily bonded together by heating. When the temporary bonding, optionally between the substrates, preferably ^{1gf / cm 2 ~50Kgf / cm 2} , more preferably carried out under a load of ^{10gf / cm 2 ~10Kgf / cm 2} .

  After the temporary bonding, the main bonding is performed. By temporarily bonding the laminated substrates temporarily bonded at 200 ° C. or higher, preferably 220 ° C. or higher, the melt viscosity of the resin composition contained in the interlayer filler composition layer is reduced, and the electrical terminals between the substrates are reduced. At the same time as the connection is promoted, solder bonding between the semiconductor substrates can be realized. The upper limit of the heating temperature may be appropriately determined as long as the epoxy compound to be used is not decomposed or deteriorated, but is usually 300 ° C. or lower.

At the time of pressure bonding is between the substrates as necessary, be preferably ^{10gf / cm 2 ~10Kgf / cm 2} , more preferably carried out under a load of 50gf ^/ cm ² ~5Kgf ^/ cm 2 Is preferred.

  EXAMPLES Hereinafter, although this invention is demonstrated still in detail using an Example, this invention is not limited to a following example, unless it deviates from the meaning.

[Composition ingredients]
Below, the compounding component used for preparation of a resin composition is as follows.

<Inorganic filler>
Alumina particles I: manufactured by Admatechs Co., Ltd. Product name “AE9104-SXE” (N-phenyl-γ-aminopropyltrimethoxysilane surface-treated alumina particles, volume average particle size 3.7 μm)
Alumina particles II: manufactured by Admatechs Co., Ltd. Product name “AC9050-SXF” (N-phenyl-γ-aminopropyltrimethoxysilane surface-treated alumina particles, volume average particle size 2.8 μm)
Alumina particles III: product name “A0310-β” manufactured by Taiyo Nippon Sanso Corporation (alumina particles, volume average particle size 3.2 μm)
Alumina particles IV: manufactured by Taiyo Nippon Sanso Corporation “Submicron alumina” (alumina particles, volume average particle size 0.3 μm)
Alumina particles V: manufactured by Tatsumori Co., Ltd. Product name “TS-AP-9” (alumina particles, volume average particle size 0.5 μm)

<Epoxy resin>
Product name “LX-01” manufactured by Daiso Chemical Co., Ltd. (bisphenol A type glycidyl ether epoxy resin, epoxy equivalent 181 g / equivalent, shear viscosity at 25 ° C. 10 Pa · s)

<Curing agent>
Acid anhydride curing agent: Mitsubishi Chemical Corporation product name “jER Cure YH306” (3,4-dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexene-1,2-dicarboxylic acid anhydride)
Amine-based curing agent I: “DDS” (2,4-diaminodiphenylsulfone) manufactured by Wakayama Seika Kogyo Co., Ltd.
Amine-based curing agent II: Product name “Elastomer 250P” (polytetramethyleneoxybis-p-aminobenzoate) manufactured by Ihara Chemical Industry Co., Ltd.

<Curing accelerator>
Product name “Novacure TMHXA3792” (mixture of bisphenol A liquid epoxy resin and microencapsulated amine curing agent)

<Flux>
Product name "Santa Cid G" (monoalkyl vinyl ether block bifunctional carboxylic acid)

[Examples 1-7, Comparative Examples 1-3]
The compounding ingredients shown in Table 1 were mixed at 60 to 80 ° C. with a rotation and revolution mixer as the compounding weight ratio shown in Table 1 to prepare a resin composition.
The prepared resin composition was applied on a release film placed on a glass substrate, and a release film and a glass substrate were further placed on this film with a spacer interposed therebetween, and then at 150 ° C. for 2 hours. By pressing (pressure 1 MPa), a cured film of a resin composition having a thickness of 500 μm was obtained by molding and curing.
However, in the resin composition of Comparative Example 1, the same operation was attempted. However, since the viscosity of the resin composition was too high, a cured film of the resin composition having a thickness of 500 μm could not be produced.

  In the said Examples 1-7 and Comparative Examples 1-3, the following evaluation was performed and the result was shown in Table 1.

<Frequency distribution of volume particle size>
For the inorganic filler used for the preparation of each resin composition, according to the formulation in the resin composition, separately prepare a sample of only the inorganic filler, and for this sample, using the following laser diffraction scattering type particle size distribution measuring device, The frequency distribution of volume particle size was measured under the conditions, and the maximum particle size was determined. In all cases, the maximum particle size was 15 μm or less.

Device used: “Shimadzu SALD-2200” manufactured by Shimadzu Corporation
Pretreatment: Put a sample in a beaker, dilute with cyclohexanone, and then disperse with an ultrasonic disperser for 2 minutes to obtain a sample solution.
Number of measurements: 2 times Particle permeability: transmission Particle refractive index: 1.60
Solvent: Cyclohexanone Solvent refractive index: 1.85

  In Examples 1 to 7 and Comparative Examples 1 to 3, the frequency distribution frequency distribution measurement results of the inorganic filler used are shown in FIGS.

<Shear viscosity>
Using Anton Paar's viscosity measuring device “MCR-301”, put 1.45 g of each resin composition sample in a disposable aluminum dish with a diameter of 50 mm, and determine the shear viscosity at 25 ° C. and 50 ° C. under the following conditions. I asked for each.
Plate: 50mm diameter aluminum parallel plate Gap: 0.50mm
Shear rate: 0.1 s ⁻¹ , 1 s ⁻¹ or 10 s ⁻¹
Moreover, the value calculated by the following formula | equation from the measured value of the obtained shear viscosity was calculated | required as an evaluation value of thixotropy.
The larger the ratio of the shear viscosity at this low shear rate to the shear viscosity at the high shear rate, the better the thixotropic property, and the above (1) high fluidity and (2) low fluidity or non-fluidity. It can be evaluated that it has the following flow characteristics.
Thixotropic = (1 s ⁻¹ shear viscosity) / (10 s ⁻¹ shear viscosity)

<Thermal conductivity>
About the cured film of each resin composition, the thermal diffusivity, specific gravity, and specific heat were measured using the following apparatuses, and the thermal conductivity was obtained by multiplying these three measured values.
1) Thermal diffusivity: Eye Phase Co., Ltd. “Eye Phase Mobile 1u”
2) Specific gravity: METTLER TOLEDO "balance" XS-204 "(using solid specific gravity measurement kit)
3) Specific heat: Seiko Instruments Inc. “DSC320 / 6200”
The thermal conductivity is preferably a higher value, but it can be evaluated as a suitable thermal conductivity if it is 1.0 W / (m · K) or more.

  From Table 1, in the frequency distribution of the volume particle size, if the inorganic filler has a maximum value in the range of the particle size of 0.01 μm or more and less than 3.0 μm and the range of 3.0 μm or more and less than 10.0 μm, the thixotropic property is obtained. It can be seen that the flow characteristics required for the interlayer filler composition of the stacked semiconductor device are sufficiently satisfied.

1 Solder bump 2 Semiconductor substrate (semiconductor chip)
3 Interlayer Filler Composition 5 Interlayer Filler Composition Layer 6 Electrode Pad 7 Semiconductor Substrate 8 Curing Adhesive Layer 10 Semiconductor Device

Claims (5)

  A resin composition containing an inorganic filler and an epoxy resin, wherein the frequency distribution of the volume-based particle size of the inorganic filler measured with a laser diffraction / scattering particle size distribution analyzer is at least 0.01 μm or more. A resin composition having a maximum value within a range of less than 3.0 μm and a particle size of 3.0 μm or more and less than 10.0 μm and a maximum particle size of less than 45 μm.   The resin composition according to claim 1, wherein the inorganic filler has a thermal conductivity of 2 W / (m · K) or more.   Furthermore, the resin composition of Claim 1 or Claim 2 containing a flux.   Furthermore, the resin composition of any one of Claims 1-3 containing a mold release agent.   The semiconductor device which has a layer which consists of a resin composition of any one of Claim 1 to 4 as a layer adjacent to a semiconductor substrate between several semiconductor substrates.

Images