Method for producing thermosetting resin composition and device for manufacturing electronic component device

Abstract

To provide a method for producing a thermosetting resin composition capable of efficiently volatilizing a solvent from a mixture in a kneader and producing a thermosetting resin composition from which the solvent has been removed and suppressing the generation of a metal foreign matter by metal touch.SOLUTION: There is provided a method for producing a thermosetting resin composition which comprises; feeding a powder component into a kneader in a state where the outlet of the kneader is not covered to form a material seal; after forming a material seal, depressurizing the inside of the kneader at the upstream from an area where the material seal is formed; and after depressurizing the inside of the kneader, feeding a mixture containing a thermosetting resin, an inorganic filler and a solvent into the depressurized area in the kneader, kneading the mixture and discharging a mixture in which at least part of the solvent is volatilized from the outlet of the kneader through the material seal.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a thermosetting resin composition and an apparatus for producing an electronic component device. [Background technology]

[0002] In recent years, semiconductor elements have become increasingly densely packed. Accordingly, surface-mounted packages have become the mainstream for resin-encapsulated semiconductor devices, replacing conventional pin-insertion packages. Surface-mounted ICs (Intergrated Circuits), LSIs (Large Scale Integration), and other devices are being packaged in thin, compact packages to increase packaging density and reduce mounting height. As a result, the area occupied by the elements in the package has increased, and the thickness of the package has become extremely thin.

[0003] Surface-mount packages differ from conventional pin-insertion packages in their mounting method. Pin-insertion packages are soldered from the backside of the wiring board after the pins are inserted into the board, preventing the package from being directly exposed to high temperatures. On the other hand, surface-mount packages are temporarily attached to the surface of the wiring board and then processed using a solder bath or reflow device, so they are directly exposed to soldering temperatures (reflow temperatures). As a result, if the IC package has absorbed moisture, the absorbed moisture evaporates during reflow, and the resulting vapor pressure acts as peel stress, causing peeling between the insert (such as the chip or lead frame) and the encapsulant, resulting in package cracks and poor electrical characteristics. Therefore, there is a need for an encapsulating material with excellent solder heat resistance (reflow resistance).

[0004] As sealing materials with excellent reflow resistance, thermosetting resins such as biphenyl-type epoxy resins and sulfur atom-containing epoxy resins are preferably used (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-007147 [Patent Document 2] International Publication No. 2018 / 181813 Summary of the Invention [Problem to be solved by the invention]

[0006] As semiconductors become smaller, the gaps between chips become narrower, and as a result, the application of top-cut inorganic fillers with specific particle sizes that can ensure insulation and accommodate narrow gaps in the field of sealing materials is being considered.

[0007] When using small particle size fillers, it is necessary to use a mixture of powder containing thermosetting resin and inorganic filler in a solvent such as methyl isobutyl ketone (MIBK).In addition, in sealing materials, the solvent must be removed by volatilization, and a method for efficiently volatilizing the solvent is required.

[0008] Furthermore, there is a risk of metal contamination occurring due to bending caused by the weight of the mixer screw, vibration during rotation, etc. Therefore, a mixing method that reduces the risk of metal contamination occurring due to metal contamination is required.

[0009] In view of the above circumstances, the present disclosure aims to provide a method for producing a thermosetting resin composition that can efficiently volatilize a solvent from a mixture in a kneading machine, thereby producing a thermosetting resin composition from which the solvent has been removed, and that can suppress the generation of metal foreign matter due to metal touch, and a method for producing an electronic component device that includes this production method. [Means for solving the problem]

[0010] Means for solving the above problems include the following aspects. <1> forming a material seal by supplying powder components into the mixer without covering the outlet of the mixer; After forming the material seal, reducing the pressure inside the mixer upstream of the region where the material seal is formed; After reducing the pressure inside the kneader, supplying a mixture containing a thermosetting resin, an inorganic filler, and a solvent to a region of the kneader where the pressure has been reduced, kneading the mixture, and discharging the mixture from which at least a portion of the solvent has volatilized through the material seal from an outlet of the kneader; A method for producing a thermosetting resin composition comprising: <2> the temperature at which the mixture is kneaded is higher than the melting point or softening point of the thermosetting resin; <1> A method for producing the thermosetting resin composition according to claim 1. <3> The thermosetting resin includes an epoxy resin. <1> or <2> A method for producing the thermosetting resin composition according to claim 1. <4> The melting point or softening point of the thermosetting resin is 60°C or higher. <1> ~ <3> 10. A method for producing the thermosetting resin composition according to claim 9. <5> The mixture is kneaded using a twin-screw kneader. <1> ~ <4> 10. A method for producing the thermosetting resin composition according to claim 9. <6> The degree of pressure reduction inside the kneader after the material seal is formed is 50 kPa or less. <1> ~ <5> 10. A method for producing the thermosetting resin composition according to claim 9. <7> The amount of the mixture fed into the kneader is 1 kg / h to 100 kg / h. <1> ~ <6> 10. A method for producing the thermosetting resin composition according to claim 9. <8> The top cut diameter of the inorganic filler is 75 μm or less. <1> ~ <7> 10. A method for producing the thermosetting resin composition according to claim 9. <9> <1> ~ <8> producing a thermosetting resin composition by the method for producing a thermosetting resin composition according to any one of the above items; encapsulating an element using the thermosetting resin composition; A method for manufacturing an electronic component device, comprising: [Effects of the Invention]

[0011] According to the present disclosure, there is provided a method for producing a thermosetting resin composition that can efficiently volatilize the solvent from the mixture in a kneader, thereby producing a thermosetting resin composition from which the solvent has been removed, and that can suppress the generation of metal foreign matter due to metal touch, and a method for producing an electronic component device that includes this production method. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a schematic cross-sectional view showing the use of a mixture to form a material seal in accordance with one embodiment of the manufacturing method of the present disclosure. [Figure 2] FIG. 2 is a schematic cross-sectional view showing the mixture being discharged from a kneading extruder in one embodiment of the manufacturing method of the present disclosure. [Figure 3] FIG. 10 is a schematic cross-sectional view showing the formation of a material seal using a mixture in Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present invention.

[0014] In the present disclosure, the term "process" includes not only a process that is independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, multiple types of particles corresponding to each component may be contained. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified. In this disclosure, solid, solid, liquid, and liquid refer to the state at 25°C. When embodiments of the present disclosure are described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Furthermore, the sizes of the components in each drawing are conceptual, and the relative size relationships between the components are not limited to these.

[0015] <Method for producing thermosetting resin composition> The method for producing a thermosetting resin composition of the present disclosure (hereinafter also referred to as the production method of the present disclosure) includes forming a material seal by supplying powder components into a kneader without placing a lid on the discharge outlet of the kneader; after forming the material seal, reducing the pressure inside the kneader upstream of the region where the material seal is formed; and after reducing the pressure inside the kneader, supplying a mixture containing a thermosetting resin, an inorganic filler, and a solvent into the reduced-pressure region inside the kneader, kneading the mixture, and discharging the mixture from which at least a portion of the solvent has volatilized through the material seal through the discharge outlet of the kneader.

[0016] In the manufacturing method disclosed herein, a material seal is formed by supplying powder components into a kneader without covering the outlet through which the kneaded thermosetting resin composition is discharged. Next, after forming the material seal, the pressure inside the kneader is reduced upstream of the region where the material seal was formed. Next, a mixture containing a thermosetting resin, an inorganic filler, and a solvent is supplied to the reduced-pressure region inside the kneader, and the mixture is kneaded. By kneading the mixture upstream of the region where the material seal was formed, such as the region where the material seal was formed, at least a portion of the solvent in the mixture volatilizes. At this time, because the material seal is formed between the region where the mixture is kneaded and the outlet, air is prevented from being supplied to the region where the mixture is kneaded through the outlet. This effectively reduces the pressure in the region where the mixture is kneaded, accelerating the volatilization of the solvent. The mixture from which the solvent has volatilized is then discharged through the material seal and the outlet of the kneader. This results in a thermosetting resin composition from which the solvent has been removed.

[0017] In the manufacturing method disclosed herein, a material seal is formed using powder components, so unlike when a material seal is formed using a mixture containing a solvent, there is no need to remove the solvent, and it is possible to form a material seal at normal pressure in a short time.

[0018] Furthermore, by forming the material seal using a powder component, it is possible to prevent metallic foreign matter from being included in the thermosetting resin composition discharged from the discharge port of the kneader. By using a powder component, the material seal is formed in a short time, and the inside of the kneader downstream of the material seal and between the material seal and the discharge port is filled with the powder component. This is thought to be because it prevents metal touch caused by bending due to the weight of the kneader screw (especially the screw near the discharge port) and vibration during rotation, thereby preventing the generation of metallic foreign matter.

[0019] The manufacturing method of the present disclosure includes supplying a powder component into a kneader with the discharge port of the kneader uncapped. The powder component is used to form a material seal within the kneader. The powder component may be any material capable of forming a material seal within the kneader, such as a mixture containing a resin component, an inorganic filler, etc., or a mixture containing a thermosetting resin, an inorganic filler, etc. The powder component may be a component obtained by removing the solvent from a mixture containing a thermosetting resin, an inorganic filler, and a solvent, as described below.

[0020] In this disclosure, a material seal refers to a region formed near the mixing section of the screw shaft in a kneader where powder, molten resin, etc. are consolidated. By forming the material seal, it is possible to volatilize and remove solvent contained in the mixture upstream of the material seal in the kneader.

[0021] When powder components are supplied into the kneader to form the material seal, the pressure inside the kneader may be atmospheric pressure or reduced pressure. In the manufacturing method disclosed herein, powder components are used to form the material seal, so the material seal can be efficiently formed even at atmospheric pressure.

[0022] The manufacturing method of the present disclosure includes reducing the pressure inside the mixer upstream of the region where the material seal is formed after the material seal is formed, and the reduced pressure inside the mixer after the material seal is formed may be 50 kPa or less, or may be 20 kPa or less. The degree of reduced pressure inside the kneader after the material seal is formed may be 0.001 MPa to 0.08 MPa, 0.003 MPa to 0.06 MPa, or 0.005 MPa to 0.05 MPa.

[0023] The manufacturing method of the present disclosure includes reducing the pressure inside a kneader, supplying a mixture containing a thermosetting resin, an inorganic filler, and a solvent to a reduced-pressure region inside the kneader, kneading the mixture, and discharging the mixture from which at least a portion of the solvent has evaporated through the material seal from an outlet of the kneader. Discharging the mixture from which at least a portion of the solvent has evaporated from the outlet of the kneader provides a thermosetting resin composition from which the solvent has been removed.

[0024] After reducing the pressure inside the kneader, a mixture having a different composition from the powder components is fed into the reduced pressure region of the kneader. At this time, the mixture may be fed through the same feed port as the powder components fed into the kneader, or through a separate feed port.

[0025] The mixture may or may not contain components other than the thermosetting resin, inorganic filler, and solvent. Examples of the other components include a curing accelerator, a coupling agent, and the additives described below. The other components may be supplied to the kneader in the form of a mixture containing the thermosetting resin, inorganic filler, and solvent, or may be supplied separately from the mixture.

[0026] The mixture is obtained by mixing a slurry containing a thermosetting resin, an inorganic filler, and a solvent with other components used as needed using a mixer such as a stirrer or a planetary mixer, or a wet disperser such as an ultrasonic disperser or a jet mill. The mixing conditions for preparing the mixture are appropriately set depending on the types of components contained in the mixture, the ratio of the components, etc.

[0027] The method for kneading the mixture supplied into the kneader is not particularly limited. For example, it can be melt-kneaded using a kneader (twin-screw kneader, triple-screw kneader, etc.), roll (three-roll, etc.), extruder, etc. that has been preheated to a desired temperature. Among these, it is preferable to knead the mixture using a twin-screw kneader. Furthermore, when kneading the mixture, it is sufficient to knead it in the region in the kneader where the material seal is formed, and it may also be kneaded both upstream and downstream thereof.

[0028] From the viewpoint of suitably volatilizing the solvent in the mixture, the mixture may be kneaded while reducing the pressure inside the kneader, or while reducing the pressure inside the kneader and heating the kneader. The degree of reduction in pressure inside the kneader is preferably 0.001 MPa to 0.08 MPa, more preferably 0.003 MPa to 0.06 MPa, and even more preferably 0.005 MPa to 0.05 MPa. The degree of pressure reduction when reducing the pressure inside the kneader may be 50 kPa or less, or 20 kPa or less.

[0029] The maximum amount of the mixture fed into the kneader can be adjusted depending on the size of the kneader, and may be, for example, 1 kg / h to 100 kg / h, 1 kg / h to 30 kg / h, or 30 kg / h to 100 kg / h.

[0030] The temperature at which the mixture is kneaded (also referred to as the kneading temperature) is preferably adjusted according to the melting temperature of the resin components, such as the thermosetting resin, used. The kneading temperature is preferably higher than the melting point or softening point of the thermosetting resin (when multiple types of thermosetting resins are used in combination, the thermosetting resin with the highest melting point or softening point). For example, the kneading temperature is preferably 1°C to 90°C higher than the melting point or softening point of the thermosetting resin (when multiple types of thermosetting resins are used in combination, the thermosetting resin with the highest melting point or softening point), more preferably 1°C to 70°C higher, and even more preferably 1°C to 50°C higher. Kneading at such a temperature allows the thermosetting resin to melt and maintain its fluidity, thereby enabling good stirring and mixing.

[0031] In the present disclosure, the term "kneading temperature (similar to the temperature of the primary kneading and the temperature of the secondary kneading described below)" refers to the temperature of the heating section of the kneading device when the mixture is kneaded by the kneading device.

[0032] In one embodiment, the kneading temperature may be 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, or 120°C or higher. From the viewpoint of more efficiently suppressing an increase in viscosity, the kneading temperature may be 200°C or lower. From this viewpoint, the kneading temperature may be 70°C to 200°C, 80°C to 200°C, 90°C to 200°C, 100°C to 200°C, 110°C to 200°C, or 120°C to 200°C. Primary kneading refers to kneading in the area where the material seal is formed or kneading upstream of that area.

[0033] After the mixture fed into the kneader is kneaded (also called primary kneading), a curing accelerator may be added to the kneaded mixture and further kneaded (also called secondary kneading). Generally, when a resin material and an inorganic filler are mixed and kneaded, shear heat occurs, but by kneading all or part of the curing accelerator in the secondary kneading, the effect of thickening due to shear heat can be reduced, and kneading tends to be performed well.

[0034] When a part of the curing accelerator is mixed in the primary kneading, the amount mixed is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, of the total curing accelerator finally added. Preferably, in the primary kneading, the thermosetting resin, inorganic filler, solvent, etc. are kneaded without adding the curing accelerator.

[0035] The temperature of the primary kneading may be higher than the onset temperature of the mixture after adding the curing accelerator during the secondary kneading, as measured by differential scanning calorimetry (DSC). In the present disclosure, the onset temperature refers to the temperature corresponding to the intersection of the tangent to the point at which the derivative of the exothermic peak in the DSC chart is maximized and the baseline of the exothermic peak in the DSC chart. If there are multiple points at which the derivative of the exothermic peak is maximized, the point with the lowest temperature among the multiple points is used.

[0036] By sequentially performing the primary kneading and the secondary kneading with the addition of the curing accelerator, the temperature of the primary kneading can be set to a relatively high temperature regardless of the onset temperature of the mixture after the addition of the curing accelerator. This allows, for example, the thermosetting resin to be sufficiently melted before the primary kneading, thereby improving the dispersibility of the resin. The manufacturing method of the present disclosure is particularly useful when the melting point or softening point of the thermosetting resin is higher than the onset temperature of the mixture after the addition of the curing accelerator.

[0037] The method for adding the curing accelerator in the secondary kneading is not particularly limited as long as it is a method that allows the curing accelerator to be added later. For example, there is a method (side feed) in which the curing accelerator is added to the mixture that has been subjected to the primary kneading through an inlet provided separately from the inlet for the components of the primary kneading.

[0038] The temperature of the secondary kneading is not particularly limited, and may be lower than the temperature of the primary kneading from the viewpoint of suppressing thickening. The temperature of the secondary kneading is preferably lower than the onset temperature of the mixture after adding the curing accelerator in the secondary kneading, as measured by differential scanning calorimetry (DSC), and is preferably, for example, 1°C to 100°C lower.

[0039] In the manufacturing method of the present disclosure, a thermosetting resin composition is obtained by discharging a mixture from which at least a portion of the solvent has evaporated through an outlet of a kneader. The kneaded thermosetting resin composition may be cooled and pulverized to obtain a powdered thermosetting resin composition. The kneaded thermosetting resin composition may also be molded into particles, tablets, pellets, or granules (e.g., cylindrical granules). The method for pulverizing or molding the thermosetting resin composition is not particularly limited, and conventionally known methods may be used.

[0040] In one embodiment, in the production method of the present disclosure, a thermosetting resin composition is produced using a kneading extruder such as that shown in FIG.

[0041] In one embodiment, the primary and secondary kneading in the manufacturing method of the present disclosure can be performed using a kneading extruder. A schematic cross-sectional view of a kneading extruder in one embodiment is shown in FIG. 1. The kneading extruder 10 includes a first feed section 1A, a second feed section 1B located downstream of the first feed section 1A in the extrusion direction, a material seal section (which also serves as a kneading section) 2 located between the first feed section 1A and the second feed section 1B, and an outlet 3 located downstream of the second feed section 1B in the extrusion direction and from which the kneaded mixture is discharged. The kneading extruder 10 includes a first inlet connected to the first feed section 1A and through which powder components are introduced into the kneading extruder 10 as indicated by arrow X1, a second inlet connected to the first feed section 1A and through which the mixture is introduced into the kneading extruder 10 as indicated by arrow X2, a side feeder 5 connected to the second feed section B, and a motor 6 for rotating the screw. The first inlet through which the powder components are introduced into the kneading extruder 10 also serves as a pressure reducing port through which the pressure inside the kneading extruder 10 is reduced, as indicated by an arrow Y in FIG.

[0042] In FIG. 1, with the discharge port 3 of the kneading extruder 10 uncapped, powder components are introduced into the first feed section 1A through the first inlet as indicated by arrow X1, and a material seal is formed in the material seal section 2. At this time, the interior of the kneading extruder 10 is at normal pressure. After the material seal is formed, the interior of the kneading extruder 10 is depressurized as indicated by arrow Y in FIG. 2, and the mixture is introduced into the first feed section 1A through the second inlet as indicated by arrow X2. The mixture introduced into the first feed section 1A is subjected to primary kneading, and the kneaded mixture is extruded and transferred to the second feed section 1B through the material seal, where it is subjected to secondary kneading. At this time, a curing accelerator is introduced into the second feed section B through a side feeder 5. The transferred mixture is combined with the curing accelerator and further kneaded. The temperatures of the primary kneading and the secondary kneading can be set independently. For example, a cooling section (not shown) may be provided between the first feed section A and the second feed section B, and the secondary kneading may be performed at a lower temperature than the primary kneading. Alternatively, the first feed section A may be set to a higher temperature and the second feed section B may be set to a lower temperature, or a mechanism may be employed in the second feed section B to gradually cool the contents in the extrusion direction.

[0043] In Figure 2, the kneaded mixture is discharged from the discharge port 3 as indicated by the arrow Z. At this time, the mixture is kneaded under reduced pressure inside the kneading extruder 10, so that the mixture from which at least a portion of the solvent has been removed is discharged from the discharge port 3, thereby obtaining a thermosetting resin composition. Note that the manufacturing method of the present disclosure is not limited to the embodiments in the drawings.

[0044] The components used in the manufacturing method of the present disclosure are described below. Examples of the components used in the manufacturing method of the present disclosure include a thermosetting resin, an inorganic filler, and a solvent. Other components that may be used in the manufacturing method of the present disclosure include a curing accelerator, a coupling agent, and additives described below.

[0045] <Thermosetting resin> The type of thermosetting resin is not particularly limited, and examples include epoxy resins, phenolic resins, urea resins, melamine resins, urethane resins, silicone resins, and unsaturated polyester resins. In the present disclosure, "thermosetting resins" include those that exhibit both thermoplastic and thermosetting properties, such as acrylic resins containing epoxy groups. Thermosetting resins may be solid or liquid at room temperature and normal pressure (e.g., 25°C and atmospheric pressure), and are preferably solid. Thermosetting resins may be used alone or in combination of two or more.

[0046] The thermosetting resin preferably includes an epoxy resin. Specific examples of epoxy resins include novolac epoxy resins (phenol novolac epoxy resins, orthocresol novolac epoxy resins, etc.) obtained by epoxidizing novolac resins obtained by condensing or co-condensing, under an acid catalyst, at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, etc., and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc., with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc.; triphenylmethane epoxy resins obtained by epoxidizing triphenylmethane phenolic resins obtained by condensing or co-condensing, under an acid catalyst, the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc.; and novolac resins obtained by co-condensing, under an acid catalyst, the above-mentioned phenolic compound and naphthol compound with an aldehyde compound. Copolymerized epoxy resins obtained by epoxidizing a fatty acid; diphenylmethane-type epoxy resins, which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl-type epoxy resins, which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins, which are diglycidyl ethers of stilbene-based phenolic compounds; sulfur-containing epoxy resins, which are diglycidyl ethers of bisphenol S, etc.; epoxy resins, which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins, which are glycidyl esters of polycarboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine-type epoxy resins, in which the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is substituted with a glycidyl group; and dicyclopentadiene-type epoxy resins, which are epoxidized co-condensation resins of dicyclopentadiene and phenolic compounds.Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, which are produced by epoxidizing the olefin bonds in the molecule; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenolic resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenolic resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenolic resins; and dicyclopentadiene-modified phenolic resins, which are glycidyl ethers of dicyclopentadiene-modified phenolic resins. Examples of suitable epoxy resins include pentadiene-modified epoxy resins, cyclopentadiene-modified epoxy resins which are glycidyl ethers of cyclopentadiene-modified phenolic resins, polycyclic aromatic ring-modified epoxy resins which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins, naphthalene-type epoxy resins which are glycidyl ethers of naphthalene ring-containing phenolic resins, halogenated phenol novolac-type epoxy resins, hydroquinone-type epoxy resins, trimethylolpropane-type epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid, and aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins. Further examples of suitable epoxy resins include epoxidized silicone resins and epoxidized acrylic resins. These epoxy resins may be used alone or in combination of two or more.

[0047] Among the above epoxy resins, biphenyl-type epoxy resins have a low melt viscosity, making them less likely to cause wire sweep problems within semiconductor packages, even when heavily loaded with inorganic fillers to improve reflow resistance. For this reason, biphenyl-type epoxy resins have become popular as encapsulating materials for surface-mount packages in recent years. Although biphenyl-type epoxy resins have a low melt viscosity around 180°C, they have a relatively high softening point. Therefore, kneading at high temperatures is desirable to thoroughly disperse the resin during kneading. According to the manufacturing method disclosed herein, even when a thermosetting resin contains a biphenyl-type epoxy resin, the thermosetting resin can be kneaded effectively while suppressing an increase in viscosity.

[0048] The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferred. Among the epoxy resins represented by the following general formula (II), R 8 When the oxygen atom is substituted at the 4 and 4' positions, the 3, 3', 5, and 5' positions are methyl groups, and the other R 8 YX-4000 and YX-4000H (Mitsubishi Chemical Corporation, product names) are hydrogen atoms, and all R 8 4,4'-bis(2,3-epoxypropoxy)biphenyl, where R is a hydrogen atom, 8 When is a hydrogen atom and R 8 When the oxygen atom is substituted at the 4 and 4' positions, the 3, 3', 5, and 5' positions are methyl groups, and the other R 8 is a hydrogen atom, YL-6121H (trade name, Mitsubishi Chemical Corporation) and the like are commercially available.

[0049] [ka]

[0050] In formula (II), R 8represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms, and may all be the same or different. n is an average value and represents a number of 0 to 10.

[0051] Further, as a further method for improving reflow resistance, there is a method for improving adhesion to a metal member and a substrate. To improve adhesion, a sulfur atom-containing epoxy resin is preferably used. Although sulfur atom-containing epoxy resins include those with very high melting points, according to the manufacturing method of the present disclosure, even when the thermosetting resin contains a sulfur atom-containing epoxy resin, the thermosetting resin can be suitably kneaded while suppressing an increase in viscosity.

[0052] The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, an epoxy resin represented by the following general formula (V) can be mentioned. Among the epoxy resins represented by the following general formula (V), R 13 When the oxygen atom is substituted at the 4 and 4' positions, the 3 and 3' positions are t-butyl groups, and the 6 and 6' positions are methyl groups. 13 YSLV-120TE (Nippon Steel Chemical & Material Co., Ltd., product name) in which is a hydrogen atom is commercially available.

[0053] [ka]

[0054] In formula (V), R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different from each other. n is an average value and represents a number of 0 to 10.

[0055] The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq. The epoxy equivalent of the epoxy resin is a value measured by a method in accordance with JIS K 7236:2009.

[0056] When the epoxy resin is solid at 25°C, the melting point or softening point of the epoxy resin is not particularly limited. From the viewpoint of blocking resistance, the melting point or softening point of the epoxy resin is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher. From the viewpoint of suppressing thickening due to kneading, the melting point or softening point of the epoxy resin is preferably 150°C or lower, more preferably 140°C or lower, and even more preferably 130°C or lower. In particular, even when an epoxy resin having a melting point or softening point of 90°C or higher, 100°C or higher, 110°C or higher, or 120°C or higher (for example, a highly crystalline resin having a melting point of 90°C or higher, 100°C or higher, 110°C or higher, or 120°C or higher) is used for the purpose of satisfying recent requirements such as high thermal conductivity and reflow resistance, the production method of the present disclosure can be suitably used. The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) in accordance with JIS K 7234:1986.

[0057] When the thermosetting resin composition contains an epoxy resin, the content of the epoxy resin is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass to 30% by mass, and even more preferably 2% by mass to 20% by mass, relative to the total mass of the thermosetting resin composition, from the viewpoints of strength, fluidity, heat resistance, moldability, etc.

[0058] The thermosetting resin composition may further contain a curing agent. The type of the curing agent is not particularly limited as long as it is a compound that undergoes a curing reaction with the thermosetting resin used in combination. The curing agent itself may be a thermosetting resin.

[0059] For example, curing agents used in combination with epoxy resins include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. One type of curing agent may be used alone, or two or more types may be used in combination. From the viewpoint of improving heat resistance, a phenol curing agent is preferred as the curing agent. The curing agent may be solid or liquid at room temperature and normal pressure (e.g., 25°C, atmospheric pressure), and is preferably solid.

[0060] The phenolic curing agent is a compound having a phenolic hydroxyl group in the molecule (hereinafter also referred to as a phenolic resin). Specific examples of the phenolic resin include polyhydric phenolic compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; novolak-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with an aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde, under an acidic catalyst; and copolymers of the above phenolic compounds with dimethoxyparaxylene, bis(methoxymethyl)bis(benzoyl)methylbenzoyl ... Examples of suitable phenolic resins include aralkyl phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenyl or the like; paraxylylene and / or metaxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above phenolic compounds with dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compounds with aromatic aldehyde compounds such as benzaldehyde or salicylaldehyde under an acidic catalyst; and phenolic resins obtained by copolymerization of two or more of these. The phenolic resins may be used singly or in combination of two or more.

[0061] The hydroxyl equivalent of the phenolic resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, the hydroxyl equivalent of the phenolic resin is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0062] The hydroxyl equivalent weight of the phenolic resin refers to a value calculated based on the hydroxyl value measured in accordance with JIS K0070:1992.

[0063] When the phenolic resin is solid, its softening point or melting point is not particularly limited. The softening point or melting point of the phenolic resin is preferably 40°C to 180°C from the viewpoint of moldability and reflow resistance when the thermosetting resin composition is used as an encapsulant, and more preferably 50°C to 130°C from the viewpoint of handleability during production of the thermosetting resin composition.

[0064] The melting point or softening point of the phenolic resin is a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0065] When the thermosetting resin composition contains a phenolic resin, the content of the phenolic resin is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass to 30% by mass, and even more preferably 2% by mass to 20% by mass, relative to the total mass of the thermosetting resin composition.

[0066] The equivalent ratio of the epoxy resin to the curing agent, i.e., the ratio of the number of functional groups in the curing agent to the number of epoxy groups in the epoxy resin (number of functional groups in the curing agent / number of epoxy groups in the epoxy resin), is not particularly limited. From the perspective of minimizing the amount of unreacted components, the equivalent ratio of the epoxy resin to the curing agent (number of functional groups in the curing agent / number of epoxy groups in the epoxy resin) is preferably set in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability when using the thermosetting resin composition as an encapsulant, it is even more preferable that the equivalent ratio of the epoxy resin to the curing agent (number of functional groups in the curing agent / number of epoxy groups in the epoxy resin) be set in the range of 0.8 to 1.2. The number of functional groups of the curing agent refers to, for example, the number of hydroxyl groups in the phenolic curing agent when a phenolic curing agent is used as the curing agent, and refers to the number of active hydrogens in the amine curing agent when an amine curing agent is used as the curing agent.

[0067] <Inorganic filler> The inorganic filler is used in the production of the thermosetting resin composition. The material of the inorganic filler is not particularly limited. Specific examples of inorganic filler materials include fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, magnesium oxide, silicon carbide, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, and mica. Inorganic fillers having flame retardant properties may also be used. Examples of inorganic fillers having flame retardant properties include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium-zinc composite hydroxide, and zinc borate. Among inorganic fillers, silica such as fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity.

[0068] The shape of the inorganic filler is not particularly limited, but from the viewpoints of filling properties and mold wear, a spherical shape is preferred.

[0069] The inorganic filler may be used alone or in combination of two or more. The term "use of two or more inorganic fillers" refers to, for example, the use of two or more inorganic fillers having the same components but different average particle sizes, the use of two or more inorganic fillers having the same average particle size but different components, and the use of two or more inorganic fillers having different average particle sizes and types.

[0070] The content of the inorganic filler is not particularly limited. From the viewpoint of further improving the properties of the cured product, such as the thermal expansion coefficient, thermal conductivity, and elastic modulus, the content of the inorganic filler is preferably 30% by volume or more of the entire thermosetting resin composition, more preferably 40% by volume or more, even more preferably 50% by volume or more, particularly preferably 60% by volume or more, and extremely preferably 70% by volume or more. From the viewpoint of improving fluidity, reducing viscosity, etc., the content of the inorganic filler is preferably 99% by volume or less of the entire thermosetting resin composition, preferably 98% by volume or less, and more preferably 97% by volume or less. Furthermore, for example, when the thermosetting resin composition is used for compression molding, the content of the inorganic filler may be 70 to 99 volume % of the entire thermosetting resin composition, 80 to 99 volume %, 83 to 99 volume %, or 85 to 99 volume %.

[0071] The content of inorganic filler in a cured product of a thermosetting resin composition can be measured as follows. First, the total mass of the cured product is measured, and the cured product is baked at 400°C for 2 hours and then at 700°C for 3 hours to evaporate the resin component, and the mass of the remaining inorganic filler is measured. The volume is calculated from the obtained masses and their respective specific gravities, and the ratio of the volume of the inorganic filler to the total volume of the cured product is determined as the inorganic filler content.

[0072] The top cut diameter of the inorganic filler is not particularly limited, and is preferably 75 μm or less, for example. From the viewpoint of filling narrow gaps of 30 μm or less, the top cut diameter of the inorganic filler is preferably 10 μm or less, more preferably 7 μm or less, even more preferably 6 μm or less, and particularly preferably 5 μm or less. From the viewpoint of suppressing an increase in viscosity of the thermosetting resin composition, the top cut diameter of the inorganic filler may be 1 μm or more. In the present disclosure, the top cut diameter of an inorganic filler refers to the particle size value (D90) at which the volume cumulative distribution curve is 90% by volume when plotted from the small diameter side using a laser diffraction scattering particle size distribution measuring device.

[0073] The average particle size of the inorganic filler is not particularly limited. For example, the volume average particle size is preferably 50 μm or less, more preferably 10 μm or less, even more preferably 0.1 μm to 10 μm, particularly preferably 0.1 μm to 8 μm, and extremely preferably 0.2 μm to 5 μm. When the volume average particle size is 10 μm or less, the ability to fill narrow gaps tends to be improved. Furthermore, when the volume average particle size is 0.1 μm or more, the increase in viscosity of the thermosetting resin composition tends to be further suppressed. The volume average particle size of the inorganic filler can be measured as the volume average particle size (D50) using a laser diffraction scattering particle size distribution measuring device.

[0074] <Solvent> In the manufacturing method of the present disclosure, a solvent is used in manufacturing the thermosetting resin composition. The type of solvent is not particularly limited, and is appropriately selected from those that can be easily removed from the mixture. The solvent may or may not dissolve the thermosetting resin, the curing agent, etc.

[0075] The boiling point of the solvent at normal pressure is preferably 50°C to 200°C, more preferably 60°C to 180°C, even more preferably 70°C to 160°C, particularly preferably 70°C to 140°C, and extremely preferably 70°C to 130°C, since this allows the solvent to be easily removed from the mixture.

[0076] Specific examples of the solvent include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone (CHN), etc. Among these, MIBK, CHN, or MEK is preferred. The solvent may be used alone or in combination of two or more.

[0077] <Curing accelerator> A cure accelerator may be used in the preparation of the thermosetting resin composition. The type of curing accelerator is not particularly limited, and examples thereof include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; and combinations of these compounds with maleic anhydride, quinone compounds such as 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone. compounds having intramolecular polarization obtained by adding a compound having a π bond, such as diazophenylmethane; cyclic amidinium compounds such as the tetraphenylborate salt of DBU, the tetraphenylborate salt of DBN, the tetraphenylborate salt of 2-ethyl-4-methylimidazole, and the tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the above tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide;organic phosphines such as primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; and tertiary phosphines such as triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, and tris(benzyl)phosphine; phosphine compounds such as complexes of the above organic phosphines with organoborons; and complexes of the above organic phosphines or the above phosphine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, compounds having intramolecular polarization obtained by adding a compound having a π bond, such as quinone compounds, such as 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and anthraquinone, or diazophenylmethane; compounds having intramolecular polarization obtained by adding the above organic phosphines or the above phosphine compounds with 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, and 4-iodophenol; compounds with intramolecular polarization obtained by reacting halogenated phenol compounds such as phenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, and 4-bromo-4'-hydroxybiphenyl, followed by a dehydrohalogenation step;Examples of the curing accelerator include tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetraphenylborate salts of tetra-substituted phosphonium such as tetraphenylphosphonium tetra-p-tolylborate, and salts of tetra-substituted phosphonium with phenolic compounds; phosphobetaine compounds; and adducts of phosphonium compounds with silane compounds. One type of curing accelerator may be used alone, or two or more types may be used in combination.

[0078] For example, when an epoxy resin is used as the thermosetting resin, examples of particularly suitable curing accelerators include triphenylphosphine and an adduct of triphenylphosphine and a quinone compound.

[0079] The content of the curing accelerator is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component (i.e., thermosetting resin (including the curing agent if the curing agent is a thermosetting resin)). When the amount of the curing accelerator is 0.1 part by mass or more per 100 parts by mass of the resin component, good curing tends to occur in a short time. When the amount of the curing accelerator is 30 parts by mass or less per 100 parts by mass of the resin component, the curing speed is not too fast, and good molded products tend to be obtained.

[0080] <Coupling agent> Coupling agents may be used in the preparation of thermosetting resin compositions. A coupling agent may be used to enhance adhesion between the resin component and the inorganic filler, including known coupling agents such as silane compounds, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds.

[0081] Examples of silane compounds include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, and methacryloxyoctyltrimethoxysilane.

[0082] Examples of titanium compounds include isopropyl triisostearoyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) 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, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecyl benzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

[0083] When the thermosetting resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 15 parts by mass, based on 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more based on 100 parts by mass of the inorganic filler, the adhesion to the metal member tends to be further improved. When the amount of the coupling agent is 20 parts by mass or less based on 100 parts by mass of the inorganic filler, the moldability tends to be improved.

[0084] <Additive> Additives other than the above-described components may be used in the production of the thermosetting resin composition. Examples of such additives include ion exchangers, mold release agents, flame retardants, colorants, stress relaxants, and the like. The thermosetting resin composition may contain various additives generally used in the art as needed, in addition to the additives exemplified below.

[0085] (Ion exchanger) An ion exchanger may be used in the production of the thermosetting resin composition. In particular, when the thermosetting resin composition is used as a molding material for encapsulation, the thermosetting resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device provided with an element to be encapsulated. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specifically, examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchanger may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.

[0086] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(A) (0<X≦0.5, m is a positive number)

[0087] When the thermosetting resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions, etc. For example, the content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the resin component.

[0088] (mold release agent) A mold release agent may be used in the production of a thermosetting resin composition. The thermosetting resin composition may contain a mold release agent from the viewpoint of obtaining good releasability from the mold during molding. There are no particular limitations on the mold release agent, and conventionally known mold release agents can be used. Specific examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. One type of mold release agent may be used alone, or two or more types may be used in combination.

[0089] When the thermosetting resin composition contains a release agent, the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin component. When the amount of the release agent is 0.01 part by mass or more per 100 parts by mass of the resin component, sufficient release properties tend to be obtained. When the amount is 10 parts by mass or less, better adhesion and curability tend to be obtained.

[0090] (Flame retardant) A flame retardant may be used in the production of a thermosetting resin composition. The thermosetting resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardants may be used alone or in combination of two or more.

[0091] When the thermosetting resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is an amount sufficient to obtain the desired flame retardant effect, and is, for example, preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, per 100 parts by mass of the resin component.

[0092] (coloring agent) A colorant may be used in the production of the thermosetting resin composition. The thermosetting resin composition may further contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide. The content of the colorant can be appropriately selected depending on the purpose, etc. The colorant may be used alone or in combination of two or more.

[0093] (stress reliever) A stress relaxation agent may be used in the production of a thermosetting resin composition. The thermosetting resin composition may contain a stress relaxation agent such as silicone oil or silicone rubber particles. By including a stress relaxation agent, warpage and cracking of the package can be reduced when the thermosetting resin composition is used as an encapsulant. Examples of the stress relaxation agent include commonly used known stress relaxation agents (flexibilizers). Specific examples include thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene elastomers; rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder; and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer. The stress relaxation agents may be used alone or in combination of two or more.

[0094] ≪Thermosetting resin composition≫ The thermosetting resin composition of the present disclosure may be obtained by the above-described production method of the present disclosure. The thermosetting resin composition may be solid or liquid at room temperature and normal pressure (for example, 25°C and atmospheric pressure), and is preferably solid. When the thermosetting resin composition is solid, its shape is not particularly limited, and examples include powder, granules, and tablets. When the thermosetting resin composition is in tablet form, it is preferable that the dimensions and mass of the tablet be set to suit the molding conditions of the package, from the viewpoint of handleability.

[0095] [Viscosity of Thermosetting Resin Composition] The viscosity of the thermosetting resin composition is not particularly limited. It is preferable to adjust the viscosity to a desired value depending on the molding method, the composition of the thermosetting resin composition, etc. When the thermosetting resin composition is used as an encapsulant, it is preferable to adjust the viscosity depending on the likelihood of wire sweep during molding. For example, when the thermosetting resin composition is used as an encapsulant, from the viewpoint of reducing wire sweep, the viscosity of the thermosetting resin composition is preferably 200 Pa·s or less at 175°C, more preferably 150 Pa·s or less, even more preferably 100 Pa·s or less, particularly preferably 70 Pa·s or less, and extremely preferably 50 Pa·s or less. The lower limit of the viscosity of the thermosetting resin composition is not particularly limited, and may be, for example, 2 Pa·s or more at 175°C. The viscosity of the thermosetting resin composition can be measured using a Koka type flow tester (for example, manufactured by Shimadzu Corporation).

[0096] [Fluidity of Thermosetting Resin Composition] The flow distance of the spiral flow determined by the following method is not particularly limited, but is preferably 70 cm or more, more preferably 80 cm or more, and even more preferably 90 cm or more. The thermosetting resin composition is molded using a spiral flow measurement mold conforming to EMMI-1-66, and the flow distance is measured. Molding is performed using a transfer molding machine under the following conditions: mold temperature 180°C, molding pressure 6.9 MPa, and curing time 90 seconds.

[0097] The disk flow distance obtained by the following test is not particularly limited, but is preferably 125 mm or more, more preferably 130 mm or more, and even more preferably 135 mm or more. Using a flat mold for measuring disk flow, which has an upper mold of 200 mm (W) × 200 mm (D) × 25 mm (H) and a lower mold of 200 mm (W) × 200 mm (D) × 15 mm (H), 5 g of a thermosetting resin composition weighed on a balance is placed in the center of the lower mold heated to 180°C. After 5 seconds, the upper mold heated to 180°C is closed, and compression molding is performed under conditions of a load of 78 N and a curing time of 90 seconds. The major axis (mm) and minor axis (mm) of the molded product are measured with vernier calipers, and the average value (mm) is taken as the disk flow.

[0098] [Heat hardness] The hot hardness measured by the following method is preferably 50 or more, more preferably 60 or more, and even more preferably 70 or more. The thermosetting resin composition is molded into a disk with a diameter of 50 mm and a thickness of 3 mm, and immediately after molding, the hot hardness is measured using a Shore D hardness tester (for example, HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.) Molding is performed using a transfer molding machine under conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds.

[0099] [Gel time] From the viewpoint of fluidity, the gel time is preferably 20 seconds or more, more preferably 30 seconds or more, and even more preferably 40 seconds or more. From the viewpoint of curability, the gel time is preferably 120 seconds or less, more preferably 100 seconds or less, and even more preferably 90 seconds or less. The gel time is a value measured by the following method. Measurement is carried out on 3 g of the thermosetting resin composition at a temperature of 180° C. using a Curelastometer (for example, manufactured by JSR Trading Co., Ltd.), and the time until the torque curve rises is taken as the gel time.

[0100] [Uses of thermosetting resin composition] The thermosetting resin composition obtained by the production method of the present disclosure can be used in various packaging techniques, for example, as a sealant for electronic component devices. The thermosetting resin composition can also be used in various applications where good fluidity and curability are desired, such as resin molded articles for various modules, resin molded articles for motors, resin molded articles for in-vehicle use, and sealants for protecting electronic circuits.

[0101] <Method for manufacturing electronic component device> The method for manufacturing an electronic component device according to the present disclosure includes producing a thermosetting resin composition by the method for producing a thermosetting resin composition according to the present disclosure, and encapsulating an element using the thermosetting resin composition.

[0102] Examples of methods for encapsulating electronic component devices using a thermosetting resin composition include low-pressure transfer molding, injection molding, and compression molding.

[0103] Examples of electronic component devices manufactured by the manufacturing method of the present disclosure include those obtained by mounting elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) on a support member such as a lead frame, a pre-wired tape carrier, a wiring board, glass, a silicon wafer, or an organic substrate, and then sealing the resulting element portion with a thermosetting resin composition. More specifically, typical resin-sealed ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package) have a structure in which an element is fixed on a lead frame, and terminal portions of the element such as bonding pads and lead portions are connected by wire bonding, bumps, or the like, and then sealed by transfer molding or the like using a thermosetting resin composition; TCP (Tape Carrier Package) has a structure in which an element connected to a tape carrier by bumps is sealed with a thermosetting resin composition; and COB (Chip On Board) has a structure in which an element is connected to wiring formed on a support member by wire bonding, flip chip bonding, solder, or the like, and then sealed with a thermosetting resin composition. Examples of suitable thermosetting resin compositions include a BGA (Ball Grid Array), a CSP (Chip Size Package), and an MCP (Multi Chip Package), each of which has a structure in which elements are mounted on the surface of a support member having terminals for connecting a wiring board formed on the back surface thereof, the elements are connected to wiring formed on the support member by bump or wire bonding, and the elements are then sealed with a thermosetting resin composition. Thermosetting resin compositions can also be suitably used in printed wiring boards. [Example]

[0104] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0105] <Preparation of Thermosetting Resin Composition> First, the following components were prepared.

[0106] (thermosetting resin) Epoxy resin 1: jER YX-4000 (trade name, Mitsubishi Chemical Corporation, biphenyl-type epoxy resin with an epoxy equivalent of 180 g / eq to 192 g / eq and a melting point of 105°C)

[0107] Hardener 1: H-4 (product name, Meiwa Kasei Co., Ltd., phenol novolac type phenolic resin with a hydroxyl group equivalent of 103 g / eq, softening point 85°C)

[0108] (curing accelerator) Curing accelerator: Phosphorus-based curing accelerator

[0109] (Other additives) Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane Release agent: Hoechst wax (Hoechst) Ion exchanger: DHT-4A (product name, Kyowa Chemical Industry Co., Ltd., hydrotalcite compound) Inorganic filler: Spherical silica with a volume average particle size of 15 μm Solvent: 20% by mass of the total material

[0110] Example 1 The thermosetting resin composition of Example 1 was prepared by the following method: As the kneading device, a twin-screw kneader (kneading extruder) the outline of which is shown in Figure 1 was used. First, the components listed in Table 1, except for the solvent and curing accelerator, were thoroughly mixed in a mixer to obtain a powder component. Furthermore, the components listed in Table 1, except for the curing accelerator, were thoroughly mixed in a mixer to obtain a mixture. The powder component was introduced into the first inlet of the twin-screw kneader as indicated by arrow X1, forming a material seal in the material seal section. After the material seal was formed, the first feed section upstream of the area where the material seal was formed was depressurized. After depressurizing the first feed section, the mixture was introduced into the second inlet of the twin-screw kneader as indicated by arrow X2, and the curing accelerator was introduced from the side feeder, followed by kneading and extrusion. The primary kneading temperature in the first feed section and material seal section was set to 150°C. In the second feed section, the temperature was gradually decreased from the side feeder connector to the outlet, reaching approximately 70°C near the side feeder connector and approximately 30°C near the twin-screw kneader outlet. The thermosetting resin composition from which the solvent had been removed was discharged from the outlet. When the amount of residual solvent in the thermosetting resin composition of Example 1 was confirmed, it was reduced from 20% by mass to 0.3% by mass, indicating that the solvent could be suitably removed. Furthermore, because the discharge port was open while the material seal was formed, mixing of the evaporated solvent with the air supplied through the discharge port was suppressed. Furthermore, by using a powder component, the material seal was formed in a shorter time than in Comparative Example 1 described below, and the inclusion of metallic foreign matter in the thermosetting resin composition discharged from the discharge port of the kneader was suppressed.

[0111] (Comparative Example 1) The thermosetting resin composition of Comparative Example 1 was prepared by the following method: As the kneading device, a twin-screw kneader (kneading extruder) the outline of which is shown in Fig. 3 was used. First, the components listed in Table 1, except for the curing accelerator, were thoroughly mixed in a mixer to obtain a mixture. The mixture was introduced into the twin-screw kneader through the inlet (as indicated by arrow X), and the curing accelerator was introduced through the side feeder. The mixture was introduced through the inlet with the discharge outlet capped, forming a material seal in the material seal section. After the material seal was formed, kneading and extrusion were performed. The primary kneading temperature in the first feed section and material seal section was set to 150°C. The second feed section was designed to gradually decrease the temperature from the side feeder connector toward the outlet, reaching approximately 70°C near the side feeder connector and approximately 30°C near the twin-screw kneader outlet. The thermosetting resin composition from which the solvent had been removed was discharged through the outlet. The residual solvent content of the thermosetting resin composition of Example 1 was confirmed, decreasing from 20% by mass to 0.5% by mass, demonstrating that the solvent could be effectively removed. Furthermore, because the lid was removed and the outlet opened while the material seal was formed, mixing of the evaporated solvent with the air supplied through the outlet was suppressed. However, at least a portion of the thermosetting resin composition discharged from the discharge port of the kneader contains metallic foreign matter.

[0112] (Comparative Example 2) A thermosetting resin composition was prepared in the same manner as in Comparative Example 1, except that the process of forming a material seal by feeding the mixture through the inlet with the discharge outlet covered was not performed. That is, the mixture was fed through the inlet with the discharge outlet uncovered, and kneading and extrusion were performed. In Comparative Example 2, a material seal was not formed in the material seal section, or it took a very long time for the material seal to be formed, so the pressure was not sufficiently reduced in the first feed section, making it difficult to remove the solvent contained in the mixture.

[0113] [Table 1] [Explanation of symbols]

[0114] 1A First feed section 1B Second feed section 2 Material seal section (mixing section) 3 outlet 4 Lid 5 Side Feeder 6 motors 10. Kneading extruder

Claims

1. forming a material seal by feeding the powder component into the mixer without covering the discharge port of the mixer; reducing pressure in the mixer upstream of a region where the material seal is formed after the material seal is formed; After reducing the pressure inside the kneader, supplying a mixture containing a thermosetting resin, an inorganic filler, and a solvent to a region of the kneader where the pressure has been reduced, kneading the mixture, and discharging the mixture from which at least a portion of the solvent has volatilized through the material seal through an outlet of the kneader; A method for producing a thermosetting resin composition comprising the steps of:

2. The method for producing a thermosetting resin composition according to claim 1 , wherein the mixture is kneaded at a temperature higher than a melting point or a softening point of the thermosetting resin.

3. The method for producing a thermosetting resin composition according to claim 1 , wherein the thermosetting resin comprises an epoxy resin.

4. The method for producing a thermosetting resin composition according to claim 1, wherein the melting point or softening point of the thermosetting resin is 60°C or higher.

5. The method for producing a thermosetting resin composition according to claim 1 , wherein the mixture is kneaded using a twin-screw kneader.

6. 2. The method for producing a thermosetting resin composition according to claim 1, wherein the degree of reduced pressure in the kneader after the material seal is formed is 50 kPa or less.

7. 2. The method for producing a thermosetting resin composition according to claim 1, wherein the amount of the mixture fed into the kneader is 1 kg / h to 100 kg / h.

8. The method for producing a thermosetting resin composition according to claim 1, wherein the inorganic filler has a top cut diameter of 75 μm or less.

9. Producing a thermosetting resin composition by the method for producing a thermosetting resin composition according to any one of claims 1 to 8; encapsulating an element with the thermosetting resin composition; A method for manufacturing an electronic component device comprising the steps of:

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