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.SOLUTION: There is provided a method for producing a thermosetting resin composition which comprises: feeding a mixture containing a thermosetting resin, an inorganic filler and a solvent into a kneader in a state where the inside of the kneader is depressurized by covering the outlet of the kneader to form a material seal between the outlet and an area to which the mixture is fed; and kneading the mixture in the kneader to discharge a mixture in which at least a part of the solvent is evaporated 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 electronic component devices. [Background technology]

[0002] In recent years, semiconductor elements have become more densely packed. Accordingly, conventional pin-insertion packages have been replaced by surface-mount packages for resin-sealed semiconductor devices. Surface-mount ICs (Intergrated Circuits), LSIs (Large Scale Integrations), etc. are being packaged in thin, small 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 very thin.

[0003] Surface mount packages have a different mounting method from conventional pin insertion packages. In pin insertion packages, the pins are inserted into the wiring board, and then soldered from the back side of the wiring board, so the package is not directly exposed to high temperatures. On the other hand, surface mount packages are temporarily attached to the surface of the wiring board and processed with a solder bath or reflow device, so they are directly exposed to the soldering temperature (reflow temperature). As a result, if the IC package has absorbed moisture, the absorbed moisture vaporizes during reflow, and the generated vapor pressure acts as a peeling stress, causing peeling between the insert such as the element or lead frame and the sealing material, resulting in package cracks and poor electrical characteristics. For this reason, there is a demand for the development of a sealing material with excellent solder heat resistance (reflow resistance).

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

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

[0006] However, as semiconductors become smaller, the gaps between chips become narrower. For this reason, the use of top-cut inorganic fillers with a specific particle size that can ensure insulation and accommodate narrow gaps in the field of sealing materials is being considered.

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

[0008] 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 kneader to produce a thermosetting resin composition from which the solvent has been removed, and a method for producing an electronic component device that includes this production method. [Means for solving the problem]

[0009] Means for solving the above problems include the following aspects. <1> a cover is placed on an outlet of a kneader, and a mixture containing a thermosetting resin, an inorganic filler, and a solvent is supplied into the kneader while reducing the pressure inside the kneader, thereby forming a material seal between the outlet and an area where the mixture is supplied; kneading the mixture in the kneader, 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; A method for producing a thermosetting resin composition comprising the steps of: <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> 13. A method for producing the thermosetting resin composition according to claim 12. <5> The mixture is kneaded using a twin-screw kneader. <1> ~ <4> 13. A method for producing the thermosetting resin composition according to claim 12. <6> The degree of vacuum in the kneader when forming the material seal is 50 kPa or less. <1> ~ <5> 13. A method for producing the thermosetting resin composition according to claim 12. <7> The amount of the mixture fed into the kneader after the material seal is formed is 1 kg / h to 100 kg / h. <1> ~ <6> 13. A method for producing the thermosetting resin composition according to claim 12. <8> The top cut diameter of the inorganic filler is 75 μm or less. <1> ~ <7> 13. A method for producing the thermosetting resin composition according to claim 12. <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 with the thermosetting resin composition; A method for manufacturing an electronic component device comprising the steps of: Effect of the Invention

[0010] According to the present disclosure, there is provided a method for producing a thermosetting resin composition that can efficiently volatilize a solvent from a mixture in a kneader to produce a thermosetting resin composition from which the solvent has been removed, and a method for producing an electronic component device that includes this production method. [Brief description of the drawings]

[0011] [Figure 1] 1 is a schematic cross-sectional view showing the use of the mixture to form a material seal in accordance with one embodiment of the manufacturing method of the present disclosure. [Diagram 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. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, the embodiment for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiment. In the following embodiment, the components (including element steps, etc.) are not essential unless specifically stated. The same applies to the numerical values ​​and their ranges, and they do not limit the present invention.

[0013] In the present disclosure, the term "step" includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present disclosure in stages, 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. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple types of the corresponding substance. 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 included. 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 properties at 25°C. When an embodiment of the present disclosure is described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. In addition, the size of the members in each drawing is conceptual, and the relative relationship between the sizes of the members is not limited to this.

[0014] <Method for producing thermosetting resin composition> A manufacturing method for a thermosetting resin composition according to the present disclosure (hereinafter also referred to as the manufacturing method according to the present disclosure) includes: covering an outlet of a kneader; supplying a mixture containing a thermosetting resin, an inorganic filler, and a solvent into the kneader while reducing the pressure inside the kneader; and forming a material seal between the outlet and the area where the mixture is supplied; kneading the mixture inside the kneader; and discharging the mixture from which at least a portion of the solvent has volatilized through the material seal, from the outlet of the kneader.

[0015] In the manufacturing method of the present disclosure, the discharge port from which the thermosetting resin composition after kneading is discharged is covered, and the above-mentioned mixture is supplied into the kneader while the inside of the kneader is depressurized to form a material seal. By kneading the mixture in the upstream of the region where the material seal is formed, the region where the material seal is formed, etc., at least a part of the solvent in the mixture is volatilized. At this time, since the material seal is formed between the region where the mixture is supplied and the discharge port with the lid removed, the air supplied into the kneader through the discharge port is suppressed from being supplied to the region where the mixture is supplied. As a result, the region where the mixture is supplied is suitably depressurized, and the volatilization of the solvent is promoted. Then, the mixture from which the solvent has volatilized is discharged from the discharge port of the kneader through the material seal. As a result, a thermosetting resin composition from which the solvent has been removed is obtained.

[0016] The manufacturing method of the present disclosure includes supplying a mixture containing a thermosetting resin, an inorganic filler, and a solvent into a kneader with a lid on the outlet of the kneader. The mixture is used to form a material seal in the kneader. The mixture used to form the material seal may also be continuously supplied into the kneader and used to manufacture a thermosetting resin composition from which the solvent is removed during supply, kneading, etc. The thermosetting resin composition may be used to manufacture an electronic component device.

[0017] In this disclosure, the material seal refers to a region formed in the kneading 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 the solvent contained in the mixture upstream of the material seal in the kneader.

[0018] The manufacturing method of the present disclosure includes covering the discharge port of a kneader, supplying a mixture containing a thermosetting resin, an inorganic filler, and a solvent into the kneader while reducing the pressure inside the kneader, and forming a material seal between the discharge port and the region where the mixture is supplied. The degree of reduction in pressure when forming the material seal is not particularly limited and may be appropriately adjusted depending on the composition of the mixture. The degree of reduction in pressure may be, for example, 50 kPa or less, or 20 kPa or less.

[0019] The manufacturing method of the present disclosure includes, after forming the material seal, supplying a mixture containing a thermosetting resin, an inorganic filler, and a solvent into a kneader upstream of a region where the material seal is formed, kneading the mixture, and discharging the mixture from an outlet of the kneader after at least a portion of the solvent has volatilized through the material seal. In the manufacturing method of the present disclosure, the composition of the mixture used to form the material seal may be the same as the composition of the mixture supplied into the kneader after forming the material seal. In addition, the mixture used to form the material seal and the mixture supplied into the kneader after forming the material seal may be continuously supplied into the kneader from the same supply port.

[0020] In the manufacturing method of the present disclosure, a mixture containing a solvent is supplied upstream of a region in a kneader where a material seal is formed, and kneaded in the region where the material seal is formed, upstream of the region, etc. This makes it possible to remove the solvent in the mixture. A thermosetting resin composition from which the solvent has been removed is obtained by discharging the mixture from which at least a part of the solvent has evaporated through an outlet of the kneader.

[0021] The mixture used to form the material seal and the mixture supplied to the kneader after forming the material seal (hereinafter collectively referred to as "mixture") may or may not contain other components besides the thermosetting resin, inorganic filler, and solvent. Examples of other components include a curing accelerator, a coupling agent, and additives described below. The other components may be supplied to the kneader in the form of a mixture mixed with the thermosetting resin, inorganic filler, and solvent, or may be supplied separately from the mixture.

[0022] The mixture is obtained by mixing a slurry containing a thermosetting resin, an inorganic filler, and a solvent with other components used as necessary using a mixer such as a stirrer or a planetary mixer, an ultrasonic disperser, a wet disperser such as a jet mill, etc. The mixing conditions when preparing the mixture are appropriately set depending on the types of components contained in the mixture, the ratio of the components, etc.

[0023] The method of kneading the mixture supplied into the kneader is not particularly limited. For example, a method of melt-kneading using a kneader (two-screw kneader, three-screw kneader, etc.), a roll (three-roll, etc.), an extruder, etc., which are preheated to a desired temperature, can be mentioned. Among them, it is preferable to knead the mixture using a two-screw kneader. In addition, when kneading the mixture, it is sufficient to knead it in the region in the kneader where the material seal is formed, and further, it may be kneaded both upstream and downstream thereof.

[0024] From the viewpoint of suitably volatilizing the solvent in the mixture, the mixture may be kneaded while reducing the pressure inside the kneader, or the mixture may be kneaded while reducing the pressure inside the kneader and heating it. 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 the inside of the kneader is reduced may be the same as the degree of pressure reduction when the material seal is formed, or may be 50 kPa or less, or may be 20 kPa or less.

[0025] The amount of the mixture fed into the kneader after the material seal is formed can be adjusted according to 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.

[0026] The temperature (also referred to as the kneading temperature) when the mixture is kneaded is preferably adjusted according to the melting temperature of the resin component 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. By kneading at such a temperature, the thermosetting resin can be melted and the fluidity can be favorably maintained, so that stirring and mixing can be performed well.

[0027] In the present disclosure, the term "kneading temperature (the same applies 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.

[0028] 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 the 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.

[0029] 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 a 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. Primary mixing refers to mixing in the area where the material seal is formed or upstream of that area.

[0030] When a part of the curing accelerator is mixed in the primary kneading, the amount mixed is preferably 30 mass % or less, more preferably 20 mass % or less, and even more preferably 10 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.

[0031] The temperature of the primary kneading may be higher than the onset temperature of the mixture after the addition of the curing accelerator in the secondary kneading, measured by differential scanning calorimetry (DSC). In the present disclosure, the onset temperature refers to the temperature corresponding to the intersection of the tangent at the point where the differential value of the exothermic peak in the DSC chart is maximum and the baseline of the exothermic peak in the DSC chart. When there are multiple points where the differential value of the exothermic peak is maximum, the point on the lowest temperature side among the multiple points is used.

[0032] 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 made relatively high 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.

[0033] The method of adding the hardening accelerator in the secondary kneading is not particularly limited as long as the hardening accelerator can be added later. For example, a method of adding the hardening accelerator to the mixture subjected to the primary kneading from an inlet provided separately from the inlet for the components of the primary kneading (side feed) can be mentioned.

[0034] 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, measured by differential scanning calorimetry (DSC), and is preferably, for example, 1°C to 100°C lower.

[0035] In the manufacturing method of the present disclosure, a mixture from which at least a part of the solvent has evaporated is discharged from the outlet of a kneader to obtain a thermosetting resin composition. The thermosetting resin composition obtained as a kneaded product may be cooled and pulverized to obtain a powdered thermosetting resin composition. The thermosetting resin composition obtained through kneading may be molded into a granular, tablet, pellet, or granular shape (cylindrical granules, etc.). The pulverization method or molding method of the thermosetting resin composition is not particularly limited, and a conventionally known method may be used.

[0036] In one embodiment, in the production method of the present disclosure, a kneading extruder as shown in FIG. 1 is used to produce a thermosetting resin composition.

[0037] In one embodiment, the primary kneading 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 in the extrusion direction of the first feed section 1A, a material seal section (also serving as a kneading section) 2 located between the first feed section 1A and the second feed section 1B, and an outlet 3 located downstream in the extrusion direction of the second feed section 1B and discharging the kneaded mixture. The kneading extruder 10 includes an inlet connected to the first feed section 1A and for injecting the mixture into the kneading extruder 10 as indicated by the arrow X, a side feeder 5 connected to the second feed section 1B, a pressure reduction port for reducing the pressure inside the kneading extruder 10 as indicated by the arrow Y, and a motor 6 for rotating the screw.

[0038] In FIG. 1, a lid 4 is provided on the discharge port 3 of the kneading extruder 10. The discharge port 3 is covered, and the inside of the kneading extruder 10 is depressurized as shown by the arrow Y. In this state, the mixture is fed from the feed port to the first feed section 1A as shown by the arrow X, and a material seal is formed in the material seal section (kneading section) 2. After the material seal is formed, the mixture fed to the first feed section 1A is subjected to primary kneading, and the kneaded product is extruded and moved to the second feed section 1B through the material seal, and the mixture is subjected to secondary kneading. At this time, a hardening accelerator is fed from the side feeder 5 to the second feed section 1B. The moved kneaded product is merged with the hardening accelerator and further kneaded. It is also possible to set the temperature of the first feed section 1A and the temperature of the second feed section 1B separately. For example, a cooling section (not shown) may be provided between the first feed section 1A and the second feed section 1B, and the secondary kneading may be performed at a lower temperature than the primary kneading. Also, the first feed section 1A may be set to a higher temperature and the second feed section 2B may be set to a lower temperature, and a mechanism may be employed in the second feed section 2B that gradually cools the contents in the extrusion direction.

[0039] After the material seal is formed, the lid 4 is removed from the outlet 3 as shown in Fig. 2, or the lid 4 is removed from the outlet 3 by secondary kneading, and the kneaded mixture is discharged from the outlet 3 as shown by the arrow Z. At this time, since the mixture is kneaded under a reduced pressure inside the kneading extruder 10, the mixture from which at least a part of the solvent has been removed is discharged from the outlet 3, and a thermosetting resin composition is obtained. Note that the manufacturing method of the present disclosure is not limited to the embodiments shown in the drawings.

[0040] Each component used in the manufacturing method of the present disclosure will be described below. The components used in the manufacturing method of the present disclosure include a thermosetting resin, an inorganic filler, and a solvent. In addition, a curing accelerator, a coupling agent, and additives described later may also be used as the components used in the manufacturing method of the present disclosure.

[0041] <Thermosetting resin> The type of thermosetting resin is not particularly limited, and examples thereof include epoxy resin, phenol resin, urea resin, melamine resin, urethane resin, silicone resin, and unsaturated polyester resin. In the present disclosure, a resin that exhibits both thermoplastic and thermosetting properties, such as an acrylic resin containing an epoxy group, is included in the "thermosetting resin". The thermosetting resin may be solid or liquid at room temperature and normal pressure (e.g., 25°C and atmospheric pressure), and is preferably solid. The thermosetting resin may be used alone or in combination of two or more types.

[0042] The thermosetting resin preferably includes an epoxy resin. Specific examples of the epoxy resin include novolac-type epoxy resins (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) obtained by epoxidizing a novolac resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcin, 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., under an acidic catalyst; triphenylmethane-type epoxy resins obtained by epoxidizing a triphenylmethane-type phenolic resin obtained by condensing or co-condensing the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, etc., under an acidic catalyst; and novolac resins obtained by co-condensing the above-mentioned phenolic compound and naphthol compound with an aldehyde compound under an acidic catalyst. copolymer epoxy resins in which epoxidized oils are used; diphenylmethane epoxy resins which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl epoxy resins which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene 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 epoxy resins which are glycidyl esters of polycarboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine epoxy resins in which active hydrogen bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is replaced with a glycidyl group; dicyclopentadiene epoxy resins in which a co-condensation resin of dicyclopentadiene and a phenolic compound is epoxidized;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 epoxy-modified epoxy resins in which the olefin bonds in the molecule have been epoxidized; 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 the epoxy resin 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; aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins; and the like. Furthermore, examples of the epoxy resin include epoxidized silicone resins and epoxidized acrylic resins. The epoxy resins may be used alone or in combination of two or more.

[0043] Among the above epoxy resins, biphenyl type epoxy resins have a low melt viscosity, so even if they are highly filled with inorganic fillers to improve reflow resistance, they are unlikely to cause wire sweep problems in semiconductor packages. For this reason, biphenyl type epoxy resins have become suitable for use as sealing 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, so kneading at high temperatures is desirable in order to thoroughly disperse the resin by kneading. According to the manufacturing method of the present disclosure, even when the thermosetting resin contains a biphenyl type epoxy resin, the thermosetting resin can be kneaded suitably while suppressing an increase in viscosity.

[0044] 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 In the above, the oxygen atoms are substituted at the 4 and 4' positions, and the 3, 3', 5 and 5' positions are methyl groups. 8 YX-4000 and YX-4000H (Mitsubishi Chemical Corporation, product names) where R is a hydrogen atom, 8 4,4'-bis(2,3-epoxypropoxy)biphenyl, where R is a hydrogen atom; 8 When is a hydrogen atom and R 8 The oxygen atom is substituted at the 4 and 4' positions, and the 3, 3', 5, and 5' positions are methyl groups. 8 is a hydrogen atom, YL-6121H (product name, Mitsubishi Chemical Corporation) and the like are commercially available.

[0045] [ka]

[0046] 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 be the same or different. n is an average value and represents a number from 0 to 10.

[0047] Further, as a further method for improving reflow resistance, there is a method for improving adhesion to metal members and substrates. In order to improve adhesion, sulfur atom-containing epoxy resins are 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 preferably kneaded while suppressing an increase in viscosity.

[0048] The sulfur-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) is included. Among the epoxy resins represented by the following general formula (V), R 13 In the above, when the oxygen atom is substituted at the 4 and 4' positions, the 3 and 3' positions are t-butyl groups, the 6 and 6' positions are methyl groups, and the remaining R 13 YSLV-120TE (product name, Nippon Steel Chemical & Material Co., Ltd.), in which R is a hydrogen atom, is commercially available.

[0049] [ka]

[0050] 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. n is an average value and represents a number from 0 to 10.

[0051] The epoxy equivalent of the epoxy resin (molecular weight / number of epoxy groups) 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 according to JIS K 7236:2009.

[0052] 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 manufacturing 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 in accordance with JIS K 7234:1986 (ring and ball method).

[0053] 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 further 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.

[0054] 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.

[0055] 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. The curing agents may be used alone or in combination of two or more. From the viewpoint of improving heat resistance, the curing agent is preferably a phenol curing agent. The curing agent may be solid or liquid at normal temperature and normal pressure (for example, 25°C, atmospheric pressure), and is preferably solid.

[0056] The phenol 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 phenol compounds such as resorcin, 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, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, and an aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde, under an acid catalyst; and polyphenol compounds such as dimethoxyparaxylene, bis(methoxymethyl)biphenol, and the like. Examples of the phenolic resin include aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenyl and 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 and dicyclopentadiene; cyclopentadiene modified phenolic resins; polycyclic aromatic ring modified phenolic resins; biphenyl type phenolic resins; triphenylmethane type phenolic resins obtained by condensing or co-condensing the above phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acid catalyst; and phenolic resins obtained by copolymerizing two or more of these. The phenolic resins may be used alone or in combination of two or more.

[0057] The hydroxyl equivalent of the phenol 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 phenol resin is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0058] The hydroxyl equivalent of the phenolic resin is a value calculated based on the hydroxyl value measured in accordance with JIS K0070:1992.

[0059] 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 for a sealing material, and more preferably 50° C. to 130° C. from the viewpoint of handling during production of the thermosetting resin composition.

[0060] The melting point or softening point of the phenol resin is a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0061] 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 further preferably 2% by mass to 20% by mass, relative to the total mass of the thermosetting resin composition.

[0062] The equivalent ratio of the epoxy resin to the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of epoxy groups in the epoxy resin (the number of functional groups in the curing agent / the number of epoxy groups in the epoxy resin) is not particularly limited. From the viewpoint of suppressing the amount of unreacted components, the equivalent ratio of the epoxy resin to the curing agent (the number of functional groups in the curing agent / the number of epoxy groups in the epoxy resin) is preferably set in the range of 0.5 to 2.0, more preferably set in the range of 0.6 to 1.3. From the viewpoint of moldability when the thermosetting resin composition is used for sealing material applications, it is more preferable that the equivalent ratio of the epoxy resin to the curing agent (the number of functional groups in the curing agent / the number of epoxy groups in the epoxy resin) is 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.

[0063] <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 the inorganic filler include inorganic materials such as 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 a flame retardant effect may be used. Examples of inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate. Among the 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.

[0064] The shape of the inorganic filler is not particularly limited, but from the viewpoints of filling properties and die wear, a spherical shape is preferred.

[0065] 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, use of two or more inorganic fillers having the same components but different average particle sizes, use of two or more inorganic fillers having the same average particle size but different components, and use of two or more inorganic fillers having different average particle sizes and types.

[0066] The content of the inorganic filler is not particularly limited. From the viewpoint of further improving the properties such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product, 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 the fluidity, reducing the 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 volume% to 99 volume%, 80 volume% to 99 volume%, 83 volume% to 99 volume%, or 85 volume% to 99 volume% of the entire thermosetting resin composition.

[0067] The content of the inorganic filler in the cured product of the 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 components, and the mass of the remaining inorganic filler is measured. The volumes are 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 obtained, which is the content of the inorganic filler.

[0068] The top cut diameter of the inorganic filler is not particularly limited, and is preferably 75 μm or less, for example, and from the viewpoint of filling into 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. The top cut diameter of the inorganic filler may be 1 μm or more from the viewpoint of suppressing an increase in the viscosity of the thermosetting resin composition. In this 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 drawn from the small diameter side using a laser diffraction scattering particle size distribution measurement device.

[0069] 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 filling ability into narrow gaps tends to be improved. Also, 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 diameter of the inorganic filler can be measured as the volume average particle diameter (D50) by a laser diffraction scattering particle size distribution measuring device.

[0070] <Solvent> In the manufacturing method of the present disclosure, a solvent is used in the production of the thermosetting resin composition. The type of the 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.

[0071] 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.

[0072] 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 kinds.

[0073] <Curing accelerator> A cure accelerator may be used in the preparation of the thermosetting resin composition. The type of the 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, e.g., ethylphosphine, phenylphosphine, etc.; secondary phosphines, e.g., dimethylphosphine, diphenylphosphine, etc.; and tertiary phosphines, e.g., 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, tris(benzyl)phosphine; phosphine compounds, e.g., complexes of the organic phosphines and organic borons; and complexes of the organic phosphines or the 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, and diazophenylmethane; compounds having intramolecular polarization obtained by adding a compound having a π bond, such as the organic phosphines or the phosphine compounds, and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, and 4-iodophenol; a compound having intramolecular polarization, which is obtained by reacting a halogenated phenol compound 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, or 4-bromo-4'-hydroxybiphenyl, followed by a dehydrohalogenation process;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. The curing accelerator may be used alone or in combination of two or more.

[0074] For example, examples of particularly suitable curing accelerators when an epoxy resin is used as the thermosetting resin include triphenylphosphine and an adduct of triphenylphosphine and a quinone compound.

[0075] 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 when 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, the resin tends to cure well 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 a good molded product tends to be obtained.

[0076] <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. Examples of the coupling agent include known coupling agents such as silane compounds, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds.

[0077] Examples of the silane-based compound 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.

[0078] 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.

[0079] 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 adhesiveness 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.

[0080] <Additive> Additives other than the components described above 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 relievers, 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.

[0081] (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 including the 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.

[0082] Mg (1-X) Al X (OH) 2 (CO 3 ) X / 2 ·mH 2 O ……(A) (0 < X ≦ 0.5, m is a positive number)

[0083] When the thermosetting resin composition contains an ion exchanger, the content 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.

[0084] (Release agent) A mold release agent may be used in the production of the 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. The mold release agent is not particularly limited, and a conventionally known one may 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, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene, etc. The mold release agent may be used alone or in combination of two or more kinds.

[0085] When the thermosetting resin composition contains a release agent, the amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the resin component. When the amount of the release agent is 0.01 parts by mass or more based on 100 parts by mass of the resin component, sufficient releasability tends to be obtained. When the amount is 10 parts by mass or less, better adhesion and curability tend to be obtained.

[0086] (Flame retardant) A flame retardant may be used in the production of the thermosetting resin composition. The thermosetting resin composition may contain a flame retardant. The flame retardant is not particularly limited, and a conventionally known one may be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, etc. The flame retardant may be used alone or in combination of two or more kinds.

[0087] When the thermosetting resin composition contains a flame retardant, the amount is not particularly limited as long as it is an amount sufficient to obtain the desired flame retardant effect. For example, the amount is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, per 100 parts by mass of the resin component.

[0088] (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. The colorant may be used alone or in combination of two or more kinds.

[0089] (Stress reliever) A stress relaxation agent may be used in the production of the thermosetting resin composition. The thermosetting resin composition may contain a stress relaxation agent such as silicone oil or silicone rubber particles. By containing a stress relaxation agent, it is possible to reduce the occurrence of warpage deformation and package cracks when the thermosetting resin composition is used for sealing material applications. Examples of the stress relaxation agent include known stress relaxation agents (flexible agents) that are generally used. Specifically, examples include thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based 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 agent may be used alone or in combination of two or more types.

[0090] ≪Thermosetting resin composition≫ The thermosetting resin composition of the present disclosure may be obtained by the production method of the present disclosure described above. 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, the shape is not particularly limited, and examples thereof include powder, granules, and tablets. When the thermosetting resin composition is in tablet form, the dimensions and mass are preferably set to be suitable for the molding conditions of the package from the viewpoint of handling.

[0091] [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 for an encapsulant, it is preferable to adjust the viscosity depending on the tendency of wire sweep during molding. For example, when the thermosetting resin composition is used as an encapsulant, from the viewpoint of reducing wire sweep, etc., 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 by a Koka type flow tester (for example, manufactured by Shimadzu Corporation).

[0092] [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. The 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.

[0093] 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 plate mold for measuring disc 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 the 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 molded under conditions of a load of 78 N and a curing time of 90 seconds, and the major axis (mm) and minor axis (mm) of the molded product are measured with a vernier caliper, and the average value (mm) is taken as the disc flow.

[0094] [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 (e.g., HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.) Molding is performed using a transfer molding machine under the conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds.

[0095] [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 at a temperature of 180° C. using a Curelastometer (eg, manufactured by JSR Trading Co., Ltd.) for 3 g of the thermosetting resin composition, and the time until the torque curve rises is regarded as the gel time.

[0096] [Uses of the thermosetting resin composition] The use of the thermosetting resin composition obtained by the manufacturing method of the present disclosure is not particularly limited, and it can be used in various mounting techniques, for example, as a sealant for electronic component devices. In addition, the thermosetting resin composition can be used in various applications in which it is desirable for the resin composition to have good fluidity and curability, such as resin molded bodies for various modules, resin molded bodies for motors, resin molded bodies for vehicles, and sealants for electronic circuit protection materials.

[0097] <<Method of manufacturing electronic component device>> The method for producing 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 described above, and encapsulating an element using the thermosetting resin composition.

[0098] Methods for encapsulating electronic device components using a thermosetting resin composition include low pressure transfer molding, injection molding, compression molding, and the like.

[0099] Examples of electronic component devices manufactured by the manufacturing method of the present disclosure include devices 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, terminal parts of the element such as bonding pads and lead parts 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 connected to wiring formed on a support member by wire bonding, flip chip bonding, solder, or the like, is 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 an element is mounted on the surface of a support member having terminals for connecting a wiring board formed on the back surface thereof, the element is connected to wiring formed on the support member by bump or wire bonding, and the element is then sealed with a thermosetting resin composition.The thermosetting resin composition can also be suitably used in printed wiring boards. EXAMPLES

[0100] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0101] <Preparation of Thermosetting Resin Composition> First, the following components were prepared.

[0102] (thermosetting resin) Epoxy resin 1: jER YX-4000 (product name, Mitsubishi Chemical Corporation, biphenyl type epoxy resin with epoxy equivalent of 180g / eq to 192g / eq and melting point of 105°C)

[0103] Hardener 1: H-4 (product name, Meiwa Kasei Co., Ltd., phenol novolac type phenolic resin with hydroxyl equivalent of 103 g / eq, softening point 85°C)

[0104] (Cure accelerator) -Cure accelerator: Phosphorus-based cure accelerator

[0105] (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 weight based on the total material weight

[0106] 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 schematic of which is shown in Fig. 1 was used. First, the components shown in Table 1, except for the curing accelerator, were thoroughly mixed in a mixer to obtain a mixture. The mixture was fed from the inlet of the twin-screw kneader as shown by the arrow X, and the curing accelerator was fed from the side feeder. At this time, the mixture was fed from the inlet with the discharge port covered, and a material seal was formed 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 the material seal section was set to 150°C. In the second feed section, the temperature was gradually lowered from the side feeder connection section to the outlet so that the temperature was about 70°C near the side feeder connection section and about 30°C near the outlet of the twin-screw kneader. The thermosetting resin composition from which the solvent had been removed was discharged from the outlet. When the amount of remaining solvent in the thermosetting resin composition of Example 1 was confirmed, it was reduced from 20% by mass to 0.5% by mass, and the solvent was able to be suitably removed. Furthermore, since the lid was removed and the outlet was opened with the material seal formed, the mixture of the evaporated solvent and the air supplied from the outlet was suppressed.

[0107] Comparative Example 1 A thermosetting resin composition was prepared in the same manner as in 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. In other words, the mixture was fed through the inlet with the discharge outlet uncovered, and kneading and extrusion were performed. In Comparative Example 1, the 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 that the pressure reduction in the first feed section was insufficient, and it was difficult to remove the solvent contained in the mixture.

[0108] [Table 1] [Explanation of symbols]

[0109] 1A First feed section 1B Second feed section 2 Material seal section (mixing section) 3 outlet 4 Lid 5. Side Feeder 6 Motor 10 Kneading extruder

Claims

1. a cover is placed on an outlet of a kneader, and a mixture containing a thermosetting resin, an inorganic filler, and a solvent is supplied into the kneader while reducing the pressure inside the kneader, thereby forming a material seal between the outlet and an area where the mixture is supplied; kneading the mixture in the kneader, 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; 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 when 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 supplied to the kneader after the material seal is formed 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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