JP2022107375A - Method for producing thermosetting resin composition, thermosetting resin composition, electronic component device, and method for manufacturing electronic component device - Google Patents

Abstract

To provide a method for producing a thermosetting resin composition applicable even to a low-temperature curable composition and capable of maintaining good fluidity and curability, a thermosetting resin composition obtained by the production method, an electronic component device including an element sealed with the thermosetting resin composition, and a method for manufacturing the same.SOLUTION: The method for producing a thermosetting resin composition includes: primary kneading in which a mixture of a thermosetting resin and an inorganic filler is kneaded in a kneader; cooling of the mixture after the primary kneading; and secondary kneading in which a curing accelerator is added to the mixture after the cooling and the mixture is further kneaded. The temperature of the secondary kneading is lower than an onset temperature measured by differential scanning calorimetry of the mixture after the addition of the curing accelerator in the secondary kneading.SELECTED DRAWING: None

Description

The present disclosure relates to a method for producing a thermosetting resin composition, a thermosetting resin composition, an electronic component device, and a method for manufacturing an electronic component device.

Thermosetting resin compositions used for sealing semiconductor devices and the like are generally produced by melt-kneading each component such as a thermosetting resin, an inorganic filler, and an additive with a kneader. After cooling, the melt-kneaded composition is subjected to treatments such as pulverization and tableting depending on the intended use.

When, for example, an epoxy resin composition is used as a sealing material for a semiconductor element, sealing is generally performed at about 175 ° C. On the other hand, the higher the temperature of the heat treatment, the more likely it is that the semiconductor device will warp due to the expansion and contraction of the resin composition, and that bonding defects will occur due to the softening of the solder. In order to minimize the influence of heat treatment on the semiconductor package, the composition and curing method of the thermosetting resin composition have been studied.

For example, in Patent Document 1, a specific naphthylene ether skeleton-containing epoxy resin and imidazole compound having an ICI viscosity at 150 ° C. of 0.1 Pa · s or less are used for the purpose of lowering the molding temperature and suppressing warpage of the semiconductor device. An epoxy resin composition for sealing containing a curing agent containing the above and an inorganic filler has been proposed. In this sealing epoxy resin composition, the naphthylene ether skeleton-containing epoxy resin has good fluidity even when the molding temperature is low, and the reactivity between the naphthylene ether skeleton-containing epoxy resin and the imidazole compound is low. It is described that since it is good, deterioration of moldability and unevenness of the sealing material are unlikely to occur even by low-temperature molding.

Japanese Unexamined Patent Publication No. 2016-089096

As described in Patent Document 1, low-temperature curing of the thermosetting resin composition may be desired in order to suppress warpage in sealing of semiconductor devices, while low-temperature curing ensures good moldability. It is difficult. If the composition design of the thermosetting resin composition is such that it can be cured at a low temperature, it is difficult to knead the composition in a state where the viscosity is sufficiently low, so that the components are likely to be unevenly distributed, and as a result, the components are likely to be unevenly distributed. This is because the fluidity tends to decrease and the curability tends to decrease.

According to the epoxy resin composition of Patent Document 1, it is described that good moldability can be obtained even by low-temperature curing and unevenness can be suppressed, but low-temperature curing is possible while ensuring moldability. In order to do so, the allowable range of the composition of the thermosetting resin, the curing agent, etc. is significantly limited. For example, in Patent Document 1, when a sealing material is formed at a low temperature by using a composition containing a crystalline epoxy resin having a high melting point, the moldability is deteriorated and the uniformity of the sealing material is deteriorated for sealing. It is described that unevenness is likely to occur in the stop material.

In view of such circumstances, the present disclosure can be applied to a low-temperature curable composition, and can be obtained by a method for producing a thermosetting resin composition capable of maintaining good fluidity and curability, and a method for producing the same. Provided are a thermosetting resin composition, an electronic component device including an element sealed with the thermosetting resin composition, and a method for manufacturing the same.

Means for solving the above problems include the following aspects.
<1> Primary kneading, in which a mixture of thermosetting resin and inorganic filler is kneaded in a kneader,
With cooling of the mixture after the primary kneading,
Secondary kneading, in which a curing accelerator is added to the cooled mixture and further kneaded,
Including
The temperature of the secondary kneading is lower than the onset temperature measured by differential scanning calorimetry of the mixture after adding the curing accelerator in the secondary kneading.
A method for producing a thermosetting resin composition.
<2> The method for producing a thermosetting resin composition according to <1>, wherein the temperature of the primary kneading is equal to or higher than the onset temperature.
<3> The method for producing a thermosetting resin composition according to <1> or <2>, wherein the melting point or softening point of the thermosetting resin is equal to or higher than the onset temperature.
<4> The method for producing a thermosetting resin composition according to any one of <1> to <3>, wherein the onset temperature is 120 ° C. or lower.
<5> The method for producing a thermosetting resin composition according to any one of <1> to <4>, wherein the temperature of the secondary kneading is less than 120 ° C.
<6> The method for producing a thermosetting resin composition according to any one of <1> to <5>, wherein the temperature of the primary kneading is 120 ° C. or higher.
<7> The method for producing a thermosetting resin composition according to any one of <1> to <6>, wherein the thermosetting resin has a melting point or a softening point of 120 ° C. or higher.
<8> The thermosetting property according to any one of <1> to <7>, which comprises adding a curing agent to at least one selected from the group consisting of the primary kneading and the secondary kneading. A method for producing a resin composition.
<9> The kneading machine
The first kneading part for performing the primary kneading and
The second kneading part for performing the secondary kneading and
A cooling section arranged between the first kneading section and the second kneading section,
The method for producing a thermosetting resin composition according to any one of <1> to <8>, which is a kneading extruder comprising the above.
<10> A thermosetting resin composition obtained by the production method according to any one of <1> to <9>.
<11> An electronic component device including an element sealed with a thermosetting resin composition obtained by the production method according to any one of <1> to <9>.
<12> Manufacture of an electronic component device including sealing an element at 120 ° C. or lower with a thermosetting resin composition obtained by the manufacturing method according to any one of <1> to <9>. Method.

According to the present disclosure, a method for producing a thermosetting resin composition which can be applied to a low-temperature curable composition and can maintain good fluidity and curability, and a thermosetting property obtained by the production method. Provided are an electronic component device including a resin composition and an element sealed with the thermosetting resin composition, and a method for manufacturing the same.

It is the schematic sectional drawing of the kneading extruder used in one aspect of the manufacturing method of this disclosure.

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, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit the present invention.

In the present disclosure, the term "process" includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. ..
The numerical range indicated by using "-" in the present disclosure includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may contain a plurality of applicable substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be contained. When a plurality of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
In the present disclosure, solid, solid, liquid, and liquid refer to properties at 25 ° C.
When the embodiment is described in the present disclosure with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Further, the size of the members in each figure is conceptual, and the relative relationship between the sizes of the members is not limited to this.

<< Manufacturing method of thermosetting resin composition >>
The method for producing the heat-curable resin composition of the present disclosure (hereinafter, also referred to as the production method of the present disclosure) is a primary kneading in which a mixture of a heat-curable resin and an inorganic filler is kneaded in a kneader, and the primary kneading. The temperature of the secondary kneading includes the subsequent cooling of the mixture and the secondary kneading in which the curing accelerator is added to the cooled mixture and further kneaded, and the temperature of the secondary kneading is the temperature of the curing accelerator in the secondary kneading. Is lower than the onset temperature of the mixture after addition, as measured by differential scanning calorimetry (DSC). According to the production method of the present disclosure, after the primary kneading, the temperature is lowered and the curing accelerator is added in the secondary kneading, so that even if the curing temperature of the composition, for example, the onset temperature is lower than the conventional one, It is possible to sufficiently knead the thermosetting resin and the inorganic filler. As a result, it is possible to suppress uneven distribution of components, generation of aggregates, and the like, and to ensure the curability of the thermosetting resin composition.

In the present disclosure, the onset temperature means a temperature corresponding to the intersection of the tangent line at the point where the differential value of the heat generation peak of the DSC chart becomes maximum and the baseline of the heat generation peak of the DSC chart. When there are a plurality of points having the maximum differential value of the exothermic peak, the point on the lowest temperature side among the plurality of points is adopted.

Examples of the kneading method include a method of melt-kneading with a kneader that has been preheated to a desired temperature. Examples of the kneading machine include a kneading extruder. Examples of the kneading extruder include a single-screw kneading extruder, a twin-screw kneading extruder, a screw extruder such as a triple-screw kneading extruder, and the like. Of these, a twin-screw kneading extruder is preferable from the viewpoint of component dispersibility and dispersibility.

In a preferred embodiment, the kneader is arranged between a first kneading section for performing primary kneading, a second kneading section for performing secondary kneading, and a first kneading section and a second kneading section. It may be a kneading extruder including a cooling unit. In the kneading extruder, the mixture can be extruded in a predetermined direction by using a motor while kneading each component. In this embodiment, the mixture that has undergone the primary kneading in the first kneading section is pushed downstream and moved to the cooling section. The cooled mixture is extruded further downstream and moves to the second kneading section, where secondary kneading is performed.

It is preferable that the kneading extruder is provided with an input port for the main material and an input port (side feeder) provided separately from the input port for the main material. For example, as described above, when a kneading extruder having a first kneading section, a second kneading section, and a cooling section is used, the components for the first kneading are extracted from the input port of the main material provided in the first kneading section. It is preferable to add the curing accelerator from the side feeder provided in the second kneading portion. The side feeder may also be provided in the first kneading portion. In this case, in the primary kneading, the components of the thermosetting resin composition can be charged simultaneously or sequentially from separate inlets.
In the present disclosure, terms such as "main material input port" and "input port (side feeder) provided separately from the main material input port" may be used for convenience, but they are added from these input ports. There is no particular limitation on the type or amount of ingredients to be produced. That is, the main material represents an arbitrary component in an arbitrary amount among the components contained in the thermosetting resin composition. Further, the structure of these inlets is not particularly limited.

For example, in one embodiment, a mixture of a thermosetting resin and an inorganic filler, and if necessary, a mixture of a curing agent, a coupling agent, and other additives are provided from the input port of the main material provided in the first kneading portion. throw into. Alternatively, the inorganic filler is charged from the input port of the main material provided in the first kneading portion, and the thermosetting resin and other components are charged as necessary from the side feeder provided in the first kneading portion. .. After the primary kneading, the curing accelerator is added to the mixture that has moved to the second kneading section from the side feeder provided in the second kneading section.

The primary kneading is preferably performed under higher shear conditions than the secondary kneading. Generally, when a resin and an inorganic filler are mixed under high shear conditions, shear heat generation is generated, but in primary kneading, thickening is difficult even if shear heat generation occurs, so kneading can be performed under high shear conditions. As a result, the thermosetting resin and the inorganic filler can be sufficiently kneaded.

A schematic cross-sectional view of the kneading extruder used in one embodiment is shown in FIG. The kneading extruder 10 includes a first kneading section A, a second kneading section C, a cooling section B arranged between the two, a main material inlet 1 provided in the first kneading section A, and a second kneading section. A side feeder 2 provided in the portion C is provided. In FIG. 1, the arrows indicate the extrusion direction of the composition. Specific examples of the kneading method are as described above.
Hereinafter, each step of the manufacturing method of the present disclosure will be described.

[Primary kneading]
In the primary kneading, a mixture of a thermosetting resin and an inorganic filler is kneaded in a kneader. At this time, a curing agent, a coupling agent, other additives and the like may be further mixed as necessary. Each component of the primary kneading may be added to the kneader as a mixture previously mixed with a mixer or the like, or may be added from separate inlets.

A part of the curing accelerator may be added in the primary kneading as long as the thickening in the primary kneading does not proceed too much and the kneading can be performed well. When a part of the curing accelerator is mixed in the primary kneading, the mixing amount is preferably 30% by mass or less, preferably 20% by mass or less, of the total curing accelerator to be finally added. More preferably, it is more preferably 10% by mass or less. From the viewpoint of simplifying the manufacturing process, preferably, in the primary kneading, the thermosetting resin and the inorganic filler are kneaded without adding a curing accelerator.

When a part of the curing accelerator is added in the primary kneading, for example, the following aspects are assumed. When a plurality of types of curing accelerators are used in combination, the kneading temperature of the primary kneading (referred to as T ₁ ) and the onset temperature of the mixture after the addition of the curing accelerator (referred to as T _x ) are T ₁ <T. A curing accelerator (referred to as curing accelerator a) satisfying the relationship of _x is added in the primary kneading. On the other hand, a curing accelerator (referred to as curing accelerator b) satisfying the relationship of T ₁ ≥ T _x is added in the secondary kneading. In this case, even if the curing accelerator a is added in the primary kneading, the curing reaction hardly proceeds at the temperature T1 of the _primary kneading, so that the kneading can be performed while suppressing the thickening.

The temperature of the primary kneading is preferably adjusted according to the melting temperature of the resin material used. The temperature of the primary kneading may be higher than the melting point or softening point of the thermosetting resin (the thermosetting resin having the highest melting point or softening point when a plurality of types of thermosetting resins are used in combination). preferable. For example, the temperature of the primary kneading is 1 ° C. to 90 ° C. higher than the melting point or softening point of the thermosetting resin (the thermosetting resin having the highest melting point or softening point when a plurality of types of thermosetting resins are used in combination). A high temperature is preferable, a temperature 1 ° C. to 70 ° C. higher is more preferable, and a temperature 1 ° C. to 50 ° C. higher is further preferable. By kneading at such a temperature, the thermosetting resin can be sufficiently melted to maintain the fluidity, so that stirring and mixing can be performed satisfactorily.

In one aspect, the temperature of the primary kneading may be greater than or equal to the onset temperature measured by differential scanning calorimetry of the mixture after the addition of the curing accelerator in the secondary kneading. Even in such a case, in the primary kneading, the kneading can be performed with almost no progress of the curing reaction. Therefore, the production method of the present disclosure is particularly useful in that the primary kneading can be performed at the onset temperature or higher even when a curing accelerator having a low onset temperature is used. The onset temperature may be, for example, 120 ° C. or lower, 110 ° C. or lower, 100 ° C. or lower, 90 ° C. or lower, or 80 ° C. or lower. It may be 70 ° C. or lower.

In one embodiment, the temperature of the primary kneading may be 70 ° C. or higher, 80 ° C. or higher, 90 ° C. or higher, 100 ° C. or higher, 110 ° C. or higher. It may be at 120 ° C. or higher. From the viewpoint of suppressing the increase in viscosity, the temperature of the primary kneading may be 200 ° C. or lower. From this point of view, the temperature of the primary kneading may be 70 ° C. to 200 ° C., 80 ° C. to 200 ° C., 90 ° C. to 200 ° C., or 100 ° C. to 200 ° C. It may be 110 ° C. to 200 ° C., or 120 ° C. to 200 ° C.

〔cooling〕
After the primary kneading, the mixture is cooled. Cooling is not particularly limited, and the entire kneader may be cooled by a cooling device, or cooling may be performed in a cooling unit provided in the extrusion kneader as described above. The cooling temperature is not particularly limited, and the set temperature of the cooling device or the cooling unit is preferably in the range of 30 ° C. to 80 ° C. from the viewpoint of kneading property and suppression of thickening.

[Secondary kneading]
In the secondary kneading, a curing accelerator is added to the cooled mixture and the mixture is further kneaded. A mixture of a curing agent and a curing accelerator may be added in the secondary kneading. The amount of the curing accelerator added is small with respect to the resin component, for example, 1 part by mass with respect to 100 parts by mass of the resin component (that is, the total of the thermosetting resin and the curing agent added as needed) as described later. Even if the amount is about 30 parts by mass, the uneven distribution of the curing accelerator can be suppressed by adding the curing accelerator as a mixture with the curing agent in the secondary kneading, and the cured product has good physical properties. It tends to be easy to secure. Further, a part of the curing agent may be added by the primary kneading, and the rest may be mixed with the curing accelerator by the secondary kneading and added.

In the secondary kneading, a mixture of a curing agent, a curing accelerator, and a part of the inorganic filler (that is, an additional portion of the inorganic filler mixed in the primary kneading) may be added. It is considered that this makes it possible to further suppress the uneven distribution of each component.

The temperature of the secondary kneading is lower than the temperature of the primary kneading and lower than the onset temperature measured by the differential scanning calorimetry of the mixture after the curing accelerator is added in the secondary kneading. As a result, in the secondary kneading, the thickening of the composition containing the curing accelerator can be suppressed and the kneading can be performed satisfactorily. The temperature of the secondary kneading is not particularly limited as long as the above conditions are satisfied, and may be, for example, less than 120 ° C, less than 110 ° C, less than 100 ° C, or less than 90 ° C. It may be lower than 80 ° C., and may be lower than 70 ° C. From the viewpoint of kneading property, the temperature of the secondary kneading is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.

[Other processes]
The manufacturing method of the present disclosure may include other steps at arbitrary timings in addition to the primary kneading and the secondary kneading. For example, any component other than the thermosetting resin, the inorganic filler, and the curing accelerator is added at the same time as or at a different time from one or more of the thermosetting resin, the inorganic filler, and the curing accelerator, and kneaded. You may. The composition obtained through the primary kneading and the secondary kneading may be cooled and pulverized to obtain a solid thermosetting resin composition. The obtained solid thermosetting resin composition may be tableted by a tableting machine.

Hereinafter, each component used in the production method of the present disclosure, that is, each component contained in the thermosetting resin composition will be described.

<Thermosetting resin>
The type of the 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 exhibiting 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 a solid or a liquid under normal temperature and pressure (for example, 25 ° C. and atmospheric pressure), and is preferably a solid. The thermosetting resin may be used alone or in combination of two or more.

The thermosetting resin preferably contains an epoxy resin. Specifically, the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene. A novolak type epoxy resin (phenol novolak) which is an epoxidation of a novolak resin obtained by condensing or cocondensing a seed phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst. Type epoxy resin, orthocresol novolac type epoxy resin, etc.); Triphenylmethane type phenol resin obtained by condensing or cocondensing the above phenolic compound with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst. Triphenylmethane type epoxide resin obtained by epoxidizing the above; a copolymerization type epoxy obtained by co-condensing the above phenol compound, naphthol compound and aldehyde compound under an acidic catalyst. Resin: Diphenylmethane type epoxy resin which is a diglycidyl ether such as bisphenol A and bisphenol F; Biphenyl type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; Stilben-type epoxy which is a diglycidyl ether of a stilben-based phenol compound. Resin: Sulfur atom-containing epoxy resin that is a diglycidyl ether such as bisphenol S; Epoxide resin that is an alcoholic glycidyl ether such as butanediol, polyethylene glycol, polypropylene glycol; A glycidyl ester type epoxy resin that is a glycidyl ester of a valent carboxylic acid compound; a glycidylamine type epoxy resin that is obtained by substituting an active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, or isocyanuric acid with a glycidyl group; Dicyclopentadiene type epoxy resin which is an epoxide of a cocondensation resin of a phenol compound; vinylcyclohexene epoxide which is an epoxide of an olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxide. Cyclohexanecarboxylate, 2- (3,4-epoxide) cyclohexy An alicyclic epoxy resin such as ru-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane; a paraxylylene-modified epoxy resin which is a glycidyl ether of a paraxylylene-modified phenol resin; a glycidyl ether of a metaxylylene-modified phenol resin. Metaxylylene-modified epoxy resin; terpen-modified epoxy resin, which is a glycidyl ether of terpen-modified phenol resin; dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of dicyclopentadiene-modified phenol resin; cyclopentadiene-modified glycidyl ether of cyclopentadiene-modified phenol resin. Epoxy resin; Polycyclic aromatic ring-modified epoxy resin which is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; Naphthalene type epoxy resin which is a glycidyl ether of a naphthalene ring-containing phenol resin; Halogenated phenol novolac type epoxy resin; Hydroquinone type epoxy resin Trimethylol propane type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Epoxy aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin. Aralkill type epoxy resin; etc. Further, an epoxy resin made of a silicone resin, an epoxy resin made of an acrylic resin, and the like can be mentioned as the epoxy resin. The epoxy resin may be used alone or in combination of two or more.

When the thermosetting resin is an epoxy resin, 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 characteristics 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 shall be a value measured by a method according to JIS K 7236: 2009.

When the thermosetting resin is solid at 25 ° C., the melting point or softening point of the thermosetting resin is not particularly limited. From the viewpoint of blocking resistance, the melting point or softening point of the thermosetting resin is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. From the viewpoint of suppressing thickening due to kneading, the melting point or softening point of the thermosetting resin is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower. ..

In one embodiment, the melting point or softening point of the thermosetting resin may be equal to or higher than the onset temperature of the mixture after the curing accelerator is added in the secondary kneading. According to the production method of the present disclosure, it is possible to select a thermosetting resin regardless of the onset temperature of the mixture after adding the curing accelerator. Therefore, the production method of the present disclosure has sufficient kneadability even when a thermosetting resin having a relatively high melting point or softening point and a curing accelerator having a low curing temperature are used in combination, and as a result, the kneading property is sufficient. It is particularly useful in that good curability can be obtained. From this point of view, in one aspect, the melting point or softening point of the thermosetting resin may be 100 ° C. or higher, 110 ° C. or higher, or 120 ° C. or higher.

The content of the heat-curable resin is preferably 0.5% by mass to 50% by mass with respect to the total mass of the heat-curable resin composition from the viewpoint of strength, fluidity, heat resistance, moldability and the like. It is more preferably 2% by mass to 30% by mass, and further preferably 2% by mass to 20% by mass.

<Inorganic filler>
The material of the inorganic filler is not particularly limited. Specifically, as the material of the inorganic filler, silica such as molten silica and crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, magnesium oxide, silicon carbide, Inorganic materials such as beryllia, zirconia, zircone, fosterite, steatite, spinel, mulite, titania, talc, clay and mica can be mentioned. An inorganic filler having a flame-retardant effect may be used. Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium and zinc composite hydroxides, and zinc borate. Among the inorganic fillers, silica such as fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity.

The shape of the inorganic filler is not particularly limited, and a spherical shape is preferable from the viewpoint of filling property and mold wear resistance.

As the inorganic filler, one type may be used alone or two or more types may be used in combination. In addition, "using two or more kinds of inorganic fillers together" means, for example, when two or more kinds of inorganic fillers having the same component but different average particle diameters are used, two inorganic fillers having the same average particle diameter but different components are used. There are cases where more than one type is used and cases where two or more types of inorganic fillers having different average particle diameters and types are used.

The content of the inorganic filler is not particularly limited. From the viewpoint of further improving the properties such as thermal expansion coefficient, thermal conductivity, and elasticity of the cured product of the thermosetting resin composition, the content of the inorganic filler is 30% by volume or more of the entire thermocurable resin composition. It is preferably 40% by volume or more, 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 of the thermosetting resin composition, lowering the viscosity, etc., the content of the inorganic filler is preferably 99% by volume or less, preferably 98% by volume or less of the entire thermosetting resin composition. It is preferably 97% by volume or less.
Further, for example, when the thermosetting resin composition is used for compression molding, the content of the inorganic filler may be 70% by volume to 99% by volume of the entire thermosetting resin composition, and 80% by volume to 80% by volume. It may be 99% by volume, 83% by volume to 99% by volume, or 85% by volume to 99% by volume.

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 fired at 400 ° C. for 2 hours and then at 700 ° C. for 3 hours to evaporate the resin component and the like, and the mass of the remaining inorganic filler is measured. The volume is calculated from each mass obtained and the specific gravity of each, and the ratio of the volume of the inorganic filler to the total volume of the cured product is obtained and used as the content of the inorganic filler.

According to the production method of the present disclosure, there is a tendency that the kneadability of the mixture of each component can be improved. Therefore, according to the manufacturing method of the present disclosure, even if the composition cannot increase the content of the inorganic filler due to the influence of the increase in viscosity according to the conventional method, for example, the concern about the occurrence of wire flow in the semiconductor package. It is considered that the inorganic filler can be highly filled.

When the inorganic filler is in the form of particles, its average particle size is not particularly limited. For example, the volume average particle diameter of the entire inorganic filler is preferably 80 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less. May be good. The volume average particle size of the entire inorganic filler is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more. When the volume average particle size of the inorganic filler is 0.1 μm or more, the increase in viscosity of the thermosetting resin composition tends to be further suppressed. When the volume average particle diameter of the inorganic filler is 80 μm or less, the filling property into a narrow gap tends to be further improved. The volume average particle size of the inorganic filler shall be measured as the particle size (D50) when the accumulation from the small diameter side is 50% in the volume-based particle size distribution measured by the laser scattering diffraction method particle size distribution measuring device. Can be done.

<Curing accelerator>
The type of curing accelerator is not particularly limited, and is 1,5-diazabicyclo [4.3.0] nonen-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), etc. Cyclic amidine compounds such as diazabicycloalkene, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; Phenol novolak salts; these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy. Add a quinone compound such as -5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, or a compound having a π bond such as diazophenylmethane. Compounds with intramolecular polarization; cyclic amidine compounds such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholin tetraphenylborate salt, etc. Tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compound; tetra-n-butylammonium acetate, Amidine salt compounds such as tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide; primary phosphine such as ethylphosphine and phenylphosphine, dimethylphosphine, diphenylphosphine and the like Secondary phosphine, 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 (tetraalkenylphenyl) phosphine, trialkylphos Organic phosphines such as fins, dialkylarylphosphines, alkyldiarylphosphines, trinaphthylphosphines, tertiary phosphines such as tris (benzyl) phosphines; phosphine compounds such as complexes of said organic phosphines with organic borons; said organic phosphines or said above. Phenol compounds and maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1 , 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone and other quinone compounds, and diazophenylmethane and other quinone compounds with a π bond added. Compounds having; Phenol iodide, phenol 2-iodide, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, Halogen such as 4-bromo-2,6-di-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl A compound having intramolecular polarization obtained through a step of dehalogenation after reacting a phenol compound; tetra-substituted phosphonium such as tetraphenylphosphonium, tetra-substituted phosphonium such as tetraphenylphosphonium tetra-p-tolylbolate. Tetra-substituted phosphonium compounds; phosphobetaine compounds; adducts of phosphonium compounds and silane compounds, such as the tetraphenylborate salt of the above, salts of tetra-substituted phosphoniums and phenolic compounds, and the like. The curing accelerator may be used alone or in combination of two or more.

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

Further, for example, when an epoxy resin is used as a thermosetting resin, examples of a curing accelerator capable of low-temperature curing include an adduct of tributylphosphine and 1,4-benzoquinone, dimethylaminopyridine, and 2-ethyl-4-methylimidazole. , 2-Methylimidazole, 1-benzyl-2-methylimidazole and the like.

The content of the curing accelerator is preferably 0.1 part by mass to 30 parts by mass, more preferably 1 part by mass to 15 parts by mass, and 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component. It may be 1 part by mass to 5 parts by mass. When the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to be cured well in a short time. When the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.

<Hardener>
In the primary kneading or the secondary kneading, a curing agent may be further added. The curing agent is not particularly limited as long as it is a compound that causes a curing reaction with a thermosetting resin that undergoes primary kneading, and may itself be a thermosetting resin. For example, examples of the curing agent used in combination with the epoxy resin include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, an isocyanate curing agent, and a blocked isocyanate curing agent. As the curing agent, one type may be used alone or two or more types may be used in combination. From the viewpoint of improving heat resistance, the curing agent is preferably a compound having a phenolic hydroxyl group in the molecule (also referred to as a phenol curing agent). The curing agent may be a solid or a liquid under normal temperature and pressure (for example, 25 ° C. and atmospheric pressure), and is preferably a solid.

Specifically, the phenolic curing agent is a polyhydric phenol compound such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol. , At least one phenolic compound selected from the group consisting of phenolic compounds such as aminophenol and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde. A novolak-type phenol resin obtained by condensing or co-condensing a compound under an acidic catalyst; a phenol aralkyl resin and naphthol aralkyl synthesized from the above phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl and the like. Aralkyl-type phenolic resin such as resin; paraxylylene and / or metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpene-modified phenolic resin; dicyclopentadiene-type phenol synthesized by copolymerization of the above phenolic compound and dicyclopentadiene. Resin and dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified phenolic resin; biphenyl-type phenolic resin; A triphenylmethane-type phenolic resin obtained by condensing or co-condensing in (1); a phenolic resin obtained by copolymerizing two or more of these types can be mentioned. The phenol curing agent may be used alone or in combination of two or more.

The functional group equivalent of the curing agent (hydroxyl equivalent in the case of a phenol curing agent, active hydrogen equivalent in the case of an amine curing agent) is not particularly limited. From the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability, the functional group equivalent of the curing agent is preferably 70 g / eq to 1000 g / eq, preferably 80 g / eq to 500 g / eq. Is more preferable.

The hydroxyl group equivalent in the case of a phenol curing agent means a value calculated based on the hydroxyl value measured in accordance with JIS K0070: 1992. The active hydrogen equivalent in the case of an amine curing agent refers to a value calculated based on the amine value measured in accordance with JIS K7237: 1995.

When the curing agent is a solid, its softening point or melting point is not particularly limited. The softening point or melting point of the curing agent is preferably 40 ° C. to 180 ° C., and is thermally curable, for example, from the viewpoint of moldability and reflow resistance when a thermosetting resin composition is used as a sealing material. From the viewpoint of handleability during production of the resin composition, the temperature is more preferably 50 ° C to 130 ° C.

The melting point or softening point of the curing agent shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.

The equivalent ratio of the thermosetting resin to the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the thermosetting resin (the number of functional groups in the curing agent / the number of functional groups in the thermosetting resin) is particularly limited. Not done. The equivalent ratio of the thermosetting resin and the curing agent is preferably set in the range of 0.5 to 2.0, preferably in the range of 0.6 to 1.3, from the viewpoint of suppressing the unreacted components of each. It is more preferable to be set. From the viewpoint of moldability, it is more preferable that the equivalent ratio of the thermosetting resin and the curing agent is set in the range of 0.8 to 1.2.

<Additives>
In addition to the above-mentioned components, the thermosetting resin composition may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, a colorant, and a stress relaxation agent. The thermosetting resin composition may contain various additives generally used in the art, if necessary, in addition to the additives exemplified below.

(Coupling agent)
The thermosetting resin composition may contain a coupling agent in order to enhance the adhesiveness 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.

Examples of the silane compound include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 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, glycid Examples thereof include xiooctyl trimethoxysilane and methacryloxyl trimethoxysilane.

Titanium compounds include isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, and tetra (2,2). -Diallyloxymethyl-1-butyl) bis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylic isostearoyl titanate, Examples thereof include isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacrylic titanate, isopropyltri (dioctyl phosphate) titanate, isopropyltricylphenyl titanate, tetraisopropylbis (dioctyl phosphate) titanate and the like.

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, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably to 15 parts by mass. When the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness with the metal member tends to be further improved. When the amount of the coupling agent is 20 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability tends to be improved.

(Ion exchanger)
The thermosetting resin composition may contain an ion exchanger. In particular, when the thermosetting resin composition is used as a molding material for sealing, it contains an ion exchanger from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device provided with the element to be sealed. Is preferable. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, hydrotalcite represented by the following general formula (A) is preferable.

Mg _(1-X) Al _X (OH) ₂ (CO ₃ ) _{X / 2}・ mH ₂ O …… (A)
(0 <X ≤ 0.5, m is a positive number)

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. For example, it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component.

(Release agent)
The thermosetting resin composition may contain a mold release agent from the viewpoint of obtaining good mold releasability from the mold at the time of molding. The release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, ester waxes such as higher fatty acid metal salts and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene. The release agent may be used alone or in combination of two or more.

When the thermosetting resin composition contains a mold release agent, the amount thereof is preferably 0.01 part by mass to 10 parts by mass, more preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the resin component. .. When the amount of the mold release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained. When it is 10 parts by mass or less, better adhesiveness and curability tend to be obtained.

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

When the thermosetting resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin component.

(Colorant)
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, lead tan, and red iron oxide. The content of the colorant can be appropriately selected according to the purpose and the like. As the colorant, one type may be used alone or two or more types may be used in combination.

(Stress relaxation agent)
The thermosetting resin composition may contain a stress relaxation agent such as silicone oil and silicone rubber particles. By containing the stress relaxation agent, it is possible to reduce the warpage deformation of the package and the occurrence of package cracks when the thermosetting resin composition is used as a sealing material. Examples of the stress relaxation agent include commonly used known stress relaxation agents (flexible agents). Specifically, thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), and acrylic. Rubber particles such as rubber, urethane rubber, silicone powder, core-shell such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer Examples include rubber particles having a structure. As the stress relaxation agent, one type may be used alone or two or more types may be used in combination.

<< Thermosetting resin composition >>
The thermosetting resin composition of the present disclosure is obtained by the above-mentioned production method of the present disclosure. The thermosetting resin composition may be solid or liquid under normal temperature and pressure (for example, 25 ° C. and atmospheric pressure), and is preferably solid. When the thermosetting resin composition is a solid, the shape is not particularly limited, and examples thereof include powder, granules, and tablets.

[Characteristics of thermosetting resin composition]
(Hardness at heat)
The thermal hardness of the cured product of the thermosetting resin composition measured by the following method is preferably 50 or more, more preferably 60 or more, and further preferably 70 or more.
The hardness at heat is measured as follows. The thermosetting resin composition is molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the conditions of a mold temperature of 150 ° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds. The thermal hardness is measured using HD-1120 (type D) manufactured by Ueshima Seisakusho Co., Ltd.

(Liquidity)
The flow distance obtained when the thermosetting resin composition is molded using the spiral flow measurement mold according to EMMI-1-66 is preferably 80 cm or more, and more preferably 100 cm or more. It is preferably 120 cm or more, and more preferably 120 cm or more. The upper limit of the flow distance is not particularly limited, and may be, for example, 300 cm or less.
The molding conditions are a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds by a transfer molding machine.

(Melting viscosity)
The minimum melt viscosity of the thermosetting resin composition at 175 ° C. is preferably 30 Pa · s or less, more preferably 20 Pa · s or less, and 10 Pa · s or less from the viewpoint of moldability. Is even more preferable. From the viewpoint of suppressing burrs, the minimum melt viscosity of the thermosetting resin composition at 175 ° C. is preferably 5 Pa · s or more, more preferably 10 Pa · s or more, and 20 Pa · s or more. Is even more preferable. The minimum melt viscosity can be measured using a high-grade flow tester (for example, manufactured by Shimadzu Corporation).

(Gel time)
The gel time of the thermosetting resin composition measured by the following method is preferably 40 seconds or more, more preferably 50 seconds or more, and more preferably 60 seconds or more from the viewpoint of suppressing thickening. Is even more preferable. From the viewpoint of curability, the gel time is preferably 150 seconds or less, more preferably 120 seconds or less, and further preferably 100 seconds or less.
The gel time is measured by the following method. Measurement using a curast meter (for example, JSR Trading Co., Ltd.) is carried out on 3 g of the thermosetting resin composition at a temperature of 175 ° C., and the time until the rise of the torque curve is defined as the gel time (seconds).

[Use of thermosetting resin composition]
The use of the thermosetting resin composition of the present disclosure is not particularly limited, and for example, as illustrated above, it can be used in various mounting techniques as a sealing material for electronic component devices. Further, the thermosetting resin composition of the present disclosure includes a thermosetting resin composition such as a resin molded body for various modules, a resin molded body for a motor, a resin molded body for a vehicle, a sealing material for a protective material for an electronic circuit, and the like. It can be used in various applications where it is desirable to have good curability.

≪Electronic parts equipment≫
The electronic component device of the present disclosure includes an element sealed with a thermosetting resin composition obtained by the above-mentioned production method of the present disclosure. That is, the electronic component device includes a cured product of the thermosetting resin composition obtained by the above-mentioned production method of the present disclosure.

Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other support members, as well as elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors, etc.). , A passive element such as a coil, etc.), and the element portion obtained by mounting the element portion is sealed with a thermosetting resin composition.
More specifically, after fixing the element on the lead frame and connecting the terminal part and the lead part of the element such as a bonding pad by wire bonding, bumps, etc., transfer molding or the like using a thermosetting resin composition or the like. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (SmallOdlinePack) General resin-sealed ICs such as Outline Package) and TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier with a bump is sealed with a thermosetting resin composition. A COB (Chip On Board) module, hybrid IC, or multi having a structure in which an element connected by wire bonding, flip chip bonding, solder, or the like is sealed to a wiring formed on a support member with a thermosetting resin composition. Chip module, etc .; After mounting the element on the front surface of the support member having terminals for connecting the wiring board on the back surface and connecting the element and the wiring formed on the support member by bump or wire bonding, the thermosetting resin composition Examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package) having a structure in which an element is sealed with an object. Further, the thermosetting resin composition can also be preferably used in the printed wiring board.

Examples of the method for sealing the electronic component device using the thermosetting resin composition include a low-pressure transfer molding method, an injection molding method, a compression molding method, and the like.

The sealing temperature of the element is not particularly limited. The sealing temperature may be, for example, 170 ° C. to 180 ° C., which is a general sealing temperature. Further, according to the method for producing a thermosetting resin composition of the present disclosure, it is possible to produce a low temperature curable thermosetting resin composition, so that the sealing temperature is less than 170 ° C. and 160 ° C. or less. It is also possible to set the temperature to 150 ° C. or lower, 140 ° C. or lower, 130 ° C. or lower, 120 ° C. or lower, or the like.

≪Manufacturing method of electronic parts equipment≫
In one aspect, the method of manufacturing an electronic component device comprises sealing the device at 150 ° C. or lower with the thermosetting resin composition obtained by the manufacturing method of the present disclosure described above. According to the method for manufacturing an electronic component device of this aspect, it is possible to reduce the influence on the element in the heat treatment at the time of sealing. The sealing temperature of the element may be 140 ° C. or lower, 130 ° C. or lower, 120 ° C. or lower, or the like.

Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

<Preparation of thermosetting resin composition>
First, each component shown below was prepared.

(Thermosetting resin)
-Epoxy resin 1: YL-6121 (trade name, Nippon Kayaku Co., Ltd., epoxy equivalent 170 g / eq to 180 g / eq, aralkyl type epoxy resin with softening point 53 ° C to 63 ° C)
-Epoxy resin 2: jER YX-4000H (trade name, Mitsubishi Chemical Corporation, epoxy equivalent 180 g / eq to 192 g / eq, biphenyl type epoxy resin with melting point 105 ° C)
-Epoxy resin 3: EPPN501HY (trade name, Nippon Kayaku Co., Ltd., epoxy equivalent 163 g / eq to 175 g / eq, triphenylmethane type epoxy resin with softening point 57 ° C to 63 ° C)

(Hardener)
-Curing agent 1: MEHC-7851 (trade name, Meiwa Kasei Co., Ltd., biphenylene aralkyl type phenol resin having a hydroxyl group equivalent of 205 g / eq, softening point 60 ° C to 70 ° C)
-Curing agent 2: SN-485 (trade name, Nittetsu Chemical & Materials Co., Ltd., naphthalene aralkyl type phenol resin with hydroxyl group equivalent of 215 g / eq, softening point 80 ° C to 90 ° C)

(Inorganic filler)
-Inorganic filler: Spherical silica filler with an average particle diameter of 1.5 μm (without surface treatment)

(Coupling agent)
-Coupling agent: KBM-573 (trade name, Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane)

(Curing accelerator)
・ Curing accelerator: Phosphorus-based curing accelerator

(Other additives)
・ Release agent: Hoechst wax (Hoechst)
・ Colorant: Carbon black

The thermosetting resin compositions of Examples 1 to 5 were prepared by the following method (referred to as "manufacturing method A"). The main supply component and the sub-supply component shown in Table 1 were mixed in each container, and pulverized and stirred with a high-speed mixer. As the kneader, a twin-screw kneading extruder including a first kneading section, a second kneading section, and a cooling section arranged between the first kneading section and the second kneading section was used. The main feed component was supplied to the first kneading section from the inlet, and melt-kneaded at the first kneading temperature in Table 1 for about 2 minutes. Then, the by-supply component was added to the second kneading section through the opening, combined with the mixture extruded from the first kneading section through the cooling section, and melt-kneaded at the second kneading temperature shown in Table 1 for about 1 minute. A powdery thermosetting resin composition was prepared by cooling the melt with a press roll in which cold water at 10 ° C. was circulated and pulverizing the sheet in the form of powder.

The thermosetting resin compositions of Comparative Examples 1 and 2 were prepared by the following method (referred to as "manufacturing method B"). All of the components shown in Table 1 were mixed in a container, pulverized and stirred with a high speed mixer. Then, it was melt-kneaded at the first kneading temperature shown in Table 1 for about 2 minutes. Then, it was melt-kneaded at the second kneading temperature for about 1 minute. A powdery thermosetting resin composition was prepared by cooling the melt with a press roll in which cold water at 10 ° C. was circulated and pulverizing the sheet in the form of powder.

<Evaluation of thermosetting resin composition>
The prepared thermosetting resin composition was evaluated by various tests shown below. The evaluation results are shown in Table 1. Unless otherwise specified, the thermosetting resin composition was molded by 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. If necessary, post-curing was performed at 175 ° C. for 6 hours.

[Spiral flow]
The thermosetting resin composition was molded under the above conditions using a spiral flow measuring die according to EMMI-1-66, and the flow distance was determined.

[Melting viscosity]
The minimum melt viscosity of the thermosetting resin composition at 175 ° C. was measured using a high-grade flow tester (manufactured by Shimadzu Corporation).

[Gel time]
Measurement using a curast meter of JSR Trading Co., Ltd. was carried out on 3 g of the thermosetting resin composition at a temperature of 175 ° C., and the time until the rise of the torque curve was defined as the gel time (seconds).

[Hardness at heat]
The thermosetting resin composition is molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the conditions of a mold temperature of 150 ° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds. The thermal hardness was measured using HD-1120 (type D) manufactured by Ueshima Seisakusho.

[Presence or absence of aggregation of inorganic filler]
The thermosetting resin composition was molded, and the appearance of the molded product was visually observed to confirm the presence or absence of aggregation of the inorganic filler.

In any of Examples 1 to 5 and Comparative Examples 1 and 2, the onset temperature of the thermosetting resin composition is 100 ° C. or higher and lower than 140 ° C.

As shown in Table 1, the thermosetting resin compositions of Examples 1 to 5 produced by the production method A have excellent fluidity, good gel time, and agglomeration of the inorganic filler in the cured product is also observed. Was not done. Further, the hot hardness of the cured product was also well maintained.
On the other hand, in Comparative Example 1, agglomeration of the inorganic filler was observed in the cured product, and the hardness at the time of heat was also low. It is considered that this is because the resin was not sufficiently melted during kneading and the kneading could not be performed well.
Further, the thermosetting resin composition of Comparative Example 2 was inferior in fluidity and gel time. It is considered that this is because the kneading was performed at 140 ° C. with the curing accelerator added, so that the reaction partially proceeded and the composition became thickened.

From these results, according to the production method of the present disclosure, the composition can be suitably applied to a composition having a low onset temperature after the addition of the curing accelerator, that is, a low-temperature curing type composition, and has fluidity and fluidity. It is considered that the curability can be ensured well.

1 Main material inlet 2 Side feeder 10 Kneading extruder A 1st kneading section B Cooling section C 2nd kneading section

Claims (12)

Primary kneading, in which a mixture of thermosetting resin and inorganic filler is kneaded in a kneader,
With cooling of the mixture after the primary kneading,
Secondary kneading, in which a curing accelerator is added to the cooled mixture and further kneaded,
Including
The temperature of the secondary kneading is lower than the onset temperature measured by differential scanning calorimetry of the mixture after adding the curing accelerator in the secondary kneading.
A method for producing a thermosetting resin composition. The method for producing a thermosetting resin composition according to claim 1, wherein the temperature of the primary kneading is equal to or higher than the onset temperature. The method for producing a thermosetting resin composition according to claim 1 or 2, wherein the melting point or softening point of the thermosetting resin is equal to or higher than the onset temperature. The method for producing a thermosetting resin composition according to any one of claims 1 to 3, wherein the onset temperature is 120 ° C. or lower. The method for producing a thermosetting resin composition according to any one of claims 1 to 4, wherein the temperature of the secondary kneading is less than 120 ° C. The method for producing a thermosetting resin composition according to any one of claims 1 to 5, wherein the temperature of the primary kneading is 120 ° C. or higher. The method for producing a thermosetting resin composition according to any one of claims 1 to 6, wherein the thermosetting resin has a melting point or a softening point of 120 ° C. or higher. The thermosetting resin composition according to any one of claims 1 to 7, further comprising adding a curing agent in at least one selected from the group consisting of the primary kneading and the secondary kneading. Manufacturing method. The kneader
The first kneading part for performing the primary kneading and
The second kneading part for performing the secondary kneading and
A cooling section arranged between the first kneading section and the second kneading section,
The method for producing a thermosetting resin composition according to any one of claims 1 to 8, which is a kneading extruder comprising the above. A thermosetting resin composition obtained by the production method according to any one of claims 1 to 9. An electronic component device comprising an element sealed with a thermosetting resin composition obtained by the production method according to any one of claims 1 to 9.
A method for manufacturing an electronic component device, which comprises sealing an element at 150 ° C. or lower with a thermosetting resin composition obtained by the manufacturing method according to any one of claims 1 to 9.

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