JP2022107373A - Method for producing thermosetting resin composition, thermosetting resin composition, and electronic component device - Google Patents

Abstract

To provide a method for producing a thermosetting resin composition which maintains good fluidity and is excellent in strength when formed into a cured product, a thermosetting resin composition obtained by the production method, and an electronic component device including an element sealed with the thermosetting resin composition.SOLUTION: The method for producing a thermosetting resin composition includes: primary kneading in which a mixture of a thermosetting resin, an inorganic filler, and a coupling agent is kneaded at 100°C or higher; and secondary kneading in which a curing accelerator is added and kneading is further performed after the primary kneading.SELECTED DRAWING: Figure 1

Description

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

Thermosetting resin compositions are widely used as materials for encapsulating semiconductor devices. As a general method for preparing a thermosetting resin composition, a method of mixing and kneading a thermosetting resin and an inorganic filler is adopted.

In a thermosetting resin composition containing an inorganic filler, a coupling agent may be used in combination in order to enhance the dispersibility of the inorganic filler. By mixing the inorganic filler with the coupling agent or surface-treating with the coupling agent, the affinity between the inorganic filler and the resin component can be enhanced. As a method of mixing the inorganic filler with the coupling agent or surface-treating with the coupling agent, a dry treatment method, a wet treatment method, an integral blend method and the like are adopted (see, for example, Patent Documents 1 and 2). ). The dry treatment method is a method in which an inorganic filler is mixed with a coupling agent in advance without a solvent to perform surface treatment of the inorganic filler. The wet treatment method is a method in which the inorganic filler and the coupling agent are mixed in advance in the presence of a solvent to perform surface treatment on the inorganic filler. The integral blending method is a method in which a coupling agent is added and mixed when the resin component and the inorganic filler are mixed, and the coupling agent reacts with the inorganic filler on the one hand and with the resin component on the other hand. By interacting, the dispersibility of the inorganic filler is enhanced.

Japanese Unexamined Patent Publication No. 2008-81590 Japanese Unexamined Patent Publication No. 2013-108024

The integral blending method may be preferably adopted in terms of simplicity, curability and physical characteristics of the cured product associated therewith, as compared with a pretreatment method such as a dry treatment method or a wet treatment method. Since the reaction between the inorganic filler and the coupling agent proceeds preferably at a specific temperature or higher, in order to efficiently improve the dispersibility of the inorganic filler by the integral blend method, the inorganic filler and the coupling agent are used. It is desirable that the kneading of the resin mixture containing the above is carried out at a temperature equal to or higher than the reaction temperature of the inorganic filler and the coupling agent, for example, 100 ° C. or higher. On the other hand, when the resin mixture containing the inorganic filler and the coupling agent is kneaded at a high temperature in the integral blending method, the resin mixture becomes thickened and cannot be sufficiently mixed, resulting in a decrease in curability and a cured product. It may lead to a decrease in strength. Further, if the resin is unevenly distributed due to insufficient kneading, the fluidity during molding may decrease. Furthermore, when high shear stress is applied for sufficient mixing, thickening is accelerated by shear heat generation.

In view of such circumstances, the present disclosure discloses a method for producing a thermosetting resin composition which maintains good fluidity and is excellent in strength when made into a cured product, and a thermosetting resin composition obtained by the production method. An object of the present invention is to provide an electronic component device including an element sealed with the thermosetting resin composition.

Means for solving the above problems include the following aspects.
<1> Primary kneading in which a mixture of a thermosetting resin, an inorganic filler, and a coupling agent is kneaded at 100 ° C. or higher.
After the primary kneading, a curing accelerator is added and further kneaded, and a secondary kneading is performed.
A method for producing a thermosetting resin composition, which comprises.
<2> The production method according to <1>, wherein the temperature of the secondary kneading is lower than the temperature of the primary kneading.
<3> The production method according to <1> or <2>, wherein the temperature of the secondary kneading is lower than the onset temperature of the mixture after adding the curing accelerator, which is measured by differential scanning calorimetry.
<4> The production method according to any one of <1> to <3>, wherein the onset temperature of the mixture after adding the curing accelerator is lower than 120 ° C. by differential scanning calorimetry. ..
<5> The production method according to any one of <1> to <4>, wherein the volume average particle diameter of the inorganic filler is 20 μm or less.
<6> A thermosetting resin composition obtained by the production method according to any one of <1> to <5>.
<7> 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 <5>.

According to the present disclosure, a method for producing a thermosetting resin composition which maintains good fluidity and is excellent in strength when made into a cured product, a thermosetting resin composition obtained by the manufacturing method, and the present invention. An electronic component device comprising an element sealed with a thermosetting resin composition is provided.

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 >>
In the method for producing a thermosetting resin composition of the present disclosure (hereinafter, also referred to as the production method of the present disclosure), a mixture of a thermosetting resin, an inorganic filler, and a coupling agent is kneaded at 100 ° C. or higher. It includes a primary kneading and a secondary kneading in which a curing accelerator is added after the primary kneading and the mixture is further kneaded. According to the production method of the present disclosure, the inorganic filler can be reacted with the coupling agent at 100 ° C. or higher in the primary kneading, so that the dispersibility of the inorganic filler is enhanced and the thermosetting resin composition is formed. It is considered that the fluidity of the plastic can be improved. Further, it is considered that the thickening in the primary kneading can be suppressed and the uneven distribution of each component can be suppressed by adding the curing accelerator afterwards. As a result, it is considered that good fluidity and curability can be achieved.

[Primary kneading]
In the primary kneading, a mixture of a thermosetting resin, an inorganic filler, and a coupling agent is kneaded at 100 ° C. or higher. At this time, other components may be further mixed if necessary. In the primary kneading, a part of the curing accelerator may be mixed as long as the influence of thickening on the kneadability does not pose a practical problem. In the present disclosure, when the curing accelerator is added in a plurality of times, for convenience, after adding the majority of the total curing accelerator to be finally added, that is, 50% by mass or more of the curing accelerator. Kneading shall be referred to as secondary kneading. 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. Preferably, in the primary kneading, the thermosetting resin, the inorganic filler, the coupling agent, and if necessary, other additives are kneaded without adding the curing accelerator.

The kneading method in the primary kneading is not particularly limited. For example, a method of melt-kneading with a kneader (biaxial kneader, triaxial kneader, etc.), a roll (three rolls, etc.), an extruder, or the like which has been preheated to a desired temperature can be mentioned.

The temperature of the primary kneading is 100 ° C. or higher, and it is preferable to adjust the temperature according to the reaction temperature of the inorganic filler and the coupling agent. The temperature of the primary kneading may be 110 ° C. or higher, or 120 ° C. or higher. By performing the primary kneading at such a temperature, the reaction between the inorganic filler and the coupling agent tends to proceed favorably, and the dispersibility of the components tends to be enhanced. From the viewpoint of efficiently suppressing the increase in viscosity in kneading, 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 100 ° C. to 200 ° C., 110 ° C. to 200 ° C., or 120 ° C. to 200 ° C.

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 melted and the fluidity can be maintained, so that stirring and mixing can be performed satisfactorily.

The shearing conditions in the primary kneading are not particularly limited. According to the production method of the present disclosure, thickening of the mixture in the primary kneading can be suppressed, so that the mixture tends to be suitably kneaded even if the shear stress and the shear rate are increased as compared with the conventional method. ..

[Secondary kneading]
Following the primary kneading, a curing accelerator is added to further perform the secondary kneading. The method of adding the curing accelerator is not particularly limited as long as the curing accelerator can be added later. For example, a method (side feed) of adding a curing accelerator to the mixture subjected to the primary kneading as described above from an inlet provided separately from the inlet of the components of the primary kneading can be mentioned.

The temperature at the time of kneading in the secondary kneading is not particularly limited, and from the viewpoint of suppressing thickening, it is preferable to set the temperature lower than the temperature of the primary kneading. The temperature of the secondary kneading is preferably lower than 120 ° C, more preferably lower than 110 ° C, and even more preferably lower than 100 ° C.

The temperature of the secondary kneading is preferably lower than the onset temperature measured by differential scanning calorimetry (DSC) of the mixture after the addition of the curing accelerator in the secondary kneading, for example, 1 ° C. to 100 ° C. As a result, thickening in the secondary kneading can be suppressed. 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.

In secondary kneading, the onset temperature measured by differential scanning calorimetry (DSC) of the mixture after the addition of the curing accelerator may be lower than 120 ° C, lower than 110 ° C, 100 ° C. May be lower. According to the manufacturing method of the present disclosure, since the primary kneading and the secondary kneading performed by adding the curing accelerator are sequentially performed, the temperature of the primary kneading is irrespective of the onset temperature of the mixture after the addition of the curing accelerator. Can be 100 ° C. or higher. Thereby, the primary kneading can be performed at a temperature at which the reaction between the inorganic filler and the coupling agent proceeds satisfactorily, for example, at a temperature at which the resin component is sufficiently melted, and the dispersibility of the resin component and the inorganic filler is enhanced. be able to.

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, prior to the primary kneading, each component may be mixed at room temperature with a mixer or the like. In addition, any component other than the thermosetting resin, the inorganic filler, the coupling agent, and the curing accelerator can be added to one or more components of the thermosetting resin, the inorganic filler, the coupling agent, and the curing accelerator. It may be added at the same time as or at a different time and kneaded. The composition obtained through the primary kneading and the secondary kneading may be cooled and pulverized to obtain a solid thermosetting resin composition.

In one aspect, the primary kneading and the secondary kneading in the production method of the present disclosure can be carried out using a kneading extruder. A schematic cross-sectional view of a kneading extruder that can be used in one embodiment is shown in FIG. The kneading extruder 10 includes a first kneading section A, a second kneading section B arranged downstream in the extrusion direction of the first kneading section A, a main material input port 1 connected to the first kneading section A, and the above. A side feeder 2 connected to the second kneading portion B is provided. In FIG. 1, the arrows indicate the extrusion direction of the composition. The thermosetting resin, the inorganic filler, and the coupling agent are charged into the first kneading section A simultaneously or sequentially from the main material charging port 1, and the curing accelerator is charged into the second kneading section B from the side feeder 2. Primary kneading is performed in the first kneading section A, and the kneaded product is extruded and moved to the second kneading section B. The transferred kneaded product merges with the hardening accelerator and is further kneaded. It is also possible to set the temperature of the primary kneading and the temperature of the secondary kneading, respectively. For example, a cooling unit (not shown) may be provided between the first kneading portion A and the second kneading portion B, and the secondary kneading may be performed at a lower temperature than the primary kneading. Further, the first kneading portion A may be set to a higher temperature and the second kneading portion B may be set to a lower temperature, and the second kneading portion B employs a mechanism for gradually cooling the contents in the extrusion direction. You may. The manufacturing method of the present disclosure is not limited to the aspect of the drawing.

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.

Among the above epoxy resins, the triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton. For example, an epoxy resin obtained by glycidyl etherification of a triphenylmethane-type phenol resin such as a novolak-type phenol resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferable, and is represented by the following general formula (VIII). The epoxy resin to be used is more preferable. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, trade name), EPPN-501HY, EPPN-502H (Nippon Kayaku Co., Ltd.) in which i is 0 and k is 0. , Product name), etc. are available as commercial products.

In formula (VIII), R ¹⁷ and R ¹⁸ represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different. i indicates an integer of 0 to 3 independently, and k indicates an integer of 0 to 4 independently. n is an average value and indicates a number from 0 to 10.

Among the above epoxy resins, 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 preferable. Among the epoxy resins represented by the following general formula (II), the 3,3', ^{5,5'positions} of R8 where the oxygen atom is substituted are the methyl groups at the 4 and 4'positions. Yes, the other R ^8s are hydrogen atoms YX-4000 and YX-4000H (Mitsubishi Chemical Co., Ltd., trade name), and all R ^8s are hydrogen atoms 4,4'-bis (2,3-epoxy). Propoxy) Biphenyl, when all R ^8s are hydrogen atoms and when the positions of R ⁸ where oxygen atoms are substituted are the 4 and 4'positions, the 3, 3', 5, 5'positions are methyl groups. Other than that, YL-6121H (Mitsubishi Chemical Co., Ltd., trade name), which is a mixed product when R ⁸ is a hydrogen atom, is available as a commercially available product.

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

Since the biphenyl type epoxy resin has a low melt viscosity, for example, when a thermosetting resin composition is used as a sealing material, even if the inorganic filler is highly filled for the purpose of improving reflow resistance, the wire sweep in the semiconductor package Less likely to cause problems. Therefore, in recent years, a biphenyl type epoxy resin has come to be preferably used as a sealing material for a surface mount type package. Although the biphenyl type epoxy resin has a low melt viscosity around 180 ° C., it has a relatively high softening point. Therefore, kneading at a high temperature is desirable in order to sufficiently disperse the resin by kneading. According to the manufacturing method of the present disclosure, since the primary kneading is performed at 100 ° C. or higher, even when the thermosetting resin contains a biphenyl type epoxy resin, the resin component and the inorganic filler are preferably kneaded while suppressing an increase in viscosity. Tends to be possible.

Among the above epoxy resins, the aralkyl type epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene and bis (methoxymethyl) biphenyl. Alternatively, the epoxy resin is not particularly limited as long as it is an epoxy resin made from a phenol resin synthesized from these derivatives. For example, a phenol resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or derivatives thereof. The epoxy resin obtained by glycidyl etherification is preferable, and the epoxy resin represented by the following general formula (X) or (XI) is more preferable.

Among the epoxy resins represented by the following general formula (X), i is 0 and R ³⁸ is a hydrogen atom NC-3000 (Nippon Kayaku Co., Ltd., trade name), i is 0, and R ³⁸ . CER-3000 (Nippon Kayaku Co., Ltd., trade name), which is a mixture of an epoxy resin in which is a hydrogen atom and an epoxy resin in which all R ^8s of the general formula (II) are hydrogen atoms at a mass ratio of 80:20, etc. It is available as a commercial product. Further, among the epoxy resins represented by the following general formula (XI), ESN-175 (Nittetsu Chemical & Materials Co., Ltd., trade name) in which l is 0, j is 0, and k is 0, etc. Is available as a commercial product.

In formulas (X) and (XI), R ³⁸ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. R ³⁷ and R ³⁹ to R ⁴¹ represent monovalent organic groups having 1 to 18 carbon atoms, and all of them may be the same or different. i is an integer of 0 to 3 independently, j is an integer of 0 to 2 independently, k is an integer of 0 to 4 independently, and l is an integer of 0 to 4 independently. show. n is an average value, and each is independently a number from 0 to 10.

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 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, and more preferably 50 ° 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 further preferably 130 ° C. or lower.
Among them, epoxy resins 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 melting point of 90 ° C. or higher) for the purpose of satisfying recent demands for high thermal conductivity, reflow resistance, etc. The production method of the present disclosure can be preferably used even when a high crystalline resin (° C. or higher, 100 ° C. or higher, 110 ° C. or higher, or 120 ° C. or higher) is used.
The melting point of the epoxy resin shall be a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin shall be a value measured by a method (ring ball method) according to JIS K 7234: 1986.

When the thermosetting resin composition contains an epoxy resin, the content of the epoxy resin is 0.5 with respect to the total mass of the thermosetting resin composition from the viewpoints of strength, fluidity, heat resistance, moldability and the like. It is preferably from mass% to 50% by mass, more preferably from 2% by mass to 30% by mass, and even more preferably from 2% by mass to 20% by mass.

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 causes a curing reaction with the thermosetting resin used in combination. The curing agent itself may 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 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.

A phenol curing agent is a compound having a phenolic hydroxyl group in the molecule (hereinafter, also referred to as a phenol resin). Specific examples of the phenolic resin include polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenyl. At least one phenolic compound selected from the group consisting of phenolic compounds such as phenol and aminophenol and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like. A novolak-type phenol resin obtained by condensing or co-condensing an aldehyde compound under an acidic catalyst; a phenol aralkyl resin and naphthol synthesized from the above phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl and the like. Aralkyl-type phenolic resin such as aralkyl resin; paraxylylene and / or metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpene-modified phenolic resin; dicyclopentadiene-type synthesized by copolymerization of the above phenolic compound and dicyclopentadiene. Phenolic resin and dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified phenolic resin; biphenyl-type phenolic resin; Examples thereof include a triphenylmethane-type phenolic resin obtained by condensing or co-condensing underneath; a phenolic resin obtained by copolymerizing two or more of these. As the phenol resin, one type may be used alone or two or more types may be used in combination.

The hydroxyl group equivalent of the phenol resin is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, the hydroxyl group equivalent of the phenol resin is preferably 70 g / eq to 1000 g / eq, and is 80 g / eq to 500 g / eq. Is more preferable.

The hydroxyl group equivalent of the phenol resin refers to a value calculated based on the hydroxyl value measured in accordance with JIS K0070: 1992.

When the phenol resin is a solid, its softening point or melting point is not particularly limited. The softening point or melting point of the phenol resin is preferably 40 ° C. to 180 ° C., and is thermally curable, for example, from the viewpoint of moldability and reflow resistance when the 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 phenol resin shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.

When the thermosetting resin composition contains a phenol resin, the content of the phenol resin is preferably 0.5% by mass to 50% by mass, preferably 2% by mass, based on the total mass of the thermosetting resin composition. It is more preferably about 30% by mass, and even more preferably 2% by mass to 20% by mass.

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. 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) should be set in the range of 0.5 to 2.0 in order to reduce the amount of each unreacted component. Is preferable, and it is more preferable to set it in the range of 0.6 to 1.3. From the viewpoint of moldability when the thermosetting resin composition is used as a sealing material, 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 0.8 to It is more preferable to set it in the range of 1.2.
The number of functional groups of the curing agent represents, for example, the number of hydroxyl groups in the phenol curing agent when a phenol curing agent is used as the curing agent, and the number of active hydrogens in the amine curing agent when an amine curing agent is used as the curing agent. Represents.

<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.

The content of the curing accelerator is 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component (that is, the thermosetting resin (including the curing agent when the curing agent is a thermosetting resin)). It is preferably 1 part by mass to 15 parts by mass, and more preferably. 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.

<Inorganic filler>
The material of the inorganic filler is not particularly limited. Specifically, as the material of the inorganic filler, molten 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, Murite, Titania, Tarku, Clay, Mica and other inorganic materials. 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 the coefficient of thermal expansion, the coefficient of thermal conductivity, and the elastic coefficient of the cured product, the content of the inorganic filler is preferably 30% by volume or more of the total amount of the heat-curable resin composition. It is more preferably 5% by volume or more, further preferably 50% by volume or more, particularly preferably 60% by volume or more, and extremely preferably 70% by volume or more. From the viewpoint of improving fluidity, reducing viscosity, etc., the content of the inorganic filler is preferably 99% by volume or less, preferably 98% by volume or less, and 97% by volume of the entire thermosetting resin composition. More preferably, it is less than or equal to the volume.
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 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.

Compared with the conventional method, according to the production method of the present disclosure, the fluidity of the mixture of each component at the time of kneading and molding tends to be kept low. Therefore, according to the production 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, the inorganic filler can be highly filled. It is thought that

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.

The smaller the particle size of the inorganic filler, the higher the viscosity of the mixture of each component tends to be. According to the production method of the present disclosure, even if the content of the inorganic filler having a small particle size cannot be increased due to the influence of the increase in viscosity according to the conventional method, the content of the inorganic filler having a small particle size is contained. It will be possible to increase the amount.

<Coupling agent>
When the thermosetting resin composition contains an inorganic filler, a coupling agent may be contained 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.

<Additives>
In addition to the above-mentioned components, the thermosetting resin composition may contain various additives such as 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.

(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. When the thermosetting resin composition is in the form of a tablet, it is preferable that the dimensions and mass match the molding conditions of the package from the viewpoint of handleability.

[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 according to the molding method, the composition of the thermosetting resin composition, and the like. When the thermosetting resin composition is used as a sealing material, it is preferable to adjust it according to the susceptibility of wire flow during molding.
For example, when the thermosetting resin composition is used as a sealing material, the viscosity of the thermosetting resin composition is preferably 200 Pa · s or less at 175 ° C., preferably 150 Pa, from the viewpoint of reducing wire flow. It is more preferably s or less, further preferably 100 Pa · s or less, particularly preferably 50 Pa · s or less, and extremely preferably 30 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 high-grade flow tester (for example, manufactured by Shimadzu Corporation).

[Fluidity of thermosetting resin composition]
The flow distance of the spiral flow obtained by the following method is not particularly limited, and is preferably 70 cm or more, more preferably 100 cm or more, further preferably 150 cm or more, and preferably 200 cm or more. More preferred.
The thermosetting resin composition is molded using a spiral flow measuring die according to EMMI-1-66, and the flow distance is determined. Molding shall be performed 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.

The distance of the disk flow obtained by the following test is not particularly limited, and is preferably 80 mm or more, more preferably 90 mm or more, and further preferably 100 mm or more.
Using a flat plate mold for disk flow measurement having a 200 mm (W) x 200 mm (D) x 25 mm (H) upper mold and a 200 mm (W) x 200 mm (D) x 15 mm (H) lower mold, the upper mold is used. 5 g of the thermosetting resin composition weighed with a dish balance is placed on the center of the lower mold heated to 180 ° C. After 5 seconds, the upper mold heated to 175 ° C. was closed, compression molding was performed under the 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 were measured with a caliper. Let the average value (mm) be the disk flow.

[Gel time]
From the viewpoint of fluidity, the gel time is preferably 20 seconds or longer, more preferably 30 seconds or longer, and even more preferably 40 seconds or longer. From the viewpoint of curability, the gel time is preferably 120 seconds or less, more preferably 100 seconds or less, and further preferably 90 seconds or less. The gel time shall be a value measured by the following method.
A measurement using a curast meter (for example, manufactured by 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.

[Bending strength of cured product]
The bending strength of the cured product of the thermosetting resin composition at room temperature (25 ° C.) measured by the following method is preferably 100 MPa or more, more preferably 110 MPa or more, and 120 MPa or more. Is more preferable, and 125 MPa or more is particularly preferable.
A cured product of the thermosetting resin composition is cut into a rectangular cuboid having a size of 2.0 mm × 5.0 mm × 40 mm to prepare a test piece for evaluating bending strength. Using this test piece, a bending test is performed with a Tensilon universal material tester (for example, Instron 5948, Instron) under the conditions of a distance between fulcrums of 32 mm and a crosshead speed of 1 mm / min. Using the measured results, a bending stress-displacement curve is created from the equation (A), and the maximum stress is taken as the bending strength.

σ = 3FL / 2bh ² ... Equation (A)

σ: Bending stress (MPa)
F: Bending load (N)
L: Distance between fulcrums (mm)
b: Test piece width (mm)
h: Test piece thickness (mm)

The flexural strength of the thermosetting resin composition at 260 ° C. measured by the above method is preferably 10 MPa or more, more preferably 12 MPa or more, and even more preferably 14 MPa or more.

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

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), TQFP (Thin Quad Flat Package), LQFP (Low Profile Quad Flat Package); elements bonded to tape carriers with bumps are sealed with a thermosetting resin composition. TCP (Tape Carrier Package) having a structure; COB (Chip) having a structure in which an element connected to a wiring formed on a support member by wire bonding, flip chip bonding, solder, etc. is sealed with a thermosetting resin composition. OnBoard) module, hybrid IC, multi-chip module, etc .; an element is mounted on the surface of a support member having terminals for connecting wiring plates on the back surface, and the element and the wiring formed on the support member by bump or wire bonding are attached. 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 a thermosetting resin composition after connection. 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.

When the thermosetting resin composition obtained by the production method of the present disclosure is used as a sealing material for an element, it is preferable that the generation of voids, blisters, flow marks and the like is suppressed in the obtained package. Voids, blister, and flow marks can be evaluated as follows.
The presence or absence of blister generation can be confirmed by transfer molding the target encapsulant and observing the obtained package surface. In addition, the flow mark can be confirmed by observing directly above the chip mounting location. Furthermore, voids can be confirmed by observing the inside of the package with a SAT (scanning acoustic tomograph) image. The molding conditions are, for example, a mold temperature: 175 ° C., a molding pressure: about 7 MPa, and a curing time: 120 seconds. Further, the SAT image can be observed by the method described in the following resin rich evaluation method, for example.

When the thermosetting resin composition obtained by the production method of the present disclosure is used as a sealing material for an element, it is preferable that the resin richness after molding is suppressed. Resin rich is a phenomenon that appears when the target encapsulant is compression molded. Although the reason is not clear, in this resin-rich region, for example, defoaming occurs due to the gas dissolved in the encapsulant due to the reduced pressure during compression molding, and the amount of the inorganic filler at the defoamed portion is locally reduced. It is thought that this is the cause. For example, in a sealing material having low fluidity, even if a region where the amount of the inorganic filler is locally reduced occurs, it is unlikely that the inorganic filler will flow into the region due to the flow. Therefore, it is considered that the region where the amount of the inorganic filler is locally reduced is cured as it is to become a resin-rich region. Resin richness can be confirmed using a SAT image as follows.
First, a SAT image is obtained by molding the encapsulant to be measured with a compression molding device and observing it with SAT (for example, Hitachi Power Solutions Co., Ltd., model number: FS200 III A). The conditions for compression molding are, for example, a mold temperature of 175 degrees, a molding pressure of about 10 MPa, and a curing time of 120 seconds. The SAT observation condition is probe frequency: 50 MHz. From the obtained SAT image, the black spots can be selectively cross-sectionally polished, and elemental analysis can be used to determine whether the black spots are resin-rich.

When the thermosetting resin composition obtained by the production method of the present disclosure is used as a sealing material for an element, the residual resin in the mold used for molding and the surface cohesive failure of the obtained package are suppressed. Is preferable. The presence or absence of the resin remaining in the mold and the cohesive failure of the package surface can be confirmed by the following method.
The target encapsulant is molded by transfer molding, and this is continuously repeated, so-called continuous molding is performed. For example, for several hundred shots, the mold is continuously molded without cleaning, and it is confirmed whether or not the resin residue of the mold and the cohesive failure of the package surface occur. The molded package is not particularly limited, but SOP or the like can be easily selected. The molding conditions are not particularly limited, but for example, the mold temperature is 175 ° C., the molding pressure is about 7 MPa, and the curing time is 120 seconds.

When the thermosetting resin composition obtained by the production method of the present disclosure is used as a sealing material for a device, it is preferable that cracks are suppressed in the obtained package. The presence or absence of package cracks can be evaluated, for example, by transfer molding the target encapsulant and performing a temperature cycle test or the like on the obtained package. For example, the obtained package was subjected to moisture absorption under the condition of MSL (Moisture Sensitivity Level): level 3 (30 ° C. or lower, 60% RH, 168 hours), and reflowed under the condition of 260 ° C. × 30 sec × 3 times. Further, it is subjected to a temperature cycle of −65 ° C./150 ° C. After 700 temperature cycles, check the package for cracks. The target package is not particularly limited, and examples thereof include LQFP. The molding conditions are, for example, a mold temperature: 175 ° C., a molding pressure: about 7 MPa, and a curing time: 120 seconds.

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: EPPN-501HY (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)
-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: NC-3000 (trade name, Nippon Kayaku Co., Ltd., epoxy equivalent 265 g / eq to 285 g / eq, aralkyl type epoxy resin with softening point 53 ° C to 63 ° C)

-Curing agent 1: H-4 (trade name, Meiwa Kasei Co., Ltd., phenol novolac type phenol resin having a hydroxyl group equivalent of 103 g / eq, softening point 85 ° C.)

(Inorganic filler)
-Inorganic filler 1: Spherical silica having a volume average particle diameter (D50) of 15 μm ・ Inorganic filler 2: Spherical silica having a volume average particle diameter (D50) of 0.5 μm

(Coupling agent)
-Coupling agent: 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 3 were prepared by the following method (referred to as "manufacturing method A"). As the kneading device, a twin-screw kneader (kneading extruder) outlined in FIG. 1 was used. The main material input port is connected to the first kneading portion, and the side feeder is connected to the second kneading portion downstream in the extrusion direction.
First, among the components shown in Table 1, components other than the curing accelerator were sufficiently mixed with a mixer. The mixture was charged from the main material input port of the twin-screw kneader, a curing accelerator was charged from the side feeder, and kneading extrusion was performed. The primary kneading temperature in the first kneading section was about 150 ° C. In the second kneading section, the temperature is gradually lowered from the side feeder connecting portion to the outlet so that the temperature is about 70 ° C. near the side feeder connecting portion and about 30 ° C. near the outlet of the twin-screw kneader. Then, the melt was cooled and the solid state was pulverized into a powder to prepare a powdery thermosetting resin composition.

The thermosetting resin compositions of Comparative Examples 1 to 6 were prepared by the following method (referred to as "manufacturing method B").
After sufficiently mixing each component shown in Table 1 with a mixer, melt-kneading was performed at about 150 ° C. using a twin-screw kneader. Then, the melt was cooled and the solid state was pulverized into a powder to prepare a powdery thermosetting resin composition.

<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 (cm) 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).

[Flexural strength]
The thermosetting resin composition was molded under the above conditions and post-cured. The cured product was cut into a rectangular cuboid of 2.0 mm × 5.0 mm × 40 mm to prepare a test piece for evaluation of bending strength. Using this test piece, a bending test was performed with a Tensilon universal material tester (Instron 5948, Instron) under the conditions of a distance between fulcrums of 32 mm and a crosshead speed of 1 mm / min. Using the measurement results, a bending stress-displacement curve was created from the formula (A), and the maximum stress was taken as the bending strength. The measurement was performed at room temperature and 260 ° C., respectively.

σ = 3FL / 2bh ² ... Equation (A)

σ: Bending stress (MPa)
F: Bending load (N)
L: Distance between fulcrums (mm)
b: Test piece width (mm)
h: Test piece thickness (mm)

[Disk flow]
Using a flat plate mold for disk flow measurement having a 200 mm (W) x 200 mm (D) x 25 mm (H) upper mold and a 200 mm (W) x 200 mm (D) x 15 mm (H) lower mold, the upper mold is used. 5 g of the thermosetting resin composition weighed with a dish balance is placed on the center of the lower mold heated to 175 ° C. After 5 seconds, the upper mold heated to 180 ° C. was closed, compression molding was performed under the 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 were measured with a caliper. The average value (mm) was defined as the disk flow.

[Package evaluation]
(Evaluation of voids, blister, and flow marks)
Voids, blister, and flow marks were evaluated by the method described above. The conditions for transfer molding were mold temperature: 175 ° C., molding pressure: about 7 MPa, and curing time: 120 seconds. The SAT observation was performed under the same conditions as the following resin-rich evaluation.

(Evaluation of resin rich)
The resin richness was evaluated by the method described above. The conditions for compression molding were mold temperature: 175 ° C., molding pressure: 10 MPa, and curing time: 120 seconds. SAT observations were carried out using Hitachi Power Solutions Co., Ltd., model number: FS200 III A, under the condition of probe frequency: 50 MHz.

(Evaluation of mold resin residue and package surface cohesive failure)
The mold resin residue and package surface cohesive failure were evaluated by the method described above. The package was SOP, and the molding conditions were mold temperature: 175 ° C., molding pressure: about 7 MPa, and curing time: 120 seconds.

(Evaluation of package cracks)
Package cracks were evaluated by the method described above. The package was LQFP, and the molding conditions were mold temperature: 175 ° C., molding pressure: 7 MPa, and curing time: 120 seconds.

"-" In the component blending amount in Table 1 indicates that the corresponding component is not blended.

The onset temperature of the compositions of Examples 1 to 3 is higher than 70 ° C.

As can be seen from the above results, the thermosetting resin compositions obtained by the production method A are the thermosetting resin compositions (Comparative Examples 1 to 3) obtained by the production method B with the same composition, and the same epoxy resin. Compared with the thermosetting resin compositions (Comparative Examples 4 to 6) obtained by the production method B by blending an inorganic filler that has been surface-treated in advance, the fluidity is as good as that of the thermosetting resin composition. It had excellent bending strength at room temperature and 260 ° C. when it was made into a cured product. Further, in the semiconductor package sealed with the thermosetting resin composition obtained by the production method A, molding defects were suppressed. Above all, since voids, flow marks, and resin-rich sites were suppressed, it is presumed that the thermosetting resin composition has good fluidity. Further, since the blister, the mold resin residue, the package coagulation fracture, and the package crack were suppressed, it is presumed that the thermosetting resin composition has good curability.

1 Main material input port 2 Side feeder 10 Kneading extruder A 1st kneading part B 2nd kneading part

Claims (7)

Primary kneading, in which a mixture of a thermosetting resin, an inorganic filler, and a coupling agent is kneaded at 100 ° C. or higher,
After the primary kneading, a curing accelerator is added and further kneaded, and a secondary kneading is performed.
A method for producing a thermosetting resin composition, which comprises. The production method according to claim 1, wherein the temperature of the secondary kneading is lower than the temperature of the primary kneading. The production method according to claim 1 or 2, wherein the temperature of the secondary kneading is lower than the onset temperature of the mixture after adding the curing accelerator, which is measured by differential scanning calorimetry. The production method according to any one of claims 1 to 3, wherein the onset temperature of the mixture after adding the curing accelerator is lower than 120 ° C. as measured by differential scanning calorimetry. The production method according to any one of claims 1 to 4, wherein the volume average particle diameter of the inorganic filler is 20 μm or less. A thermosetting resin composition obtained by the production method according to any one of claims 1 to 5. 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 5.

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