CN116724393A

CN116724393A - Method for producing thermosetting resin composition, and electronic component device

Info

Publication number: CN116724393A
Application number: CN202280008716.9A
Authority: CN
Inventors: 姜东哲; 山浦格; 中村岳博; 野泽博; 洪昌勲; 平嶋克至
Original assignee: Lishennoco Co ltd
Current assignee: Lishennoco Co ltd
Priority date: 2021-01-08
Filing date: 2022-01-06
Publication date: 2023-09-08
Also published as: JPWO2022149594A1; TW202233736A; WO2022149594A1

Abstract

The method for producing the thermosetting resin composition comprises: mixing once, and mixing thermosetting resin; and secondary mixing, wherein hardening accelerator is added after the primary mixing for further mixing.

Description

Method for producing thermosetting resin composition, and electronic component device

Technical Field

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

Background

In recent years, high-density mounting of semiconductor elements has been advanced. With this, a surface-mount type package is a mainstream of a resin-sealed semiconductor device, as opposed to a conventional pin-inserted type package. Surface-mounted integrated circuits (Intergrated Circuit, IC), large-scale integrated circuits (Large Scale Integration, LSI) and the like are thin and small packages in order to increase the mounting density and reduce the mounting height. Therefore, the occupied area of the element with respect to the package becomes large, and the thickness of the package becomes extremely thin.

The surface mount type package is different from the existing pin insertion type package in mounting method. The lead-in package is soldered from the back surface of the wiring board after the leads are inserted into the wiring board, and thus the package is not directly exposed to high temperature. On the other hand, the surface-mounted package is temporarily fixed to the surface of the wiring board and is processed by a solder bath, a reflow apparatus, or the like, and thus is directly exposed to a soldering temperature (reflow temperature). As a result, when the IC package absorbs moisture, the absorbed moisture evaporates during reflow, and the generated vapor pressure acts as a peeling stress, and peeling occurs between the element, the lead frame, and other interposer and the sealing material, which causes package cracking and poor electrical characteristics. Therefore, development of a sealing material excellent in solder heat resistance (reflow resistance) is desired.

As a sealing material having excellent reflow resistance, a thermosetting resin such as a biphenyl type epoxy resin or a sulfur atom type epoxy resin can be preferably used (for example, refer to patent document 1 and patent document 2).

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2015-007147

Patent document 2: international publication No. 2018/181813

Disclosure of Invention

Problems to be solved by the invention

On the other hand, the resin material having improved reflow resistance and other properties may not be easily handled. For example, when a thermosetting resin having a high melting point or softening point such as a biphenyl type epoxy resin or a sulfur atom type epoxy resin is used, the resin material is kneaded at a high temperature while adding a shear stress thereto in order to sufficiently stir the resin material. However, if the resin material is kneaded at a high temperature while applying a shear stress, the resin material may be thickened and may not be sufficiently mixed, and the hardenability may be lowered. In addition, if the resin is biased to exist due to insufficient kneading, fluidity at the time of molding may be lowered. On the other hand, in order to perform kneading so as not to cause thickening, kneading conditions and components must be sufficiently selected, and there is a problem in that the degree of freedom of design is limited.

In view of the above, the present disclosure relates to a method for producing a thermosetting resin composition capable of producing a thermosetting resin composition excellent in fluidity and curability, a thermosetting resin composition obtained by the production method, and an electronic component device including an element sealed with the thermosetting resin composition.

Technical means for solving the problems

Means for solving the above problems include the following means.

1 > a method for producing a thermosetting resin composition, comprising:

mixing once, and mixing thermosetting resin; and

and (3) secondary mixing, and adding a hardening accelerator after the primary mixing for further mixing.

< 2 > the production method according to < 1 >, wherein the temperature of the primary kneading is higher than the melting point or softening point of the thermosetting resin.

< 3 > according to < 1 > or < 2 > wherein the temperature of the primary kneading is higher than the initial temperature of the mixture after addition of the hardening accelerator as determined by differential scanning calorimetry.

The production method according to any one of < 1 > to < 3 >, wherein the temperature of the secondary kneading is lower than the temperature of the primary kneading.

< 5 > the production method according to any one of < 1 > to < 4 >, wherein the temperature of the secondary kneading is lower than the initial temperature of the mixture after the addition of the hardening accelerator as measured by differential scanning calorimetry.

The production method according to any one of < 6 > to < 1 > to < 5 >, wherein the melting point or softening point of the thermosetting resin is higher than the initial temperature of the mixture after the addition of the hardening accelerator as measured by differential scanning calorimetry.

The method of producing a thermosetting resin according to any one of < 1 > to < 6 >, wherein the melting point or softening point of the thermosetting resin is 60 ℃ or higher.

The production method according to any one of < 1 > to < 7 >, wherein the thermosetting resin contains at least one selected from the group consisting of biphenyl type epoxy resins and sulfur-containing protonic type epoxy resins.

The production method according to any one of < 1 > to < 8 >, wherein the inorganic filler is further kneaded in the primary kneading.

A thermosetting resin composition of < 10 > obtained by the production method according to any one of < 1 > to < 9 >.

< 11 > an electronic part device comprising an element sealed with the thermosetting resin composition obtained by the production method according to any one of < 1 > to < 9 >.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present disclosure, a method for producing a thermosetting resin composition capable of producing a thermosetting resin composition excellent in fluidity and curability, a thermosetting resin composition obtained by the production method, and an electronic component device including an element sealed with the thermosetting resin composition can be provided.

Drawings

Fig. 1 is a schematic cross-sectional view of a kneading extruder used in one embodiment of the production method of the present disclosure.

Detailed Description

Hereinafter, embodiments of the present disclosure will be described in detail. The embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, the constituent elements (including the element steps) are not necessarily required unless otherwise specifically indicated. As such, the numerical values and ranges thereof are not limiting embodiments of the present disclosure.

In the present disclosure, the term "process" includes not only a process independent of other processes, but also a process which is not clearly distinguished from other processes, if the purpose of the process is achieved.

In the present disclosure, the numerical values described before and after the numerical values indicated by the "to" are used as the minimum value and the maximum value, respectively.

In the numerical ranges described in stages 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 the numerical range described in other stages. In addition, in the numerical ranges 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 comprise a plurality of conforming substances. When a plurality of substances corresponding to the respective components are present in the composition, unless otherwise specified, the content or content of the respective components means the total content or content of the plurality of substances present in the composition.

In the present disclosure, a plurality of particles corresponding to each component may be included. When a plurality of particles corresponding to each component are present in the composition, the particle diameter of each component refers to a value of a mixture of the plurality of particles present in the composition unless otherwise specified.

In the present disclosure, solid, liquid, and liquid refer to properties at 25 ℃.

In the present disclosure, when the embodiments are described with reference to the drawings, the structures of the embodiments are not limited to those shown in the drawings. The sizes of the members in the drawings are conceptual sizes, and the relative relationship between the sizes of the members is not limited thereto.

Method for producing thermosetting resin composition

The method for producing a thermosetting resin composition of the present disclosure (hereinafter, also referred to as a production method of the present disclosure) includes: mixing once, and mixing thermosetting resin; and secondary mixing, wherein hardening accelerator is added after the primary mixing for further mixing.

According to the manufacturing method of the present disclosure, since the hardening accelerator is added after the thermosetting resin is kneaded, the thermosetting resin can be preferably mixed and dispersed while suppressing thickening. In particular, even when a resin having a high melting point or softening point is used as the thermosetting resin, the resin can be well stirred and mixed while suppressing thickening even when the resin is kneaded at a high temperature. In addition, in the conventional method, when a high shear stress is applied to the thermosetting resin, there is a problem that the temperature of the thermosetting resin increases due to shear heat generation and further thickening is increased, but according to the manufacturing method of the present disclosure, the increase in viscosity can be suppressed even when a high shear stress is applied, and thus the resin material can be sufficiently mixed. It is considered that the dispersibility of the resin can be improved by the method and that good hardenability can be obtained. In addition, it is considered that the resin is less likely to be biased and the fluidity during molding is also good.

[ Primary mixing ]

In the primary kneading, the thermosetting resin is mixed and kneaded. In this case, an inorganic filler, a coupling agent, and other additives may be further mixed as necessary. In general, shear heat generation occurs when a resin material is mixed with an inorganic filler and kneaded, but the influence of thickening due to shear heat generation can be reduced by kneading the total amount or a part of the hardening accelerator by secondary kneading, and kneading tends to be performed satisfactorily. In the primary kneading, a part of the hardening accelerator may be mixed as long as the influence of thickening on the kneading property is within a range that is not practically problematic. In the present disclosure, when the hardening accelerator is added in a plurality of times, the kneading after adding 50 mass% or more of the hardening accelerator, which is half of the total hardening accelerator added finally, is referred to as secondary kneading for convenience. When a part of the hardening accelerator is mixed in the primary kneading, the amount of the mixture is preferably 30 mass% or less, more preferably 20 mass% or less, and still more preferably 10 mass% or less of the total hardening accelerator to be finally added. In the primary kneading, the thermosetting resin, and if necessary, the inorganic filler, the coupling agent, and other additives are preferably kneaded without adding a hardening accelerator.

The kneading method in the primary kneading is not particularly limited. Examples of the method include a method of melt-kneading by a kneader (a biaxial kneader, a triaxial kneader, etc.), rolls (a three-roll, etc.), an extruder, etc. which are heated to a desired temperature in advance.

The temperature of the primary kneading is preferably adjusted according to the melting temperature of the resin material used. The temperature of primary kneading is preferably a temperature higher than the melting point or softening point of the thermosetting resin (in the case of using plural kinds of thermosetting resins in combination, the thermosetting resin having the highest melting point or softening point). For example, the temperature for primary kneading is preferably a temperature 1 to 90 ℃ higher than the melting point or softening point of the thermosetting resin (in the case of using plural kinds of thermosetting resins in combination, the thermosetting resin having the highest melting point or softening point), more preferably a temperature 1 to 70 ℃ higher, still more preferably a temperature 1 to 50 ℃ higher. By kneading at the above temperature, the thermosetting resin can be melted to maintain fluidity, and therefore stirring and mixing can be performed well.

The temperature of the primary kneading may be higher than the initial temperature of the mixture after adding the hardening accelerator at the time of the secondary kneading, which will be described later, as measured by differential scanning calorimetry (differential scanning calorimetry, DSC). In the present disclosure, the initial temperature refers to a temperature corresponding to a tangent line at a point where a differential value of a heat generation peak of the DSC chart becomes maximum, and an intersection point with a base line of the heat generation peak of the DSC chart. When there are a plurality of points at which the differential value of the heat generation peak becomes maximum, the point on the lowest temperature side among the plurality of points is adopted.

According to the production method of the present disclosure, the primary kneading and the secondary kneading by adding the hardening accelerator are sequentially performed, and therefore the temperature of the primary kneading can be set to a high temperature regardless of the initial temperature of the mixture after adding the hardening accelerator. Thus, for example, the thermosetting resin can be sufficiently melted and kneaded once, and the dispersibility of the resin can be improved. The manufacturing method of the present disclosure is particularly useful in the case where the melting point or softening point of the thermosetting resin is higher than the starting temperature of the mixture after the addition of the hardening accelerator.

In one embodiment, the temperature of the primary kneading may be 70℃or higher, 80℃or higher, 90℃or higher, 100℃or higher, 110℃or higher, or 120℃or higher. The temperature of the primary kneading may be 200℃or less, 190℃or less, or 180℃or less from the viewpoint of more effectively suppressing the increase in viscosity. From the viewpoint of the above, the temperature of the primary kneading may be 70 to 200 ℃, or 80 to 200 ℃, or 90 to 200 ℃, or 100 to 200 ℃, or 110 to 200 ℃, or 120 to 200 ℃.

The shearing condition in the primary kneading is not particularly limited. According to the production method of the present disclosure, thickening of the thermosetting resin can be suppressed, and therefore, kneading can be preferably performed even if shear stress and shear rate are increased as compared with the conventional method.

[ secondary mixing ]

After the primary kneading, a hardening accelerator was added to further conduct secondary kneading. The method of adding the hardening accelerator is not particularly limited as long as the hardening accelerator can be added later. For example, the following method (side feed) can be exemplified: the hardening accelerator is added to the mixture once kneaded as described above from a charging port provided separately from the charging port of the once kneaded component.

The temperature of the secondary kneading is not particularly limited, and may be set to a temperature lower than the temperature of the primary kneading in view of suppressing thickening. The temperature of the secondary kneading is preferably lower than the initial temperature of the mixture after adding the hardening accelerator during the secondary kneading, as measured by Differential Scanning Calorimetry (DSC), and is preferably lower than 1℃to 100℃and may be lower than 2℃to 80℃or may be lower than 3℃to 60 ℃.

As one particularly useful embodiment of the production method of the present disclosure, the following can be mentioned: the primary kneading is performed at a temperature higher than the initial temperature of the mixture after the hardening accelerator is added, and the secondary kneading is performed at a temperature lower than the initial temperature.

The production method of the present disclosure may include other steps at any time, in addition to the primary kneading and the secondary kneading. For example, the thermosetting resin and other optional components may be mixed at normal temperature by a mixer or the like before primary kneading. Further, any component other than the thermosetting resin and the curing accelerator may be added at the same time or at a different time from one or more components of the thermosetting resin and the curing accelerator, and kneaded. The composition obtained by the primary kneading and the secondary kneading may be cooled and pulverized to obtain a solid thermosetting resin composition.

In one aspect, the primary and secondary blending in the manufacturing methods of the present disclosure may be performed using a blending extruder. Fig. 1 is a schematic cross-sectional view of a kneading extruder usable in one embodiment. The kneading extruder 10 includes: the extruder comprises a first kneading part A, a second kneading part B arranged downstream of the first kneading part A in the extrusion direction, a main material inlet 1 connected with the first kneading part A, and a side feeder 2 connected with the second kneading part B. In fig. 1, the arrow indicates the extrusion direction of the composition. The thermosetting resin is fed from the main material inlet 1 to the first kneading section a, and the curing accelerator is fed from the side feeder 2 to the second kneading section B. The first kneading unit a performs one kneading, and the kneaded product is extruded and moved to the second kneading unit B. The moved kneaded material and the hardening accelerator are joined and further kneaded. The temperature of the primary kneading and the temperature of the secondary kneading can be set separately. For example, a cooling unit (not shown) may be provided between the first kneading unit a and the second kneading unit B, and the secondary kneading may be performed at a temperature lower than that of the primary kneading. The first kneading unit a may be set to a higher temperature and the second kneading unit B may be set to a lower temperature, or a mechanism may be employed in which the content is gradually cooled in the extrusion direction in the second kneading unit B. The manufacturing method of the present disclosure is not limited to the embodiment shown in the drawings.

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 resins, phenol resins, urea resins, melamine resins, urethane resins, silicone resins, unsaturated polyester resins, and the like. In the present disclosure, the "thermosetting resin" includes an acrylic resin having both thermoplastic and thermosetting properties such as an epoxy group-containing acrylic resin. The thermosetting resin may be solid or liquid at ordinary temperature and pressure (for example, 25 ℃ C. And atmospheric pressure), and is preferably solid. The thermosetting resin may be used alone or in combination of two or more.

The thermosetting resin preferably contains an epoxy resin. Specific examples of the epoxy resin include: a novolac type epoxy resin (phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, etc.) obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol, cresol, xylenol, resorcinol, catechol, bisphenol a, bisphenol F, etc. phenol compounds, α -naphthol, β -naphthol, dihydroxynaphthalene, etc. with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst to obtain a novolac resin, and epoxidizing the novolac resin; a triphenylmethane epoxy resin obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde in the presence of an acidic catalyst to obtain a triphenylmethane phenol resin, and epoxidizing the triphenylmethane phenol resin; a copolymerized epoxy resin obtained by co-condensing the phenol compound and the naphthol compound with an aldehyde compound in the presence of an acidic catalyst to obtain a novolak resin, and epoxidizing the novolak resin; diphenylmethane-type epoxy resins as diglycidyl ethers of bisphenol a, bisphenol F, and the like; biphenyl epoxy resins as diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; a stilbene type epoxy resin as a diglycidyl ether of a stilbene (styrene) based phenol compound; sulfur atom-containing epoxy resins as diglycidyl ethers of bisphenol S and the like; epoxy resins as glycidyl ethers of alcohols such as butanediol, polyethylene glycol, polypropylene glycol, etc.; glycidyl ester type epoxy resins as glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, etc.; glycidyl amine type epoxy resins obtained by substituting active hydrogen bonded to nitrogen atom such as aniline, diaminodiphenylmethane and isocyanuric acid with glycidyl group; a dicyclopentadiene epoxy resin obtained by epoxidizing a cocondensated resin of dicyclopentadiene and a phenol compound; alicyclic epoxy resins such as a bisepoxylated vinylcyclohexene, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, and 2- (3, 4-epoxy) cyclohexyl-5, 5-spiro (3, 4-epoxy) cyclohexane-m-dioxane, each obtained by epoxidizing an intramolecular olefin bond; para-xylene modified epoxy resins as glycidyl ethers of para-xylene modified phenol resins; meta-xylene modified epoxy resin as glycidyl ether of meta-xylene modified phenol resin; terpene-modified epoxy resins as glycidyl ethers of terpene-modified phenol resins; dicyclopentadiene modified epoxy resins as glycidyl ethers of dicyclopentadiene modified phenol resins; cyclopentadiene-modified epoxy resins as glycidyl ethers of cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified epoxy resins as glycidyl ethers of polycyclic aromatic ring-modified phenol resins; naphthalene type epoxy resins as glycidyl ethers of naphthalene ring-containing phenol resins; halogenated phenol novolac type epoxy resins; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; aralkyl type epoxy resins obtained by epoxidizing aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins. Further, epoxy resins such as epoxy resins of silicone resins and epoxy resins of acrylic resins are also exemplified. The epoxy resin may be used alone or in combination of two or more.

Among the above epoxy resins, biphenyl type epoxy resins have low melt viscosity, and therefore, even if an inorganic filler is highly filled for the purpose of improving reflow resistance, a problem of wire sweep (wire sweep) in a semiconductor package is not easily caused. Therefore, as a sealing material for a surface mount type package in recent years, a biphenyl type epoxy resin can be preferably used. The biphenyl type epoxy resin has a low melt viscosity in the vicinity of 180 ℃, but has a high softening point, and therefore kneading at a high temperature is desirable in order to sufficiently disperse the resin by kneading. According to the production method of the present disclosure, even in the case where the thermosetting resin contains a biphenyl type epoxy resin, the thermosetting resin can be preferably kneaded while suppressing an increase in viscosity.

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. In the epoxy resin represented by the following general formula (II), R ⁸ When the position of the oxygen atom is replaced with the 4-position and the 4' -position, the 3,3', 5' -position is methyl and the other R ⁸ YX-4000 and YX-4000H (Mitsubishi chemical Co., ltd., trade name) as hydrogen atoms, all of R ⁸ 4,4' -bis (2, 3-epoxypropoxy) biphenyl as hydrogen atom, all R ⁸ In the case of a hydrogen atom, R ⁸ When the position of the oxygen atom is replaced with the 4-position and the 4' -position, the 3,3', 5' -position is methyl and the other R ⁸ The mixture of hydrogen atoms, that is, YL-6121H (trade name of Mitsubishi chemical Co., ltd.) or the like can be obtained as a commercial product.

[ chemical 1]

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

Further, as a method for improving reflow resistance, there is a method for improving adhesion to a metal member and a base material. In order to improve the adhesion, a sulfur atom-containing epoxy resin may be preferably used. The sulfur atom-containing epoxy resin contains an epoxy resin having a very high melting point, but according to the production method of the present disclosure, even in the case where the thermosetting resin contains a sulfur atom-containing epoxy resin, the thermosetting resin can be preferably kneaded while suppressing an increase in viscosity.

The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, an epoxy resin represented by the following general formula (V) can be mentioned. In the epoxy resin represented by the following general formula (V), R ¹³ R is a tertiary butyl group at the 3,3' position, a methyl group at the 6,6' position and the other positions when the position of the oxygen atom is 4 and 4' positions ¹³ YSLV-120TE (daily iron chemistry) as a hydrogen atom&Material stock, trade name), etc. are available as commercial products.

[ chemical 2]

In the formula (V), R ¹³ The monovalent organic groups each representing a hydrogen atom or a carbon number of 1 to 18 may be the same or different. n is an average value and represents a number of 0 to 10.

The epoxy equivalent (molecular weight/epoxy number) of the epoxy resin is not particularly limited. From the viewpoint of balance of various properties such as formability, reflow resistance, and electrical reliability, it is preferably 100g/eq to 1000g/eq, more preferably 150g/eq to 500g/eq. The epoxy equivalent of the epoxy resin was set to be as per Japanese Industrial Standard (Japanese Industrial Standards, JIS) K7236: 2009, a value measured by the method of the present invention.

In the case where the epoxy resin is solid at 25 ℃, 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 ℃ or higher, more preferably 50 ℃ or higher. From the viewpoint of suppressing thickening due to kneading, the melting point or softening point of the epoxy resin is preferably 150 ℃ or less, more preferably 140 ℃ or less, and further preferably 130 ℃ or less. From the above viewpoint, the melting point or softening point of the epoxy resin is preferably 40 to 150 ℃, more preferably 50 to 140 ℃, and even more preferably 50 to 130 ℃. Among them, the production method of the present disclosure can be preferably used even when an epoxy resin having a melting point or softening point of 90 ℃ or higher, 100 ℃ or higher, 110 ℃ or higher, or 120 ℃ or higher (for example, a highly crystalline resin having a melting point of 90 ℃ or higher, 100 ℃ or higher, 110 ℃ or higher, or 120 ℃ or higher) is used for the purpose of satisfying the requirements of high thermal conductivity, reflow resistance, etc. in recent years.

The melting point of the epoxy resin was determined by Differential Scanning Calorimetry (DSC), and the softening point of the epoxy resin was determined by the method according to JIS K7234: 1986 (cycloball method).

When the thermosetting resin composition contains an epoxy resin, the content of the epoxy resin is preferably 0.5 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 2 to 20% by mass, based on the total mass of the thermosetting resin composition, in terms of strength, flowability, heat resistance, moldability, and the like.

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

For example, as a hardener used in combination with an epoxy resin, there may be mentioned: phenol hardeners, amine hardeners, anhydride hardeners, polythiol hardeners, polyamide hardeners, isocyanate hardeners, blocked isocyanate hardeners, and the like. The hardening agent may be used alone or in combination of two or more. The curing agent is preferably a phenol curing agent from the viewpoint of improving heat resistance. The hardener may be solid or liquid at normal temperature and pressure (e.g., 25 ℃ C., atmospheric pressure), and is preferably solid.

The phenol hardener is a compound having a phenolic hydroxyl group in a molecule (hereinafter also referred to as a phenol resin). Specific examples of the phenol resin include: polyhydric phenol compounds such as resorcinol, catechol, bisphenol a, bisphenol F, and substituted or unsubstituted biphenol; a novolak phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol, cresol, xylenol, resorcinol, catechol, bisphenol a, bisphenol F, phenylphenol, aminophenol and other phenol compounds, α -naphthol, β -naphthol, dihydroxynaphthalene and other naphthol compounds, with an aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like in the presence of an acidic catalyst; an aralkyl type phenol resin such as a phenol aralkyl resin synthesized from the phenolic compound and dimethoxyp-xylene, bis (methoxymethyl) biphenyl, etc.; para-xylene and/or meta-xylene modified phenol resin; melamine modified phenol resins; terpene modified phenol resins; dicyclopentadiene type phenol resin and dicyclopentadiene type naphthol resin synthesized by copolymerizing the phenol compound and dicyclopentadiene; cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified phenol resins; biphenyl type phenol resins; a triphenylmethane-type phenol resin obtained by condensing or co-condensing the phenol compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde in the presence of an acidic catalyst; and phenol resins obtained by copolymerizing two or more of these. The phenol resin may be used alone or in combination of two or more.

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

The hydroxyl equivalent of the phenol resin means based on the resin according to JIS K0070:1992, a value calculated from the measured hydroxyl value.

In the case where the phenol resin is solid, its softening point or melting point is not particularly limited. The softening point or melting point of the phenol resin is preferably 40 to 180 ℃ in terms of, for example, moldability and reflow resistance when the thermosetting resin composition is used for sealing material applications, and more preferably 50 to 130 ℃ in terms of operability in the production of the thermosetting resin composition.

The melting point or softening point of the phenol resin is determined 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 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 2 to 20% by mass, based on the total mass of the thermosetting resin composition.

The equivalent ratio of the epoxy resin to the hardener, that is, the ratio of the number of functions in the hardener to the number of epoxy in the epoxy resin (the number of functions in the hardener/the number of epoxy in the epoxy resin) is not particularly limited. In terms of the relation of suppressing the respective unreacted components to a small extent, the equivalent ratio of the epoxy resin to the hardener (the number of functional groups in the hardener/the number of epoxy groups in the epoxy resin) is preferably set to a range of 0.5 to 2.0, more preferably set to a range of 0.6 to 1.3. In view of moldability when the thermosetting resin composition is used for a sealing material, the equivalent ratio of the epoxy resin to the hardener (the number of functions in the hardener/the number of epoxy in the epoxy resin) is preferably set to a range of 0.8 to 1.2.

The number of functions of the hardener means, for example, the number of hydroxyl groups in the phenol hardener in the case of using the phenol hardener as the hardener, and the number of active hydrogen groups in the amine hardener in the case of using the amine hardener as the hardener.

< hardening accelerator >)

The type of the hardening accelerator is not particularly limited, and examples thereof include: cyclic amidine compounds such as diazabicycloolefins such as 1,5-Diazabicyclo [4.3.0] nonene-5 (1, 5-diazabicycloo [4.3.0] nonene-5, DBN), 1,8-Diazabicyclo [5.4.0] undecene-7 (1, 8-diazabicycloo [5.4.0] undecene-7, DBU), 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; a phenol novolac salt of the cyclic amidine compound or a derivative thereof; a compound having intramolecular polarization, which is formed by adding a quinone compound such as maleic anhydride, 1, 4-benzoquinone, 2, 5-toluquinone, 1, 4-naphthoquinone, 2, 3-dimethylbenzoquinone, 2, 6-dimethylbenzoquinone, 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone, 2, 3-dimethoxy-1, 4-benzoquinone, phenyl-1, 4-benzoquinone, or a compound having pi bond such as diazophenylmethane to these compounds; cyclic amidinium compounds such as tetraphenylborate of DBU, tetraphenylborate of DBN, tetraphenylborate of 2-ethyl-4-methylimidazole, and tetraphenylborate of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyl dimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like; derivatives of the tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide, and the like; organic phosphines such as primary phosphines, e.g., ethylphosphine, phenylphosphine, secondary phosphines, e.g., dimethylphosphine, diphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris (benzyl) phosphine, etc.; phosphine compounds such as complexes of the organic phosphine and organoboron compounds; a compound having intramolecular polarization, which is obtained by adding a quinone compound such as maleic anhydride, 1, 4-benzoquinone, 2, 5-toluquinone, 1, 4-naphthoquinone, 2, 3-dimethylbenzoquinone, 2, 6-dimethylbenzoquinone, 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone, 2, 3-dimethoxy-1, 4-benzoquinone, phenyl-1, 4-benzoquinone, anthraquinone, or the like, or a compound having pi bond such as diazophenylmethane to the organic phosphine or the phosphine compound; a compound having an intramolecular polarization obtained by a dehydrohalogenation step after reacting the organic phosphine or the phosphine compound with a halogenated phenol compound such as 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2, 6-dimethylphenol, 4-bromo-3, 5-dimethylphenol, 4-bromo-2, 6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4' -hydroxybiphenyl and the like; tetra-substituted phosphonium compounds such as tetra-substituted phosphonium such as tetraphenylphosphonium tetra-p-tolylborate, tetraphenylborate of tetra-substituted phosphonium, and salts of tetra-substituted phosphonium with phenol compounds; a phosphobetaine (phosphobetaine) compound; and adducts of phosphonium compounds and silane compounds. The hardening accelerator may be used alone or in combination of two or more.

For example, as a hardening accelerator particularly preferable when an epoxy resin is used as the thermosetting resin, triphenylphosphine, an adduct of triphenylphosphine and a quinone compound, and the like can be mentioned.

The content of the hardening accelerator is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component (that is, the thermosetting resin (the curing agent is also included in the case of the thermosetting resin)). When the amount of the hardening accelerator is 0.1 part by mass or more based on 100 parts by mass of the resin component, the hardening accelerator tends to be satisfactorily cured in a short time. If the amount of the hardening accelerator is 30 parts by mass or less based on 100 parts by mass of the resin component, a good molded article having a hardening rate that is not too high tends to be obtained.

< inorganic filler >)

The thermosetting resin composition may contain an inorganic filler. The material of the inorganic filler is not particularly limited.

Specific examples of the material of the inorganic filler include: inorganic materials such as fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, magnesium oxide, silicon carbide, beryllium oxide, zirconium oxide, zircon, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, and mica. Inorganic fillers having a flame retardant effect may also be used. Examples of the inorganic filler having a flame retardant effect include: composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and composite hydroxide of magnesium and zinc, and zinc borate.

Among the inorganic fillers, silica such as fused silica is preferable from the viewpoint of a decrease in linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity.

The shape of the inorganic filler is not particularly limited, and is preferably spherical in terms of filling property and mold abrasion property.

The inorganic filler may be used alone or in combination of two or more. The "two or more inorganic fillers are used in combination" includes, for example: the inorganic filler having the same composition and different average particle diameters may be used in two or more cases, the inorganic filler having the same average particle diameter and different composition may be used in two or more cases, and the inorganic filler having different average particle diameters and different types may be used in two or more cases.

The content of the inorganic filler is not particularly limited. The content of the inorganic filler is preferably 30% by volume or more, more preferably 40% by volume or more, still more preferably 50% by volume or more, particularly preferably 60% by volume or more, and most preferably 70% by volume or more of the entire thermosetting resin composition, from the viewpoint of further improving the characteristics such as the thermal expansion coefficient, thermal conductivity, and elastic coefficient of the cured product. The content of the inorganic filler is preferably 99% by volume or less, preferably 98% by volume or less, more preferably 97% by volume or less of the entire thermosetting resin composition, from the viewpoints of improvement in fluidity, reduction in viscosity, and the like.

In the case of using the thermosetting resin composition for compression molding, for example, the content of the inorganic filler may be 70 to 99% by volume, 80 to 99% by volume, 83 to 99% by volume, or 85 to 99% by volume of the entire thermosetting resin composition.

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 was measured, the cured product was calcined at 400℃for 2 hours, and then calcined at 700℃for 3 hours, and the resin component was evaporated, and the mass of the remaining inorganic filler was measured. The volume was calculated from the obtained mass and specific gravity, and the ratio of the volume of the inorganic filler to the total volume of the cured product was obtained and was set as the content of the inorganic filler.

According to the production method of the present disclosure, fluidity at the time of kneading and molding of a mixture of the components tends to be kept low, as compared with a conventional method in which all of the thermosetting resin, the curing accelerator, and other optional components are added and kneaded. Therefore, it is considered that according to the conventional method, even if there is a concern that coil flow occurs due to an influence of viscosity increase, for example, the composition of the inorganic filler cannot be increased, and according to the manufacturing method of the present disclosure, it is possible to achieve high filling of the inorganic filler.

In the case where the inorganic filler is in the form of particles, the average particle diameter thereof is not particularly limited. For example, the volume average particle diameter of the whole inorganic filler is preferably 80 μm or less, and may be 50 μm or less, or may be 40 μm or less, or may be 30 μm or less, or may be 20 μm or less. The volume average particle diameter of the entire inorganic filler is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more. When the volume average particle diameter of the inorganic filler is 0.1 μm or more, the viscosity of the thermosetting resin composition tends to be further suppressed from rising. 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 diameter of the inorganic filler can be measured as the particle diameter (D50) when the cumulative amount from the small diameter side becomes 50% in the volume-based particle size distribution measured by the laser scattering diffraction particle size distribution measuring apparatus.

< coupling agent >

When the thermosetting resin composition contains an inorganic filler, a coupling agent may be contained in order to improve adhesion between the resin component and the inorganic filler. Examples of the coupling agent include: silane compounds, titanium compounds, aluminum chelate compounds, aluminum/zirconium compounds, and the like.

The silane-based compounds include: 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2-aminoethyl) aminopropyl trimethoxysilane, 3- (2-aminoethyl) aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-ureidopropyl triethoxysilane, octenyl trimethoxysilane, glycidoxctyl trimethoxysilane, methacryloxyoctyl trimethoxysilane, and the like.

Examples of the titanium compound include: isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (N-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2, 2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl isostearoyl titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacrylate titanate, isopropyl tris (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, and the like.

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

< additive >)

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, in addition to the above-mentioned components. The thermosetting resin composition may contain, in addition to the additives exemplified below, various additives generally used in the above technical field, if necessary.

(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 is preferable to contain an ion exchanger in view of improving moisture resistance and high-temperature storage characteristics of an electronic component device including a sealed element. The ion exchanger is not particularly limited, and a conventional ion exchanger can be used. Specifically, hydrotalcite compounds, and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth, and the like are exemplified. The ion exchanger may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (a) is preferable.

Mg _(1-X) Al _X (OH) ₂ (CO ₃ ) _X/2 ·mH ₂ O……(A)

(X is more than 0 and less than or equal to 0.5, m is a positive number)

In the case where the thermosetting resin composition contains an ion exchanger, the content of the ion exchanger is not particularly limited as long as it is a sufficient amount for capturing halogen ion plasma. For example, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the resin component.

(Release agent)

The thermosetting resin composition may contain a release agent from the viewpoint of obtaining good releasability from a mold at the time of molding. The release agent is not particularly limited, and conventional release agents can be used. Specifically, there may be mentioned: and ester waxes such as palm wax (carnauba wax), higher fatty acids such as octacosanoic acid and stearic acid, higher fatty acid metal salts and octacosanoic acid esters, and polyolefin waxes such as oxidized polyethylene and nonoxidized polyethylene. The release agent may be used alone or in combination of two or more.

When the thermosetting resin composition contains a release agent, the amount of the release agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin component. When the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, releasability tends to be sufficiently obtained. When the amount is 10 parts by mass or less, better adhesion and hardening properties tend to be obtained.

(flame retardant)

The thermosetting resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventional flame retardants can be used. Specifically, an organic compound or an inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, a metal hydroxide, or the like can be cited. The flame retardant may be used singly or in combination of two or more.

In the case where the thermosetting resin composition contains a flame retardant, the amount of the flame retardant is not particularly limited as long as it is a sufficient amount to obtain a desired flame retardant effect. For example, the amount is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, based on 100 parts by mass of the resin component.

(colorant)

The thermosetting resin composition may further contain a colorant. Examples of the coloring agent include: carbon black, organic dye, organic pigment, titanium oxide, lead oxide, iron oxide and other existing colorants. The content of the colorant may be appropriately selected depending on the purpose and the like. The colorant may be used alone or in combination of two or more.

(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, warpage of the package and occurrence of package cracks when the thermosetting resin composition is used for a sealing material can be reduced. As the stress relaxation agent, a conventional stress relaxation agent (flexible agent) generally used can be mentioned. Specifically, there may be mentioned: thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based, rubber particles such as Natural Rubber (NR), acrylonitrile-butadiene rubber (NBR), acrylic rubber, urethane rubber, silicone powder, and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (methyl methacrylate-butadiene-styrene, MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer. The stress relaxation agent may be used alone or in combination of two or more kinds.

Thermosetting resin composition

The thermosetting resin composition of the present disclosure is obtained by the manufacturing method of the present disclosure.

The thermosetting resin composition may be solid or liquid at normal temperature and pressure (for example, 25 ℃ C. And atmospheric pressure), and is preferably solid. The shape of the thermosetting resin composition when it is solid is not particularly limited, and examples thereof include: powder, granules, flakes, etc. From the viewpoint of operability, the size and quality of the thermosetting resin composition in the form of a sheet are preferably such that they match the molding conditions of the package.

[ viscosity of thermosetting resin composition ]

The viscosity of the thermosetting resin composition is not particularly limited. It is preferable to adjust the composition of the thermosetting resin composition to a desired viscosity according to the molding method. When the thermosetting resin composition is used for a sealing material, it is preferable to adjust the composition according to the easiness of occurrence of coil flow during molding.

For example, when the thermosetting resin composition is used for a sealing material, the viscosity of the thermosetting resin composition is preferably 200pa·s or less, more preferably 150pa·s or less, still more preferably 100pa·s or less, particularly preferably 70pa·s or less, and most preferably 50pa·s or less at 175 ℃ from the viewpoint of reducing coil flow or the like. The lower limit of the viscosity of the thermosetting resin composition is not particularly limited, and may be, for example, 2pa·s or more at 175 ℃.

The viscosity of the thermosetting resin composition can be measured by a high-flow tester (Koka-type flow tester) (for example, manufactured by Shimadzu corporation).

[ fluidity of thermosetting resin composition ]

The flow distance of the swirling flow obtained by the following method is not particularly limited, but is preferably 70cm or more, more preferably 80cm or more, and still more preferably 90cm or more.

The thermosetting resin composition was molded using a swirl flow measuring mold according to EMMI-1-66, and the flow distance was determined. The molding was performed using a transfer molding machine under a mold temperature of 180℃and a molding pressure of 6.9MPa for a curing time of 90 seconds.

The distance of the disk flow obtained by the following test is not particularly limited, but is preferably 125mm or more, more preferably 130mm or more, and further preferably 135mm or more.

A flat plate mold for measuring circular plate flow having an upper mold of 200mm (W). Times.200 mm (D). Times.25 mm (H) and a lower mold of 200mm (W). Times.200 mm (D). Times.15 mm (H) was used, and 5g of a thermosetting resin composition weighed by a disk balance was placed in the center of the lower mold heated to 180 ℃. After 5 seconds, the upper mold heated to 180℃was closed, compression molding was performed under a load of 78N for 90 seconds, and the long diameter (mm) and the short diameter (mm) of the molded article were measured by a vernier caliper, and the average value (mm) was set as a circular plate flow.

[ hardness at Heat ]

The hot-time hardness measured by the following method is preferably 50 or more, more preferably 60 or more, and further preferably 70 or more.

The thermosetting resin composition was formed into a disk having a diameter of 50mm by a thickness of 3mm, and immediately after the formation, the hardness at hot time was measured by using a Shore D-type durometer (for example, manufactured by Shandong Kogyo Co., ltd., HD-1120 (D type)). The molding was performed using a transfer molding machine under a mold temperature of 180℃and a molding pressure of 6.9MPa for a curing time of 90 seconds.

[ gel time ]

From the viewpoint of fluidity, the gel time is preferably 20 seconds or more, more preferably 30 seconds or more, and still more preferably 40 seconds or more. In addition, from the viewpoint of hardenability, 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 was determined by the following method.

The time until the rise of the torque curve was set to be the gel time by performing measurement of 3g of the thermosetting resin composition at 180℃using a vulcanization tester (for example, manufactured by JSR trade Co., ltd.).

[ use of thermosetting resin composition ]

The use of the thermosetting resin composition of the present disclosure is not particularly limited, and for example, the composition can be used as a sealing material for electronic component devices in various mounting techniques. The thermosetting resin composition of the present disclosure is preferably used for various applications such as resin compositions for various modules, motor, vehicle-mounted, and electronic circuit protective sealing materials, and is preferably excellent in fluidity and hardenability.

Electronic parts device

The electronic part device of the present disclosure includes an element sealed with the thermosetting resin composition obtained by the manufacturing method of the present disclosure.

As an electronic component device, there is a device in which an element portion obtained by mounting an element (an active element such as a semiconductor chip, a transistor, a diode, a thyristor, or the like, a passive element such as a capacitor, a resistor, or a coil, or the like) on a support member such as a lead frame, a wired carrier tape, a wiring board, glass, a silicon wafer, or an organic substrate is sealed with a thermosetting resin composition.

More specifically, it is possible to list: a general resin-sealed IC such as a DIP package (Dual Inline Package, DIP), a plastic lead chip carrier (Plastic Leaded Chip Carrier, PLCC), a quad flat package (Quad Flat Package, QFP), a Small Outline package (Small Outline Package, SOP), a Small Outline J-lead package (SOJ), a thin Small Outline package (Thin Small Outline Package, TSOP), a thin quad flat package (Thin Quad Flat Package, TQFP), etc., which has a structure in which a terminal portion and a lead portion of an element such as a bonding pad are fixed to a lead frame and connected by wire bonding, bumps, etc., and then the element is sealed by transfer molding using a thermosetting resin composition; a tape carrier package (Tape Carrier Package, TCP) having a structure in which a component connected to a tape carrier by bumps is sealed with a thermosetting resin composition; a Chip On Board (COB) module, a hybrid IC, a polycrystalline module, or the like, which has a structure in which an element On a wiring formed by wire bonding, flip Chip bonding, solder, or the like connected to a support member is sealed with a thermosetting resin composition; ball Grid Array (BGA), chip scale package (Chip Size Package, CSP), multi-chip package (Multi Chip Package, MCP), and the like have a structure in which an element is mounted on a surface of a support member having wiring board connection terminals formed on a back surface thereof, the element is connected to wiring formed on the support member by bump or wire bonding, and then the element is sealed with a thermosetting resin composition. In addition, the thermosetting resin composition can be preferably used also in a printed wiring board.

As a method for sealing an electronic component device using the thermosetting resin composition, there are: low pressure transfer molding, injection molding, compression molding, and the like.

Examples

Next, embodiments of the present disclosure will be specifically described by way of examples, but the embodiments of the present disclosure are not limited to these examples.

Preparation of thermosetting resin composition

First, the following components were prepared.

(thermosetting resin)

Epoxy resin 1: biphenyl type epoxy resin with epoxy equivalent of 180 g/eq-192 g/eq and melting point of 105 DEG C

Epoxy resin 2: thioether epoxy resin with epoxy equivalent of 238-254 g/eq and melting point of 116-126 deg.c

Hardener 1: phenol novolac type phenol resin with hydroxyl equivalent of 103g/eq and softening point of 85 DEG C

Hardener 2: xylene-type phenol resin with hydroxyl equivalent of 175g/eq and softening point of 70 DEG C

(hardening accelerator)

Hardening accelerator: phosphorus hardening accelerator

(other additives)

Coupling agent: n-phenyl-3-aminopropyl trimethoxysilane

Mold release agent: hearst wax (Hoechst wax)

Coloring agent: carbon black

Ion exchanger: hydrotalcite-like compound

Inorganic filler: spherical silica having a volume average particle diameter of 15 μm

The thermosetting resin compositions of examples 1 to 4 were produced by the following method (referred to as "production method a"). As the kneading apparatus, a biaxial kneader (kneading extruder) schematically shown in fig. 1 was used. The main material inlet is connected to the first kneading section, and the side feeder is connected to the second kneading section downstream in the extrusion direction.

First, the components other than the hardening accelerator in the components shown in tables 1 and 2 were thoroughly mixed by a mixer. The mixture was fed from a main material feeding port of a biaxial kneader, and a hardening accelerator was fed from a side feeder, followed by kneading and extrusion. The primary kneading temperatures of the first kneading unit were set to the temperatures shown in tables 1 and 2. In the second kneading section, a mechanism for gradually lowering the temperature from the side feeder connecting section toward the outlet is provided so that the temperature reaches about 70 ℃ in the vicinity of the side feeder connecting section and about 30 ℃ in the vicinity of the outlet of the biaxial kneader. Thereafter, the melt is cooled, and the solid substance is pulverized into powder, thereby preparing a powdered thermosetting resin composition.

The thermosetting resin compositions of comparative examples 1 to 4 were produced by the following method (referred to as "production method B").

After the components shown in tables 1 and 2 were thoroughly mixed by a mixer, melt-kneading was performed at the kneading temperatures shown in tables 1 and 2 by a biaxial kneader. Thereafter, the melt is cooled, and the solid substance is pulverized into powder, thereby preparing a powdered thermosetting resin composition.

Evaluation of thermosetting resin composition

The produced thermosetting resin composition was evaluated by various tests shown below. The evaluation results are shown in tables 1 and 2. Further, unless explicitly stated otherwise, molding of the thermosetting resin composition is performed by a transfer molding machine under conditions of a mold temperature of 180 ℃, a molding pressure of 6.9MPa, and a curing time of 90 seconds.

[ rotational flow ]

Using a swirl flow measuring die according to EMMI-1-66, the thermosetting resin composition was molded under the above conditions and the flow distance (cm) was determined.

[ hardness at Heat ]

The thermosetting resin composition was molded into a disk having a diameter of 50 mm. Times.3 mm under the above-mentioned conditions, and immediately after the molding, the hardness at hot time was measured by using a Shore D-type durometer (manufactured by Shimadzu corporation, HD-1120 (D-type)).

[ melt viscosity ]

The minimum melt viscosity of the thermosetting resin composition at 175℃was measured using a high-flow tester (manufactured by Shimadzu corporation).

[ gel time ]

The time until the rise of the torque curve was set to be gel time (seconds) for 3g of the thermosetting resin composition, which was measured at 180℃using a vulcanization tester of JSR trade Co., ltd.

[ circular plate flow ]

TABLE 1

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TABLE 2

The initial temperature of the compositions in examples 1 to 4 was lower than the primary kneading temperature and higher than the secondary kneading temperature.

From the above results, it was found that the thermosetting resin composition obtained by the production method a was excellent in fluidity and low in melt viscosity at 175 ℃. In addition, according to the production method a, even if the thermosetting resin is kneaded at a relatively high temperature, the gel time is not excessively shortened, and the kneading can be satisfactorily performed. Further, from the evaluation of the hardness at heat, it was found that the thermosetting resin composition obtained by the production method a tends to have preferable hardenability. It is found that, particularly when the kneading temperature before adding the hardening accelerator is high, good hardenability and fluidity can be obtained.

The disclosure of japanese patent application No. 2021-002289 is incorporated by reference into this specification in its entirety.

All documents, patent applications, and technical specifications described in this specification are incorporated by reference into this specification to the same extent as if each individual document, patent application, and technical specification was specifically and individually indicated to be incorporated by reference.

Description of symbols

1: main material inlet

2: lateral feeder

10: mixing extruder

A: first mixing section

B: second mixing part

Claims

1. A method for producing a thermosetting resin composition, comprising:

mixing once, and mixing thermosetting resin; and

2. The production method according to claim 1, wherein the primary kneading temperature is higher than a melting point or a softening point of the thermosetting resin.

3. The production method according to claim 1 or 2, wherein the temperature of the primary kneading is higher than the initial temperature of the mixture after the addition of the hardening accelerator, as measured by differential scanning calorimetry.

4. The production method according to any one of claims 1 to 3, wherein the temperature of the secondary kneading is lower than the temperature of the primary kneading.

5. The production method according to any one of claims 1 to 4, wherein the temperature of the secondary kneading is lower than the initial temperature of the mixture after the addition of the hardening accelerator, as measured by differential scanning calorimetry.

6. The production method according to any one of claims 1 to 5, wherein the melting point or softening point of the thermosetting resin is higher than the starting temperature of the mixture after the addition of the hardening accelerator, as measured by differential scanning calorimetry.

7. The production method according to any one of claims 1 to 6, wherein the thermosetting resin has a melting point or softening point of 60 ℃ or higher.

8. The manufacturing method according to any one of claims 1 to 7, wherein the thermosetting resin comprises at least one selected from the group consisting of a biphenyl type epoxy resin and a sulfur atom type epoxy resin.

9. The production method according to any one of claims 1 to 8, wherein the inorganic filler is further kneaded in the primary kneading.

10. A thermosetting resin composition obtained by the production method according to any one of claims 1 to 9.

11. An electronic part device comprising an element sealed with the thermosetting resin composition obtained by the manufacturing method according to any one of claims 1 to 9.