CN116724394A

CN116724394A - Method for producing thermosetting resin composition and method for producing electronic component device

Info

Publication number: CN116724394A
Application number: CN202280008959.2A
Authority: CN
Inventors: 山浦格; 中村岳博; 洪昌勲; 姜东哲; 平嶋克至; 野泽博
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: KR20230128479A; WO2022149603A1; JP2022107397A; TW202233737A

Abstract

The method for producing the thermosetting resin composition comprises: a desolvation step of removing a solvent from a first mixture containing a thermosetting resin, a hardener, and a slurry containing an inorganic filler and the solvent at a first desolvation temperature to obtain a second mixture; and a kneading step of adding a hardening accelerator to the second mixture, and kneading the second mixture to which the hardening accelerator is added at a first kneading temperature lower than the first desolventizing temperature.

Description

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

Technical Field

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

Background

In recent years, in order to realize cost reduction, miniaturization, thinning, weight reduction, high performance and high functionality of electronic component devices, high density mounting is being advanced by miniaturization, multilayering, multi-pin formation, miniaturization and thinning of packages of element-based wirings. In response to this, chip scale packages (Chip Size Package, CSP) which are electronic component devices having substantially the same size as elements such as integrated circuits (Integrated Circuit, ICs) are widely used. Further, a system in package (System in Package, siP) in which a plurality of elements are embedded in one package has been developed.

As a sealing material for sealing elements of an electronic component device, a thermosetting resin composition containing a thermosetting resin, a curing agent, and an inorganic filler is widely used in terms of productivity, cost, and the like. With further higher density and higher functionality of elements mounted on electronic component devices, the bump-chip distance in CSP or the distance between elements in SiP is becoming narrower. Therefore, the diameter of the cut point (cut point) of the inorganic filler is being reduced. However, as the diameter of the cut point is reduced, the specific surface area of the inorganic filler is increased, which makes it difficult to uniformly disperse, and as a result, the high filling of the inorganic filler is a problem.

As an example of a method for producing a thermosetting resin composition, a method for producing an epoxy resin molding material for sealing a semiconductor is disclosed, which is characterized by comprising: all the raw materials including the epoxy resin, the hardener, and the inorganic filler are mixed in a solvent, dissolved to prepare a mixed solution, and then the solvent is removed (for example, see patent document 1 and patent document 2).

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open publication No. 2011-252041

Patent document 2: japanese patent laid-open publication No. 2011-252042

Disclosure of Invention

Problems to be solved by the invention

In the manufacturing method described in patent document 1 or patent document 2, the raw materials are brought into a mixed solution state in order to remove metallic foreign matters in the epoxy resin molding material for semiconductor encapsulation. However, in the manufacturing method described in patent document 1 or patent document 2, there are cases where: it is difficult to impart a strong shearing force to the mixed solution and to uniformly disperse the inorganic filler at a low cut point.

In view of the foregoing, an object of an aspect of the present disclosure is to provide a method for producing a thermosetting resin composition capable of achieving high filling of an inorganic filler, and a method for producing an electronic component device using the thermosetting resin composition obtained by the production method.

Technical means for solving the problems

Specific means for achieving the above-described object are as follows.

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

a desolvation step of removing a solvent from a first mixture containing a thermosetting resin, a hardener, and a slurry containing an inorganic filler and the solvent at a first desolvation temperature to obtain a second mixture; and

A kneading step of adding a hardening accelerator to the second mixture, and kneading the second mixture to which the hardening accelerator is added at a first kneading temperature lower than the first desolventizing temperature.

<2> a method for producing a thermosetting resin composition, comprising:

a solvent removing step of removing the solvent from a third mixture containing one of a thermosetting resin and a hardener and a slurry containing an inorganic filler and a solvent at a second solvent removing temperature, and then adding the other of the thermosetting resin and the hardener to obtain a fourth mixture, or adding the other of the thermosetting resin and the hardener to a third mixture containing one of a thermosetting resin and a hardener and a slurry containing an inorganic filler and a solvent at a second solvent removing temperature while removing the solvent to obtain a fourth mixture; and

and a kneading step of adding a hardening accelerator to the fourth mixture, and kneading the fourth mixture to which the hardening accelerator is added at a second kneading temperature lower than the second desolventizing temperature.

<3> the method for producing a thermosetting resin composition according to <1>, wherein the first kneading temperature is a temperature at which the reaction rate becomes 40% or less as measured by measuring the second mixture to which the hardening accelerator is added by differential scanning calorimetry.

<4> the method for producing a thermosetting resin composition according to <2>, wherein the second kneading temperature is a temperature at which the reaction rate becomes 40% or less as measured by measuring the fourth mixture to which the hardening accelerator is added by differential scanning calorimetry.

<5> the method for producing a thermosetting resin composition according to any one of <1> to <4>, wherein the desolvation step and the kneading step are continuously performed.

<6> the method for producing a thermosetting resin composition according to any one of <1> to <4>, wherein the solvent removal step can be performed in a batch manner.

<7> the method for producing a thermosetting resin composition according to any one of <1> to <6>, wherein the first desolvation temperature or the second desolvation temperature is higher than the melting point or softening point of the thermosetting resin.

<8> the method for producing a thermosetting resin composition according to any one of <1> to <7>, wherein the slurry further comprises a coupling agent.

<9> the method for producing a thermosetting resin composition according to any one of <1> to <8>, wherein the top cut diameter of the inorganic filler is 10 μm or less.

<10> the method for producing a thermosetting resin composition according to any one of <1> to <9>, wherein the boiling point of the solvent is 50 ℃ to 200 ℃.

<11> the method for producing a thermosetting resin composition according to any one of <1> to <10>, wherein a solid content ratio of the inorganic filler in the slurry is 40 to 90 mass%.

<12> the method for producing a thermosetting resin composition according to any one of <1> to <11>, wherein a solid content ratio of the first mixture or the third mixture is 30 to 90 mass%.

<13> a method for manufacturing an electronic component device, comprising a step of sealing an element by using the thermosetting resin composition obtained by the method for manufacturing a thermosetting resin composition according to any one of <1> to <12 >.

ADVANTAGEOUS EFFECTS OF INVENTION

According to one aspect of the present disclosure, a method for producing a thermosetting resin composition capable of achieving high filling of an inorganic filler and a method for producing an electronic component device using the thermosetting resin composition obtained by the production method can be provided.

Detailed Description

The following is a detailed description of the manner in which the present disclosure is implemented. The present disclosure is 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 present disclosure is not limited with respect to values and ranges thereof.

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, as long as the purpose of the process is achieved.

In the present disclosure, the numerical values described before and after the use of the numerical values indicated by the "to" include the "to" values 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, a plurality of conforming substances may be included in each component. 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 may be contained in particles corresponding to each component. When a plurality of particles corresponding to each component are present in the composition, the particle diameter of each component refers to a value related to a mixture of the plurality of particles present in the composition unless otherwise specified.

In the present disclosure, the term "solid component" refers to a component remaining from a mixture, slurry, or thermosetting resin composition, in which volatile components such as solvents are removed.

< method for producing thermosetting resin composition >

The method for producing a thermosetting resin composition according to the first embodiment of the present disclosure includes: a desolvation step of removing a solvent from a first mixture containing a thermosetting resin, a hardener, and a slurry containing an inorganic filler and the solvent at a first desolvation temperature to obtain a second mixture; and a kneading step of adding a hardening accelerator to the second mixture, and kneading the second mixture to which the hardening accelerator is added at a first kneading temperature lower than the first desolventizing temperature.

In addition, a method for producing a thermosetting resin composition according to a second embodiment of the present disclosure includes: a solvent removing step of removing the solvent from a third mixture containing one of a thermosetting resin and a hardener and a slurry containing an inorganic filler and a solvent at a second solvent removing temperature, and then adding the other of the thermosetting resin and the hardener to obtain a fourth mixture, or adding the other of the thermosetting resin and the hardener to a third mixture containing one of a thermosetting resin and a hardener and a slurry containing an inorganic filler and a solvent at a second solvent removing temperature while removing the solvent to obtain a fourth mixture; and a kneading step of adding a hardening accelerator to the fourth mixture, and kneading the fourth mixture to which the hardening accelerator is added at a second kneading temperature lower than the second desolventizing temperature.

Hereinafter, the method for producing the thermosetting resin composition according to the first embodiment and the method for producing the thermosetting resin composition according to the second embodiment are sometimes collectively referred to as a production method of the present disclosure.

The method for producing the thermosetting resin composition according to the first embodiment is sometimes referred to as a first production method, and the method for producing the thermosetting resin composition according to the second embodiment is sometimes referred to as a second production method.

The first desolvation temperature and the second desolvation temperature may be referred to as a specific desolvation temperature, and the first kneading temperature and the second kneading temperature may be referred to as a specific kneading temperature.

According to the manufacturing method of the present disclosure, high filling of the inorganic filler can be achieved. The reason for this is not clear, but is presumed as follows.

Since the solvent contained in the first mixture or the third mixture functions as a dispersion medium and the viscosity of the first mixture or the third mixture is reduced, the generation of shearing heat at the time of preparing the first mixture or the third mixture or at the time of removing the solvent from the first mixture or the third mixture while stirring or the like at a specific desolvation temperature can be suppressed. In the conventional method for producing a thermosetting resin composition without using a solvent as a dispersion medium, it is difficult to reduce the cohesive force of the inorganic filler, and particularly in the case of using an inorganic filler having a low cut point, there is a case where large shearing heat is generated to cause gelation of the thermosetting resin composition.

In the production method of the present disclosure, since the solvent is used when the first mixture or the third mixture is obtained, the temperature rise of the first mixture or the third mixture can be suppressed as compared with the conventional production method in which the solvent is not used, and a sufficient shear force can be imparted to the first mixture or the third mixture without concern of gelation of the thermosetting resin composition in the solvent removal step. By imparting a sufficient shear force to the first mixture or the third mixture, the inorganic filler in the thermosetting resin composition is easily and uniformly dispersed.

In addition, by setting the specific desolvation temperature to be higher than the specific kneading temperature, the viscosity of the first mixture or the third mixture can be further reduced in the desolvation step, and therefore, the stirring of the first mixture or the third mixture becomes easier, and the inorganic filler in the thermosetting resin composition can be more easily uniformly dispersed.

Further, by setting the specific kneading temperature to be lower than the specific desolvation temperature, progress of the hardening reaction between the thermosetting resin and the hardening agent due to the hardening accelerator in the kneading step can be suppressed, and the concern of gelation of the thermosetting resin composition can be reduced.

From the above, it is presumed that the dispersibility of the inorganic filler is further improved, and as a result, the inorganic filler can be highly filled in the thermosetting resin composition.

In the present disclosure, the "kneading temperature" refers to a temperature of a heating portion of the kneading device when the kneading device is used to knead the mixture.

In the present disclosure, the term "desolvation temperature" refers to a temperature of a heating portion of an apparatus for heating a mixture, which is used when removing a solvent from the mixture. For example, in the case of performing the solvent removal process in a batch manner using a vacuum dryer, the temperature of the heating portion of the container for accommodating the mixture is set to the solvent removal temperature. On the other hand, in the case of performing the desolvation step using the kneading device, the temperature of the heating portion of the kneading device is set to the desolvation temperature.

In this disclosure, "mixing" and "kneading" all refer to mixing a mixture. The case where the materials having relatively low viscosity such as the powder and the solvent are mixed without shearing is referred to as "mixing", and the case where the molten resin or solvent is dispersed and mixed while shearing is applied in a state where the content of the resin or solvent is relatively small and the viscosity is high is referred to as "kneading".

The value of the solvent content in the mixture to distinguish between "mixing" and "kneading" is not determined to be an exact value of a particular numerical value.

The steps constituting the manufacturing method of the present disclosure and the steps used as needed will be described below.

(preparation of mixture)

In the first production method, in the desolvation step, a first mixture including a thermosetting resin, a hardener, and a slurry containing an inorganic filler and a solvent may be used. The first mixture may optionally contain other components such as a stress relaxation agent and an ion exchanger.

The first mixture may be obtained by: the thermosetting resin, the curing agent, the slurry containing the inorganic filler and the solvent, the stress relaxation agent used if necessary, and other components such as the ion exchanger are mixed using a mixer such as a stirrer or a planetary mixer, a wet-type disperser such as an ultrasonic disperser or a jet mill, or the like. The mixing conditions in preparing the first mixture may be appropriately set according to the types of components contained in the first mixture, the ratio of the components, and the like.

In the first production method, in the desolvation step, a composite mixture obtained by mixing a mixture containing a thermosetting resin, a slurry containing an inorganic filler and a solvent, and a mixture containing a hardener, a slurry containing an inorganic filler and a solvent may be used as the first mixture.

A mixture containing a thermosetting resin, a slurry containing an inorganic filler and a solvent, a mixture containing a hardener, a slurry containing an inorganic filler and a solvent, and a composite mixture can be obtained in the same manner as the first mixture.

In the second production method, a third mixture including one of a thermosetting resin and a curing agent and a slurry containing an inorganic filler and a solvent can be used. The third mixture may optionally contain other components such as a stress relaxation agent and an ion exchanger. The third mixture may contain the other of the thermosetting resin and the curing agent. When the other of the thermosetting resin and the curing agent is contained in the third mixture, a part of the thermosetting resin or the curing agent contained in the thermosetting resin composition produced by the second production method may be added to the third mixture.

The third mixture may be obtained as in the first mixture.

The solid content ratio of the first mixture or the third mixture is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and even more preferably 50 to 80% by mass, from the viewpoint of liquid conveyability in the desolvation step.

(desolvation step)

In the first production method, in the desolvation step, the solvent is removed from the first mixture at a first desolvation temperature to obtain a second mixture. In removing the solvent from the first mixture, the solvent may be removed while mixing the first mixture.

The method for removing the solvent from the first mixture is not particularly limited, and examples thereof include: a method of heating the first mixture, a method of placing the first mixture under a reduced pressure environment, a method of heating the first mixture while placing the first mixture under a reduced pressure environment, and the like.

In the case where the first mixture is placed under a reduced pressure environment, an existing vacuum dryer may be used. At this time, the first mixture may be stirred.

In the case where the solvent is removed while mixing the first mixture, an existing kneading apparatus may be used. Examples of the kneading apparatus include: screw type mixers such as a single-shaft mixer, a double-shaft mixer, and a multi-shaft mixer having three or more shafts; roller mills such as a twin roller mill and a three roller mill.

The stirring blade of the screw kneader may be supported by the root end and the tip end, or may be supported by the root end alone. From the viewpoint of improving the mixing property and productivity, the stirring blade is preferably supported only by the root end.

Among these, a screw kneader as an example of a closed kneading device capable of removing a solvent by reducing pressure is preferable, and a biaxial kneader is more preferable in view of easy control of shearing force.

In order to add the hardening accelerator to the second mixture, the second mixture to which the hardening accelerator is added is further kneaded at the first kneading temperature, and it is also preferable to use a screw kneader as the kneading device.

In the second production method, in the desolvation step, the solvent is removed from the third mixture containing one of the thermosetting resin and the hardener and the slurry containing the inorganic filler and the solvent at the second desolvation temperature, and then the other of the thermosetting resin and the hardener is added to obtain a fourth mixture, or the other of the thermosetting resin and the hardener is added to the third mixture containing the one of the thermosetting resin and the hardener and the slurry containing the inorganic filler and the solvent at the second desolvation temperature while removing the solvent to obtain the fourth mixture.

In the second production method, the method for obtaining the fourth mixture is not particularly limited, and the fourth mixture may be obtained by the same method as in the case of the first production method. For example, when solvent is removed from the third mixture at a second desolvation temperature, a vacuum dryer may be used. In addition, when the other of the thermosetting resin and the curing agent is added to the third mixture while removing the solvent at the second desolventizing temperature, a screw kneader may be used.

Further, it is preferable to use a screw kneader in view of easiness of the addition of the other of the thermosetting resin and the curing agent to the third mixture. In the case of using a screw kneader to perform the solvent removal step in the second production method, the other of the thermosetting resin and the hardener may be added to the third mixture by side feeding.

The specific desolvation temperature is not particularly limited, but is preferably higher than the melting point or softening point of the thermosetting resin in view of suppressing the tendency of the thermosetting resin to exist. In the case where two or more thermosetting resins are used in combination, the specific desolvation temperature is preferably a temperature higher than the melting point or softening point of the thermosetting resin having the highest melting point or softening point.

The specific desolvation temperature is preferably a temperature 1 to 90℃higher than the melting point or softening point of the thermosetting resin (the thermosetting resin having the highest melting point or softening point in the case of using a plurality of thermosetting resins in combination), more preferably a temperature 1 to 70℃higher, still more preferably a temperature 1 to 60℃higher. By performing the desolventizing treatment using, for example, a screw kneader at the above temperature, the thermosetting resin can be melted to maintain fluidity, and therefore stirring and mixing can be performed satisfactorily.

In one embodiment, the specific desolvation temperature is preferably 30 to 200 ℃, more preferably 50 to 180 ℃, and still more preferably 80 to 160 ℃.

When a screw kneader is used as the kneading device, the solvent is preferably removed by depressurizing the inside of the screw kneader.

When a screw kneader is used as the kneading device, the pressure in the screw kneader is preferably 0.001 to 0.08MPa, more preferably 0.003 to 0.06MPa, and still more preferably 0.005 to 0.05MPa, from the viewpoint of distillation removal of the solvent.

(mixing step)

In the production method of the present disclosure, a hardening accelerator is added to the second mixture or the fourth mixture obtained in the desolvation step, and the second mixture or the fourth mixture to which the hardening accelerator is added is kneaded at a specific kneading temperature lower than the specific desolvation temperature to obtain a kneaded product.

In terms of suppressing progress of the hardening reaction of the thermosetting resin and the hardening agent, the temperature of the second mixture or the fourth mixture when the hardening accelerator is added to the second mixture or the fourth mixture is preferably lower than the specific desolvation temperature.

The specific kneading temperature is not particularly limited as long as it is a temperature lower than the specific desolvation temperature. In terms of suppressing gelation of the kneaded material in the kneading step, the specific kneading temperature is preferably set such that the reaction rate at the specific kneading temperature calculated based on differential scanning calorimetry with respect to the second mixture or the fourth mixture to which the hardening accelerator is added becomes small, preferably the reaction rate is 40% or less, more preferably the reaction rate is 30% or less, and even more preferably the reaction rate is 20% or less.

In the present disclosure, the reaction rate at a prescribed temperature can be measured by the following method.

Differential scanning calorimeter (Differential Scanning Calorimetry, DSC) profiles were measured for samples having a hardening accelerator added to the second or fourth mixtures at a lifting temperature rate of 10 ℃/min from 50 ℃. Then, the area from the rising temperature of the heat generation peak observed in the obtained DSC chart to the temperature set as the predetermined temperature and the total heat generation area of the heat generation peak are calculated. The reaction rate at the predetermined temperature is set to a value obtained by dividing the area from the rising temperature of the heat generation peak to the predetermined temperature by the total heat generation area and multiplying by 100.

In one embodiment, the specific kneading temperature is preferably 1 to 100℃lower than the specific desolvation temperature, more preferably 10 to 90℃lower, and still more preferably 20 to 85℃lower.

In some embodiments, the specific kneading temperature is preferably 50 to 150 ℃, more preferably 60 to 140 ℃, and still more preferably 70 to 120 ℃.

The method of adding the hardening accelerator to the second mixture or the fourth mixture is not particularly limited. In the case of using a screw kneader as the kneading device, a method of kneading the first mixture or the third mixture at a specific desolventizing temperature to obtain a second mixture or a fourth mixture, and then adding a hardening accelerator to the second mixture or the fourth mixture by side feeding is preferable.

In the case of adding the hardening accelerator to the second mixture or the fourth mixture by side feeding, the hardening accelerator may be directly added to the second mixture or the fourth mixture, or the hardening accelerator may be mixed with a hardening agent, an inorganic filler, or the like to prepare a master batch, and the master batch may be added to the second mixture or the fourth mixture. In order to improve the accuracy of the addition amount of the hardening accelerator, it is preferable to add a master batch to the second mixture or the fourth mixture.

When the masterbatch is added to the second mixture or the fourth mixture, the masterbatch is preferably present in an amount of 50 mass% or less in the thermosetting resin composition obtained as a kneaded product in the kneading step.

In one embodiment, the proportion of the masterbatch in the thermosetting resin composition obtained as the kneaded material is preferably less than 50% by mass, more preferably less than 30% by mass, and still more preferably less than 25% by mass. If the content is 50 mass% or less, the mixing property tends to be improved after the masterbatch is added to the second mixture or the fourth mixture. The ratio of the master batch may be 5 mass% or more.

(post-treatment)

In the production method of the present disclosure, the thermosetting resin composition obtained as a kneaded product can be cooled and pulverized to obtain a powdery thermosetting resin composition. The thermosetting resin composition obtained by kneading may be formed into a pellet, a tablet, a pellet or a granule (a columnar granule or the like). The method for pulverizing or molding the thermosetting resin composition is not particularly limited, and any method conventionally used can be used.

In the production method of the present disclosure, the solvent removal step and the kneading step may be performed continuously. In the production method of the present disclosure, the solvent removal step may be performed in batch.

In the case where the solvent removal step and the kneading step are performed continuously, it is preferable to use a screw kneader for the implementation of the solvent removal step and the kneading step. In the case of using a screw kneader, the solvent removal step and the kneading step can be performed continuously by performing the kneading step immediately after the solvent removal step.

In the case of performing the solvent removal step in a batch manner, the second mixture or the fourth mixture obtained in the solvent removal step may be cooled and pulverized to obtain a powder, and the hardening accelerator may be added to the powder-like second mixture or the powder-like fourth mixture and kneaded by a screw kneader to obtain the thermosetting resin composition. In this case, the method of adding the hardening accelerator to the second mixture or the fourth mixture is not particularly limited, and the second mixture or the fourth mixture and the hardening accelerator may be mixed by a screw kneader, or the hardening accelerator may be added to the second mixture or the fourth mixture by side feeding.

Next, details of various components used in the production method of the present disclosure will be described.

(thermosetting resin)

The thermosetting resin composition produced by the production method of the present disclosure contains a thermosetting resin.

The type of the thermosetting resin is not particularly limited, and examples thereof include: epoxy resins, phenol resins, urea resins, thiol resins, melamine resins, urethane resins, silicone resins, maleimide 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.

The type of the epoxy resin is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule.

Specifically, there may be mentioned: 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 aminophenol type epoxy resins which are glycidyl ethers of aminophenol are also exemplified. One kind of these epoxy resins may be used alone, or two or more kinds may be used in combination.

Among the above epoxy resins, epoxy resins selected from the group consisting of biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, sulfur atom-containing type epoxy resins, novolak type epoxy resins, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, copolymerization type epoxy resins, and aralkyl type epoxy resins (these are referred to as "specific epoxy resins") are preferable from the viewpoint of balance between heat resistance and fluidity. The specific epoxy resin may be used singly or in combination of two or more.

When the epoxy resin contains a specific epoxy resin, the content of the specific epoxy resin is preferably 30 mass% or more, more preferably 50 mass% or more of the entire epoxy resin, from the viewpoint of exhibiting the performance of the specific epoxy resin.

Among the specific epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, or sulfur-containing ortho-type epoxy resins are more preferable from the viewpoint of fluidity, and dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, or aralkyl type epoxy resins are preferable from the viewpoint of heat resistance. Hereinafter, specific examples of the preferable epoxy resin are shown.

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-4000H (Mitsubishi chemical Co., ltd., trade name) as a hydrogen atom, 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.

The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferable. Among the epoxy resins represented by the following general formula (III), R is exemplified ⁹ The 3,3', 5' position when the position of the oxygen atom is 4 position and 4' position is methylAnd other than R ⁹ Is a hydrogen atom, R ¹⁰ All being hydrogen atoms, R ⁹ Three of the 3,3', 5' positions in (a) are methyl, one is tert-butyl and the other R ⁹ Is a hydrogen atom, R ¹⁰ And mixtures of hydrogen atoms.

[ chemical 2]

In the formula (III), R ⁹ R is R ¹⁰ 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 diphenylmethane epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferable. In the epoxy resin represented by the following general formula (IV), R ¹¹ All are hydrogen atoms, R ¹² 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 ¹² YSLV-80XY (daily iron chemistry) as a hydrogen atom&Material stock, trade name), etc. are available as commercial products.

[ chemical 3]

In the formula (IV), R ¹¹ R is R ¹² 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 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 The positions of the oxygen atoms in the formula are the 4-position and the 4' -position, the 3,3' -position is tert-butyl, the 6,6' -position is methyl, and the other positions are methylR ¹³ YSLV-120TE (daily iron chemistry) as a hydrogen atom&Material stock, trade name), etc. are available as commercial products.

[ chemical 4]

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 novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin. For example, epoxy resins obtained by epoxidizing a novolak type phenol resin such as a phenol novolak resin, a cresol novolak resin, and a naphthol novolak resin by a method such as glycidyl etherification are preferable, and epoxy resins represented by the following general formula (VI) are more preferable. In the epoxy resin represented by the following general formula (VI), R ¹⁴ All are hydrogen atoms, R ¹⁵ ESCN-190 and ESCN-195 (Sumitomo chemical Co., ltd.); r is R ¹⁴ N-770 and N-775 (diegasen (DIC) corporation, trade name) each of which is a hydrogen atom, i=0; with R ¹⁴ Each hydrogen atom, i=0 and i=1, R ¹⁵ is-CH (CH) ₃ ) Part of the Ph styrene-modified phenol novolac type epoxy resin, YDA-1000-10C (Nitro iron chemistry)&Material stock, trade name); with R ¹⁴ Are all hydrogen atoms, i=1, R ¹⁵ Moieties that are methyl with i=2, R ¹⁵ Benzyl-modified cresol novolac type epoxy resins and the like in which one of them is methyl and the other is benzyl are available as commercial products.

[ chemical 5]

In the formula (VI), R ¹⁴ Represents a hydrogen atom or a C1-18 radicalThe valence organic groups may be the same or different. R is R ¹⁵ The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidation of a compound having a dicyclopentadiene skeleton as a raw material. For example, an epoxy resin represented by the following general formula (VII) is preferable. Among the epoxy resins represented by the following general formula (VII), HP-7200 (trade name of Diegasin (DIC) stock, inc.) having i=0 and the like are available as commercial products.

[ chemical 6]

In the formula (VII), R ¹⁶ The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin using a compound having a triphenylmethane skeleton as a raw material. For example, an epoxy resin obtained by subjecting a triphenylmethane type phenol resin obtained from an aromatic aldehyde compound and a phenolic compound to glycidyl etherification is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable. Of the epoxy resins represented by the following general formula (VIII), 1032H60 (trade name of Mitsubishi chemical corporation) having i of 0 and k of 0, EPPN-502H (trade name of Japanese chemical corporation) and the like are available as commercial products.

[ chemical 7]

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

The copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound and a phenol compound with an aldehyde compound is not particularly limited as long as it is an epoxy resin using a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. For example, an epoxy resin obtained by subjecting a novolac-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton to glycidyl etherification is preferable, and an epoxy resin represented by the following general formula (IX) is more preferable. In the epoxy resin represented by the following general formula (IX), R ²¹ NC-7300 (trade name of Japanese chemical Co., ltd.) in which i is methyl, j is 0, and k is 0, etc. are available as commercial products.

[ chemical 8]

In the formula (IX), R ¹⁹ ～R ²¹ The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. i each independently represents an integer of 0 to 3, j each independently represents an integer of 0 to 2, and k each independently represents an integer of 0 to 4. l and m are each an average value of 0 to 10, and (1+m) represents a number of 0 to 10. The terminal of the epoxy resin represented by the formula (IX) is either the following formula (IX-1) or formula (IX-2). In the formula (IX-1) and the formula (IX-2), R ¹⁹ ～R ²¹ Definition of i, j and k and R in formula (IX) ¹⁹ ～R ²¹ The definitions of i, j and k are the same. n is 1 (in the case of bonding via a methylene group) or 0 (in the case of bonding without a methylene group).

[ chemical 9]

The epoxy resin represented by the general formula (IX) may be: random copolymers comprising 1 structural unit and m structural units randomly, alternating copolymers comprising 1 structural unit and m structural units alternately, copolymers comprising 1 structural unit and m structural units regularly, block copolymers comprising 1 structural unit and m structural units in blocks, and the like. Any one of these may be used alone, or two or more may be used in combination.

As the copolymerized epoxy resin, it is also preferable that the following two structural units are contained in random, alternating or block order, namely Ai Bike long (EPICLON) HP-5000 (Di Aisheng (DIC) Co., ltd., trade name) which is a methoxy naphthalene-cresol formaldehyde co-condensed epoxy resin. In the following general formula, n and m are each an average value of 0 to 10, and (n+m) is a number of 0 to 10, preferably n and m are each an average value of 1 to 9, and (n+m) is a number of 2 to 10.

[ chemical 10]

The aralkyl type epoxy resin is not particularly limited as long as it is an epoxy resin using, as a raw material, 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 dimethoxy-para-xylene, bis (methoxymethyl) biphenyl or derivatives of these. For example, an epoxy resin obtained by glycidyletherifying at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol with a phenol resin synthesized from dimethoxy paraxylene, bis (methoxymethyl) biphenyl or a derivative of these, and more preferably an epoxy resin represented by the following general formula (X) and general formula (XI) is preferable.

In the epoxy resin represented by the following general formula (X), i is 0 and R ³⁸ NC-3000S (trade name of Japanese chemical Co., ltd.) which is a hydrogen atom, in a mass ratio of 80:20 will i be 0 and R ³⁸ An epoxy resin having a hydrogen atom and all R's of the formula (II) ⁸ Epoxy resin mixture as hydrogen atomSynthetic CER-3000 (trade name of Japanese chemical Co., ltd.) and the like are available as commercial products. In addition, ESN-175 (Nitro iron chemistry) in which 1 is 0, j is 0, and k is 0 in the epoxy resin represented by the following general formula (XI)&Material stock, trade name), etc. are available as commercial products.

[ chemical 11]

In the formula (X) and the formula (XI), R ³⁸ The monovalent organic groups each representing a hydrogen atom or a carbon number of 1 to 18 may be the same or different. R is R ³⁷ 、R ³⁹ ～R ⁴¹ The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. i is an integer of 0 to 3, j is an integer of 0 to 2, k is an integer of 0 to 4, and 1 is an integer of 0 to 4. n is an average value and each independently is a number from 0 to 10.

R in the general formulae (II) to (XI) ⁸ ～R ²¹ R is R ³⁷ ～R ⁴¹ The term "may be the same or different from each other" means, for example, 8 to 88R in the formula (II) ⁸ May be the same or different. Concerning other R ⁹ ～R ²¹ R is R ³⁷ ～R ⁴¹ It is also meant that the numbers of the respective compounds contained in the formulae may be the same or different. In addition, R ⁸ ～R ²¹ R is R ³⁷ ～R ⁴¹ May be the same or different. For example, R ⁹ And R is R ¹⁰ May be the same or different.

The monovalent organic group having 1 to 18 carbon atoms in the general formulae (III) to (XI) is preferably an alkyl group or an aryl group.

N in the general formulae (II) to (XI) is an average value, and is preferably each independently in the range of 0 to 10. When n is 10 or less, the melt viscosity of the resin component is not excessively high, and the viscosity at the time of melt molding of the thermosetting resin composition is reduced, so that the occurrence of filling failure, deformation of bonding wires (wires connecting elements and leads) and the like tends to be suppressed. n is more preferably set to a range of 0 to 4.

Specific examples of preferable epoxy resins that can be used in the thermosetting resin composition are described above along the general formulae (II) to (XI), and as more specific preferable epoxy resins, 4 '-bis (2, 3-epoxypropoxy) -3,3',5 '-tetramethylbiphenyl is exemplified from the viewpoint of heat resistance, and 4,4' -bis (2, 3-epoxypropoxy) -biphenyl from the viewpoint of moldability and heat resistance.

The epoxy equivalent of the epoxy resin is not particularly limited. The epoxy equivalent of the epoxy resin is preferably 60g/eq to 1000g/eq, more preferably 80g/eq to 500g/eq, from the viewpoint of balance of various properties such as moldability, heat resistance and electrical reliability.

The epoxy resin may be in a liquid state or in a solid state. In the case where the epoxy resin is solid, the softening point or melting point of the epoxy resin is not particularly limited. The temperature is preferably 40 to 180℃in terms of moldability and heat resistance, and more preferably 50 to 130℃in terms of handleability in the preparation of the thermosetting resin composition.

In the present disclosure, the softening point means a softening point obtained by passing japanese industrial standard (Japanese Industrial Standards, JIS) K7234: 1986, measured by the world method.

In the present disclosure, the melting point means that according to JIS K0064: 1992, values determined by visual-based methods.

The content of the epoxy resin in the thermosetting resin composition is preferably 0.5 to 60% by mass, more preferably 2 to 50% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, and the like.

(hardener)

The thermosetting resin composition produced by the production method of the present disclosure contains a curing agent.

The type of the curing agent is not particularly limited, and is not particularly limited as long as it is a compound that causes a curing reaction with the thermosetting resin used in combination. For example, as a hardener used in combination with an epoxy resin, there may be mentioned: phenolic hardeners, amine hardeners, acid anhydride hardeners, polythiol hardeners, polyaminoamide hardeners, isocyanate hardeners, blocked isocyanate hardeners, and the like. The hardening agent may be used alone or in combination of two or more. The hardener may be solid or liquid at normal temperature and pressure (e.g., 25 ℃ C., atmospheric pressure), and is preferably solid.

In the case where the thermosetting resin is an epoxy resin, the curing agent is preferably a phenol curing agent or an amine curing agent from the viewpoint of heat resistance.

Examples of the phenolic hardener include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, there may be mentioned: 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 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 modified phenol resin, 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. These phenolic hardeners may be used singly or in combination of two or more.

Among the phenolic hardeners, at least one selected from the group consisting of an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin, a copolymerized type phenol resin of a triphenylmethane type phenol resin and an aralkyl type phenol resin, and a novolac type phenol resin is preferable from the viewpoint of heat resistance (these are referred to as "specific phenolic hardeners"). The specific phenolic hardener may be used alone or in combination of two or more.

When the phenol-based hardener contains a specific phenol-based hardener, the content of the specific phenol-based hardener is preferably 30 mass% or more, more preferably 50 mass% or more of the entire phenol-based hardener, from the viewpoint of sufficiently exhibiting the performance thereof.

Examples of the aralkyl type phenol resin include phenol aralkyl resins and naphthol aralkyl resins synthesized from a phenolic compound, dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and the like. The aralkyl type phenol resin may be further copolymerized with other phenol resins. Examples of the copolymerized aralkyl phenol resin include: and copolymerized phenol resins of triphenylmethane type phenol resin and aralkyl type phenol resin, copolymerized phenol resins of salicylaldehyde type phenol resin and aralkyl type phenol resin, copolymerized phenol resins of novolak type phenol resin and aralkyl type phenol resin, and the like.

The aralkyl type phenol resin is not particularly limited as long as it is a phenol resin synthesized from at least one selected from the group consisting of phenol compounds and naphthol compounds and dimethoxy para-xylene, bis (methoxymethyl) biphenyl, or derivatives of these. For example, phenol resins represented by the following general formulae (XII) to (XIV) are preferable.

[ chemical 12]

In the formulae (XII) to (XIV), R ²³ The monovalent organic groups each representing a hydrogen atom or a carbon number of 1 to 18 may be the same or different. R is R ²² 、R ²⁴ 、R ²⁵ R is R ²⁸ Monovalent organic groups having 1 to 18 carbon atoms may be the same or differentDifferent. R is R ²⁶ R is R ²⁷ The hydroxyl group or the monovalent organic group having 1 to 18 carbon atoms may be the same or different. i is an integer of 0 to 3, j is an integer of 0 to 2, k is an integer of 0 to 4, and p is an integer of 0 to 4. n is an average value and each independently is a number from 0 to 10.

In the phenol resin represented by the general formula (XII), i is 0 and R ²³ MEH-7851 (trade name) and the like, both of which are hydrogen atoms, are available as commercial products.

Among the phenol resins represented by the general formula (XIII), XL-225, XLC (trade name of Sanchi chemical Co., ltd.), MEH-7800 (trade name of Ming and Chemie Co., ltd.) and the like having i of 0 and k of 0 are available as commercial products.

In the phenol resin represented by the general formula (XIV), SN-170 (daily iron chemistry) wherein j is 0, k is 0 and p is 0&Trade name of Material Co., ltd.), j is 0, k is 1, R ²⁷ SN-395 (Nitro iron chemistry) with hydroxyl and p 0&Material stock, trade name), etc. are available as commercial products.

The dicyclopentadiene phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), a phenol resin having i of 0 can be obtained as a commercially available product.

[ chemical 13]

In the formula (XV), R ²⁹ The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

The triphenylmethane type phenol resin is not particularly limited as long as it is a phenol resin obtained by using an aromatic aldehyde compound as a raw material. For example, the phenol resin represented by the following general formula (XVI) is preferable.

Among the phenol resins represented by the following general formula (XVI), MEH-7500 (trade name, minand chemical Co., ltd.) having i of 0 and k of 0 and the like are available as commercial products.

[ chemical 14]

In the formula (XVI), R ³⁰ R is R ³¹ The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. i is an integer of 0 to 3, and k is an integer of 0 to 4. n is an average value and is a number from 0 to 10.

The copolymerized phenol resin of the triphenylmethane-type phenol resin and the aralkyl-type phenol resin is not particularly limited as long as it is a copolymerized phenol resin of a phenol resin obtained by using a compound having a benzaldehyde skeleton as a raw material and an aralkyl-type phenol resin. For example, the phenol resin represented by the following general formula (XVII) is preferable.

Among the phenol resins represented by the following general formula (XVII), HE-510 (trade name, available from air Water chemistry (Air Water Chemical) Co., ltd.) in which i is 0, k is 0 and q is 0, and the like are available as commercial products.

[ 15]

In the formula (XVII), R ³² ～R ³⁴ The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. i is an integer of 0 to 3, k is an integer of 0 to 4, and q is an integer of 0 to 5. 1 and m are each an average value and are each independently a number of 0 to 11. Wherein the sum of 1 and m is a number of 1 to 11.

The novolak type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds with an aldehyde compound in the presence of an acidic catalyst. For example, the phenol resin represented by the following general formula (XVIII) is preferable.

In the phenol resin represented by the following general formula (XVIII), i is 0 or R ³⁵ Teminol (Tamanol) 758, 759 (trade name of Nakawa chemical industry Co., ltd.), H-4 (trade name of Ming He Chemicals Co., ltd.) and the like, which are all hydrogen atoms, are available as commercial products.

[ 16]

In the formula (XVIII), R ³⁵ The monovalent organic groups each representing a hydrogen atom or a carbon number of 1 to 18 may be the same or different. R is R ³⁶ The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

R in the general formulae (XII) to (XVIII) ²² ～R ³⁶ The term "may be the same or different" as used herein refers to, for example, i R in formula (XII) ²² May be the same or different from each other. Concerning other R ²³ ～R ³⁶ It is also meant that the numbers of each contained in the formulae may be the same or different from each other. In addition, R ²² ～R ³⁶ The two may be the same or different. For example, R ²² R is R ²³ May be the same or different, R ³⁰ R is R ³¹ May be the same or different.

In the general formulae (XII) to (XVIII), n is preferably in the range of 0 to 10. If the melt viscosity of the resin component is 10 or less, the viscosity at the time of melt molding of the thermosetting resin composition is not excessively high, and filling failure, deformation of the bonding wire (wire connecting element and lead wire) and the like are less likely to occur. The average n in one molecule is preferably set to a range of 0 to 4.

Specific examples of the amine-based hardener include: aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4' -diamino-dicyclohexylmethane; aromatic amine compounds such as diethyl toluenediamine, 3 '-diethyl-4, 4' -diaminodiphenylmethane, dimethyl thiotoluenediamine and 2-methylaniline; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole and 2-isopropylimidazole; imidazoline compounds such as imidazoline, 2-methylimidazoline and 2-ethylimidazoline. Among these, aromatic amine compounds are preferable from the viewpoint of storage stability, and diethyl toluenediamine, 3 '-diethyl-4, 4' -diaminodiphenylmethane and dimethyl thiotoluenediamine are more preferable.

The functional group equivalent of the hardener (hydroxyl equivalent in the case of a phenol hardener, active hydrogen equivalent in the case of an amine hardener) is not particularly limited. From the viewpoint of balance of various properties such as moldability, heat resistance, and electrical reliability, it is preferably 10g/eq to 1000g/eq, more preferably 30g/eq to 500g/eq.

The hydroxyl equivalent in the case of the phenolic hardener means that based on the resin composition according to JIS K0070:1992, a value calculated by measuring the resulting hydroxyl value. The active hydrogen equivalent in the case of the amine-based hardener means that the catalyst is based on the catalyst according to JIS K7237:1995, a value calculated by measuring the resulting amine value.

The softening point or melting point when the hardener is solid is not particularly limited. The temperature is preferably 40 to 180℃in terms of moldability and heat resistance, and more preferably 50 to 130℃in terms of handleability in the production of the thermosetting resin composition.

When the thermosetting resin is an epoxy resin, the equivalent ratio of the epoxy resin to the hardener (the number of moles of epoxy groups in the resin/the number of moles of active hydrogen in the hardener) is not particularly limited, and is preferably, for example, 0.7 to 1.6, more preferably 0.8 to 1.4, and still more preferably 0.9 to 1.2, from the viewpoint of suppressing the respective unreacted amounts to a small extent.

(slurry)

In the manufacturing method of the present disclosure, a slurry including an inorganic filler and a solvent may be used.

The slurry can be obtained by: the inorganic filler, the solvent, and optionally the coupling agent, the dispersing agent, and the like are mixed using a mixer such as a stirrer or a planetary mixer, a wet-type dispersing machine such as an ultrasonic dispersing machine or a jet mill, and the like. The mixing conditions in preparing the slurry may be appropriately set according to the types of components contained in the slurry, the ratio of the components, and the like.

In addition, the inorganic filler contained in the slurry may be subjected to wet sieving treatment. The wet sieving treatment tends to reduce the top cutting diameter, which will be described later, more easily than the dry sieving treatment.

The solid content ratio of the inorganic filler in the slurry is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and still more preferably 60 to 80% by mass, from the viewpoint of suppressing sedimentation.

Inorganic filler material

The slurry contains an inorganic filler.

The kind of the inorganic filler is not particularly limited. Specifically, there may be mentioned: silica such as spherical silica and crystalline silica; inorganic materials such as glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, aluminum nitride, diaspore, beryllium oxide, magnesium oxide, zirconium oxide, zircon, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, mica, and titanate. 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 them, spherical 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 inorganic filler may be used alone or in combination of two or more. Examples of the state of the inorganic filler include a powder form, a bead formed by spheroidizing a powder, and a fiber.

The top cut diameter of the inorganic filler is not particularly limited. In terms of filling properties in a narrow gap of 30 μm or less, the top cut diameter of the inorganic filler is preferably 10 μm or less, more preferably 7 μm or less, still more preferably 6 μm or less, and particularly preferably 5 μm or less. The top cut diameter of the inorganic filler may be 1 μm or more from the viewpoint of suppressing the viscosity increase of the thermosetting resin composition.

In the present disclosure, the top cut diameter of the inorganic filler is a particle diameter value when the volume cumulative distribution curve is drawn from the small diameter side by the laser diffraction scattering particle size distribution measuring apparatus, and the volume cumulative value is 90% by volume.

The average particle diameter of the inorganic filler is not particularly limited. For example, the volume average particle diameter is preferably 10 μm or less, more preferably 0.1 μm to 10 μm, still more preferably 0.1 μm to 8 μm, particularly preferably 0.2 μm to 6 μm. When the volume average particle diameter is 10 μm or less, the filling property in the narrow slit tends to be improved. Further, when the volume average particle diameter is 0.1 μm or more, the viscosity of the thermosetting resin composition tends to be further suppressed from rising.

The volume average particle diameter of the inorganic filler can be measured as a volume average particle diameter (D50) by a laser diffraction scattering particle size distribution measuring apparatus.

In view of fluidity of the thermosetting resin composition, the particle shape of the inorganic filler is preferably spherical rather than square, and the particle size distribution of the inorganic filler is preferably distributed over a wide range.

The content of the inorganic filler in the thermosetting resin composition is not particularly limited. From the viewpoint of fluidity and strength, the total amount of the thermosetting resin composition is preferably 30 to 95% by volume, more preferably 35 to 90% by volume, and even more preferably 40 to 80% by volume. When the content of the inorganic filler is 30% by volume or more of the entire thermosetting resin composition, the properties such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 95% by volume or less of the entire thermosetting resin composition, the thermosetting resin composition tends to be inhibited from increasing in viscosity, and fluidity is further improved, so that moldability tends to be improved.

Solvent-

The slurry contains a solvent.

The type of the solvent is not particularly limited, and may be appropriately selected from solvents that can be easily removed from the first mixture or the third mixture in the solvent removal step.

The solvent contained in the first mixture or the third mixture may dissolve or may not dissolve one of the thermosetting resin and the curing agent.

The boiling point of the solvent at normal pressure is preferably 50 to 200 ℃, more preferably 60 to 180 ℃, still more preferably 70 to 160 ℃, particularly preferably 70 to 140 ℃, and most preferably 70 to 130 ℃, in terms of being easily removable from the first mixture or the third mixture.

Specific examples of the solvent include: methyl ethyl ketone (Methyl Ethyl Ketone, MEK), methyl isobutyl ketone (Methyl Isobutyl Ketone, MIBK), toluene, propylene glycol monomethyl ether acetate, cyclohexanone (CHN), and the like. Of these, MIBK, CHN or MEK are preferable.

The solvent may be used alone or in combination of two or more.

Coupling agent-

The slurry may also contain a coupling agent. The kind of the coupling agent is not particularly limited, and conventional coupling agents can be used. Examples of the coupling agent include a silane coupling agent and a titanium coupling agent. The coupling agent may be used alone or in combination of two or more.

Specific examples of the silane coupling agent 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 and methacryloxyoctyl trimethoxysilane.

Examples of the titanium coupling agent 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 slurry contains a coupling agent, the content of the coupling agent is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and even more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the inorganic filler, in terms of the adhesion of the interface between the thermosetting resin and the inorganic filler.

By containing the coupling agent in the slurry, the surface treatment can be performed uniformly by the coupling agent of the inorganic filler, as compared with the dry treatment method. Accordingly, the fluidity of the thermosetting resin composition produced by the production method of the present disclosure is further improved.

(hardening accelerator)

The thermosetting resin composition produced by the production method of the present disclosure contains a hardening accelerator. The type of the curing accelerator is not particularly limited, and may be selected according to the type of the thermosetting resin, desired properties of the thermosetting resin composition, and the like.

Specifically, there may be mentioned: 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.

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

Further, examples of the curing accelerator that can be cured at a low temperature when an epoxy resin is used as the thermosetting resin include: an adduct of tributylphosphine and 1, 4-benzoquinone, dimethylaminopyridine, 2-ethyl-4-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole and the like.

The hardening accelerator may be used alone or in combination of two or more.

The content of the curing accelerator in the thermosetting resin composition is preferably 0.1 to 8% by mass, more preferably 0.3 to 6% by mass, and even more preferably 0.5 to 5% by mass, based on the total amount of the thermosetting resin and the curing agent.

(colorant)

The thermosetting resin composition produced by the production method of the present disclosure may contain a colorant.

Examples of the coloring agent include: carbon black, black titanium oxide, organic dyes, organic pigments, red lead, iron oxide and other existing colorants. The content of the colorant may be appropriately selected according to the purpose or the like. The colorant may be used alone or in combination of two or more.

When the thermosetting resin composition contains a colorant, the content of the colorant is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass.

In the case where the thermosetting resin composition contains a colorant, the colorant may be added to the first mixture or the third mixture.

(ion exchanger)

The thermosetting resin composition produced by the production method of the present disclosure may contain an ion exchanger.

In particular, the ion exchanger is preferably contained in order to improve the moisture resistance and the high-temperature storage characteristics of the semiconductor device. The ion exchanger is not particularly limited, and a conventional ion exchanger can be used. Specifically, for example, hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth are cited. 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)

(0<X is 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 5 parts by mass, per 100 parts by mass of the thermosetting resin.

In the case where the thermosetting resin composition contains an ion exchanger, the ion exchanger may be added to the first mixture or the third mixture.

(Release agent)

The thermosetting resin composition produced by the production method of the present disclosure may contain a release agent in order to obtain good releasability from a mold during 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 content of the release agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the thermosetting resin. When the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the thermosetting resin, releasability tends to be sufficiently obtained. When the amount of the release agent is 15 parts by mass or less based on 100 parts by mass of the thermosetting resin, better adhesion tends to be obtained.

In the case where the thermosetting resin composition contains a release agent, the release agent may be added to the first mixture or the third mixture.

(flame retardant)

The thermosetting resin composition produced by the production method of the present disclosure 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, per 100 parts by mass of the thermosetting resin.

In the case where the thermosetting resin composition contains a flame retardant, the flame retardant may be added to the first mixture or the third mixture.

(stress relaxation agent)

The thermosetting resin composition produced by the production method of the present disclosure may contain a stress relaxation agent such as silicone oil or silicone rubber particles. The thermosetting resin composition contains a stress relaxation agent, so that warpage of the package and occurrence of package cracks can be further reduced. The stress relaxation agent may be a conventional stress relaxation agent (flexible agent) which is generally used. Specifically, there may be mentioned: thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene, rubber particles such as Natural Rubber (NR), acrylonitrile-butadiene rubber (acrylonitrile butadiene rubber, NBR), acrylic rubber, urethane rubber, and 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. Among them, silicone-based stress relaxation agents are preferable. As the silicone-based stress relaxation agent, there can be mentioned: silicone-based stress relaxation agents having an epoxy group, silicone-based stress relaxation agents having an amino group, silicone-based stress relaxation agents obtained by modifying these with polyether, and the like.

When the thermosetting resin composition contains a stress relaxation agent, the content of the stress relaxation agent is preferably 0.1 to 30 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the thermosetting resin.

In the case where the thermosetting resin composition contains a stress relaxation agent, the stress relaxation agent may be added to the first mixture or the third mixture.

In the case of using the stress relaxation agent, the stress relaxation agent may be added to the first mixture or the third mixture in the form of slurry, similarly to the inorganic filler.

When the stress relaxing agent is used, the solid content ratio of the stress relaxing agent in the slurry is preferably 0.1 to 50% by mass, more preferably 0.2 to 30% by mass, and still more preferably 0.5 to 20% by mass, from the viewpoint of moldability.

The solvent for dispersing the stress relaxation agent may be the same as the solvent used in the slurry of the inorganic filler.

(solvent)

The thermosetting resin composition produced by the production method of the present disclosure may also contain a solvent. The thermosetting resin composition contains a solvent, and thus tends to improve fluidity during molding.

When the thermosetting resin composition contains a solvent, the content of the solvent in the entire thermosetting resin composition is preferably 0.1 to 2% by mass, more preferably 0.1 to 0.5% by mass. If the content of the solvent in the entire thermosetting resin composition is 2 mass% or less, the thermosetting resin composition is less likely to adhere to the molding machine such as a press machine, and the thermosetting resin composition tends to be easily supplied. When the content of the solvent in the entire thermosetting resin composition is 0.1 mass% or more, fluidity at the time of molding tends to be further improved.

The solvent contained in the thermosetting resin composition may be a solvent remaining in the solvent contained in the slurry. The solvent contained in the thermosetting resin composition is sometimes referred to as "residual solvent amount".

The content of the solvent was calculated from the mass change before and after heating the thermosetting resin composition at 175℃for 1 hour.

(physical Properties 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, the viscosity of the thermosetting resin composition is preferably adjusted according to the easiness of occurrence of wire misalignment 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 ℃. 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).

(use of thermosetting resin composition)

The use of the thermosetting resin composition produced by the production method of the present disclosure is not particularly limited, and the composition can be used as a sealing material for electronic component devices, for example, in various mounting techniques. The thermosetting resin composition produced by the production method of the present disclosure can be used for various applications, for example, resin compositions for various modules, motor resin, vehicle resin, and sealing materials for electronic circuit protection materials, and it is desirable to have excellent fluidity and hardenability.

< method for manufacturing electronic component device >

The method for manufacturing an electronic component device of the present disclosure includes a step of sealing an element by using the thermosetting resin composition obtained by the method for manufacturing 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), CSP, multi-chip package (Multi Chip Package, MCP), siP, and the like have a structure in which elements are mounted on the surface of a support member having wiring board connection terminals formed on the back surface thereof, and the elements are connected to wiring lines formed on the support member by bump or wire bonding, and then the elements are sealed with a thermosetting resin composition. In addition, the thermosetting resin composition can be suitably used for 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.

< thermosetting resin composition >

The thermosetting resin composition of the present disclosure can be 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, granule, tablet, pellet, granule, etc. From the viewpoint of operability, the size and quality of the thermosetting resin composition in the form of a pellet or a pellet are preferably such that they are compatible with molding conditions of the package.

Examples

Hereinafter, the present disclosure will be specifically described with reference to examples, but the present disclosure is not limited to these examples.

< preparation of thermosetting resin composition >

First, the following components were prepared.

(thermosetting resin)

Epoxy resin 1: aralkyl type epoxy resin with epoxy equivalent 265 g/eq-285 g/eq and softening point 53-63 DEG C

Epoxy resin 2: biphenyl type epoxy resin with epoxy equivalent of 180 g/eq-192 g/eq and melting point of 105 DEG C

Epoxy resin 3: triphenylmethane type epoxy resin with epoxy equivalent of 163 g/eq-175 g/eq and softening point of 57-63 DEG C

(hardener)

Hardener 1: aralkyl phenol resin with hydroxyl equivalent 205g/eq and softening point 60-70 DEG C

Hardener 2: aralkyl phenol resin with hydroxyl equivalent 170g/eq and softening point 60-70 DEG C

(coupling agent)

Coupling agent: n-phenyl-3-aminopropyl trimethoxysilane

(inorganic filler)

Slurry 1: 70 mass% of solid content of methyl isobutyl ketone solution of spherical silica having a volume average particle size of 1.5 μm (top cut size 5 μm) (N-phenyl-3-aminopropyl trimethoxysilane treatment)

Slurry 2: 60 mass% of solid content of methyl isobutyl ketone solution of spherical silica having a volume average particle size of 0.3 μm (top cut size 5 μm) (N-phenyl-3-aminopropyl trimethoxysilane treatment)

Inorganic filler: : spherical silica (no surface treatment) having a volume average particle diameter of 0.8 μm (top cut diameter of 20 μm)

(hardening accelerator)

Hardening accelerator: phosphorus hardening accelerator

(other additives)

Mold release agent: hearst wax (Hoechst wax) (Hurst (Hoechst) Co.)

Coloring agent: carbon black

MIBK: methyl isobutyl ketone

CHN: cyclohexanone

MEK: methyl ethyl ketone

The thermosetting resin compositions of examples 1 to 9 were produced by the following method (referred to as "production method a"). The main ingredients shown in table 1 were mixed in a container and stirred for 1 hour by a stirrer. The obtained mixture corresponds to the first mixture. Thereafter, the mixture was melt-kneaded using a biaxial kneader (extruder) under reduced pressure of 0.02MPa at the desolventizing temperature of Table 1 for about 5 minutes. The melt-kneaded mixture corresponds to the second mixture. Next, the sub-feed components were added (side-feed) from the openings, and melt-kneaded at the kneading temperature of table 1 for about 2 minutes. The melt was cooled by a press roll in which cold water of 10℃was circulated, and the melt in the form of a sheet was pulverized, whereby a powdery thermosetting resin composition was prepared. The production method a is a method in which the solvent removal step and the kneading step are continuously performed.

The thermosetting resin composition of example 10 was produced by the following method (referred to as "production method B"). The main ingredients shown in table 1 were mixed in a container and stirred for 1 hour by a stirrer. The obtained mixture corresponds to the first mixture. The solvent was distilled off under reduced pressure of 0.02MPa at 140 ℃ for 2 hours using a vacuum dryer. The obtained mixture corresponds to the second mixture. The melt was cooled and the obtained resin composition was pulverized, whereby a thermosetting resin composition to which no hardening accelerator was added was prepared in powder form. Then, the thermosetting resin composition to which the hardening accelerator was not added was kneaded using a biaxial kneader (extruder). At this time, the sub-feed components were added (side-fed) from the opening, and melt-kneaded at the kneading temperature of table 1 for about 2 minutes. The melt was cooled by a press roll in which cold water of 10℃was circulated, and the melt in the form of a sheet was pulverized, whereby a powdery thermosetting resin composition was prepared. The production method B is a method of performing the solvent removal process in a batch manner.

The thermosetting resin compositions of comparative examples 1 to 3 were produced by the following method (referred to as "production method C"). All the components shown in Table 2 were mixed in a vessel and stirred by a stirrer for 1 hour. Thereafter, the mixture was melt-kneaded using a biaxial kneader (extruder) under reduced pressure of 0.02MPa at the first kneading temperature of table 2 for about 5 minutes. Next, melt-kneading was performed at the second kneading temperature for about 2 minutes. The melt was cooled by a press roll in which cold water of 10℃was circulated, and the melt in the form of a sheet was pulverized, whereby a powdery thermosetting resin composition was prepared.

The thermosetting resin composition of comparative example 4 was produced by the following method (referred to as "production method D"). All the components shown in Table 2 were mixed in a vessel and stirred by a stirrer for 1 hour. Thereafter, the solvent was distilled off under reduced pressure of 0.02MPa at 140℃for 2 hours using a vacuum dryer. The obtained melt was cooled and pulverized to prepare a powdery 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 carried out by transferring the molding machine under conditions of a mold temperature of 180 ℃, a molding pressure of 6.9MPa, and a curing time of 90 seconds. Further, post-hardening was performed at 175℃for 6 hours, if necessary.

[ spiral flow ]

Using a spiral 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.

[ agglomeration of inorganic filler ]

The appearance of the molded article of the thermosetting resin composition using the transfer molding machine was visually observed, and the presence or absence of aggregation of the inorganic filler (hereinafter, sometimes referred to as filler aggregation) was evaluated. The case where filler aggregation was observed was designated "a", and the case where filler aggregation was not observed was designated "B".

[ gel time ]

For 3g of the thermosetting resin composition, measurement using a cure measurement tester (Curlastometer) manufactured by JSR trade (tracking) Co., ltd was carried out at 175℃and the Time until the rise of the torque curve was set to Gel Time (GT (Gel Time), sec).

[ residual solvent amount ]

Regarding 5g of the thermosetting resin composition, the residual solvent amount was calculated from equation 1 by treating it with an explosion-proof dryer at 175 ℃/1 hour, and from the viewpoint of void generation after molding, the residual solvent amount was "a" of 0.5 mass% or less, the residual solvent amount was "B" of more than 0.5 mass%, and the residual solvent amount was "C" of 2 mass% or less.

Residual solvent amount (mass%) = ((mass before heat treatment-mass after heat treatment)/mass before heat treatment) ×100

TABLE 1

TABLE 2

In tables 1 and 2, the term "nonvolatile component" means a content of a nonvolatile component based on the mass of the nonvolatile component when the main supply component is added to the container, and corresponds to a solid content ratio of the mixture. In tables 1 and 2, the "filler content" refers to the content of the inorganic filler in the thermosetting resin composition based on the volume.

From the evaluation results in tables 1 and 2, it is clear that: when the filler content is 70% by volume or more, the thermosetting resin composition obtained by the production method of the example is superior in characteristics to those obtained by the production method of the comparative example. From this, it can be seen that: according to the manufacturing method of the examples, the inorganic filler can be highly filled without deteriorating the characteristics of the thermosetting resin composition, as compared with the manufacturing method of the comparative examples.

The entire disclosure of japanese patent application No. 2021-002321, filed on 1/8 of 2021, is incorporated herein by reference.

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

Claims

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

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

3. The method for producing a thermosetting resin composition according to claim 1, wherein the first kneading temperature is a temperature at which a reaction rate becomes 40% or less as measured by measuring the second mixture to which the hardening accelerator is added by differential scanning calorimetry.

4. The method for producing a thermosetting resin composition according to claim 2, wherein the second kneading temperature is a temperature at which a reaction rate becomes 40% or less as measured by measuring the fourth mixture to which the hardening accelerator is added by differential scanning calorimetry.

5. The method for producing a thermosetting resin composition according to any one of claims 1 to 4, wherein the desolvation step and the kneading step are performed continuously.

6. The method for producing a thermosetting resin composition according to any one of claims 1 to 4, wherein the desolvation step is performed in a batch type.

7. The method for producing a thermosetting resin composition according to any one of claims 1 to 6, wherein the first desolvation temperature or the second desolvation temperature is higher than a melting point or a softening point of the thermosetting resin.

8. The method for producing a thermosetting resin composition according to any one of claims 1 to 7, wherein the slurry further contains a coupling agent.

9. The method for producing a thermosetting resin composition according to any one of claims 1 to 8, wherein the inorganic filler has a top cut diameter of 10 μm or less.

10. The method for producing a thermosetting resin composition according to any one of claims 1 to 9, wherein the solvent has a boiling point of 50 ℃ to 200 ℃.

11. The method for producing a thermosetting resin composition according to any one of claims 1 to 10, wherein a solid content ratio of the inorganic filler in the slurry is 40 to 90 mass%.

12. The method for producing a thermosetting resin composition according to any one of claims 1 to 11, wherein a solid content ratio of the first mixture or the third mixture is 30 to 90 mass%.

13. A method for manufacturing an electronic component device, comprising a step of sealing an element by using the thermosetting resin composition obtained by the method for manufacturing a thermosetting resin composition according to any one of claims 1 to 12.