WO2022186361A1

WO2022186361A1 - Curable resin composition and electronic component device

Info

Publication number: WO2022186361A1
Application number: PCT/JP2022/009257
Authority: WO
Inventors: 智雄西山; 東哲姜; 貴耶山本; 貴和金
Original assignee: 昭和電工マテリアルズ株式会社
Priority date: 2021-03-05
Filing date: 2022-03-03
Publication date: 2022-09-09
Also published as: JPWO2022186361A1; TW202246410A; CN117120543A

Abstract

Provided is a curable resin composition containing: an epoxy resin; a curing agent; and a linear polysiloxane compound that has a structural unit having an epoxy group and an alkoxy group, and that also has a polymerization degree of 3 or more.

Description

Curable resin composition and electronic component device

The present disclosure relates to curable resin compositions and electronic component devices.

In recent years, high-density mounting of semiconductor elements is progressing. Along with this, resin-encapsulated semiconductor devices are shifting from conventional pin-insertion type packages to surface-mount type packages. Surface-mounted ICs (Integrated Circuits), LSIs (Large Scale Integration), and the like have thin and small packages in order to increase the mounting density and reduce the mounting height. As a result, the area occupied by the device with respect to the package has increased, and the thickness of the package has become extremely thin.

In addition, these packages are mounted differently than pin insertion packages. That is, in the pin-insertion type package, the pins are inserted into the wiring board and then soldered from the rear surface of the wiring board, so the package is not directly exposed to high temperatures.
However, surface-mounted ICs are temporarily fixed to the surface of the wiring board and processed by a solder bath, a reflow device, or the like, so the package is directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the absorbed moisture evaporates during reflow, and the generated vapor pressure acts as peeling stress, causing peeling between the sealing material and the supporting member such as the element or lead frame. , the occurrence of package cracks, poor electrical characteristics, and the like. Therefore, there is a demand for the development of a sealing material that has excellent adhesiveness to a support member and, in turn, excellent solder heat resistance (reflow resistance).

As a sealing material having excellent reflow resistance, a curable resin composition containing an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and an alkoxysilane polymer having a specific structure is disclosed in JP-A-2008-111101. proposed in
Further, for the purpose of improving reflow resistance, for example, the surface of the lead frame is roughened before plating to improve adhesion to the encapsulant.

However, from the viewpoint of manufacturing efficiency and manufacturing cost, the development of a sealing material having excellent adhesion to non-roughened lead frames is desired. The resin composition has room for further improvement.
The present disclosure has been made in view of the above circumstances, and provides a curable resin composition having excellent adhesion to a non-roughened lead frame and excellent reflow resistance, and its curability. An object of the present invention is to provide an electronic component device having an element sealed with a resin composition.

<1> A curable resin composition comprising an epoxy resin, a curing agent, and a linear polysiloxane compound having a structural unit having an epoxy group and an alkoxy group and having a degree of polymerization of 3 or more.
<2> The curable resin composition according to <1>, wherein the structural unit is represented by the following general formula (1).

In general formula (1),
R ¹ represents an epoxy-containing group,
R ² represents an alkoxy group having 1 to 10 carbon atoms.
<3> The curable resin composition according to <2>, wherein the linear polysiloxane compound further has a structural unit represented by the following general formula (2).

In general formula (2),
R ¹ represents an epoxy-containing group.
<4> The curable resin composition according to <2> or <3>, wherein the epoxy-containing group is represented by the following general formula (3).

In general formula (3),
R ⁴ and R ⁵ each independently represent an alkylene group having 1 to 10 carbon atoms,
* represents the bonding position with Si.
<5> The curable resin composition according to any one of <1> to <4>, wherein the linear polysiloxane compound is a compound represented by the following general formula (4).

In general formula (4),
R ¹ represents an epoxy-containing group,
each R ⁶ independently represents an alkoxy group having 1 to 10 carbon atoms or a hydroxyl group;
each R ⁷ independently represents an alkoxy group having 1 to 10 carbon atoms,
n represents an integer of 1 or more,
However, at least one R ⁶ represents an alkoxy group having 1 to 10 carbon atoms.
<6> The curable resin composition according to any one of <1> to <5>, wherein the epoxy resin comprises a copolymerized epoxy resin having a structural unit derived from cresol and a structural unit derived from methoxynaphthalene. thing.
<7> The curable resin composition according to <6>, wherein the copolymerizable epoxy resin has the following structural unit.

wherein n is a number from 1-10.
<8> The curable resin composition according to any one of <1> to <7>, wherein the curing agent contains a phenol-based curing agent.
<9> The curable resin composition according to <8>, wherein the phenol-based curing agent contains an aralkyl-type phenol resin.
<10> The curable resin composition according to any one of <1> to <9>, wherein the linear polysiloxane compound is liquid at 25°C.
<11> The curable resin composition according to any one of <1> to <10>, wherein the number of structural units contained in the linear polysiloxane compound is 15 or less.
<12> Any one of <1> to <11>, wherein the content of the linear polysiloxane compound relative to the total mass of the curable resin composition is 0.05% by mass to 5% by mass. A curable resin composition.
<13> An electronic component device comprising an element and a cured product of the curable resin composition according to any one of <1> to <12> for sealing the element.
<14> The electronic component device according to <13>, comprising a lead frame for mounting the element on one surface.
<15> The electronic component device according to <14>, wherein the lead frame has a plated layer containing at least one of Au, Pd and Ni on at least part of the surface.

According to the present disclosure, a curable resin composition having excellent adhesion to a non-roughened lead frame and excellent reflow resistance, and an element sealed with this curable resin composition It is possible to provide an electronic component device comprising

A detailed description will be given below of the embodiment for implementing the present disclosure. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present disclosure.

In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . In addition, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in Synthetic Examples.
In the present disclosure, each component may contain multiple types of applicable compounds. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
Particles corresponding to each component in the present disclosure may include a plurality of types. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.
In the present disclosure, the term "laminate" refers to stacking layers, and two or more layers may be bonded or two or more layers may be detachable.
In the notation of a group (atomic group) of the present disclosure, the notation without describing substitution and unsubstitution includes not only those not having substituents but also those having substituents.
In the present disclosure, the number of structural units represents an integer value for a single molecule, but represents a rational number which is an average value for an aggregate of multiple types of molecules.
In the present disclosure, the number of carbon atoms means the total number of carbon atoms contained in a group as a whole, and when the group does not have a substituent, it represents the number of carbon atoms forming the skeleton of the group. When has a substituent, it represents the total sum of the number of carbon atoms forming the skeleton of the group plus the number of carbon atoms in the substituent.
In the present disclosure, a linear polysiloxane compound refers to a polysiloxane compound that has D units without T and Q units.
D units have silicon atoms bonded to 2 oxygen atoms, T units have silicon atoms bonded to 3 oxygen atoms, and Q units have silicon atoms bonded to 4 oxygen atoms. , which are represented by the following structural formula (D), structural formula (T), and structural formula (Q), respectively.
In the present disclosure, polysiloxane compounds having T units or Q units are referred to as branched polysiloxane compounds.

In the present disclosure, "epoxy-containing group" means a group having an epoxy structure.
In the present disclosure, the weight average molecular weight (Mw), number average molecular weight (Mn) and degree of polymerization are measured using the following GPC measurement device under the following measurement conditions, and converted using a standard polystyrene calibration curve. is. In addition, a calibration curve was prepared using a set of 5 samples (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) as standard polystyrene.
However, for compounds that cannot be accurately measured for Mw, Mn or degree of polymerization by GPC due to their small molecular weight, the molecular weight obtained from the chemical structure of the compound is adopted as the Mw, Mn or degree of polymerization of the compound.
(GPC measuring device)
GPC device: High-speed GPC device "HCL-8320GPC", detector is differential refractometer or UV, column manufactured by Tosoh Corporation: column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Tosoh stock Company made (measurement conditions)
Solvent: Tetrahydrofuran (THF)
Measurement temperature: 40°C
Flow rate: 0.35 mL/min Sample concentration: 10 mg/THF5 mL
Injection volume: 20 μL

<Curable resin composition>
The curable resin composition of the present disclosure includes an epoxy resin, a curing agent, and a linear polysiloxane compound having a structural unit having an epoxy group and an alkoxy group and having a degree of polymerization of 3 or more.

The curable resin composition of the present disclosure has excellent adhesion to non-roughened lead frames and has excellent reflow resistance.

The reason why the curable resin composition of the present disclosure achieves the above effects is not clear, but is presumed as follows.
The curable resin composition of the present disclosure contains a linear polysiloxane compound having at least three structural units having an epoxy group and an alkoxy group, so that the cured product of the curable resin composition and the support member Internal stress differences are reduced. As a result, the adhesiveness between the cured product of the curable resin composition and the supporting member is improved, and the curable resin composition of the present disclosure provides a non-roughened lead frame and a non-roughened lead made of copper or the like. It is presumed that it has excellent adhesiveness to the plating layer composed of gold, palladium, nickel, etc. formed on the frame surface, and thus has excellent reflow resistance. Hereinafter, the adhesion to the non-roughened lead frame and the adhesion to the plating layer formed on the surface of the non-roughened lead frame may be collectively referred to as the adhesion to the non-roughened lead frame.
In addition, the linear polysiloxane compound contained in the curable resin composition of the present disclosure includes epoxy resins, lead frame materials (copper, etc.), and plating layer materials (gold, palladium, nickel, etc.). It has excellent adhesion to As a result, it is presumed that the curable resin composition of the present disclosure has excellent adhesion to non-roughened lead frames, and thus has excellent reflow resistance.

Various materials that can be included in the curable resin composition are described below.

(Epoxy resin)
A curable resin composition of the present disclosure comprises an epoxy resin. The type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. In addition, in the present disclosure, the linear polysiloxane compound is not included in the epoxy resin.
Specific examples of epoxy resins are described below, but are not limited thereto.

Specifically, at least one phenol selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. A novolak type epoxy resin (phenol novolac type epoxy resin, ortho-cresol novolak-type epoxy resins, etc.); epoxidized triphenylmethane-type phenolic resins obtained by condensation or co-condensation of the above phenolic compounds and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst. A triphenylmethane type epoxy resin; a copolymer type epoxy resin obtained by epoxidizing a novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound in the presence of an acidic catalyst; bisphenol A, bisphenol diphenylmethane-type epoxy resins that are diglycidyl ethers such as F; biphenyl-type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; Sulfur atom-containing epoxy resins that are diglycidyl ethers; Epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; Glycidyl polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid and tetrahydrophthalic acid Glycidyl ester-type epoxy resins that are esters; glycidylamine-type epoxy resins in which active hydrogens bonded to nitrogen atoms of aniline, diaminodiphenylmethane, isocyanuric acid, etc. are substituted with glycidyl groups; co-condensation resins of dicyclopentadiene and phenol compounds Dicyclopentadiene type epoxy resin which is obtained by epoxidizing the; vinylcyclohexene diepoxide obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2- (3,4-epoxy)cyclohexyl-5,5-spiro(3 ,4-epoxy)cyclohexane-m-dioxane and other alicyclic epoxy resins; para-xylylene-modified epoxy resins that are glycidyl ethers of para-xylylene-modified phenol resins; meta-xylylene-modified epoxy resins that are glycidyl ethers of meta-xylylene-modified phenol resins; terpene-modified phenol resins a terpene-modified epoxy resin that is a glycidyl ether of dicyclopentadiene-modified phenol resin; a dicyclopentadiene-modified epoxy resin that is a glycidyl ether of a cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resins that are glycidyl ethers of resins; naphthalene type epoxy resins that are glycidyl ethers of naphthalene ring-containing phenol resins; halogenated phenol novolac type epoxy resins; hydroquinone type epoxy resins; trimethylolpropane type epoxy resins; linear aliphatic epoxy resin obtained by oxidizing the bond with peracid such as peracetic acid; aralkyl-type epoxy resin obtained by epoxidizing aralkyl-type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin; . Further examples of epoxy resins include aminophenol-type epoxy resins, which are glycidyl ethers of aminophenol. These epoxy resins may be used singly or in combination of two or more.

Among the above epoxy resins, from the viewpoint of adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame and from the viewpoint of the balance between heat resistance and fluidity, a copolymer type epoxy resin or a biphenyl type epoxy resin is preferred. The curable resin composition of the present disclosure preferably contains a copolymer type epoxy resin and a biphenyl type epoxy resin.

The biphenyl-type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferred.

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

In formula (III), R ⁹ and R ¹⁰ each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is the average value and represents a number from 0 to 10.

The diphenylmethane-type 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 preferred.

In formula (IV), R ¹¹ and R ¹² each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is the average value and represents a number from 0 to 10.

The sulfur atom-containing type epoxy resin is not particularly limited as long as it is an epoxy resin containing sulfur atoms. Examples thereof include epoxy resins represented by the following general formula (V).

In formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. n is the average value and represents a number from 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.

In formula (VI), R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. R ¹⁵ represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different. i each independently represents an integer of 0 to 3; n is the average value and represents a number from 0 to 10.

The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material.

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

The triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton.

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

The copolymer type epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound, a phenolic compound, and an aldehyde compound is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenolic skeleton. .

In formula (IX), R ¹⁹ to R ²¹ represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3, each j independently represents an integer of 0 to 2, and each k independently represents an integer of 0 to 4. l and m are average values, numbers from 0 to 10, and (l+m) shows numbers from 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either one of formula (IX-1) or (IX-2) below. Definitions of R ^{19 to R 21 , i, j and k in formulas (IX-1) and (IX-2) are the same as definitions of R 19} ^{to R 21} ^, ⁱ , j and k in formula (IX). . n is 1 (when linked via a methylene group) or 0 (when not linked via a methylene group).

The epoxy resin represented by the general formula (IX) includes a random copolymer having l structural units and m structural units at random, an alternating copolymer having alternating structural units, and a copolymer having regularly , a block copolymer having a block shape, and the like. Any one of these may be used alone, or two or more may be used in combination.

From the viewpoint of the adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the copolymerized epoxy resin has a cresol-derived structural unit and a methoxynaphthalene-derived structural unit. A resin is preferred (hereinafter referred to as a specific copolymer type epoxy resin).
The specific copolymerization type epoxy resin preferably has the following structural units.
In the following structural units, each n is an average value, a number from 1 to 10, preferably a number from 2 to 8.

The aralkyl-type epoxy resin is composed of at least one selected from the group consisting of phenol compounds such as phenol and cresol, and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof. There is no particular limitation as long as it is an epoxy resin made from a synthesized phenol resin. For example, a phenolic resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl or derivatives thereof is preferably an epoxy resin obtained by glycidyl etherification, and more preferably an epoxy resin represented by the following general formulas (X) and (XI).

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

Regarding R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ in general formulas (II) to (XI) above, “all of which may be the same or different” means, for example, 8 to R 41 in formula (II). It means that all 88 R ⁸ may be the same or different. Other R ⁹ to R ²¹ and R ³⁷ to R ⁴¹ also mean that the respective numbers contained in the formula may all be the same or different. Also, R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ may be the same or different. For example, all of R ⁹ and R ¹⁰ may be the same or different.
Further, the monovalent organic group having 1 to 18 carbon atoms in general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

n in the above general formulas (II) to (XI) is an average value, and each independently preferably ranges from 0 to 10. If n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the curable resin composition during melt molding decreases, resulting in insufficient filling and deformation of the bonding wire (gold wire that connects the element and the lead). etc. tend to be suppressed. More preferably, n is set in the range of 0-4.

The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 40 g/eq to 1000 g/eq, more preferably 45 g/eq to 500 g/eq, and 50 g/eq. eq to 350 g/eq is more preferred.
Let the epoxy equivalent of an epoxy resin be the value measured by the method according to JISK7236:2009.

The epoxy resin may be solid or liquid at 25°C. If the epoxy resin is solid at 25°C, the softening point or melting point of the epoxy resin is not particularly limited.
From the viewpoint of the balance between moldability and heat resistance, the softening point or melting point of the epoxy resin is preferably 40°C to 180°C. Also, from the viewpoint of handleability during production of the curable resin composition, the softening point or melting point of the epoxy resin is preferably 50°C to 130°C.
In the present disclosure, softening point refers to a value measured by the ring and ball method of JIS K 7234:1986.
In the present disclosure, melting point refers to a value measured according to the visual observation method of JIS K 0064:1992.

From the viewpoint of the balance between moldability and heat resistance, the Mw of the epoxy resin is preferably 550-1050, more preferably 650-950.

The content of the epoxy resin in the curable resin composition is preferably 0.5% by mass to 60% by mass from the viewpoint of strength, fluidity, heat resistance, moldability, etc., and is preferably 2% by mass to 50% by mass. more preferably 3% by mass to 45% by mass.

When the epoxy resin contains a copolymerized epoxy resin, from the viewpoint of the adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the total mass of the epoxy resin contained in the curable resin composition is The content of the polymerizable epoxy resin is preferably 50% to 90% by mass, more preferably 55% to 80% by mass, and even more preferably 60% to 75% by mass.

When the copolymerized epoxy resin contains a specific copolymerized epoxy resin, from the viewpoint of adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the specific copolymerization of the total mass of the copolymerized epoxy resin The content of the type epoxy resin is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 70% by mass to 100% by mass.

When the epoxy resin contains a biphenyl-type epoxy resin, from the viewpoint of the adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the biphenyl-type epoxy resin relative to the total mass of the epoxy resin contained in the curable resin composition The content of the epoxy resin is preferably 10% by mass to 50% by mass, more preferably 20% by mass to 45% by mass, even more preferably 25% by mass to 40% by mass.

(curing agent)
The curable resin composition of the present disclosure contains a curing agent. The type of curing agent is not particularly limited, and can be selected from those commonly used as components of curable resin compositions. The curing agent may be used singly or in combination of two or more.
In the present disclosure, the curing agent is only required to have a structure capable of reacting with the epoxy resin contained in the curable resin composition and curing the curable resin composition. Even compounds that contribute little to the curing reaction of the curable resin composition are included in the curing agent.

Examples of curing agents include phenol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, polymercaptan-based curing agents, polyaminoamide-based curing agents, isocyanate-based curing agents, and blocked isocyanate-based curing agents.
Among these, from the viewpoint of heat resistance, the curing agent is preferably a phenol-based curing agent or an amine-based curing agent. From the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to a non-roughened lead frame and the viewpoint of heat resistance, the curing agent is preferably a phenol-based curing agent.

Phenol-based curing agents include, for example, phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc. At least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde are condensed under an acidic catalyst or Novolac-type phenolic resin obtained by cocondensation; Aralkyl-type phenolic resin such as phenol aralkyl resin and naphthol aralkyl resin synthesized from the above phenolic compound and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc.; Para-xylylene and/or or meta-xylylene-modified phenolic resin; melamine-modified phenolic resin; terpene-modified phenolic resin; dicyclopentadiene-type phenolic resin and dicyclopentadiene-type naphthol resin synthesized by copolymerization from the above phenolic compound and dicyclopentadiene; cyclopentadiene-modified Phenolic resin; Polycyclic aromatic ring-modified phenolic resin; Biphenyl-type phenolic resin; Triphenylmethane type obtained by condensation or co-condensation of the above phenolic compound and an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst. Phenolic resin; Phenolic resins obtained by copolymerizing two or more of these can be mentioned. These phenol-based curing agents may be used singly or in combination of two or more.

From the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to a non-roughened lead frame and the viewpoint of heat resistance, aralkyl-type phenolic resins are preferable among phenolic curing agents.

Aralkyl-type phenol resins include phenol aralkyl resins and naphthol aralkyl resins synthesized from phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, and the like. The aralkyl-type phenolic resin may be further copolymerized with another phenolic resin. Copolymerized aralkyl-type phenolic resins include copolymerized phenolic resins of triphenylmethane-type phenolic resin and aralkyl-type phenolic resin, copolymerized phenolic resins of salicylaldehyde-type phenolic resin and aralkyl-type phenolic resin, and novolac-type phenolic resin. A copolymer type phenol resin of a resin and an aralkyl type phenol resin can be used.

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

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

From the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to a non-roughened lead frame and the viewpoint of heat resistance, the aralkyl-type phenolic resin is preferably a phenolic resin represented by general formula (XIII).
Both i and k are preferably 0 in general formula (XIII), from the viewpoint of the adhesiveness of the curable resin composition of the present disclosure to a non-roughened lead frame and from the viewpoint of heat resistance.

The dicyclopentadiene-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained using a compound having a dicyclopentadiene skeleton as a raw material.

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

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

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

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

In formula (XVII), R ³² to R ³⁴ each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. Each i is independently an integer of 0 to 3, each k is independently an integer of 0 to 4, and each q is independently an integer of 0 to 5. Each l and m is an average value and each independently represents a number from 0 to 11. However, the sum of l and m is a number from 1 to 11.

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

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

"All of which may be the same or different" described for R ²² to R ³⁶ in the general formulas (XII) to (XVIII) means, for example, that all i R ²² in formula (XII) are the same However, it means that they may be different from each other. Other R ²³ to R ³⁶ also mean that the respective numbers contained in the formula may all be the same or different from each other. Also, R ²² to R ³⁶ may be the same or different. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

n in the general formulas (XII) to (XVIII) is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity of the curable resin composition during melt molding becomes low, and filling defects, deformation of the bonding wire (gold wire that connects the element and the lead), etc. less likely to occur. The average n in one molecule is preferably set in the range of 0-4.

Specific examples of amine curing agents include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4′-diamino-dicyclohexylmethane, Aromatic amine compounds such as diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane, dimethylthiotoluenediamine, 2-methylaniline, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropyl Examples include imidazole compounds such as imidazole, imidazoline compounds such as imidazoline, 2-methylimidazoline and 2-ethylimidazoline.

The functional group equivalent weight of the curing agent (hydroxyl group equivalent weight in the case of a phenol-based curing agent, and active hydrogen equivalent weight in the case of an amine-based curing agent) is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance and electrical reliability, it is preferably 10 g/eq to 1000 g/eq, more preferably 30 g/eq to 500 g/eq.
The hydroxyl equivalent in the case of a phenol-based curing agent is a value calculated based on the hydroxyl value measured according to JIS K 0070:1992. In addition, the active hydrogen equivalent in the case of an amine-based curing agent is a value calculated based on the amine value measured according to JIS K 7237:1995.

If the curing agent is solid at 25°C, its softening point or melting point is not particularly limited. From the viewpoint of moldability and heat resistance, the softening point or melting point of the curing agent is preferably 40°C to 180°C. Also, from the viewpoint of handleability during production of the curable resin composition, the softening point or melting point of the curing agent is preferably 50°C to 130°C.

When the curing agent is a phenolic curing agent, the equivalent ratio of the phenolic hydroxyl group (active hydrogen) of the phenolic curing agent to the epoxy group of the epoxy resin in the curable resin composition (the phenolic hydroxyl group (active hydrogen) of the phenolic curing agent )/the number of moles of epoxy groups in the epoxy resin) is not particularly limited, but can be set to about 1, for example.

When the curing agent contains a phenolic curing agent, from the viewpoint of the adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the content of the phenolic curing agent relative to the total mass of the curing agent is It is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 70% by mass to 100% by mass.

When the phenolic curing agent contains an aralkyl-type phenolic resin, the content of the aralkyl-type phenolic resin relative to the total mass of the phenolic curing agent is considered from the viewpoint of the adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame. The ratio is more preferably 60% to 100% by mass, even more preferably 70% to 100% by mass.

(Linear polysiloxane compound)
A linear polysiloxane compound has a structural unit having an epoxy group and an alkoxy group, and has a degree of polymerization of 3 or more.
The structural units possessed by the linear polysiloxane compound may be structural units all having epoxy groups and alkoxy groups, or may be structural units partially having epoxy groups and alkoxy groups.
When some of the structural units of the linear polysiloxane compound are structural units having an epoxy group and an alkoxy group, the structural units having an epoxy group and an alkoxy group may be randomly or alternately. It may be provided regularly, or may be provided in a block shape.

From the viewpoint of dispersibility of the linear polysiloxane compound in the curable resin composition of the present disclosure, the degree of polymerization of the linear polysiloxane compound is preferably 15 or less, more preferably 10 or less. , 8 or less.

From the viewpoint of adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the structural unit having an epoxy group and an alkoxy group possessed by the linear polysiloxane compound is represented by the following general formula (1). preferably.
Hereinafter, the structural unit represented by general formula (1) will be referred to as the "specific structural unit", and the linear polysiloxane compound having the specific structural unit will be referred to as the "specific polysiloxane compound".

In general formula (1), R ¹ represents an epoxy-containing group.
When the specific polysiloxane compound has two or more specific structural units, R ¹ in the specific structural units may be different groups or the same group.
From the viewpoint of adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the epoxy-containing group represented by ^R1 is preferably a group represented by the following general formula (3).

In general formula (3), R ⁴ and R ⁵ each independently represent an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.
In addition, in general formula (3), * represents the bonding position with Si which a specific structural unit has.

In general formula (1), R ² represents an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.
When the specific polysiloxane compound has two or more specific structural units, R ² in the specific structural units may be different groups or the same group.

When the linear polysiloxane compound contains the specific polysiloxane compound, from the viewpoint of the adhesion of the curable resin composition of the present disclosure to the non-roughened lead frame, the total 100 mol% of the structural units possessed by the specific polysiloxane compound The ratio of the specific structural unit is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 65 mol %, even more preferably 15 mol % to 60 mol %.

The specific polysiloxane compound preferably further has a structural unit represented by the following general formula (2). In the synthesis of the specific polysiloxane compound, by using a monomer that provides a structural unit represented by the following general formula (2), it tends to be possible to suppress the synthesis of a branched polysiloxane compound. .

In general formula (2), R ¹ represents an epoxy-containing group. Epoxy-containing groups are as described above.

When the linear polysiloxane compound contains a specific polysiloxane compound having a structural unit represented by general formula (2), from the viewpoint of adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, The ratio of the structural unit represented by the general formula (2) to the total 100 mol% of the structural units possessed by the specific polysiloxane compound is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 65 mol%. , 15 mol % to 60 mol %.

The linear polysiloxane compound is preferably a compound represented by the following general formula (4).

In general formula (4), each R ⁶ independently represents an alkoxy group having 1 to 10 carbon atoms or a hydroxyl group. However, at least one R ⁶ is an alkoxy group having 1 to 10 carbon atoms. The alkoxy group having 1 to 10 carbon atoms is as described above.
In general formula (4), each R ⁷ independently represents an alkoxy group having 1 to 10 carbon atoms.
In general formula (4), n represents the number of structural units and is 1 or more. n is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
In general formula (4), R ¹ is as described above.

In the linear polysiloxane compound represented by the general formula (4), the content of hydroxyl groups with respect to the total 100 mol% of the alkoxy groups and hydroxyl groups represented by R ⁶ is preferably 2 mol% to 75 mol%, and 2 mol. % to 65 mol %, more preferably 5 mol % to 50 mol %.

The linear polysiloxane compound may be solid or liquid at 25° C. From the viewpoint of dispersibility of the linear polysiloxane in the curable resin composition of the present disclosure, , preferably liquid.
When the linear polysiloxane compound is solid at 25°C, the softening point or melting point of the linear polysiloxane compound is not particularly limited. From the viewpoint of moldability and heat resistance, the softening point or melting point of the linear polysiloxane compound is preferably −100° C. to 15° C., more preferably −90° C. to 10° C., and −80° C. °C to 5°C is more preferred.

The epoxy equivalent of the linear polysiloxane compound is not particularly limited. From the viewpoint of adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the epoxy equivalent of the linear polysiloxane compound is preferably 100 g/eq to 300 g/eq, and 120 g/eq. It is more preferably eq to 280 g/eq, even more preferably 140 g/eq to 260 g/eq.

From the viewpoint of adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the content of the linear polysiloxane compound in the curable resin composition of the present disclosure is 0.05% by mass to 5% by mass. %, more preferably 0.1% by mass to 3% by mass, even more preferably 0.15% by mass to 1% by mass.

When the linear polysiloxane compound contains a specific polysiloxane compound, from the viewpoint of the adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the linear polysiloxane contained in the curable resin composition The content of the specific polysiloxane compound with respect to the total mass of the compounds is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and 70% by mass to 100% by mass. is more preferable.

The linear polysiloxane compound may be synthesized using a conventionally known method, or a commercially available product may be used.
Examples of conventionally known methods include a method of hydrolyzing an alkoxy group possessed by an alkoxysilane compound to obtain a silanol compound having a hydroxyl group, followed by dehydration condensation of the hydroxyl groups possessed by two or more silanol compounds.

Examples of the alkoxysilane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyldimethoxysilane, γ-glycidoxypropyldiethoxysilane, γ-glycid. xypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like.

(Inorganic filler)
The curable resin composition of the present disclosure may contain inorganic fillers. When the curable resin composition contains an inorganic filler, the hygroscopicity of the curable resin composition tends to decrease, and the strength in the cured state tends to improve. When the curable resin composition is used as a sealing material for semiconductor packages, it preferably contains an inorganic filler.

The inorganic material that constitutes the inorganic filler is not particularly limited. Specific examples of inorganic materials include spherical silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, aluminum nitride, boehmite, beryllia, magnesium oxide, Zirconia, zircon, forsterite, steatite, spinel, mullite, titania, talc, clay, mica, titanate and the like.
An inorganic filler composed of an inorganic material having a flame retardant effect may also be used. Inorganic materials having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate.
An inorganic filler may be used individually by 1 type, or may be used in combination of 2 or more types.

The shape of the inorganic filler is not particularly limited, and examples include powdery, spherical, and fibrous. From the viewpoints of fluidity during molding of the curable resin composition and resistance to mold wear, it is preferably spherical.

The average particle size of the inorganic filler is not particularly limited. From the viewpoint of the balance between the viscosity of the curable resin composition and the filling property, etc., the volume average particle size of the inorganic filler is preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 30 μm. , 0.5 μm to 25 μm.
The volume-average particle size of the inorganic filler can be measured as the volume-average particle size (D50) with a particle size distribution analyzer using a laser diffraction scattering method.

When the curable resin composition contains an inorganic filler, its content is not particularly limited. It is preferably 30% by mass to 90% by mass, more preferably 35% by mass to 80% by mass, and even more preferably 40% by mass to 70% by mass of the total curable resin composition.
When the content of the inorganic filler is 30% by mass or more of the entire curable resin composition, the properties of the cured product, such as coefficient of thermal expansion, thermal conductivity and elastic modulus, tend to be further improved.
When the content of the inorganic filler is 90% by mass or less of the entire curable resin composition, the increase in viscosity of the curable resin composition is suppressed, the fluidity is further improved, and the moldability tends to be better. It is in.

(Curing accelerator)
The curable resin composition of the present disclosure may contain a curing accelerator. The type of curing accelerator is not particularly limited, and can be selected according to the type of epoxy resin, desired properties of the curable resin composition, and the like. A hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more types. Specific examples of the curing accelerator are described below, but are not limited to these.
Curing accelerators include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), Cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolak salts of the cyclic amidine compounds or derivatives thereof; 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 and other quinone compounds, and diazophenylmethane and other compounds having π bonds, which have intramolecular polarization. Compound; Cyclic amidinium compounds such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholine tetraphenylborate salt; Tertiary amine compounds such as ethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-phosphate Ammonium salt compounds such as butylammonium, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide; primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; Phenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris( tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialky organic phosphines such as tertiary phosphines such as diarylphosphine, alkyldiarylphosphine, trinaphthylphosphine and tris(benzyl)phosphine; phosphine compounds such as complexes of the above organic phosphines and organic borons; the above organic phosphines or the above phosphine compounds and 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, quinone compounds such as anthraquinone, and compounds having a π bond such as diazophenylmethane, which have intramolecular polarization. Compound; the above organic phosphine or the above phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodidephenol, 3-iodide Phenol, 2-iodinated phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4- Halogenated phenols such as bromo-2,6-di-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl Compounds with intramolecular polarization obtained through the step of dehydrohalogenation after reacting the compounds; tetra-substituted phosphoniums such as tetraphenylphosphonium, tetra- tetrasubstituted phosphonium compounds such as phenylborate salts and salts of tetrasubstituted phosphonium and phenolic compounds; phosphobetaine compounds; addition reaction products of phosphonium compounds and silane compounds;
Suitable curing accelerators include triphenylphosphine, quinone compound adducts of triphenylphosphine, and the like.

When the curable resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.1% by mass to 8% by mass with respect to 100 parts by mass of the total amount of the epoxy resin and the curing agent. , more preferably 0.3% by mass to 7% by mass, more preferably 0.5% by mass to 6% by mass. By setting the content of the curing accelerator within the above numerical range, the curing speed of the curable resin composition of the present disclosure becomes an appropriate numerical value, and the production of molded articles becomes easy.

(Various additives)
In addition to the components described above, the curable resin composition of the present disclosure may contain various additives such as coupling agents, stress relaxation agents, release agents, colorants, flame retardants, and ion exchangers. Moreover, the curable resin composition of the present disclosure may contain a siloxane compound having a structural unit having an epoxy group and an alkoxy group and having a degree of polymerization of 2. The curable resin composition may contain various additives well known in the art as necessary, in addition to the additives exemplified below.

(coupling agent)
The curable resin composition of the present disclosure may contain a coupling agent. The type of coupling agent is not particularly limited, and known coupling agents can be used. Examples of coupling agents include silane coupling agents and titanium coupling agents. A coupling agent may be used individually by 1 type, or may use 2 or more types together.

The silane coupling agent is not particularly limited as long as it is a compound other than the linear polysiloxane compound described above. sidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)amino propyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercapto propyltriethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, methacryloxyoctyltrimethoxysilane and the like.

Titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2, 2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctanoyltitanate, isopropyldimethacrylisostearoyltitanate , isopropyltridodecylbenzenesulfonyltitanate, isopropylisostearoyldiacryltitanate, isopropyltri(dioctylphosphate)titanate, isopropyltricumylphenyltitanate, tetraisopropylbis(dioctylphosphite)titanate and the like.

When the curable resin composition contains a coupling agent, the content of the coupling agent should be adjusted to the inorganic filler 100 contained in the curable resin composition from the viewpoint of the adhesiveness of the interface between the epoxy resin and the inorganic filler. It is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and 0.05 to 5 parts by mass based on the mass. More preferred.

(Stress relaxation agent)
The curable resin composition of the present disclosure may contain stress relaxation agents such as silicone oil and silicone rubber particles. By including a stress relaxation agent in the curable resin composition, it is possible to further reduce the warpage deformation of the package and the occurrence of package cracks. Examples of the stress relaxation agent include commonly used known stress relaxation agents (flexible agents). Specifically, stress relaxation agents include thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene, natural rubber (NR), and acrylonitrile-butadiene. Copolymer (NBR), acrylic rubber, urethane rubber, rubber particles such as silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate Examples include rubber particles having a core-shell structure such as copolymers. A stress relaxation agent may be used individually by 1 type, or may be used in combination of 2 or more types. Among them, a silicone-based stress relieving agent is preferable. Examples of silicone-based stress relieving agents include those having epoxy groups, those having amino groups, and those modified with polyethers.

When the curable resin composition contains a stress relaxation agent, the content is preferably 0.1 parts by mass to 30 parts by mass with respect to 100 parts by mass of the epoxy resin contained in the curable resin composition. It is more preferably 1 part by mass to 5 parts by mass.

(Release agent)
The curable resin composition of the present disclosure may contain a mold release agent from the viewpoint of releasability from the mold when using a mold for molding. The release agent is not particularly limited, and conventionally known agents can be used. Examples of release agents include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The release agent may be used singly or in combination of two or more.

When the curable resin composition of the present disclosure contains a release agent, the content of the release agent is 0.01 parts by mass to 15 parts by mass with respect to 100 parts by mass of the epoxy resin contained in the curable resin composition. preferably 0.1 parts by mass to 10 parts by mass. When the amount of the release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, there is a tendency that sufficient releasability can be obtained. When it is 15 parts by mass or less, there is a tendency that better releasability can be obtained.

(coloring agent)
The curable resin composition of the present disclosure may contain a colorant. Examples of coloring agents include known coloring agents such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide. The content of the coloring agent can be appropriately selected according to the purpose and the like. The colorants may be used singly or in combination of two or more.

When the curable resin composition contains a colorant, its content is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass, and 0 More preferably, it is 0.01% by mass to 1% by mass.

(Flame retardants)
The curable resin composition of the present disclosure may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Flame retardants include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more types.

When the curable resin composition of the present disclosure contains a flame retardant, its content is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. The content of the flame retardant is preferably 1 part by mass to 300 parts by mass, more preferably 2 parts by mass to 150 parts by mass, based on 100 parts by mass of the epoxy resin contained in the curable resin composition.

(Ion exchanger)
The curable resin composition of the present disclosure may contain an ion exchanger. When the curable resin composition is used as a sealing material for a semiconductor package, it preferably contains an inorganic filler from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the electronic component device including the element to be sealed. .
The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. The ion exchangers may be used singly or in combination of two or more. Specifically, the ion exchanger includes hydrotalcite represented by the following general formula (A).

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

When the curable resin composition of the present disclosure contains an ion exchanger, its content is not particularly limited as long as it is sufficient to capture ions such as halogen ions. The content of the ion exchanger is preferably 0.1 to 30 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin contained in the curable resin composition. more preferred.

(Physical properties of curable resin composition)
From the viewpoint of the adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the linear expansion coefficient at 10 ° C. to 30 ° C. of the cured product of the curable resin composition is 7 ppm / ° C. to 15 ppm / ° C. preferably 7.3 ppm/°C to 14.5 ppm/°C, even more preferably 7.5 ppm/°C to 14 ppm/°C.
From the viewpoint of the adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the linear expansion coefficient at 200 ° C. to 220 ° C. of the cured product of the curable resin composition is 20 ppm / ° C. to 50 ppm / ° C. preferably 24 ppm/°C to 37 ppm/°C, and even more preferably 28 ppm/°C to 35 ppm/°C.
In the present disclosure, the coefficient of linear expansion is the slope of the tangential line when strain of a cured product is plotted against temperature by thermal mechanical analysis (TMA) based on JIS K 7197:2012.
The test load is 5 g, and the temperature rise rate is 5° C./min.
Also, the linear expansion coefficient can be measured using a thermomechanical analyzer (for example, TMA/SS6100) manufactured by Seiko Instruments Inc. or an equivalent device.
The cured product was obtained by molding the curable resin composition using a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, followed by post-curing at 175°C for 5 hours. It is produced by performing
Moreover, the cured product has a rectangular shape with a short side of 5.1 mm, a long side of 20 mm, and a thickness of 2 mm.

From the viewpoint of heat resistance, etc., the glass transition temperature (Tg) of the cured product of the curable resin composition is preferably 80° C. to 120° C., more preferably 85° C. to 115° C., and 90° C. to It is more preferably 110°C.
In the present disclosure, the glass transition temperature of the cured product is the temperature at the intersection of the tangent line at 10° C. to 30° C. and the tangent line at 200° C. to 220° C. obtained by measuring the coefficient of linear expansion.

From the viewpoint of adhesion of the curable resin composition of the present disclosure to a non-roughened lead frame, the curing shrinkage of the curable resin composition is preferably 0.1% to 0.8%, and 0.1% to 0.8%. More preferably 15% to 0.75%, even more preferably 0.2% to 0.7%.
In the present disclosure, the cure shrinkage of the curable resin composition is measured as follows.
A disk-shaped cured product (test piece) of the curable resin composition is molded by transfer molding using a mold whose dimensions have already been measured, and then the test piece is allowed to cool to 25°C.
After cooling to 25°C, the specimen is heated in an oven heated to 175°C for 5 hours, and then allowed to cool to 25°C.
After cooling, the average value of the diameters at the two points on the front and back of the test piece is Rm (mm), and the inner diameter at the two points of the mold corresponding to the front of the test piece and the inside diameter of the mold corresponding to the back of the test piece The average value of the inner diameters at two points is defined as Rd (mm), and by substituting it into the following formula, the curing shrinkage rate of the curable resin composition is obtained.
Cure shrinkage rate (%) = (Rd - Rm) / Rd x 100

The elastic modulus of the cured product of the curable resin composition at 25° C. is preferably 25 GPa to 38 GPa, more preferably 26 GPa to 33 GPa.
The elastic modulus of the cured product of the curable resin composition at 260° C. is preferably 0.45 GPa to 0.70 GPa, more preferably 0.48 GPa to 0.67 GPa.
The elastic modulus of the curable resin composition was measured from 20° C. to 300° C. by a three-point bending method using a viscoelasticity measuring device (RSA III, manufactured by TA Instruments) at a span distance of 40 mm and a frequency of 1 Hz. Determined by increasing the temperature at °C/min. The cured product prepared by the method described above has a rectangular shape with a short side of 5.1 mm, a long side of 20 mm and a thickness of 2 mm.

(Method for producing curable resin composition)
The method for producing the curable resin composition is not particularly limited. As a general method, there can be mentioned a method of thoroughly mixing components in predetermined amounts with a mixer or the like, melt-kneading the mixture with a mixing roll, an extruder or the like, cooling, and pulverizing. More specifically, for example, predetermined amounts of the components described above are uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like preheated to 70° C. to 140° C., cooled, and pulverized. can be mentioned.

The curable resin composition is preferably solid at 25°C. When the curable resin composition is solid at 25° C., the shape of the curable resin composition is not particularly limited, and examples thereof include powder, granules, tablets, and the like. When the curable resin composition is in the form of a tablet, it is preferable from the standpoint of handleability that the dimensions and mass are such that they meet the molding conditions of the package.

(Use of curable resin composition)
Applications of the curable resin composition of the present disclosure are not particularly limited, and it can be used in various mounting techniques, for example, as a sealing material for electronic component devices. In addition, the curable resin composition of the present disclosure is used for resin moldings for various modules, resin moldings for motors, vehicle-mounted resin moldings, sealing materials for protective materials for electronic circuits, etc. The resin composition has good fluidity. And it can be used for various applications where it is desirable to have curability.

<Electronic parts equipment>
An electronic component device of the present disclosure includes an element and a cured product of the curable resin composition that seals the element.

The electronic component device can have a support member on which the element is mounted.
Examples of supporting members include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and the like. Among the supporting members, a lead frame is preferable from the viewpoint of adhesion to the cured product of the curable resin composition.

The lead frame may or may not have a roughened surface, but from the viewpoint of manufacturing cost, a non-roughened lead frame is preferable, and from the viewpoint of adhesiveness, a roughened lead frame is preferred. Planarized leadframes are preferred.
The roughening method is not particularly limited, and includes alkali treatment, silane coupling treatment, sand mat treatment, plasma treatment, corona discharge treatment and the like.

The lead frame can have a plated layer containing at least one of Au, Pd and Ni on at least part of the surface.
Further, the plated layer may be a single layer or multiple layers. As the multi-layer plating layer, a plating layer having a three-layer configuration in which a Ni plating layer, a Pd plating layer, and an Au plating layer are laminated from the lead frame side, or the like can be used.
Examples of the three-layer lead frame include a lead frame called PPF (Pre Plating Lead Frame), which is a copper lead frame plated with Ni--Pd--Au.

The thickness of the plating layer is not particularly limited, and is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less.

Examples of elements included in electronic component devices include active elements such as silicon chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils.

Specific configurations of the electronic component device include, but are not limited to, the following configurations.
(1) A structure in which an element is fixed on a lead frame, terminal portions of the element such as bonding pads and lead portions are connected using wire bonding, bumps, or the like, and then sealed using a curable resin composition.有するＤＩＰ（ＤｕａｌＩｎｌｉｎｅＰａｃｋａｇｅ）、ＰＬＣＣ（ＰｌａｓｔｉｃＬｅａｄｅｄＣｈｉｐＣａｒｒｉｅｒ）、ＱＦＰ（ＱｕａｄＦｌａｔＰａｃｋａｇｅ）、ＳＯＰ（ＳｍａｌｌＯｕｔｌｉｎｅＰａｃｋａｇｅ）、ＳＯＪ（ＳｍａｌｌＯｕｔｌｉｎｅＪ－ｌｅａｄＰａｃｋａｇｅ）、ＴＳＯＰ（ＴｈｉｎＳｍａｌｌＯｕｔｌｉｎｅＰａｃｋａｇｅ）、ＴＱＦＰ（ general resin-encapsulated IC such as Thin Quad Flat Package;
(2) TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier using bumps is sealed with a curable resin composition;
(3) A COB (Chip On Board) module having a structure in which an element connected to wiring formed on a support member by wire bonding, flip chip bonding, soldering, or the like is sealed with a curable resin composition. , hybrid ICs, multi-chip modules, etc.;
(4) After mounting an element on the surface of a support member on which terminals for wiring board connection are formed on the back surface, and connecting the element and the wiring formed on the support member using bumps or wire bonding, a curable resin composition is formed. BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), SiP (System in a Package), etc., having a structure in which elements are sealed using materials

The method of sealing the element using the curable resin composition is not particularly limited, and known methods can be applied. As a sealing method, for example, low-pressure transfer molding is generally used, but injection molding, compression molding, cast molding, or the like may also be used.

Although the present disclosure will be specifically described below with reference to examples, the present disclosure is not limited to these examples. Numerical values in the table mean "mass parts" unless otherwise specified.

(Examples 1 to 7 and Comparative Examples 1 to 6)
After pre-mixing (dry blending) the materials of the formulation shown in Table 1, they are kneaded for about 15 minutes with a biaxial roll (roll surface temperature: about 80 ° C.), cooled, and pulverized to obtain a powdery curable resin composition. manufactured.

The details of the materials in Table 1 are as follows.

Epoxy resin A: copolymer type epoxy resin having the following structural units, epoxy equivalent: 250 g/eq, melt viscosity at 150°C: 0.7 dPa s

・ Epoxy resin B: biphenyl type epoxy resin, epoxy equivalent 220 g / eq to 250 g / eq

・Curing agent: aralkyl-type phenolic resin, hydroxyl equivalent 175 g/eq

Linear polysiloxane compound: linear polysiloxane represented by the following chemical formula (melting point: -70 ° C., epoxy equivalent 120 g / eq to 150 g / eq, where n represents a number of 3 to 6, R ⁶ each independently represents a methoxy group or a hydroxyl group, and the content of the hydroxyl group is 5 mol % to 50 mol % with respect to the total 100 mol % of the methoxy group and the hydroxyl group represented by R ^6. )

・ Inorganic filler: spherical silica particles with a volume average particle size of 19.9 μm ・ Curing accelerator: 1,4-benzoquinone adduct of triphenylphosphine ・ Coupling agent A: N-phenyl-3-aminopropyltrimethoxysilane ・Coupling agent B: 3-glycidoxypropyltrimethoxysilane Coupling agent C: 3-glycidoxypropylmethyldimethoxysilane Stress relaxation agent: branched polysiloxane compound, solid at 25° C. Release agent: Oxidized polyethylene wax/coloring agent: carbon black

<<Evaluation of curable resin composition>>
The properties of the curable resin compositions produced in Examples and Comparative Examples were evaluated by the following property tests. Table 1 shows the evaluation results.
In addition, unless otherwise specified, the formation of a cured product using a curable resin composition is performed using a transfer molding machine under the conditions of a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. It was carried out by performing post-curing under the condition of 5 hours.

<Measurement of coefficient of linear expansion>
Under the above conditions, cured products of the curable resin compositions obtained in the above Examples and Comparative Examples were formed. A cured product having a rectangular shape with a short side of 5.1 mm, a long side of 20 mm and a thickness of 2 mm was used.
Then, according to JIS K 7197: 2012, the slope of the tangent line when the strain of the cured product is plotted against temperature is measured in the range of 10 ° C. to 30 ° C. and in the range of 200 ° C. to 220 ° C. by thermal mechanical analysis. sought in each. Table 1 shows the slope of the tangent line in the range of 10° C. to 30° C. as CTE1 and the slope of the tangent line in the range of 200° C. to 220° C. as CTE2.
The test load was 5 g and the heating rate was 5° C./min.
A TMA high-precision two-sample thermal analyzer (device name SS6100) manufactured by Seiko Instruments Inc. was used for the measurement of the coefficient of linear expansion.

<Glass transition temperature (Tg) of cured product>
The temperature at the intersection of the tangent line at 10° C. to 30° C. and the tangent line at 200° C. to 220° C. obtained by measuring the coefficient of linear expansion was taken as the glass transition temperature of the cured product.

<Measurement of cure shrinkage>
Using a mold whose dimensions have already been measured, the disk-shaped cured product (test piece) of the curable resin composition obtained in the above Examples and Comparative Examples was transferred by transfer molding at a mold temperature of 175 ° C. and a molding pressure of 6.9 MPa. , under the conditions of a curing time of 90 seconds, and then allowed to cool to 25°C.
After cooling to 25°C, the test piece was heated in an oven heated to 175°C for 5 hours, and then allowed to cool to 25°C.
After cooling, the average value of the diameters at the two points on the front and back of the test piece is Rm (mm), and the inner diameter at the two points of the mold corresponding to the front of the test piece and the inside diameter of the mold corresponding to the back of the test piece The cure shrinkage rate of the curable resin composition was determined by substituting the average value of the inner diameters at two points as Rd (mm) into the following formula.
Cure shrinkage rate (%) = (Rd - Rm) / Rd x 100

<Measurement of elastic modulus>
Based on the above conditions, a cured product similar to the cured product used in measuring the coefficient of linear expansion was formed.
Using a viscoelasticity measuring device (RSA III, manufactured by TA Instruments), the temperature was raised from 20 ° C. to 300 ° C. at a rate of 5 ° C./min by a three-point bending method under the conditions of a span distance of 40 mm and a frequency of 1 Hz. and 260° C., respectively.

<Adhesion evaluation>
A column having a contact area of 3 mmφ was formed on the surface of a copper alloy plate (Pd-PPF) from the curable resin compositions obtained in the above Examples and Comparative Examples under the above conditions.
Thereafter, using a bond tester (Dage Japan Co., Ltd., Series 4000), the shear adhesive strength (MPa) was determined at a shear rate of 50 µm/s while maintaining the temperature of the copper alloy plate at 25°C.
After heating the cured product under conditions of 85° C. and 60% RH for 168 hours, the shear adhesive strength (MPa) was determined at a shear rate of 50 μm/s while maintaining the temperature of the copper alloy plate at 260° C.

<Reflow resistance evaluation>
A silicon chip (length 8 mm, width 10 mm, thickness 0.4 mm) sealed using a cured product of the curable resin composition formed under the above conditions is mounted. An 80-pin flat package (lead frame material: copper alloy (Pd-PPF)) was produced.
The package was heated at 85° C. and 60% RH for 168 hours.
After that, reflow treatment is performed at 260 ° C. for 10 seconds, and the presence or absence of cracks outside the package is visually checked, and the presence or absence of peeling inside the package is checked with an ultrasonic flaw detector (HYE-FOCUS, manufactured by Hitachi Construction Machinery Co., Ltd.). observed each. Reflow resistance was evaluated by summing the number of packages in which either cracks or peeling occurred with respect to the number of test packages (64).

<Fluidity evaluation (spiral flow)>
Using a spiral flow measurement mold according to EMMI-1-66, the curable resin composition was molded under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and the flow distance (cm ).

As is clear from Table 1, according to the curable resin composition of the present disclosure, the curable resin composition has excellent adhesion to non-roughened lead frames and excellent reflow resistance. is found to be provided.

The disclosure of Japanese Patent Application No. 2021-035808 filed on March 5, 2021 is incorporated herein by reference in its entirety. All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually indicated to be incorporated by reference. incorporated herein by reference.

Claims

A curable resin composition containing an epoxy resin, a curing agent, and a linear polysiloxane compound having a structural unit having an epoxy group and an alkoxy group and having a degree of polymerization of 3 or more.
The curable resin composition according to claim 1, wherein the structural unit is represented by the following general formula (1).

In general formula (1),
R 1 represents an epoxy-containing group,
R 2 represents an alkoxy group having 1 to 10 carbon atoms.
The curable resin composition according to claim 2, wherein the linear polysiloxane compound further has a structural unit represented by the following general formula (2).

In general formula (2),
R 1 represents an epoxy-containing group.
The curable resin composition according to claim 2 or 3, wherein the epoxy-containing group is represented by the following general formula (3).

In general formula (3),
R 4 and R 5 each independently represent an alkylene group having 1 to 10 carbon atoms,
* represents the bonding position with Si.
The curable resin composition according to any one of claims 1 to 4, wherein the linear polysiloxane compound is a compound represented by the following general formula (4).

In general formula (4),
R 1 represents an epoxy-containing group,
each R 6 independently represents an alkoxy group having 1 to 10 carbon atoms or a hydroxyl group;
each R 7 independently represents an alkoxy group having 1 to 10 carbon atoms,
n represents an integer of 1 or more,
However, at least one R 6 represents an alkoxy group having 1 to 10 carbon atoms.
The curable resin composition according to any one of claims 1 to 5, wherein the epoxy resin comprises a copolymerized epoxy resin having a structural unit derived from cresol and a structural unit derived from methoxynaphthalene.
7. The curable resin composition according to claim 6, wherein the copolymerizable epoxy resin has the following structural units.

wherein n is a number from 1-10.
The curable resin composition according to any one of claims 1 to 7, wherein the curing agent contains a phenolic curing agent.
The curable resin composition according to claim 8, wherein the phenolic curing agent contains an aralkyl-type phenolic resin.
The curable resin composition according to any one of claims 1 to 9, wherein the linear polysiloxane compound is liquid at 25°C.
The curable resin composition according to any one of claims 1 to 10, wherein the number of structural units contained in the linear polysiloxane compound is 15 or less.
Curing according to any one of claims 1 to 11, wherein the content of the linear polysiloxane compound with respect to the total mass of the curable resin composition is 0.05% by mass to 5% by mass. elastic resin composition.
An electronic component device comprising an element and a cured product of the curable resin composition according to any one of claims 1 to 12, which seals the element.
14. The electronic component device according to claim 13, comprising a lead frame for mounting the element on one surface.
The electronic component device according to claim 14, wherein the lead frame has a plated layer containing at least one of Au, Pd and Ni on at least part of the surface.