CN117120543A

CN117120543A - Curable resin composition and electronic component device

Info

Publication number: CN117120543A
Application number: CN202280018109.0A
Authority: CN
Inventors: 西山智雄; 姜东哲; 山本贵耶; 金贵和
Original assignee: Lishennoco Co ltd
Current assignee: Lishennoco Co ltd
Priority date: 2021-03-05
Filing date: 2022-03-03
Publication date: 2023-11-24
Also published as: TW202246410A; JPWO2022186361A1; WO2022186361A1

Abstract

A curable resin composition comprising: an epoxy resin; a hardening agent; and a linear polysiloxane compound having a structural unit containing an epoxy group and an alkoxy group, and having a degree of polymerization of 3 or more.

Description

Curable resin composition and electronic component device

Technical Field

The present disclosure relates to a curable resin composition and an electronic component device.

Background

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

Further, these packages are different from the pin-inserted packages in mounting method. That is, since the lead-in package is soldered from the back surface of the wiring board after the lead is inserted into the wiring board, the package is not directly exposed to high temperature.

However, since the surface-mounted IC is temporarily fixed to the surface of the wiring board and is processed by a solder bath, a reflow apparatus, or the like, the package is directly exposed to a soldering temperature (reflow temperature). As a result, in the case of package moisture absorption, moisture absorption and vaporization occur at the time of reflow, and the generated vapor pressure acts as a peeling stress, and peeling between the sealing material and the supporting member such as an element and a lead frame occurs, which causes package cracking, and electrical characteristics are poor. Accordingly, it is desired to develop a sealing material which is excellent in adhesion to a support member and further excellent in solder heat resistance (reflow resistance).

As a sealing material having excellent reflow resistance, japanese patent application laid-open No. 2008-111101 proposes a curable resin composition comprising an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and an alkoxysilane polymer having a specific structure.

In addition, for the purpose of improving reflow resistance, for example, the following operations are performed: the surface of the lead frame is roughened before the plating treatment to improve adhesion to the sealing material.

Disclosure of Invention

Problems to be solved by the invention

However, from the viewpoints of production efficiency and production cost, it is desired to develop a sealing material having excellent adhesion to an unglazed lead frame, and there is room for further improvement in the curable resin composition disclosed in japanese patent application laid-open No. 2008-111101.

The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a curable resin composition having excellent adhesion to an unpainted lead frame and excellent reflow resistance, and an electronic component device including an element sealed with the curable resin composition.

Technical means for solving the problems

<1> a curable resin composition comprising: an epoxy resin; a hardening agent; and a linear polysiloxane compound having a structural unit containing 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 formula (1).

[ chemical 1]

In the general formula (1),

R ¹ represents an epoxy-containing group and is preferably a hydroxyl group,

R ² 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).

[ chemical 2]

In the 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).

[ chemical 3]

In the general formula (3),

R ⁴ r is R ⁵ Each independently represents an alkylene group having 1 to 10 carbon atoms,

* The bonding position with Si is shown.

<5> the curable resin composition according to any one of <1> to <4>, wherein the linear silicone compound is a compound represented by the following general formula (4).

[ chemical 4]

In the general formula (4),

R ¹ represents an epoxy-containing group and is preferably a hydroxyl group,

R ⁶ each independently represents an alkoxy group having 1 to 10 carbon atoms or a hydroxyl group,

R ⁷ each independently represents an alkoxy group having 1 to 10 carbon atoms,

n represents an integer of 1 or more,

wherein at least one R ⁶ 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.

<7> the curable resin composition according to <6>, wherein the copolymerizable epoxy resin has the following structural unit.

[ chemical 5]

Wherein n is a number of 1 to 10.

<8> the curable resin composition according to any one of <1> to <7>, wherein the curing agent comprises a phenolic curing agent.

<9> the curable resin composition according to <8>, wherein the phenol-based curing agent comprises an aralkyl-type phenol resin.

<10> the curable resin composition according to any one of <1> to <9>, wherein the linear silicone compound is a liquid at 25 ℃.

<11> the curable resin composition according to any one of <1> to <10>, wherein the number of structural units contained in the linear silicone compound is 15 or less.

<12> the curable resin composition according to 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 to 5 mass%.

<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> sealing the element.

<14> the electronic component device according to <13>, comprising a lead frame having an element mounted on one surface thereof.

<15> the electronic component device according to <14>, wherein at least a part of the surface of the lead frame comprises a plating layer containing at least one of Au, pd and Ni.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present disclosure, it is possible to provide a curable resin composition having excellent adhesion to an unpinned lead frame and excellent reflow resistance, and an electronic part device including an element sealed with the curable resin composition.

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 specifically indicated. The values and ranges are also the same and do not limit the disclosure.

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 the numerical ranges described in the present disclosure, the upper limit or the lower limit of the numerical ranges may be replaced with the values shown in the synthesis examples.

In the present disclosure, each component may comprise a plurality of conforming compounds. When a plurality of substances corresponding to the respective components are present in the composition, unless otherwise specified, the content or content of the respective components means the total content or content of the plurality of substances present in the composition.

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

In the present disclosure, "stacked" is used to mean that layers are stacked, and two or more layers may be combined or may be attached and detached.

In the expression of the group (radical) of the present disclosure, the expression of not recording substituted and unsubstituted includes both having no substituent and having a substituent.

In the present disclosure, regarding the number of structural units, an integer value is expressed for a single molecule, and a rational number is expressed as an average value as an aggregate of a plurality of molecules.

In the present disclosure, the carbon number refers to the total number of carbon atoms contained in the whole of a certain group, and when the group has no substituent, the number of carbon atoms forming the skeleton of the group is represented, and when the group has a substituent, the total number of carbon atoms forming the skeleton of the group added to the number of carbon atoms in the substituent is represented.

In the present disclosure, the linear polysiloxane compound refers to a polysiloxane compound having no T unit and no Q unit, but having a D unit.

The D unit has a silicon atom bonded to two oxygen atoms, the T unit has a silicon atom bonded to three oxygen atoms, and the Q unit has a silicon atom bonded to four oxygen atoms, which are represented by the following structural formulae (D), (T) and (Q), respectively.

In the present disclosure, a polysiloxane compound having a T unit or a Q unit is referred to as a branched polysiloxane compound.

[ chemical 6]

In the present disclosure, the term "epoxy-containing group" refers to a group having an epoxy structure.

In the present disclosure, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the polymerization degree are measured using a gel permeation chromatography (Gel Permeation Chromatography, GPC) measuring device described below under the following measurement conditions, and are converted using a calibration curve of standard polystyrene. In addition, as standard polystyrene, five sample groups ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Co., ltd.) were used in the preparation of the calibration curve.

Among them, as a compound whose Mw, mn, or polymerization degree cannot be measured accurately by GPC because of its small molecular weight, a compound whose Mw, mn, or polymerization degree is determined from the chemical structure is used.

(GPC measurement apparatus)

GPC apparatus: high speed GPC apparatus "HCL-8320GPC", detector is differential refractometer or UV manufactured by Tosoh Co., ltd

And (3) pipe column: TSKgel Super Multipore HZ-H (length of column: 15cm, inner diameter of column: 4.6 mm), manufactured by Tosoh Co., ltd

(measurement conditions)

A solvent: tetrahydrofuran (THF)

Measuring temperature: 40 DEG C

Flow rate: 0.35 mL/min

Sample concentration: 10mg/THF 5mL

Injection amount: 20 mu L

< curable resin composition >

The curable resin composition of the present disclosure comprises: an epoxy resin; a hardening agent; and a linear polysiloxane compound having a structural unit containing 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 and excellent reflow resistance relative to an unfused lead frame.

The reason why the effect is exerted by the curable resin composition of the present disclosure is not clear, but is presumed as follows.

The curable resin composition of the present disclosure can reduce the difference in internal stress between the cured product of the curable resin composition and the support member by including a linear polysiloxane compound having at least three structural units having an epoxy group and an alkoxy group. As a result, it is presumed that the adhesiveness between the cured product of the curable resin composition and the support member is improved, and the curable resin composition of the present disclosure has excellent adhesiveness and thus excellent reflow resistance with respect to an unpeeled lead frame containing copper or the like and a plating layer containing gold, palladium, nickel or the like formed on the surface of the unpeeled lead frame. 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 are sometimes referred to collectively as adhesion to the non-roughened lead frame.

The linear polysiloxane compound contained in the curable resin composition of the present disclosure has excellent adhesion to an epoxy resin, a material constituting a lead frame (copper, etc.), and a material constituting a plating layer (gold, palladium, nickel, etc.). As a result, it is presumed that the curable resin composition of the present disclosure has excellent adhesion to an unpainted lead frame and further has excellent reflow resistance.

Hereinafter, various materials that can be contained in the curable resin composition will be described.

(epoxy resin)

The curable resin composition of the present disclosure includes an epoxy resin. The kind of the epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. In the present disclosure, the linear polysiloxane compound is not included in the epoxy resin.

Specific examples of the epoxy resin are described below, but the present invention is not limited thereto.

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.; glycidylamine-type epoxy resins obtained by substituting active hydrogen bonded to nitrogen atom such as aniline, diaminodiphenylmethane and isocyanuric acid with a 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, an aminophenol type epoxy resin which is a glycidyl ether of an aminophenol, and the like can be exemplified as the epoxy resin. One kind of these epoxy resins may be used alone, or two or more kinds may be used in combination.

Among the epoxy resins, the curable resin composition of the present disclosure is preferably a copolymerized epoxy resin or a biphenyl epoxy resin from the viewpoint of adhesion to an unpeened lead frame and the viewpoint of balance between heat resistance and fluidity. The curable resin composition of the present disclosure preferably contains a copolymerized epoxy resin and a biphenyl 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 preferable.

[ chemical 7]

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.

[ chemical 8]

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.

[ chemical 9]

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.

[ chemical 10]

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.

[ chemical 11]

In the formula (VI), R ¹⁴ 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 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.

[ chemical 12]

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.

[ chemical 13]

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 an integer of 0 to 3, and 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.

[ chemical 14]

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).

[ 15]

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

In view of the adhesion of the curable resin composition of the present disclosure to an unpuldered lead frame, a copolymerizable epoxy resin having a structural unit derived from cresol and a structural unit derived from methoxynaphthalene (hereinafter, referred to as a specific copolymerizable epoxy resin) is preferable as the copolymerizable epoxy resin.

The specific copolymerized epoxy resin preferably has the following structural units.

In the following structural units, n is an average value, and is a number of 1 to 10, preferably a number of 2 to 8.

[ 16]

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.

[ chemical 17]

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 of the curable resin composition at the time of melt molding 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.

The epoxy equivalent of the epoxy resin is not particularly limited. The epoxy equivalent of the epoxy resin is preferably 40g/eq to 1000g/eq, more preferably 45g/eq to 500g/eq, and still more preferably 50g/eq to 350g/eq, from the viewpoint of balance of various properties such as moldability, heat resistance, and electrical reliability.

The epoxy equivalent of the epoxy resin was set to be as per Japanese Industrial Standard (Japanese Industrial Standards, JIS) K7236: 2009, a value measured by the method of the present invention.

The epoxy resin may be solid or liquid at 25 ℃. In the case where the epoxy resin is solid at 25 ℃, the softening point or melting point of the epoxy resin is not particularly limited.

The softening point or melting point of the epoxy resin is preferably 40 to 180 ℃ from the viewpoint of balance between moldability and heat resistance. In addition, from the viewpoint of workability in the production of the curable resin composition, the softening point or melting point of the epoxy resin is preferably 50 to 130 ℃.

In the present disclosure, the softening point means a softening point obtained by the method of 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 Mw of the epoxy resin is preferably 550 to 1050, more preferably 650 to 950, from the viewpoint of balance between moldability and heat resistance.

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

In the case where the epoxy resin includes a copolymerized epoxy resin, the content of the copolymerized epoxy resin relative to the total mass of the epoxy resin contained in the curable resin composition is preferably 50 to 90 mass%, more preferably 55 to 80 mass%, and even more preferably 60 to 75 mass% in view of the adhesion of the curable resin composition of the present disclosure to an unpicked lead frame.

In the case where the copolymerizable epoxy resin contains a specific copolymerizable epoxy resin, the content of the specific copolymerizable epoxy resin with respect to the total mass of the copolymerizable epoxy resin is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass, from the viewpoint of the adhesion of the curable resin composition of the present disclosure to the non-roughened lead frame.

In the case where the epoxy resin includes a biphenyl type epoxy resin, the content of the biphenyl type epoxy resin with respect to the total mass of the epoxy resin contained in the curable resin composition is preferably 10 to 50 mass%, more preferably 20 to 45 mass%, and even more preferably 25 to 40 mass% in view of the adhesion of the curable resin composition of the present disclosure to an unpicked lead frame.

(hardener)

The curable resin composition of the present disclosure includes a hardener. The type of the curing agent is not particularly limited, and may be selected from the components generally used as curable resin compositions. The hardening agent may be used alone or in combination of two or more.

In the present disclosure, the hardener may be a compound which reacts with the epoxy resin contained in the curable resin composition and cures the curable resin composition, and may be contained in the hardener even if the content of the compound is small and the compound contributes little to the curing reaction of the curable resin composition.

Examples of the hardening agent include: phenolic hardeners, amine hardeners, acid anhydride hardeners, polythiol hardeners, polyaminoamide hardeners, isocyanate hardeners, blocked isocyanate hardeners, and the like.

Among these, the curing agent is preferably a phenol curing agent or an amine curing agent from the viewpoint of heat resistance. In addition, the curing agent is preferably a phenol curing agent from the viewpoint of adhesion to an unglazed lead frame and from the viewpoint of heat resistance of the curable resin composition of the present disclosure.

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 and/or meta-xylene modified phenol resin; melamine modified phenol resins; terpene modified phenol resins; dicyclopentadiene type phenol resin and dicyclopentadiene type naphthol resin synthesized by copolymerizing the phenol compound and dicyclopentadiene; cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified phenol resins; biphenyl type phenol resins; a triphenylmethane-type phenol resin obtained by condensing or co-condensing the phenol compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde in the presence of an acidic catalyst; and phenol resins obtained by copolymerizing two or more of these. These phenolic hardeners may be used singly or in combination of two or more.

Among the phenolic hardeners, an aralkyl type phenolic resin is preferable from the viewpoint of adhesion to an unglazed lead frame and the viewpoint of heat resistance.

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 18]

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 The monovalent organic groups having 1 to 18 carbon atoms may be the same or different. 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.

The aralkyl type phenol resin is preferably a phenol resin represented by the general formula (XIII) from the viewpoint of adhesion to an unpuldered lead frame and from the viewpoint of heat resistance.

In the curable resin composition of the present disclosure, i and k are preferably 0 in the general formula (XIII) from the viewpoint of adhesion to an unglazed lead frame and from the viewpoint of heat resistance.

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.

[ chemical 19]

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.

[ chemical 20]

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.

[ chemical 21]

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.

[ chemical 22]

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 curable 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.

The functional group equivalent of the hardener (hydroxyl equivalent in the case of a phenol-based hardener, active hydrogen equivalent in the case of an amine-based 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 weight 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.

In the case where the hardener is solid at 25 ℃, its softening point or melting point is not particularly limited. The softening point or melting point of the hardener is preferably 40 to 180 ℃ from the viewpoint of moldability and heat resistance. In addition, from the viewpoint of workability in producing the curable resin composition, the softening point or melting point of the curing agent is preferably 50 to 130 ℃.

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

In the case where the curing agent contains a phenolic curing agent, the content of the phenolic curing agent with respect to the total mass of the curing agent is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, and even more preferably 70 to 100 mass% in view of the adhesion of the curable resin composition of the present disclosure to the non-roughened lead frame.

In the case where the phenol-based hardener contains an aralkyl-type phenol resin, the content of the aralkyl-type phenol resin relative to the total mass of the phenol-based hardener is more preferably 60 to 100 mass%, and still more preferably 70 to 100 mass%, from the viewpoint of adhesion of the curable resin composition of the present disclosure to an unglazed lead frame.

(Linear polysiloxane Compound)

The linear polysiloxane compound has a structural unit containing an epoxy group and an alkoxy group, and has a degree of polymerization of 3 or more.

The structural units of the linear polysiloxane compound may be all structural units having an epoxy group and an alkoxy group, or may be a part of the structural units having an epoxy group and an alkoxy group.

In the case where a part of the structural units included in the linear silicone compound is a structural unit having an epoxy group and an alkoxy group, the structural units may have a structural unit having an epoxy group and an alkoxy group randomly, may have a structural unit having an epoxy group and an alkoxy group alternately, may have a structural unit having an epoxy group and an alkoxy group regularly, and may have a structural unit having an epoxy group and an alkoxy group in a block form.

In view 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, and further preferably 8 or less.

In view of adhesion of the curable resin composition of the present disclosure to an unpeened lead frame, the structural unit containing an epoxy group and an alkoxy group of the linear polysiloxane compound is preferably represented by the following general formula (1).

Hereinafter, the structural unit represented by the general formula (1) is referred to as a "specific structural unit", and the linear polysiloxane compound having a specific structural unit is referred to as a "specific polysiloxane compound".

[ chemical 23]

In the general formula (1), R ¹ Represents an epoxy-containing group.

In the case where a specific polysiloxane compound has two or more specific structural units, R in the specific structural units ¹ Each of them may be different groups or the same group.

From the viewpoint of adhesion of the curable resin composition of the present disclosure to an unglazed lead frame, R ¹ The epoxy-containing group represented by the following general formula (3) is preferable.

[ chemical 24]

In the general formula (3), R ⁴ R is R ⁵ Each independently represents an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

In general formula (3), the bonding position to Si of a specific structural unit is represented.

In the general formula (1), R ² An alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

In the case where a specific polysiloxane compound has two or more specific structural units, R in the specific structural units ² Each of them may be different groups or the same group.

In the case where the linear polysiloxane compound contains a specific polysiloxane compound, the proportion of the specific structural unit to the total 100mol% of the structural units of the specific polysiloxane compound is preferably 5mol% to 70mol%, more preferably 10mol% to 65mol%, and even more preferably 15mol% to 60mol% in view of the adhesion of the curable resin composition of the present disclosure to the non-roughened lead frame.

The specific polysiloxane compound preferably further has a structural unit represented by the following general formula (2). In the synthesis of a specific silicone compound, a monomer having a structural unit represented by the following general formula (2) is used, whereby the tendency of the synthesis of a branched silicone compound can be suppressed.

[ chemical 25]

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

In the case where the linear polysiloxane compound includes a specific polysiloxane compound having a structural unit represented by the general formula (2), the proportion of the structural unit represented by the general formula (2) to the total 100mol% of the structural units of the specific polysiloxane compound is preferably 5mol% to 70mol%, more preferably 10mol% to 65mol%, and even more preferably 15 mol% to 1 mol% from the viewpoint of adhesion of the curable resin composition of the present disclosure to an unpicked lead frame.

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

[ chemical 26]

In the general formula (4), R ⁶ Each independently represents an alkoxy group having 1 to 10 carbon atoms or a hydroxyl group. Wherein at least one R ⁶ An alkoxy group having 1 to 10 carbon atoms. The alkoxy group having 1 to 10 carbon atoms is as described above.

In the general formula (4), R ⁷ Each independently represents an alkoxy group having 1 to 10 carbon atoms.

In the general formula (4), n represents the number of structural units and is a number of 1 or more. n is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

In the general formula (4), R ¹ As described above.

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

The linear polysiloxane compound may be solid or liquid at 25 ℃, and is preferably liquid from the viewpoint of dispersibility of the linear polysiloxane in the curable resin composition of the present disclosure.

In the case where the linear polysiloxane compound is solid at 25 ℃, the softening point or melting point of the linear polysiloxane compound is not particularly limited. The softening point or melting point of the linear silicone compound is preferably-100 to 15 ℃, more preferably-90 to 10 ℃, and even more preferably-80 to 5 ℃ from the viewpoints of moldability and heat resistance.

The epoxy equivalent of the linear polysiloxane compound is not particularly limited. In view of the adhesion of the curable resin composition of the present disclosure to an unglazed lead frame, the linear silicone compound preferably has an epoxy equivalent of 100g/eq to 300g/eq, more preferably 120g/eq to 280g/eq, and still more preferably 140g/eq to 260g/eq.

The content of the linear silicone compound in the curable resin composition of the present disclosure is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.15 to 1% by mass, from the viewpoint of adhesion of the curable resin composition of the present disclosure to an unpuldered lead frame.

In the case where the linear polysiloxane compound includes a specific polysiloxane compound, the content of the specific polysiloxane compound relative to the total mass of the linear polysiloxane compound contained in the curable resin composition is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, and even more preferably 70 to 100 mass% in view of the adhesion of the curable resin composition of the present disclosure to an unglazed lead frame.

The linear polysiloxane compound may be synthesized by a conventional method, or commercially available compounds may be used.

As a conventional method, there is a method in which an alkoxy group of an alkoxysilane compound is hydrolyzed to prepare a silanol compound having a hydroxyl group, and then two or more hydroxyl groups of the silanol compound are dehydrated and condensed with each other.

Examples of the alkoxysilane compound include: gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl dimethoxy silane, gamma-glycidoxypropyl diethoxy silane, gamma-glycidoxypropyl methyl dimethoxy silane, gamma-glycidoxypropyl methyl diethoxy silane, etc.

(inorganic filler)

The curable resin composition of the present disclosure may also include an inorganic filler. The curable resin composition contains an inorganic filler, so that hygroscopicity of the curable resin composition tends to be reduced and strength in a cured state tends to be improved. When the curable resin composition is used as a sealing material for a semiconductor package, it is preferable to contain an inorganic filler.

The inorganic material constituting the inorganic filler is not particularly limited. Specific examples of the inorganic material include: spherical silica, crystalline silica, 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, titanate, and the like.

An inorganic filler containing an inorganic material having a flame retardant effect may also be used. As the inorganic material having a flame retardant effect, there are listed: composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and composite hydroxide of magnesium and zinc, and zinc borate.

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

The shape of the inorganic filler is not particularly limited, and examples thereof include: powdery, spherical, fibrous, etc. The curable resin composition is preferably spherical in terms of fluidity and mold abrasion during molding.

The average particle diameter of the inorganic filler is not particularly limited. The volume average particle diameter of the inorganic filler is preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 30 μm, and still more preferably 0.5 μm to 25 μm, from the viewpoint of balance of viscosity, filling property, and the like of the curable resin composition.

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 the case where the curable resin composition contains an inorganic filler, the content of the inorganic filler is not particularly limited. The amount of the curable resin composition is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and still more preferably 40 to 70% by mass.

When the content of the inorganic filler is 30 mass% or more of the entire curable resin composition, the properties such as the thermal expansion coefficient, thermal conductivity, and elastic modulus of the cured product tend to be further improved.

If the content of the inorganic filler is 90 mass% or less of the entire curable resin composition, the increase in viscosity of the curable resin composition can be suppressed, and the fluidity can be further improved, so that the moldability tends to be further improved.

(hardening accelerator)

The curable resin composition of the present disclosure may also contain a hardening accelerator. The type of the hardening accelerator is not particularly limited, and may be selected according to the type of the epoxy resin, desired properties of the curable resin composition, and the like. The hardening accelerator may be used alone or in combination of two or more. Specific examples of the hardening accelerator are described below, but the hardening accelerator is not limited to these.

Examples of the hardening accelerator include: cyclic amidine compounds such as diazabicycloolefins such as 1,5-Diazabicyclo [4.3.0] nonene-5 (1, 5-diazabicycloo [4.3.0] nonene-5, DBN), 1,8-Diazabicyclo [5.4.0] undecene-7 (1, 8-diazabicycloo [5.4.0] undecene-7, DBU), 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; a phenol novolac salt of the cyclic amidine compound or a derivative thereof; a compound having intramolecular polarization, which is formed by adding a quinone compound such as maleic anhydride, 1, 4-benzoquinone, 2, 5-toluquinone, 1, 4-naphthoquinone, 2, 3-dimethylbenzoquinone, 2, 6-dimethylbenzoquinone, 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone, 2, 3-dimethoxy-1, 4-benzoquinone, phenyl-1, 4-benzoquinone, or a compound having pi bond such as diazophenylmethane to these compounds; cyclic amidinium compounds such as tetraphenylborate of DBU, tetraphenylborate of DBN, tetraphenylborate of 2-ethyl-4-methylimidazole, and tetraphenylborate of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyl dimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like; derivatives of the tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide, and the like; organic phosphines such as primary phosphines, e.g., ethylphosphine, phenylphosphine, secondary phosphines, e.g., dimethylphosphine, diphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris (benzyl) phosphine, etc.; phosphine compounds such as complexes of the organic phosphine and organoboron compounds; a compound having intramolecular polarization, which is obtained by adding a quinone compound such as maleic anhydride, 1, 4-benzoquinone, 2, 5-toluquinone, 1, 4-naphthoquinone, 2, 3-dimethylbenzoquinone, 2, 6-dimethylbenzoquinone, 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone, 2, 3-dimethoxy-1, 4-benzoquinone, phenyl-1, 4-benzoquinone, anthraquinone, or the like, or a compound having pi bond such as diazophenylmethane to the organic phosphine or the phosphine compound; a compound having an intramolecular polarization obtained by a dehydrohalogenation step after reacting the organic phosphine or the phosphine compound with a halogenated phenol compound such as 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2, 6-dimethylphenol, 4-bromo-3, 5-dimethylphenol, 4-bromo-2, 6-di-t-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 addition reaction products of phosphonium compounds and silane compounds.

Examples of suitable hardening accelerators include triphenylphosphine and quinone compound adducts of triphenylphosphine.

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

(various additives)

The curable resin composition of the present disclosure may contain various additives such as a coupling agent, a stress relaxing agent, a mold release agent, a colorant, a flame retardant, and an ion exchanger, in addition to the above-described components. The curable resin composition of the present disclosure may contain a silicone compound having a structural unit containing an epoxy group and an alkoxy group and having a polymerization degree of 2. The curable resin composition may contain various additives known in the art, as required, in addition to the additives exemplified below.

(coupling agent)

The curable resin composition of the present disclosure 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.

The silane coupling agent is not particularly limited as long as it is a compound other than the linear polysiloxane compound, and examples thereof include: 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2-aminoethyl) aminopropyl trimethoxysilane, 3- (2-aminoethyl) aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-ureidopropyl triethoxysilane, octenyl trimethoxysilane, glycidoxctyl trimethoxysilane, methacryloxyoctyl trimethoxysilane, and the like.

Examples of the titanium 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 curable resin composition 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 contained in the curable resin composition, in terms of adhesion of the interface between the epoxy resin and the inorganic filler.

(stress relaxation agent)

The curable resin composition of the present disclosure may also contain a stress-relaxing agent such as silicone oil or silicone rubber particles. By including the stress-relaxing agent in the curable resin composition, warpage of the package and occurrence of package cracks can be further reduced. The stress-relaxing agent may be a conventional stress-relaxing agent (flexible agent) which is generally used. Specifically, as the stress-relaxing agent, 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 copolymer (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-relaxing agent may be used alone or in combination of two or more. Among them, silicone-based stress relaxation agents are preferable. As the silicone-based stress relaxation agent, there can be mentioned: having an epoxy group, having an amino group, polyether-modified with these, and the like.

When the curable resin composition contains a stress-relieving agent, the content of the stress-relieving agent is preferably 0.1 to 30 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the epoxy resin contained in the curable resin composition.

(Release agent)

In the case of using a mold at the time of molding, the curable resin composition of the present disclosure may contain a release agent from the viewpoint of releasability from the mold. The release agent is not particularly limited, and conventional release agents can be used. As the release agent, 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 curable resin composition of the present disclosure 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, relative to 100 parts by mass of the epoxy resin contained in the curable resin composition. When the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, releasability tends to be sufficiently obtained. When the amount is 15 parts by mass or less, a better releasability tends to be obtained.

(colorant)

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

When the curable 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, and still more preferably 0.01 to 1% by mass.

(flame retardant)

The curable resin composition of the present disclosure may also include a flame retardant. The flame retardant is not particularly limited, and conventional flame retardants can be used. Examples of the flame retardant include organic compounds or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides, and the like. The flame retardant may be used singly or in combination of two or more.

In the case where the curable resin composition of the present disclosure contains a flame retardant, the content of the flame retardant is not particularly limited as long as it is a sufficient amount to obtain a desired flame retardant effect. The content of the flame retardant is preferably 1 to 300 parts by mass, more preferably 2 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 also include an ion exchanger. When the curable resin composition is used as a sealing material for a semiconductor package, it is preferable to contain an inorganic filler in view of improving moisture resistance and high-temperature storage characteristics of an electronic component device including a sealed element.

The ion exchanger is not particularly limited, and a conventional ion exchanger can be used. Specifically, hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth are exemplified. The ion exchanger may be used alone or in combination of two or more. Specifically, the ion exchanger may be 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 is less than or equal to 0.5, m is a positive number)

In the case where the curable resin composition of the present disclosure 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. The content of the ion exchanger is preferably 0.1 to 30 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the epoxy resin contained in the curable resin composition.

(physical Properties of curable resin composition)

In view of the adhesion of the curable resin composition of the present disclosure to an unpicked lead frame, the linear expansion coefficient of a cured product of the curable resin composition is preferably 7 ppm/. Degree.C.to 15 ppm/. Degree.C.and more preferably 7.3 ppm/. Degree.C.to 14.5 ppm/. Degree.C.and still more preferably 7.5 ppm/. Degree.C.to 14 ppm/. Degree.C.at 10℃to 30 ℃.

In view of the adhesion of the curable resin composition of the present disclosure to an unpicked lead frame, the linear expansion coefficient of a cured product of the curable resin composition is preferably 20 ppm/. Degree.C.to 50 ppm/. Degree.C.and more preferably 24 ppm/. Degree.C.to 37 ppm/. Degree.C.and still more preferably 28 ppm/. Degree.C.to 35 ppm/. Degree.C.of the cured product is 200 to 220 ℃.

In the present disclosure, the so-called linear expansion coefficient is based on LIS K7197: 2012 and by thermo-mechanical analysis (Thermal Mechanical Analysis, TMA), the strain of the cured product is plotted against the inclination of the tangent line at the time of temperature mapping.

The test load was reset to 5g, and the temperature rise rate was set to 5℃per minute.

The linear expansion coefficient may be measured using a thermo-mechanical analysis device (e.g., TMA/SS 6100) manufactured by fine instruments (Seiko Instruments) corporation or a device of the same degree.

The cured product was produced by the following method: the curable resin composition was molded by a transfer molding machine at a mold temperature of 175℃under a molding pressure of 6.9MPa for a curing time of 90 seconds, and then post-cured at 175℃for 5 hours.

The cured product had a rectangular shape with a short side of 5.1mm, a long side of 20mm, and a thickness of 2 mm.

The glass transition temperature (Tg) of the cured product of the curable resin composition is preferably 80 to 120 ℃, more preferably 85 to 115 ℃, and even more preferably 90 to 110 ℃ from the viewpoint of heat resistance and the like.

In the present disclosure, the glass transition temperature of the cured product is set to a temperature at which a tangential line at 10 to 30 ℃ and a tangential line at 200 to 220 ℃ intersect, which is obtained by measuring the linear expansion coefficient.

In view of the adhesion of the curable resin composition of the present disclosure to an unpeeled lead frame, the cure shrinkage of the curable resin composition is preferably 0.1% to 0.8%, more preferably 0.15% to 0.75%, and 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 cured product (test piece) of the disk-shaped curable resin composition was molded by transfer molding using a mold having a size measured, and then the test piece was left to cool to 25 ℃.

After cooling to 25 ℃, the test piece was heated for 5 hours by using an oven heated to 175 ℃, and then the test piece was left to cool to 25 ℃.

After cooling, the average value of the diameters at two points on the front and back of the test piece was Rm (mm), the average value of the inner diameters at two points on the mold corresponding to the front of the test piece and the inner diameters at two points on the mold corresponding to the back of the test piece was Rd (mm), and the curing shrinkage of the curable resin composition was obtained by substituting the following formula.

Hardening shrinkage (%) = (Rd-Rm)/rd×100

The elastic modulus of the cured product of the curable resin composition at 25℃is preferably 25GPa to 38GPa, more preferably 26GPa to 33GPa.

The elastic modulus at 260℃of the cured product of the curable resin composition is preferably 0.45GPa to 0.70GPa, more preferably 0.48GPa to 0.67GPa.

The elastic modulus of the curable resin composition was determined as follows: using a viscoelasticity measuring device (TA Instruments, RSAIII), the temperature was raised from 20℃to 300℃by a three-point bending method at 5℃per minute under a span distance of 40mm and a frequency of 1 Hz. The cured product produced by the above method was used, and had a rectangular shape with a short side of 5.1mm, a long side of 20mm, 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, the following methods are listed: after the components of a predetermined amount are sufficiently mixed by a mixer or the like, melt-kneading is performed by a mixing roll, an extruder or the like, and the mixture is cooled and pulverized. More specifically, the following methods are exemplified: the components are uniformly stirred and mixed in predetermined amounts, kneaded by a kneader, a roll, an extruder, etc. preheated to 70 to 140 ℃, cooled, and pulverized.

The curable resin composition is preferably solid at 25 ℃. In the case where the curable resin composition is solid at 25 ℃, the shape of the curable resin composition is not particularly limited, and examples thereof include powder, granule, tablet, and the like. From the viewpoint of handleability, the size and quality of the sheet-like curable resin composition are preferably such that they match the molding conditions of the package.

(use of curable resin composition)

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

< electronic parts device >

The electronic component device of the present disclosure includes an element and a cured product of the curable resin composition sealing the element.

The electronic component device may include a support member on which the element is mounted.

As the support member, there may be mentioned: lead frames, carrier tapes after wiring, wiring boards, glass, silicon wafers, organic substrates, and the like. The support member is preferably a lead frame in terms of adhesion to a cured product of the curable resin composition.

The surface of the lead frame may be roughened or may not be roughened, and is preferably an unglazed lead frame from the viewpoint of manufacturing cost, and is preferably a roughened lead frame from the viewpoint of adhesion.

The roughening method is not particularly limited, and examples thereof include alkali treatment, silane coupling treatment, sand bedding treatment, plasma treatment, corona discharge treatment, and the like.

The lead frame may include a plating layer including at least one of Au, pd, and Ni on at least a portion of the surface.

The plating layer may be a single layer or a plurality of layers. Examples of the multilayered plating layer include a plating layer having a three-layer structure in which a Ni-plated layer, a Pd-plated layer, and an Au-plated layer are laminated from the lead frame side.

Examples of the three-layer lead frame include a lead frame obtained by plating a copper lead frame called PPF (preplated lead frame (Pre Plating Lead Flame)) with ni—pd—au.

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

Examples of the element included in the electronic component device include an active element such as a silicon chip, a transistor, a diode, and a thyristor, and a passive element such as a capacitor, a resistor, and a coil.

The specific configuration of the electronic component device is as follows, but is not limited thereto.

(1) 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 are connected by wire bonding, bumps, etc., and then sealed with a curable resin composition;

(2) A tape carrier package (Tape Carrier Package, TCP) having a structure in which a component connected to a tape carrier by a bump is sealed with a curable resin composition;

(3) A Chip On Board (COB) module, a hybrid IC, a polycrystalline module, or the like, which has a structure in which an element connected to a wiring formed On a support member by wire bonding, flip Chip bonding, solder, or the like is sealed with a curable resin composition;

(4) Ball Grid Array (BGA), chip size package (Chip Size Package, CSP), multi-chip package (Multi Chip Package, MCP), system in package (System in a Package, siP) and the like, which has a structure in which an element is mounted on the surface of a support member having wiring board connection terminals formed on the back surface thereof, the element is connected to wiring formed on the support member by bump or wire bonding, and then the element is sealed by a curable resin composition

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

Examples

Hereinafter, the present disclosure will be specifically described with reference to examples, but the present disclosure is not limited to these examples. Unless otherwise specified, the numerical values in the table refer to "parts by mass".

(examples 1 to 7 and comparative examples 1 to 6)

After premixing (dry blending) the materials of the formulations shown in Table 1, they were kneaded by a biaxial roll (roll surface temperature: about 80 ℃ C.) for about 15 minutes, cooled and pulverized to prepare powdery curable resin compositions.

Details of the materials in table 1 are as follows.

Epoxy resin a: a copolymerized epoxy resin having the following structural unit: melt viscosity at 150℃at 250 g/eq: 0.7 dPa.s

[ chemical 27]

Epoxy resin B: biphenyl type epoxy resin with epoxy equivalent weight of 220 g/eq-250 g/eq

Hardening agent: aralkyl type phenol resin, hydroxyl equivalent 175g/eq

Linear polysiloxane compound: a linear polysiloxane represented by the following chemical formula (melting point: 70 ℃ below zero, epoxy equivalent weight 120g/eq to 150g/eq, wherein n represents a number of 3 to 6, R) ⁶ Each independently represents methoxy or hydroxy; hydroxy relative to R ⁶ The total content of methoxy groups and hydroxyl groups represented by the formula is 5 to 50 mol%)

[ chemical 28]

Inorganic filler: spherical silica particles having a volume average particle diameter of 19.9 μm

Hardening accelerator: 1, 4-benzoquinone adduct of triphenylphosphine

Coupling agent A: n-phenyl-3-aminopropyl trimethoxysilane

Coupling agent B: 3-glycidoxypropyl trimethoxysilane

Coupling agent C: 3-glycidoxypropyl methyldimethoxy silane

Stress-relieving agent: branched polysiloxane compounds which are solid at 25 DEG C

Mold 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. The evaluation results are shown in table 1.

The formation of the cured product using the curable resin composition is performed by the following method unless explicitly described otherwise: after molding at a mold temperature of 175℃and a molding pressure of 6.9MPa for 90 seconds by a transfer molding machine, post-curing was performed at 175℃and 5 hours.

< measurement of coefficient of linear expansion >

Based on the above conditions, cured products of the curable resin compositions obtained in the examples and comparative examples were formed. The cured product was a rectangular cured product having a short side of 5.1mm, a long side of 20mm, and a thickness of 2 mm.

Then, based on JIS K7197: 2012, and the inclination ratio of the strain of the cured product with respect to the tangent line when the temperature is plotted is determined by a thermo-mechanical analysis method in the range of 10 to 30 ℃ and in the range of 200 to 220 ℃, respectively. Table 1 shows that the inclination ratio of the tangent line in the range of 10℃to 30℃is CTE1, and the inclination ratio of the tangent line in the range of 200℃to 220℃is CTE 2.

Further, a TMA high-precision two-sample thermal analyzer (device name SS 6100) manufactured by fine instruments (Seiko Instruments) corporation was used for the measurement of the linear expansion coefficient.

< glass transition temperature (Tg) of cured product >

The temperature at the intersection point of the tangential line at 10 to 30 ℃ and the tangential line at 200 to 220 ℃ obtained by the measurement of the linear expansion coefficient is set as the glass transition temperature of the cured product.

< measurement of cure shrinkage >

The disk-shaped cured products (test pieces) of the curable resin compositions obtained in the examples and comparative examples were molded by transfer molding under conditions of a mold temperature of 175℃and a molding pressure of 6.9MPa and a curing time of 90 seconds using a mold having a size measured, and then the test pieces were left to cool to 25 ℃.

Hardening shrinkage (%) = (Rd-Rm)/rd×100

< measurement of elastic modulus >

Based on the above conditions, a cured product similar to that used for measuring the linear expansion coefficient was formed.

The elastic modulus at each temperature of 25℃and 260℃was determined by heating from 20℃to 300℃at 5℃per minute using a viscoelasticity measuring apparatus (manufactured by TA Instruments, RSAIII) with a span distance of 40mm and a frequency of 1Hz by a three-point bending method.

< evaluation of adhesion >

Based on the conditions, the curable resin compositions obtained in the examples and comparative examples were fabricated into cylinders having a contact area of 3mm phi on the surface of a copper alloy sheet (Pd-PPF).

Thereafter, the temperature of the copper alloy sheet was kept at 25℃using a bond strength tester (DAGE JAPAN Co., ltd., series 4000), and the shear adhesion (MPa) was determined at a shear rate of 50 μm/s.

After heating the cured product at 85℃and 60% RH for 168 hours, the temperature of the copper alloy sheet was kept at 260℃and the shear adhesion (MPa) was determined at a shear rate of 50 μm/s.

< evaluation of reflow resistance >

An 80-pin flat package (lead frame material: copper alloy (Pd-PPF)) was fabricated on which a silicon chip (8 mm in the longitudinal direction, 10mm in the transverse direction, 0.4mm in the thickness) sealed with a cured product of a curable resin composition formed under the above conditions was mounted, the external dimensions of which were 20mm in the longitudinal direction, 14mm in the transverse direction, and 2mm in the thickness.

The package was heated at 85 ℃ at 60% rh for 168 hours.

Thereafter, reflow treatment was performed at 260℃for 10 seconds, and the outside of the package was visually inspected for cracks, and the inside of the package was inspected for the occurrence of peeling by an ultrasonic flaw detector (HYE-FOCUS, manufactured by Hitachi-Makeup Co., ltd.). Reflow resistance was evaluated with respect to the number of test packages (64) by the sum of the number of packages in which any of cracks and peeling occurred.

< flowability evaluation (spiral flow) >

The curable resin composition was molded using a mold for spiral flow measurement according to EMMI-1-66 under conditions of a mold temperature of 180 ℃, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and a flow distance (cm) was obtained.

TABLE 1

As is clear from table 1, according to the curable resin composition of the present disclosure, a curable resin composition having excellent adhesion to an unpainted lead frame and excellent reflow resistance can be provided.

The entire disclosure of japanese patent application No. 2021-035808, filed on 3/5 of 2021, is incorporated by reference into the present specification. All documents, patent applications, and technical specifications described in this specification are incorporated by reference into this specification to the same extent as if each document, patent application, and technical specification were specifically and individually indicated to be incorporated by reference.

Claims

1. A curable resin composition comprising: an epoxy resin; a hardening agent; and a linear polysiloxane compound having a structural unit containing an epoxy group and an alkoxy group, and having a degree of polymerization of 3 or more.

2. The curable resin composition according to claim 1, wherein the structural unit is represented by the following general formula (1).

[ chemical 1]

In the general formula (1),

R ¹ represents an epoxy-containing group and is preferably a hydroxyl group,

R ² an alkoxy group having 1 to 10 carbon atoms.

3. 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).

[ chemical 2]

In the general formula (2),

R ¹ represents an epoxy-containing group.

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

[ chemical 3]

In the general formula (3),

* The bonding position with Si is shown.

5. 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).

[ chemical 4]

In the general formula (4),

R ¹ represents an epoxy-containing group and is preferably a hydroxyl group,

n represents an integer of 1 or more,

wherein at least one R ⁶ An alkoxy group having 1 to 10 carbon atoms.

6. 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.

[ chemical 5]

Wherein n is a number of 1 to 10.

8. The curable resin composition according to any one of claims 1 to 7, wherein the hardener comprises a phenolic hardener.

9. The curable resin composition according to claim 8, wherein the phenolic hardener comprises an aralkyl type phenolic resin.

10. The curable resin composition according to any one of claims 1 to 9, wherein the linear polysiloxane compound is liquid at 25 ℃.

11. The curable resin composition according to any one of claims 1 to 10, wherein the number of the structural units contained in the linear polysiloxane compound is 15 or less.

12. The curable resin composition according to any one of claims 1 to 11, wherein the linear polysiloxane compound has a content of 0.05 to 5 mass% relative to the total mass of the 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 claims 1 to 12 sealing the element.

14. The electronic component device according to claim 13, comprising a lead frame, wherein the element is mounted on one surface of the lead frame.

15. The electronic component device according to claim 14, wherein at least a portion of the surface of the lead frame includes a plating layer containing at least one of Au, pd, and Ni.