Resin composition for sealing and electronic component device

Abstract

The encapsulating resin composition includes: a first epoxy resin having an epoxy equivalent of 200 g / eq or more, a plurality of naphthalene skeletons in the molecule, and ether bonds between at least some of the naphthalene skeletons; a second epoxy resin having a viscosity at 150°C of 0.02 Pa·sec or less and a number average molecular weight of 1,000 or less; and a curing agent.

Description

Technical Field

[0001] The present invention relates to a resin composition for sealing and an electronic component device.

Background Art

[0002] With the recent miniaturization, weight reduction, and high performance of electronic devices, the density of mounting has been increasing. As a result, the mainstream of electronic component devices is changing from conventional pin insertion type packages to surface mounting type packages.

[0003] The mounting method of surface mounting type packages is different from that of conventional pin insertion type packages. That is, when attaching pins to a wiring board, in the conventional pin insertion type package, after inserting the pins into the wiring board, soldering is performed from the back surface of the wiring board, so the package is not directly exposed to high temperatures. However, in the surface mounting type package, since the entire electronic component device is processed by a solder bath, a reflow device, etc., the package is directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the moisture due to moisture absorption expands rapidly during soldering, and the generated vapor pressure acts as a peeling stress, causing peeling between inserts such as elements and lead frames and the encapsulant, which may cause package cracks, poor electrical characteristics, etc. For this reason, the development of a sealing material with excellent solder heat resistance (reflow resistance) is desired.

[0004] In order to meet these requirements, various studies have been made on epoxy resins, which are the main materials of the sealing material. For example, as an epoxy resin, a method of using a biphenyl type epoxy resin or a naphthalene type epoxy resin has been studied (see, for example, JP-A-64-65116 and JP-A-2007-231159).

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, there has been a demand for the development of a mold underfill material (hereinafter also referred to as "MUF material") used in the double side mold (DSM, hereinafter also referred to as "DSM") method in which chips are mounted on both the upper and lower surfaces of a substrate for high-density mounting.

[0006] As described above, the encapsulant used for surface-mount packages is required to have reflow resistance. In particular, in the DSM method, since the package structure is complex and has a high density, higher reflow resistance is required. The reflow resistance is improved by reducing the water absorption rate, reducing the elastic modulus at high temperature (for example, 260 °C), and the like. On the other hand, in order to improve the reliability in a high-temperature environment, it is also required to increase the glass transition temperature (for example, to 150 °C or higher) after the encapsulant is cured. However, for example, if an attempt is made to increase the glass transition temperature by increasing the number of crosslinking points, the reflow resistance tends to decrease, and it is difficult to achieve both a high glass transition temperature and high reflow resistance. Furthermore, fluidity is required for the encapsulant used for surface-mount packages. In particular, in the DSM method package, since the chips are arranged at a high density, the MUF material used for the DSM method package is required to have particularly high fluidity that can fill narrow gaps. However, for example, if an attempt is made to improve the fluidity by containing a low-viscosity component, the glass transition temperature tends to decrease, and it is difficult to achieve both high fluidity and a high glass transition temperature.

[0007] The present disclosure has been made in view of such circumstances, and an object thereof is to provide a sealing resin composition that can obtain a cured product having both a low elastic modulus at high temperature and a high glass transition temperature, and having high fluidity, and an electronic component device using the same.

Means for Solving the Problems

[0008] Means for solving the above problems include the following embodiments. <1> A first epoxy resin having an epoxy equivalent of 200 g / eq or more, having a plurality of naphthalene skeletons in the molecule, and having an ether bond in at least a part between the plurality of naphthalene skeletons, a second epoxy resin having a viscosity at 150 °C of 0.02 Pa·sec or less and a number average molecular weight of 1000 or less, a curing agent, and a resin composition for encapsulation containing the same. <2> The resin composition for encapsulation according to <1>, wherein the second epoxy resin contains at least one selected from the group consisting of a biphenyl type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin. <3> The resin composition for encapsulation according to <1> or <2>, wherein the viscosity of the curing agent at 150 °C is 0.15 Pa·sec or less. <4> The resin composition for encapsulation according to any one of <1> to <3>, wherein the functional group equivalent of the curing agent is 120 g / eq to 200 g / eq. <5> The resin composition for encapsulation according to any one of <1> to <4>, wherein the first epoxy resin has at least two naphthalene skeletons directly bonded to one ether bond in the molecule. <6> The resin composition for encapsulation according to any one of <1> to <5>, wherein the first epoxy resin has three naphthalene skeletons in the molecule. <7> The resin composition for encapsulation according to any one of <1> to <6>, wherein all of the plurality of naphthalene skeletons in the molecule of the first epoxy resin are directly bonded to the ether bond. <8> The resin composition for encapsulation according to any one of <1> to <7>, wherein the content of the second epoxy resin with respect to 100 parts by mass of the first epoxy resin is 3 parts by mass to 70 parts by mass. <9> The resin composition for encapsulation according to any one of <1> to <8>, wherein the curing agent contains at least one selected from the group consisting of a phenol resin and a polyhydric phenol compound. <10> The phenolic resin-containing sealing resin composition according to <9>, wherein the phenolic resin contains at least one selected from the group consisting of novolak-type phenolic resins, aralkyl-type phenolic resins, and triphenylmethane-type phenolic resins. <11> The sealing resin composition according to <9> or <10>, wherein the phenolic resin contains an aralkyl-type phenolic resin. <12> The sealing resin composition according to any one of <1> to <11>, wherein the curing agent contains a compound having a biphenyl skeleton in the molecule. <13> An electronic component device including an element and a cured product of the sealing resin composition according to any one of <1> to <12> that seals the element.

Advantages of the Invention

[0009] According to the present disclosure, it is possible to provide a cured product that achieves both a low elastic modulus at high temperatures and a high glass transition temperature, and a sealing resin composition having high fluidity and an electronic component device using the same.

Modes for Carrying Out the Invention

[0010] Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present invention.

[0011] In the present disclosure, in the numerical range indicated by using "~", the numerical values described before and after "~" are included as the minimum value and the maximum value, respectively. In the numerical ranges described step by step 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 step-by-step descriptions. Also, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. In the present disclosure, each component may contain a plurality of corresponding substances. When there are a plurality of substances corresponding to each component in the composition, the content rate of each component means the total content rate of the plurality of substances present in the composition, unless otherwise specified.

[0012] <Sealing resin composition> The sealing resin composition according to the present disclosure (hereinafter also simply referred to as "composition") includes a first epoxy resin having an epoxy equivalent of 200 g / eq or more, having a plurality of naphthalene skeletons in the molecule, and having an ether bond in at least a part between the plurality of naphthalene skeletons, a second epoxy resin having a viscosity at 150°C of 0.02 Pa·sec or less and a number average molecular weight of 1000 or less, and a curing agent. The above composition can obtain a cured product that combines low elastic modulus at high temperature (hereinafter also referred to as "low elastic modulus at high temperature") and high glass transition temperature (hereinafter also referred to as "high Tg"), and has high fluidity.

[0013] As described above, for the sealing resin composition used for sealing surface mount packages, a low elastic modulus at high temperature of the cured product is required to improve the reflow resistance, while a high Tg of the cured product is required to improve the reliability in a high temperature environment. Also, for the above sealing resin composition, it is required that the composition itself has high fluidity so that it can be injected into a narrow gap. In particular, as described above, for the sealing resin composition used in DSM, the above low elastic modulus at high temperature, high Tg, and high fluidity are required at high levels respectively. However, it is difficult to achieve both a high temperature low elastic modulus and a high Tg for the cured product. Specifically, for example, when the number of crosslinking points of the resin is increased, the glass transition temperature of the cured product tends to be high, but the elastic modulus at high temperatures also tends to be high. When the number of crosslinking points of the resin is decreased, not only does the elastic modulus of the cured product at high temperatures decrease, but the glass transition temperature also tends to be low. Also, it is difficult to achieve both a high Tg and high fluidity. Specifically, when a low-viscosity component is contained to improve fluidity, the glass transition temperature of the cured product tends to be low.

[0014] In contrast, the composition of the present disclosure includes a first epoxy resin having an ether bond in at least a part between a plurality of naphthalene skeletons and an epoxy equivalent within the above range, and a second epoxy resin having a viscosity and a number average molecular weight at 150 °C within the above range. Therefore, high fluidity can be obtained while achieving both a high temperature low elastic modulus and a high Tg for the cured product. The reason is not clear, but it is presumed that since the first epoxy resin has a plurality of naphthalene skeletons, a high Tg of the cured product can be obtained even if the epoxy equivalent is large, and since there is an ether bond between the naphthalene skeletons, a high temperature low elastic modulus of the cured product can be obtained. In addition, although the reason is not clear, for example, compared with the case where a polyfunctional cresol novolak type epoxy resin with a small epoxy equivalent is used instead of the first epoxy resin, the decrease in the glass transition temperature when combined with the second epoxy resin is small. Therefore, it is presumed that high fluidity can be obtained while achieving both a high temperature low elastic modulus and a high Tg for the cured product. In addition, since the composition of the present disclosure includes the first epoxy resin and the second epoxy resin, a cured product with a low water absorption rate can be obtained.

[0015] Hereinafter, each component constituting the composition of the present disclosure will be described in detail.

[0016] (Epoxy Resin) The composition of the present disclosure includes, as an epoxy resin, at least a first epoxy resin and a second epoxy resin, and may include other epoxy resins as necessary. However, the total content ratio of the first epoxy resin and the second epoxy resin is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more based on the total epoxy resin contained in the composition.

[0017] - First epoxy resin - The first epoxy resin is not particularly limited as long as it has an epoxy equivalent of 200 g / eq or more, has a plurality of naphthalene skeletons in the molecule, and has an ether bond in at least a part between the plurality of naphthalene skeletons. The first epoxy resin may be used alone or in combination of two or more.

[0018] From the viewpoint of achieving both a low high-temperature elastic modulus and a high Tg of the cured product, the epoxy equivalent in the first epoxy resin is preferably 200 g / eq to 300 g / eq, more preferably 200 g / eq to 270 g / eq, and even more preferably 200 g / eq to 240 g / eq. Here, the epoxy equivalent is measured by dissolving the weighed epoxy resin in a solvent such as methyl ethyl ketone, adding acetic acid and a tetraethylammonium acetate solution of bromide, and then performing potentiometric titration with a perchloric acid acetate standard solution. An indicator may be used for this titration.

[0019] The number average molecular weight of the first epoxy resin is not particularly limited as long as the epoxy equivalent is in the above range, and examples thereof include a range of 50 to 3000. From the viewpoint of fluidity, it is preferably 50 to 2000, and more preferably 50 to 800. The number average molecular weight is measured by a usual method using gel permeation chromatography (GPC).

[0020] When the first epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of handleability in the preparation of the encapsulating resin composition, the softening point or melting point is preferably 50°C to 130°C, more preferably 50°C to 100°C, and even more preferably 50°C to 70°C. Note that the melting point of the epoxy resin is the value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is the value measured by the method (ring and ball method) according to JIS K 7234:1986.

[0021] From the viewpoint of achieving both fluidity and a high Tg of the cured product, the viscosity of the first epoxy resin at 150°C is preferably 0.01 Pa·sec to 0.2 Pa·sec, more preferably 0.02 Pa·sec to 0.1 Pa·sec, and even more preferably 0.03 Pa·sec to 0.07 Pa·sec. Here, the viscosity at 150°C is measured with a rheometer MCR301 (Anton Paar). Specifically, a temperature decrease process of decreasing the temperature of the measurement object from 150°C to 30°C and a temperature increase process of increasing the temperature of the measurement object from 30°C to 150°C are carried out in this order, and the viscosity (Pa·sec) at 150°C in the temperature increase process is measured. The measurement conditions are: frequency: 1 Hz, plate: φ12 mm, gap: 0.2 mm, temperature decrease rate in the temperature decrease process: 2°C / min, and temperature increase rate in the temperature increase process: 2°C / min.

[0022] The number of multiple naphthalene skeletons in one molecule of the first epoxy resin is not particularly limited as long as it is at least 2 or more, and examples include the range of 2 to 6, preferably 2 to 5, more preferably 2 to 4, and most preferably 3.

[0023] The first epoxy resin only needs to have at least 1 or more ether bonds connecting between multiple naphthalene skeletons in one molecule, and may have 2 or more, and preferably has them in the range of 2 to 5. In addition, when the first epoxy resin has two naphthalene skeletons in one molecule, it has an ether bond between the two naphthalene skeletons. On the other hand, when the first epoxy resin has three or more naphthalene skeletons in one molecule, at least some of the naphthalene skeletons among the plurality of naphthalene skeletons may have an ether bond, and it is preferable that all of the naphthalene skeletons have an ether bond.

[0024] Between the naphthalene skeletons having an ether bond, they may have other linking groups (hydrocarbon groups such as alkylene groups, carbonyl groups, etc.) other than the ether bond, and may have two or more ether bonds. Among them, it is preferable to have only one ether bond. That is, the two naphthalene skeletons bonded via an ether bond may be bonded via an ether bond and other linking groups, or may be bonded via two or more ether bonds. Among them, it is preferable to be directly bonded to one ether bond. That is, it is preferable that the first epoxy resin has two naphthalene skeletons directly bonded to one ether bond in the molecule. In addition, it is preferable that all of the plurality of naphthalene skeletons possessed by the first epoxy resin are directly bonded to an ether bond.

[0025] The first epoxy resin has at least two or more epoxy groups in one molecule. The number of epoxy groups that the first epoxy resin has in one molecule is not particularly limited as long as the epoxy equivalent in the first epoxy resin is in the above range, and examples include 2 to 8, preferably 2 to 6, more preferably 2 to 3, and particularly preferably 2. The above two or more epoxy groups may be bonded to one naphthalene skeleton or to different naphthalene skeletons, and among them, it is preferable that they are bonded to different naphthalene skeletons. Further, when the first epoxy resin has three or more naphthalene skeletons, the epoxy group may be bonded to the terminal naphthalene skeleton (that is, the naphthalene skeleton to which only one other naphthalene skeleton is bonded), or to a naphthalene skeleton other than the terminal (that is, the naphthalene skeleton to which a plurality of other naphthalene skeletons are bonded), and among them, it is preferable that the epoxy group is bonded to at least the terminal naphthalene skeleton.

[0026] The epoxy group may be directly bonded to the naphthalene skeleton or may be bonded to the naphthalene skeleton via a linking group (a hydrocarbon group such as an alkylene group, a carbonyl group, an oxygen atom, etc.), and among them, it is preferable that the epoxy group is bonded to the naphthalene skeleton via a linking group. Examples of the form in which the epoxy group is bonded to the naphthalene skeleton via a linking group include a form in which at least one selected from a glycidyl group, a glycidyloxy group, a glycidyloxycarbonyl group, an epoxycycloalkyl group (an epoxycyclopentyl group, an epoxycyclohexyl group, an epoxycyclooctyl group, etc.) is directly bonded to the naphthalene skeleton, and among them, a form in which the glycidyloxy group is directly bonded to the naphthalene skeleton is preferable.

[0027] The first epoxy resin may further have other substituents (an alkyl group, an alkoxy group, an aryl group, an aralkyl group, an amino group, etc.).

[0028] Examples of the first epoxy resin include an epoxy resin represented by the following general formula (I).

[0029]

Chemical formula

[0030] In the above general formula (I), R 1 ~R 6independently represents a monovalent organic group having 1 to 18 carbon atoms, a1 to a6 independently represent an integer of 0 to 3, and m represents 0 to 4.

[0031] R in the general formula (I) 1 ~R 6 Examples of the monovalent organic group having 1 to 18 carbon atoms represented by include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a glycidyloxy group, and the like. In the general formula (I), a1 to a6 are preferably an integer of 0 to 1, and more preferably 0. In the general formula (I), m is preferably 0 to 2, and more preferably 1.

[0032] The content of the first epoxy resin with respect to the total epoxy resin contained in the composition is preferably 30% by mass to 99% by mass, more preferably 40% by mass to 98% by mass, and even more preferably 60% by mass to 95% by mass. Also, the content of the first epoxy resin with respect to the total of the resin components contained in the composition is preferably 20% by mass to 90% by mass, more preferably 25% by mass to 80% by mass, and even more preferably 30% by mass to 70% by mass. Also, the content of the first epoxy resin with respect to the whole composition is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, and even more preferably 3% by mass to 10% by mass.

[0033] -Second Epoxy Resin- The second epoxy resin is an epoxy resin other than the first epoxy resin, and is not particularly limited as long as it is an epoxy resin having a viscosity at 150 °C of 0.02 Pa·sec or less and a number average molecular weight of 1000 or less. The second epoxy resin may be used alone or in combination of two or more.

[0034] The viscosity of the second epoxy resin at 150 °C is 0.02 Pa·sec or less, and from the viewpoints of fluidity and high Tg, it is preferably 0.0001 Pa·sec to 0.02 Pa·sec, more preferably 0.001 Pa·sec to 0.02 Pa·sec, and even more preferably 0.005 Pa·sec to 0.02 Pa·sec.

[0035] The number average molecular weight of the second epoxy resin is 1000 or less, and from the viewpoints of fluidity and high Tg, it is preferably 150 to 850, more preferably 200 to 700, and even more preferably 300 to 600.

[0036] The epoxy equivalent in the second epoxy resin is not particularly limited as long as the viscosity and the number average molecular weight at 150 °C are within the above ranges, and examples thereof include 150 g / eq to 300 g / eq. From the viewpoint of curability, 165 g / eq to 275 g / eq is preferable, and more preferably 180 g / eq or more and less than 250 g / eq.

[0037] [[ID=eleven]] When the second epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of handleability during the preparation of the encapsulating resin composition, the softening point or melting point is preferably 50 °C to 130 °C, more preferably 75 °C to 125 °C, and even more preferably 100 °C to 120 °C.

[0038] Specific examples of the second epoxy resin include novolak epoxy resins obtained by epoxidizing novolak resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst (phenol novolak epoxy resins, orthocresol novolak epoxy resins, etc.); triphenylmethane-type epoxy resins obtained by epoxidizing triphenylmethane-type phenolic resins obtained by condensing or co-condensing the above phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; copolymer-type epoxy resins obtained by epoxidizing novolak resins obtained by co-condensing the above phenolic compounds and naphthol compounds with aldehyde compounds under an acidic catalyst; diphenylmethane-type epoxy resins which are diglycidyl ethers such as bisphenol A and bisphenol F; biphenyl-type epoxy resins which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenol; stilbene-type epoxy resins which are diglycidyl ethers of stilbene-based phenolic compounds; sulfur atom-containing epoxy resins which are diglycidyl ethers such as bisphenol S; epoxy resins which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins which are glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine-type epoxy resins in which active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, and isocyanuric acid is substituted with a glycidyl group; dicyclopentadiene-modified epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenolic compound;Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, etc., which are obtained by epoxidizing the olefin bond within the molecule; Para-xylylene modified epoxy resin, which is the glycidyl ether of para-xylylene modified phenolic resin; Meta-xylylene modified epoxy resin, which is the glycidyl ether of meta-xylylene modified phenolic resin; Terpene modified epoxy resin, which is the glycidyl ether of terpene modified phenolic resin; Dicyclopentadiene modified epoxy resin, which is the glycidyl ether of dicyclopentadiene modified phenolic resin; Cyclopentadiene modified epoxy resin, which is the glycidyl ether of cyclopentadiene modified phenolic resin; Polycyclic aromatic ring modified epoxy resin, which is the glycidyl ether of polycyclic aromatic ring modified phenolic resin; Naphthalene type epoxy resin, which is the glycidyl ether of naphthalene ring-containing phenolic resin; Halogenated phenolic novolak type epoxy resin; Hydroquinone type epoxy resin; Trimethylolpropane type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing the olefin bond with a peracid such as peracetic acid; Aralkyl type epoxy resin, which is obtained by epoxidizing aralkyl type phenolic resins such as phenol aralkyl resin and naphthol aralkyl resin; and the like. Furthermore, epoxy compounds of silicone resins, epoxy compounds of acrylic resins, etc. are also mentioned as epoxy resins.;

[0039] From the viewpoint of the balance between reflow resistance and fluidity, the second epoxy resin is preferably a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom-containing type epoxy resin, a novolak type epoxy resin, a dicyclopentadiene-modified epoxy resin, a triphenylmethane type epoxy resin, a copolymer type epoxy resin, or an aralkyl type epoxy resin. Further, from the viewpoint of fluidity, a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, and a sulfur atom-containing type epoxy resin are more preferable, a biphenyl type epoxy resin, a diphenylmethane type epoxy resin, and a sulfur atom-containing type epoxy resin are further preferable. Among the biphenyl type epoxy resin, the diphenylmethane type epoxy resin, a bisphenol F type epoxy resin having a bisphenol F skeleton is particularly preferable, and among the sulfur atom-containing type epoxy resins, a bisphenol S type epoxy resin having a bisphenol S skeleton is particularly preferable, and a biphenyl type epoxy resin is extremely preferable. In addition, the second epoxy resin is preferably an epoxy resin having no naphthalene skeleton or having one naphthalene skeleton, and an epoxy resin having a plurality of naphthalene skeletons and no ether bond connecting between the naphthalene skeletons. An epoxy resin having no plurality of naphthalene skeletons is more preferable, and an epoxy resin having no naphthalene skeleton is further preferable.

[0040] The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferable. Among the epoxy resins represented by the following general formula (II), when the positions where oxygen atoms are substituted among Rs are the 4- and 4'-positions, the 3, 3', 5, 5'-positions are methyl groups, and the other Rs 8 are hydrogen atoms, YX-4000H (Mitsubishi Chemical Corporation, trade name), all Rs 8 are hydrogen atoms, 4,4'-bis(2,3-epoxypropoxy)biphenyl, all Rs 8 are hydrogen atoms, and when all Rs 8 are hydrogen atoms and Rs 8Among them, when the positions substituted by oxygen atoms are the 4- and 4'-positions, the 3,3',5,5'-positions are methyl groups and the other R 8 YL-6121H (Mitsubishi Chemical Corporation, trade name), etc., which are mixed products when R is a hydrogen atom, are available as commercial products.

[0041]

Chemical formula

[0042] 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, and all of them may be the same or different. n is an average value and represents a number from 0 to 2. In formula (II), R 8 is preferably independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. Also, in formula (II), n is preferably 0 or 1, more preferably 0.

[0043] 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. Among the epoxy resins represented by the following general formula (III), when the positions substituted by oxygen atoms are the 4- and 4'-positions, the 3,3',5,5'-positions are methyl groups, and the other R 9 is a hydrogen atom, and a mixture of the case where all of R 9 are hydrogen atoms and the case where three of the 3,3',5,5'-positions of R 10 are methyl groups and one is a t-butyl group, and the other R 9 is a hydrogen atom, and all of R 9 are hydrogen atoms, such as ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), etc., are available as commercial products. 10 is a hydrogen atom, and a mixture of the case where all of R

[0044]

Chemical formula

[0045] In formula (III), R 9 and R 10 each 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 an average value and represents a number from 0 to 2. In addition, in formula (III), R 9 and R 10 each independently represents a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, in formula (III), n is preferably 0 or 1, more preferably 0.

[0046] The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. Among them, an epoxy resin represented by the following general formula (IV) is preferred, and a bisphenol F type epoxy resin which is an epoxy resin having a bisphenol F skeleton is more preferred. Among the epoxy resins represented by the following general formula (IV), when all of R 11 are hydrogen atoms, and when the positions where oxygen atoms are substituted among R 12 are the 4- and 4'-positions, the 3,3',5,5'-positions are methyl groups, and the other R 12 are hydrogen atoms, YSLV-80XY (bisphenol F type epoxy resin, Nippon Steel Chemical & Material Co., Ltd., trade name) and the like are commercially available.

[0047]

Chemical formula

[0048] In formula (IV), R 11 and R 12 each 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 an average value and represents a number from 0 to 2. In addition, in formula (IV), R 11 and R 12Each is independently preferably a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. In formula (IV), n is preferably 0 or 1, more preferably 0.

[0049] The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. Among them, an epoxy resin represented by the following general formula (V) is preferable, and a bisphenol S-type epoxy resin, which is an epoxy resin having a bisphenol S skeleton, is more preferable. Among the epoxy resins represented by the following general formula (V), when the positions where oxygen atoms are substituted among R 13 are the 4- and 4'-positions, the 3,3'-positions are t-butyl groups, the 6,6'-positions are methyl groups, and the other R 13 is a hydrogen atom, YSLV-120TE (bisphenol S-type epoxy resin, Nippon Steel Chemical & Material Co., Ltd., trade name) and the like are commercially available.

[0050]

Chemical formula

[0051] 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 from each other. n is an average value and represents a number from 0 to 2. In formula (V), R 13 is independently preferably a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In formula (V), n is preferably 0 or 1, more preferably 0.

[0052] The content of the second epoxy resin with respect to the total epoxy resin contained in the composition is preferably 1% by mass to 70% by mass, more preferably 2% by mass to 60% by mass, still more preferably 5% by mass to 50% by mass, particularly preferably 5% by mass to 40% by mass, extremely preferably 8% by mass to 40% by mass, and most preferably 10% by mass to 30% by mass. The content of the second epoxy resin with respect to 100 parts by mass of the first epoxy resin is preferably 3 to 70 parts by mass, more preferably 5 to 50 parts by mass, still more preferably 10 to 40 parts by mass, and particularly preferably 15 to 35 parts by mass. Also, the content rate of the second epoxy resin with respect to the total of the resin components contained in the composition is preferably 5% to 25% by mass, more preferably 8% to 20% by mass, and still more preferably 10% to 15% by mass. Also, the content rate of the second epoxy resin with respect to the whole composition is preferably 0.5% to 3% by mass, more preferably 0.8% to 2% by mass, and still more preferably 1% to 1.5% by mass.

[0053] (Hardener) The composition contains at least one kind of hardener. The hardener may be one generally used in a sealing resin composition containing an epoxy resin, and there is no particular limitation. Examples of the hardener include phenolic hardeners, amine hardeners, acid anhydride hardeners, polymercaptan hardeners, polyaminoamide hardeners, isocyanate hardeners, blocked isocyanate hardeners, etc. From the viewpoint of obtaining an epoxy resin composition having excellent reflow resistance while maintaining fluidity, phenolic hardeners, amine hardeners, and acid anhydride hardeners are preferable, and phenolic hardeners are more preferable.

[0054] Examples of phenolic curing agents include phenolic resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenyl; phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc. At least one phenolic compound selected from the group consisting of, and aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, etc., a novolak-type phenolic resin obtained by condensing or co-condensing under an acidic catalyst; an aralkyl-type phenolic resin (phenol aralkyl resin, naphthol aralkyl resin, etc.) synthesized from the above phenolic compound and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc.; a paraxylylene-modified phenolic resin; a metaxylylene-modified phenolic resin; a melamine-modified phenolic resin; a terpene-modified phenolic resin; a dicyclopentadiene-modified phenolic resin and a dicyclopentadiene-modified naphthol resin synthesized by copolymerizing the above phenolic compound and dicyclopentadiene; a cyclopentadiene-modified phenolic resin; a polycyclic aromatic ring-modified phenolic resin; a biphenyl-type phenolic resin; a triphenylmethane-type phenolic resin obtained by condensing or co-condensing the above phenolic compound and aromatic aldehyde compounds such as benzaldehyde, salicylaldehyde, etc. under an acidic catalyst; a phenolic resin obtained by copolymerizing two or more of these; and the like. These phenolic resins and polyhydric phenol compounds may be used alone or in combination of two or more. Among these, novolac-type phenolic resins, aralkyl-type phenolic resins, and triphenylmethane-type phenolic resins are preferable as the phenolic curing agent, aralkyl-type phenolic resins are more preferable, and phenolic resins represented by the following general formula (VI) are even more preferable. Further, the phenolic curing agent preferably has a biphenyl skeleton in the molecule, and an aralkyl-type phenolic resin having a biphenyl skeleton is more preferable.

[0055]

Chemical formula

[0056] In the above general formula (VI), R 21 ~R 25 each independently represents a monovalent organic group having 1 to 18 carbon atoms, b1 to b3 each independently represents an integer of 0 to 4, b4 to b5 each independently represents an integer of 0 to 3, n1 represents 0 to 3, and n2 represents 0 to 3.

[0057] Examples of the monovalent organic group having 1 to 18 carbon atoms represented by R 21 ~R 25 in the general formula (VI) include substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, and substituted or unsubstituted aralkyl groups. In the general formula (VI), b1 to b5 are preferably integers of 0 to 1, and more preferably 0. In the general formula (VI), n1 is preferably 0 to 2, and more preferably 0 to 1. In the general formula (VI), n2 is preferably 0 to 2, and more preferably 0 to 1.

[0058] The functional group equivalent weight of the curing agent is not particularly limited, and from the viewpoint of the balance of high temperature low elastic modulus, high Tg, and fluidity, it is preferably 70 g / eq to 1000 g / eq, more preferably 80 g / eq to 500 g / eq, still more preferably 100 g / eq to 300 g / eq, particularly preferably 120 g / eq to 200 g / eq, and extremely preferably 140 g / eq to 180 g / eq. The functional group equivalent weight refers to the value measured in accordance with JIS K0070:1992.

[0059] When the curing agent is solid, its softening point or melting point is not particularly limited. From the viewpoints of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of handleability during the production of the encapsulating resin composition, the softening point or melting point is more preferably 50°C to 130°C, and still more preferably 55°C to 100°C. The melting point or softening point of the curing agent shall be the value measured in the same manner as the melting point or softening point of the epoxy resin.

[0060] The number average molecular weight of the curing agent is not particularly limited, and examples thereof include the range of 80 to 1500. From the viewpoint of fluidity, it is preferably 200 to 1300, and more preferably 300 to 1200.

[0061] The viscosity of the curing agent at 150°C is preferably 0.01 Pa·sec to 0.15 Pa·sec, more preferably 0.02 Pa·sec to 0.1 Pa·sec, and still more preferably 0.03 Pa·sec to 0.08 Pa·sec from the viewpoint of achieving both fluidity and high Tg of the cured product.

[0062] The content of the curing agent with respect to 100 parts by mass of the total epoxy resin (i.e., the entire epoxy resin including the first epoxy resin and the second epoxy resin) contained in the composition is preferably 50 parts by mass to 150 parts by mass, more preferably 60 parts by mass to 120 parts by mass, and still more preferably 70 parts by mass to 90 parts by mass. Also, the content rate of the curing agent with respect to the total of the resin components contained in the composition is preferably 5% by mass to 65% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 35% by mass to 55% by mass. Also, the content rate of the curing agent with respect to the whole composition is preferably 0.2% by mass to 15% by mass, more preferably 1% by mass to 12% by mass, and even more preferably 3% by mass to 10% by mass.

[0063] From the viewpoint of minimizing the unreacted components of each, the mixing ratio of the epoxy resin and the curing agent is preferably set such that the ratio of the number of functional groups of the curing agent (phenolic hydroxyl group in the case of a phenolic curing agent) to the number of epoxy groups of the epoxy resin (number of functional groups of the curing agent / number of epoxy groups of the epoxy resin) is within the range of 0.5 to 2.0, more preferably within the range of 0.6 to 1.3, and even more preferably within the range of 0.8 to 1.2.

[0064] (Curing accelerator) The composition may further contain a curing accelerator as needed. The curing accelerator is not limited as long as it is a compound that promotes the reaction between the epoxy resin and the curing agent contained in the composition.

[0065] Examples of the curing accelerator include cycloamidine compounds such as 1,8-diazabicyclo(5,4,0)undecene-7, 1,5-diazabicyclo(4,3,0)nene, 5,6-dibutylamino-1,8-diazabicyclo(5,4,0)undecene-7; compounds having intramolecular polarization formed by adding compounds having a π bond such as maleic anhydride, quinone compounds (for example, 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, and phenyl-1,4-benzoquinone), diazophenylmethane, and phenolic resin to the cycloamidine compound; tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol and their derivatives; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole and their derivatives; phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, diphenylphosphine, and phenylphosphine; phosphorus compounds having intramolecular polarization formed by adding compounds having a π bond such as maleic anhydride, the quinone compound, diazophenylmethane, and phenolic resin to the phosphine compound; tetraphenylborate salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and N-methylmorpholine tetraphenylborate and their derivatives; and the like. These curing accelerators may be used alone or in combination of two or more.

[0066] When the composition contains a curing accelerator, the content of the curing accelerator with respect to the whole composition is not particularly limited as long as the curing accelerating effect is achieved, and is preferably 0.005% by mass to 2% by mass, more preferably 0.01% by mass to 0.5% by mass.

[0067] (Inorganic filler) The composition may further contain an inorganic filler, if necessary. The inorganic filler can be used, for example, for the purposes of hygroscopicity, reduction of the linear expansion coefficient, improvement of thermal conductivity, and improvement of strength.

[0068] The type of the inorganic filler is not particularly limited. Specifically, inorganic materials such as spherical silica (e.g., fused silica), crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, mica, etc. can be mentioned. An inorganic filler having a flame retardant effect may be used. Examples of the inorganic filler having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and composite hydroxide of magnesium and zinc, zinc borate, zinc molybdate, etc. Examples of the shape of the inorganic filler include powder, beads obtained by spheroidizing the powder, fibers, etc.

[0069] These inorganic fillers may be used alone or in combination of two or more. Among them, spherical silica is preferable from the viewpoints of fillability and reduction of the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The spherical shape is preferable for the shape of the inorganic filler from the viewpoints of fillability and mold wear.

[0070] When the composition contains an inorganic filler, the content of the inorganic filler with respect to the whole composition is preferably 60% by mass or more, more preferably 60% by mass to 95% by mass from the viewpoints of flame retardancy, moldability, hygroscopicity, reduction of the linear expansion coefficient, improvement of strength, and reflow resistance, and still more preferably 70% by mass to 90% by mass from the viewpoint of flame retardancy.

[0071] (Coupling agent) When the composition contains an inorganic filler, the composition may further contain a coupling agent, if necessary, to enhance the adhesion between the resin component and the inorganic filler. The coupling agent may be any one generally used in a sealing resin composition containing an epoxy resin, and there is no particular limitation. Examples include silane compounds having at least one of a primary amino group, a secondary amino group, and a tertiary amino group, various silane compounds such as epoxy silane, mercapto silane, alkyl silane, ureido silane, vinyl silane, titanium compounds, aluminum chelates, aluminum / zirconium compounds, and the like. From the viewpoint of reflow resistance, it is preferable to use the above-mentioned silane compound as the coupling agent, and among them, it is more preferable to use a silane compound having a secondary amino group in the molecule.

[0072] When the composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and more preferably 0.1 parts by mass to 2.5 parts by mass with respect to 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness to the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

[0073] (Release agent) The composition may further contain a release agent from the viewpoint of obtaining good releasability from the mold during molding, if necessary. The release agent is not particularly limited, and conventionally known ones can be used. Specific examples of the release agent include higher fatty acids such as carnauba wax, 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 alone or in combination of two or more.

[0074] When the composition contains a release agent, the amount of the release agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the resin component. When the amount of the release agent is 0.01 part by mass or more based on 100 parts by mass of the resin component, the releasability tends to be sufficiently obtained. When it is 10 parts by mass or less, better adhesiveness tends to be obtained.

[0075] (Colorant) The composition may further contain a colorant, if necessary. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide. The content of the colorant can be appropriately selected according to the purpose and the like. The colorant may be used alone or in combination of two or more.

[0076] (Stress reliever) The composition may further contain a stress reliever, if necessary. By including a stress reliever, the warping deformation of the package and the occurrence of package cracks can be further reduced. Examples of the stress reliever include generally used known stress relievers (plasticizers) such as silicone oil and silicone rubber particles. Specifically, as the stress reliever, thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based, rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder, and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer can be mentioned. The stress reliever may be used alone or in combination of two or more.

[0077] (Other additives) The composition may further contain other additives, if necessary. Examples of other additives include flame retardants, anion exchangers, adhesion promoters, etc. Further, various additives well-known in the art may be added to the composition as necessary.

[0078] (Method for preparing the encapsulating resin composition) The method for preparing the composition is not particularly limited. As a general method, there can be mentioned a method in which components in predetermined blending amounts are sufficiently mixed by a mixer or the like, and then melt-kneaded by a mixing roll, an extruder, etc., cooled, and pulverized. More specifically, for example, there can be mentioned a method in which predetermined amounts of the above-described components are uniformly stirred and mixed, and kneaded by a kneader, a roll, an extruder, etc. that have been preheated to 70°C to 140°C, cooled, and pulverized.

[0079] The composition is preferably solid under normal temperature and pressure (for example, 25°C, under atmospheric pressure). The shape of the composition when it is solid is not particularly limited, and examples include powdery, granular, tablet-like, etc. From the viewpoint of handleability, it is preferable that the dimensions and mass of the curable resin composition when it is tablet-like be such that they match the molding conditions of the package.

[0080] (Use of the encapsulating resin composition) The use of the composition is not particularly limited, and it can be used for various electronic component devices. As described above, the composition of the present disclosure can obtain a cured product having a low elastic modulus at high temperature and a high glass transition temperature, and also has high fluidity. Therefore, the composition of the present disclosure is particularly preferably used also as a mold underfill material for filling the narrow gap of DSM in which chips are mounted on both the top surface and the bottom surface of a substrate for high-density mounting.

[0081] <Electronic component device> The electronic component device according to an embodiment of the present invention includes an element and a cured product of the above-described encapsulating resin composition for encapsulating the element. Examples of electronic component devices include electronic component devices in which elements (such as active elements like semiconductor chips, transistors, diodes, thyristors, etc., and passive elements like capacitors, resistors, coils, etc.) are mounted on a support member or mounting substrate such as a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, etc., and necessary portions are encapsulated with the above-described encapsulating resin composition.

[0082] Here, the mounting substrate is not particularly limited, and specific examples include interposer substrates such as organic substrates, organic films, ceramic substrates, and glass substrates, liquid crystal glass substrates, substrates for MCM (Multi Chip Module), substrates for hybrid ICs, and the like.

[0083] Specific examples of electronic component devices include, for example, semiconductor devices. More specifically, elements such as semiconductor chips are arranged on a lead frame (island, tab), and after connecting the terminal portions of the elements such as bonding pads and the lead portions by wire bonding, bumps, etc., they are encapsulated by transfer molding or the like using the above-mentioned encapsulating resin composition. Resin-encapsulated ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc.; TCP (Tape Carrier Package) in which a semiconductor chip bonded to a tape carrier is encapsulated with the above-mentioned encapsulating resin composition; Bare chip-mounted semiconductor devices such as COB (Chip On Board), COG (Chip On Glass), etc., in which semiconductor chips connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. are encapsulated with the above-mentioned encapsulating resin composition; Hybrid ICs, MCMs in which at least one of active elements (semiconductor chips, transistors, diodes, thyristors, etc.) and passive elements (capacitors, resistors, coils, etc.) connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. are encapsulated with the above-mentioned encapsulating resin composition; BGAs (Ball Grid Array), CSPs (Chip Size Package), MCPs (Multi Chip Package) in which a semiconductor chip is mounted on an interposer substrate formed with terminals for motherboard connection, and the semiconductor chip and the wiring formed on the interposer substrate are connected by bumps or wire bonding, and then the semiconductor chip mounting side is encapsulated with the above-mentioned encapsulating resin composition; and so on. In addition, these semiconductor devices may be stacked (laminated) type packages in which two or more elements are mounted on a mounting substrate in an overlapping manner, or may be batch mold type packages in which two or more elements are encapsulated at once with an encapsulating resin composition.Alternatively, these semiconductor devices may be packages of the DSM (Double Side Mold) method in which chips are mounted on both the upper and lower surfaces of the substrate for high-density mounting.

[0084] In addition, as a method for obtaining an electronic component device such as a semiconductor device in which an element is encapsulated using the above-described encapsulating resin composition as an encapsulant, there may be mentioned a low-pressure transfer molding method, an injection molding method, a compression molding method, and the like. As a method for obtaining an electronic component device such as a semiconductor device in which an element is encapsulated, a dispensing method, a casting method, a printing method, or the like may be used.

Examples

[0085] Hereinafter, the above-described embodiments will be specifically described with reference to examples, but the scope of the above-described embodiments is not limited to these examples. Unless otherwise specified, "parts" and "%" are based on mass.

[0086] [Preparation of Encapsulating Resin Composition] The following materials were mixed at the compositions (parts by mass) shown in Tables 1 and 2, and roll kneading was performed under the conditions of a kneading temperature of 90°C and a kneading time of 15 minutes to prepare the encapsulating resin compositions of the examples and comparative examples. The blanks in Tables 1 and 2 mean that the corresponding components were not used.

[0087] (Epoxy Resin) Epoxy resin 1-1: The epoxy resin represented by the general formula (I) (where a1 to a6 are all 0 and m is 1), epoxy equivalent 215 g / eq, softening point 59°C, viscosity at 150°C 0.05 Pa·sec, number average molecular weight 188, manufactured by DIC Corporation, trade name "HP-6000L" The number average molecular weight of the above epoxy resin 1-1 is a value obtained by measurement under the following conditions. · Measuring device: HLC-8320 manufactured by Tosoh Corporation · Column: TSK gel Hxl series manufactured by Tosoh Corporation · Temperature: 40 degrees · Eluent: THF · Flow rate: 1.0 mL / min · Detection device: RI · Standard sample type: Polystyrene

[0088] Epoxy resin 2-1: Biphenyl type epoxy resin, epoxy equivalent 192 g / eq, softening point 107 °C, viscosity at 150 °C 0.012 Pa·sec, number average molecular weight 354, Mitsubishi Chemical Corporation, product name "YX-4000H" Epoxy resin 2-2: Bisphenol F type epoxy resin, epoxy equivalent 192 g / eq, melting point 66 °C, viscosity at 150 °C 0.01 Pa·sec, number average molecular weight 384, Nippon Steel Chemical & Material Co., Ltd., product name "YSLV-80XY" Epoxy resin 2-3: Bisphenol S type epoxy resin, epoxy equivalent 245 g / eq, melting point 111 °C, viscosity at 150 °C 0.01 Pa·sec, number average molecular weight 490, Nippon Steel Chemical & Material Co., Ltd., product name "YSLV-120TE" Epoxy resin C-1: Novolac type epoxy resin, epoxy equivalent 200 g / eq, softening point 60 °C, viscosity at 150 °C 0.13 Pa·sec, number average molecular weight 800, DIC Corporation, product name "N500P-1" Epoxy resin C-2: Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq, softening point 61 °C, viscosity at 150 °C 0.11 Pa·sec, number average molecular weight 850, Nippon Kayaku Co., Ltd., product name "EPPN-501HY" Epoxy resin C-3: Naphthalene type epoxy resin, epoxy equivalent 167 g / eq, softening point 66 °C, viscosity at 150 °C 0.3 Pa·sec, number average molecular weight 330, Nippon Steel Chemical & Material Co., Ltd., product name "ESN-375"

[0089] (Hardener) Hardener 1: Phenolic resin represented by the general formula (VI) (where b1 to b5 are all 0, n1 ≥ 0, n2 ≥ 0), hydroxyl equivalent 166 g / eq, softening point 66 °C, viscosity at 150 °C 0.05 Pa·sec, number average molecular weight 1100, Meiwa Kasei Co., Ltd., product name "MEHC-7841-4S" Hardener 2: Triphenylmethane type phenolic resin, hydroxyl equivalent 103 g / eq, softening point 83 °C, viscosity at 150 °C 0.10 Pa·sec, number average molecular weight 550, Meiwa Kasei Co., Ltd., trade name "MEH-7500-3S"

[0090] (Other components) Hardening accelerator: Phosphorus-based hardening accelerator, adduct of tributylphosphine and benzoquinone Coupling agent: 3-Phenylaminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name "KBM-573" Release agent: Hostwax, Clariant, trade name "HW-E" Pigment: Carbon black, Mitsubishi Chemical Corporation, trade name "MA600" Additive: Adhesion promoter, gallic acid Silicone 1: Stress reliever, polysiloxane, Toray Dow Corning Silicone Co., Ltd., trade name "AY42-119" Silicone 2: Stress reliever, indene-styrene-coumarone copolymer, Nippon Paint Chemical Co., Ltd., trade name "NH-100S" Inorganic filler 1: Spherical fused silica, Denka Co., Ltd., trade name "FB-510MDC" Inorganic filler 2: Spherical fused silica, average particle diameter 0.5 μm, specific surface area 5.5 m 2 / g, Admatechs Co., Ltd., trade name "Admafine SC2500-SQ"

[0091] [Evaluation of encapsulating resin composition] The properties of the encapsulating resin compositions prepared in the examples and comparative examples were evaluated by the following property tests. The evaluation results are shown in Tables 1 to 2 below. Note that the molding of the encapsulating resin composition was carried out using a transfer molding machine, setting the mold temperature to the molding temperature shown below, and under the conditions of a molding pressure of 6.9 MPa and a curing time of 120 seconds.

[0092] (Spiral flow) Using a mold for spiral flow measurement according to EMMI-1-66, the encapsulating resin composition was molded by a transfer molding machine under the above molding conditions (however, the molding temperature: 180 °C), and the flow distance (cm) was determined.

[0093] (Hot hardness) The encapsulating resin composition was molded into a disk with a diameter of 50 mm and a thickness of 3 mm under the above molding conditions (however, the molding temperature: 175 °C). Immediately after molding, the hot hardness was measured using a Shore D type hardness tester (manufactured by Kobunshi Keiki Co., Ltd., Asker, Type D durometer).

[0094] (Gel time) Using a curastometer of JSR Trading Co., Ltd., 3 g of the encapsulating resin composition was measured at a temperature of 175 °C, and the time until the torque curve rose was defined as the gel time (seconds).

[0095] (Glass transition temperature and coefficient of linear expansion) The encapsulating resin composition was molded under the above molding conditions (however, the molding temperature: 175 °C), and a test piece with a shape of 19 mm × 3 mm × 3 mm was prepared. Using a thermomechanical analyzer (TAS-100) of Rigaku Corporation, the glass transition temperature (hereinafter abbreviated as Tg) was determined from the inflection point of the linear expansion curve measured for the test piece under the condition of a heating rate of 5 °C / min. Also, the coefficient of linear expansion (hereinafter, the former is abbreviated as α1 and the latter as α2) was determined from the slopes below and above Tg, respectively.

[0096] (High-temperature bending test) The encapsulating resin composition was molded under the above molding conditions (however, the molding temperature: 175 °C), and a test piece with a shape of 70 mm × 10 mm × 3 mm was prepared. Using a tensilon of A&D, a three-point support type bending test in accordance with JIS-K-6911 (2006) was performed at 250 °C, and the high-temperature bending elastic modulus, high-temperature bending strength, and high-temperature fracture elongation of the test piece were determined, respectively. The bending elastic modulus E is defined by the following formula. However, in the following formula, E is the bending elastic modulus (MPa), P is the value of the load cell (N), y is the displacement amount (mm), l is the span = 48 mm, w is the test piece width = 10 mm, and h is the test piece thickness = 3 mm.

[0097] [Number]

[0098] (Molding shrinkage rate) The resin composition for sealing was molded into a size of 80 mm in length × 10 mm in width × 3 mm in thickness under the above molding conditions (however, the molding temperature: 175°C), and post-cured at 180°C for 90 seconds. The molding shrinkage rate (%) was obtained from the length D of the mold cavity at the previously measured molding temperature (180°C) and the length d of the cured product at room temperature (25°C) using the following formula. Molding shrinkage rate (%) = ((D - d) / D) × 100

[0099] (Water absorption rate) The resin composition for sealing was molded into a disc with a diameter of 50 mm and a thickness of 3 mm under the above molding conditions (however, the molding temperature: 175°C), and a pressure cooker treatment was performed for 20 hours under the conditions of 2 atm (0.2 MPa) and 121°C using a pressure cooker test apparatus manufactured by Hirayama Seisakusho Co., Ltd. The mass of the disc before and after the pressure cooker treatment was measured, and the water absorption rate (mass%) was obtained using the following formula. Water absorption rate (mass%) = ((mass after treatment - mass before treatment) / mass before treatment) × 100

[0100] (Adhesion strength) The resin composition for sealing was molded into a frustum of a cone shape with a circular bottom (adhesive surface) having an area of 10 mm 2 in diameter, a circular top having an area of 8 mm 2 in diameter, and a height of 4 mm on a copper plate under the above molding conditions (however, the molding temperature: 175°C), and post-cured at 180°C for 90 seconds. Then, using a bond tester (manufactured by Nordson Advanced Technology Co., Ltd., product name "Dage 4000"), while maintaining the temperature of the copper plate at room temperature (25°C), the shear rate was set to 50 μm / s and the height was set to 100 μm for measurement, and the shear adhesive force (MPa) applied when the test piece fell off was determined as the adhesion strength.

[0101] (Reflow resistance test) An 80-pin flat package (QFP) with an outer dimension of 20 mm × 14 mm × 2 mm, mounted with an 8 mm × 10 mm × 0.4 mm silicon chip (lead frame material: copper alloy, lead tip silver-plated product), was molded using a sealing resin composition under the above molding conditions (however, the molding temperature was 175°C), and then post-cured at 180°C for 5 hours to produce a test package. The test package was humidified under the conditions of 85°C, 60% RH, and 168 hours, and then reflowed under the conditions of 260°C for 10 seconds. For the test package after the reflow process, the presence or absence of peeling at the lead frame die paddle top part was observed using an ultrasonic imaging device (SAT), and the number of packages with peeling was evaluated for the total number of test packages (10). In addition, for the test package after the reflow process, the presence or absence of cracks was observed with a microscope, and the number of packages with crack generation was evaluated for the total number of test packages (10).

[0102]

Table 1

[0103]

Table 2

[0104] As shown in the above table, in this example, it can be seen that the glass transition temperature in the cured product is 150°C or higher, the high-temperature flexural modulus in the cured product is low, and a sealing composition with high fluidity is obtained. In particular, in this example, it can be seen that the spiral flow (fluidity) is improved without significantly changing the glass transition temperature and high-temperature flexural modulus compared to Reference Example 1. On the other hand, in Comparative Example 2, the glass transition temperature has significantly decreased compared to Comparative Example 1. Also, in this example, it can be seen that the water absorption rate is lower compared to the comparative examples.

[0105] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A first epoxy resin having an epoxy equivalent of 200 g / eq to 240 g / eq, having a plurality of naphthalene skeletons in the molecule, and having an ether bond in at least a part between the plurality of naphthalene skeletons; A second epoxy resin having a viscosity at 150° C. of 0.0001 Pa·sec to 0.02 Pa·sec and a number average molecular weight of 150 to 1000; A curing agent; A resin composition for encapsulation containing the same, The content ratio of the first epoxy resin with respect to the total epoxy resin contained in the resin composition for encapsulation is 60% by mass to 95% by mass, The resin composition for encapsulation, wherein the first epoxy resin is an epoxy resin represented by the following general formula (I-1). 【Chemical 1】 (In the general formula (I-1), m represents 0 to 4.)

2. The resin composition for encapsulation according to claim 1, wherein the second epoxy resin contains at least one selected from the group consisting of a biphenyl type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin.

3. The resin composition for encapsulation according to claim 1 or claim 2, wherein the viscosity of the curing agent at 150° C. is 0.01 Pa·sec to 0.15 Pa·sec.

4. The resin composition for encapsulation according to any one of claims 1 to 3, wherein the functional group equivalent of the curing agent is 120 g / eq to 200 g / eq.

5. The resin composition for encapsulation according to any one of claims 1 to 4, wherein the first epoxy resin has three naphthalene skeletons in the molecule.

6. The resin composition for encapsulation according to any one of claims 1 to 5, wherein the content of the second epoxy resin with respect to 100 parts by mass of the first epoxy resin is 5 parts by mass to 50 parts by mass.

7. The resin composition for encapsulation according to any one of claims 1 to 6, wherein the curing agent contains at least one selected from the group consisting of a phenol resin and a polyhydric phenol compound.

8. The resin composition for encapsulation according to claim 7, wherein the phenol resin contains at least one selected from the group consisting of a novolak type phenol resin, an aralkyl type phenol resin, and a triphenylmethane type phenol resin.

9. The resin composition for encapsulation according to claim 7 or claim 8, wherein the phenol resin contains an aralkyl type phenol resin.

10. 10. The encapsulating resin composition according to claim 1, wherein the curing agent contains a compound having a biphenyl skeleton in the molecule.

11. An electronic component device comprising: an element; and a cured product of the encapsulating resin composition according to any one of claims 1 to 10 that encapsulates the element.

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