JP2018172545A - Solid sealing material for compression molding, semiconductor device, and semiconductor device production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid sealing material for a compression molding that has excellent stability of warpage behavior after molding and heat treatment, and a semiconductor device and a semiconductor device production method using the solid sealing material.SOLUTION: A solid sealing material for a compression molding contains an epoxy resin, a curing agent, and an inorganic filler, where the epoxy resin contains an epoxy modified silicone compound with an epoxy equivalent of 1000 g/mol or more.SELECTED DRAWING: None

Description

  The present invention relates to a solid molding material for compression molding, a method for manufacturing a semiconductor device, and a semiconductor device.

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, sealing with resin has been the mainstream in terms of productivity and cost. As a resin for sealing, an epoxy group having an excellent balance of various characteristics such as electrical characteristics, moisture resistance, heat resistance, mechanical characteristics, and adhesion to an insert is mainly used.

  In recent years, along with the high density mounting of electronic components on a printed wiring board, a surface mounting type package has become the mainstream as a mounting form of a semiconductor device from a conventional pin insertion type package. Surface mount packages are becoming thinner and smaller in order to increase the mounting density and reduce the mounting height. In addition, the increase in the chip area and the increase in the number of pins have progressed due to the multi-functionality and large capacity of the elements, and further, the reduction in the pad pitch and the reduction in the pad dimensions, the so-called narrow pad pitch due to the increase in the number of pads (electrodes). Progress is also being made. In addition, in order to cope with further reduction in size and weight, CSP (Quad Flat Package), SOP (Small Outline Package), and other forms of packages are easy to cope with higher pin count and CSP capable of higher density mounting. (Chip Size Package) and BGA (Ball Grid Array).

  Along with the miniaturization and multi-functionality of the package, the built-in wire has become thinner, and the occurrence of wire flow has become a problem in normal transfer molding. In order to solve these problems, compression molding was developed. Currently, compression molding is used not only for BGA type packages but also for FO (Fan Out) type packages. At present, among them, it is often used in FO-WLP (Fan Out Wafer Level Package).

  As a sealing material for compression molding, a liquid material is widely used (for example, see Patent Document 1). On the other hand, since the liquid sealing material is relatively expensive, the manufacturing cost of the package tends to increase. In addition, in the mounting technology by compression molding, a plurality of elements arranged on a large-area substrate are sealed together, resulting in molding caused by a difference in thermal expansion coefficient between the substrate and the sealing material. Later warping is a problem. Furthermore, in the mounting technology by compression molding, various thermal histories may be received not only at the time of molding but also in a rewiring process after molding. There is a concern that the warping behavior will change in the process, which makes handling to other processes difficult. Then, solidification of the sealing material for compression molding is examined (for example, refer nonpatent literature 1).

WO 09/142065 pamphlet

Wafer Level Embedding Technology for 3D Wafer Level Embedded Package (ECTC 2009 1289-1296)

As described above, the solid encapsulant is superior in the effect of suppressing warpage compared to the liquid encapsulant, but further improvement in the stability of warpage behavior after molding and after heat treatment is desired for the solid encapsulant. ing.
In view of the above circumstances, an object of the present invention is to provide a solid sealing material for compression molding that is excellent in stability of warpage behavior after molding and after heat treatment, a method for manufacturing a semiconductor device using the same, and a semiconductor device. .

Means for solving the above problems include the following embodiments.
<1> A solid sealing material for compression molding containing an epoxy resin, a curing agent, and an inorganic filler, wherein the epoxy resin contains an epoxy-modified silicone compound having an epoxy equivalent of 1000 g / mol or more.

<2> The solid sealing material for compression molding according to <1>, wherein the epoxy-modified silicone compound includes a compound represented by any one of the following general formulas (1) to (4).

[In General Formula (1), l represents an integer of 1 or more. R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ² each independently represents a monovalent organic group having an epoxy group or a carbon number. 1 to 18 substituted or unsubstituted monovalent hydrocarbon groups (wherein at least one of R ² is a monovalent organic group having an epoxy group). ]

[In General Formula (2), m represents an integer of 0 or 1 or more, and n represents an integer of 1 or more. R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ² independently represents a monovalent organic group having an epoxy group. ]

[In General Formula (3), p represents 0 or an integer of 1 or more, q represents an integer of 1 or more, and r represents an integer of 1 or more. In addition, each R ¹ independently represents a monovalent substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, each R ² independently represents a monovalent organic group having an epoxy group, R ³ each independently represents an alkyloxy, phenyl group, aralkyl group or phenol group. ]

[In the general formula (4), s represents 0 or an integer of 1 or more, and t represents an integer of 1 or more. R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ² independently represents a monovalent organic group having an epoxy group. ]

<3> The solid sealing material for compression molding according to <1> or <2>, wherein the ratio of the epoxy-modified silicone compound in the epoxy resin is 5% by mass to 100% by mass.

<4> The solid sealing material for compression molding according to any one of <1> to <3>, wherein the epoxy resin further includes a triphenylmethane type epoxy resin.

<5> The solid sealing material for compression molding according to any one of <1> to <4>, wherein the curing agent includes a triphenylmethane type phenol resin.

<6> The glass transition temperature when cured under conditions of a molding temperature of 175 ° C. or lower and a heat treatment temperature of 150 ° C. or lower after molding is any one of <1> to <5>. Solid sealing material for compression molding.

<7> The solid sealing material for compression molding according to any one of <1> to <6>, wherein the inorganic filler can pass through a sieve having an opening of 75 μm or less.

<8> The step of disposing a semiconductor chip on a support, and the solid sealing material for compression molding according to any one of <1> to <7> on the support on which the semiconductor chip is disposed. A method of manufacturing a semiconductor device, comprising: a step of arranging; and a step of sealing the semiconductor chip by curing the solid molding material for compression molding arranged on the support.

<9> The solid sealing material for compression molding according to any one of <1> to <7>, in which the support, the semiconductor chip disposed on the support, and the semiconductor chip are sealed. And a cured product.

  ADVANTAGE OF THE INVENTION According to this invention, the solid sealing material for compression molding excellent in the stability of the curvature behavior after shaping | molding and after heat processing, the manufacturing method of a semiconductor device using the same, and a semiconductor device are provided.

  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 components (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and the present invention is not limited thereto.

In the present disclosure, the term “process” includes a process that is independent of other processes and includes the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other processes. .
In the present disclosure, the numerical ranges indicated using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise 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 another numerical description. . Further, 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 values shown in the examples.
In the present disclosure, each component may contain a plurality of corresponding substances. When multiple types of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.
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 means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
In the present disclosure, the term “layer” or “film” includes only a part of the region in addition to the case where the layer or film is formed over the entire region. The case where it is formed is also included.
In the present disclosure, the term “lamination” indicates that layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.

<Solid sealing material for compression molding>
The solid molding material for compression molding of the present embodiment (hereinafter also referred to as “sealing material”) contains an epoxy resin, a curing agent, and an inorganic filler, and the epoxy resin has an epoxy equivalent of 1000 g. / Mol or more of an epoxy-modified silicone compound (hereinafter also referred to as “specific silicone compound”).

  Since the sealing material is solid, thermal shrinkage after molding is small compared to a liquid sealing material, and warping is unlikely to occur. Furthermore, as a result of the study by the present inventors, it has been found that the sealing material is superior in the stability of the warping behavior after the heat treatment after molding as compared with the conventional solid sealing material. Although the reason is not necessarily clear, it is considered that the specific silicone compound contained in the sealing material contributes to the improvement in the stability of the warping behavior after the heat treatment.

  In the present disclosure, the “solid sealing material” means a sealing material that is solid at room temperature (25 ° C.). “Silicone compound” means a compound having a main chain formed by a siloxane bond. “Epoxy-modified silicone compound” means a silicone compound having an epoxy group.

(Epoxy resin)
The epoxy resin contains a specific silicone compound. The proportion of the specific silicone compound in the epoxy resin is preferably 5% by mass to 100% by mass, preferably 10% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass.

  The specific silicone compound is not particularly limited as long as it is an epoxy-modified silicone compound having an epoxy equivalent of 1000 g / mol or more. The specific silicone compound contained in the sealing material may be one type or two or more types.

  From the viewpoint of improving the stability of the warpage behavior after heat treatment, the epoxy equivalent (molecular weight per epoxy group) of the specific silicone compound is 1000 g / mol or more, preferably 2000 g / mol or more, preferably 3000 g / mol. More preferably, it is at least mol.

  From the viewpoint of fluidity, the epoxy equivalent of the specific silicone compound is preferably 100000 g / mol or less, more preferably 50000 g / mol or less, and still more preferably 10,000 g / mol or less.

  The position of the epoxy group in the specific silicone compound is not particularly limited. For example, it may be the end of the main chain formed by siloxane bonds (one end or both ends), the side chain, or both. The epoxy group in the specific silicone compound may be an alicyclic epoxy group.

  Examples of the specific silicone compound include compounds represented by the following general formulas (1) to (4).

In general formula (1), l represents an integer of 1 or more. R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ² each independently represents a monovalent organic group having an epoxy group or a carbon number. 1 to 18 substituted or unsubstituted monovalent hydrocarbon groups (wherein at least one of R ² is a monovalent organic group having an epoxy group).

In general formula (2), m represents 0 or an integer of 1 or more, and n represents an integer of 1 or more. R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ² independently represents a monovalent organic group having an epoxy group.

In general formula (3), p represents 0 or an integer of 1 or more, q represents an integer of 1 or more, and r represents an integer of 1 or more. In addition, each R ¹ independently represents a monovalent substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, each R ² independently represents a monovalent organic group having an epoxy group, R ³ each independently represents an alkyloxy group, a phenyl group, an aralkyl group or a phenol group.

In the general formula (4), s represents 0 or an integer of 1 or more, and t represents an integer of 1 or more. R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ² independently represents a monovalent organic group having an epoxy group.

In the general formulas (1) to (4), the substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms represented by R ¹ or R ² includes an alkyl group, an aryl group, an alkenyl group, and the like. Can be mentioned. Among them, an alkyl group having 1 to 18 carbon atoms or a phenyl group is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is further preferable, and a methyl group is particularly preferable. The alkyl group may be linear, cyclic or branched.

In the general formulas (1) to (4), examples of the monovalent organic group having an epoxy group represented by R ² include an epoxy group, a glycidyl ether group, a glycidyl ester group, a glycidylamino group, and these groups. Is a group formed by bonding to a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In General Formula (3), examples of the alkyloxy group represented by R ³ include a group in which an alkyl group having 1 to 10 carbon atoms is bonded to an oxygen atom, and an alkyl group having 1 to 5 carbon atoms is bonded to an oxygen atom. A bonded group is preferable, a group in which an alkyl group having 1 to 3 carbon atoms is bonded to an oxygen atom is more preferable, and a methoxy group is further preferable.

In the general formula (3), examples of the aralkyl group represented by R ³ include a group in which an aryl group is bonded to an alkyl group having 1 to 10 carbon atoms, and an aryl group is bonded to an alkyl group having 1 to 5 carbon atoms. The group which the aryl group couple | bonded with the C1-C3 alkyl group is more preferable, and the group (benzyl group) which the phenyl group couple | bonded with the methyl group is more preferable.

  In the general formulas (1) to (4), l, m, n, p, q, r, s, and t are the number of siloxane units represented by the corresponding parenthesized structure. The values of l, (m + n), (p + q + r) and (s + t) are not particularly limited. For example, it may be in the range of 1-100, and is preferably in the range of 1-60.

  In the general formulas (2) to (4), the siloxane units represented by the structures in parentheses corresponding to m, n, p, q, r, s, and t may be arranged in a block shape and randomly. May be arranged. Moreover, when the number of each siloxane unit is two or more, those structures may be the same or different.

  The specific silicone compound is also available as a commercial product. For example, “X-22-163A” (epoxy equivalent: 1000 g / mol), “X-22-163B” (epoxy equivalent: 1750 g / mol), “X” having epoxy groups at both ends, manufactured by Shin-Etsu Chemical Co., Ltd. "-22-163C" (epoxy equivalent: 2700 g / mol), having an alicyclic epoxy group at both ends, "X-22-169B" (epoxy equivalent: 1700 g / mol), having an epoxy group at one end " "X-22-1730X" (epoxy equivalent: 4500 g / mol), "X-22-9002" (epoxy equivalent: 5000 g / mol) having an epoxy group on the side chain and both ends, "KF-1001" (epoxy equivalent: 3500 g / mol), “X-22-4741” (epoxy equivalent: 2500 g / mol), “KF-1002” (epoxy equivalent) 4300 g / mol), and having an alicyclic epoxy group in its side chain "KF-102" (epoxy equivalent: 3600 g / mol) and the like.

The epoxy resin may contain an epoxy resin other than the specific silicone compound. Epoxy resins other than the specific silicone compound are not particularly limited, and can be selected from those generally used as a sealing material.
Specifically, at least one phenol selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene. Novolak type epoxy resin (phenol novolac type epoxy resin, which is obtained by epoxidizing a novolak resin obtained by condensing or co-condensing an organic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst. Orthocresol novolac type epoxy resin, etc.]; obtained by condensing or cocondensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde in the presence of an acidic catalyst. Epoxidized triphenylmethane-type phenolic resin; epoxidized novolak resin obtained by co-condensation of the above phenolic and naphtholic compounds with an aldehyde compound under an acidic catalyst A diphenylidyl ether that is a diglycidyl ether such as bisphenol A or bisphenol F; a biphenyl type epoxy resin that is a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; a diglycidyl of a stilbene phenol compound Stilbene type epoxy resins that are ethers; sulfur atom-containing epoxy resins that are diglycidyl ethers such as bisphenol S; polymers such as butanediol, polyethylene glycol, and polypropylene glycol Epoxy resin that is glycidyl ether of chols; Glycidyl ester type epoxy resin that is glycidyl ester of polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid, tetrahydrophthalic acid; Bonded to nitrogen atom such as aniline, diaminodiphenylmethane, isocyanuric acid Glycidylamine-type epoxy resin obtained by substituting the activated hydrogen with a glycidyl group; dicyclopentadiene-type epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; epoxidizing intramolecular olefin bonds Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4) Epoxy) cycloaliphatic epoxy resin such as cyclohexane-m-dioxane; paraxylylene-modified epoxy resin that is glycidyl ether of paraxylylene-modified phenol resin; metaxylylene-modified epoxy resin that is glycidyl ether of metaxylylene-modified phenol resin; glycidyl ether of terpene-modified phenol resin Terpene-modified epoxy resin; dicyclopentadiene-modified epoxy resin, glycidyl ether of dicyclopentadiene-modified phenol resin; cyclopentadiene-modified epoxy resin, glycidyl ether of cyclopentadiene-modified phenol resin; glycidyl of polycyclic aromatic ring-modified phenol resin Polycyclic aromatic ring-modified epoxy resin which is ether; Naphthalene which is glycidyl ether of phenol resin containing naphthalene ring Ren type epoxy resin; Halogenated phenol novolak type epoxy resin; Hydroquinone type epoxy resin; Trimethylolpropane type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing olefinic bonds with peracid such as peracetic acid; Phenol aralkyl resin And an aralkyl type epoxy resin obtained by epoxidizing an aralkyl type phenol resin such as a naphthol aralkyl resin. These epoxy resins may be used alone or in combination of two or more.

  The epoxy resin preferably contains a triphenylmethane type epoxy resin. When the sealing material contains a triphenylmethane type epoxy resin, it is possible to impart good heat resistance and low warpage to the sealing material, and the stabilization of the warping behavior tends to be further improved.

  A triphenylmethane type epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more type. In order to fully demonstrate the performance of the triphenylmethane type epoxy resin, the content of the triphenylmethane type epoxy resin in the entire epoxy resin is preferably 20% by mass or more, and more preferably 30% by mass or more. 50% by mass or more is more preferable.

  From the viewpoint of balance of various properties as the sealing material, the epoxy resin preferably contains a triphenylmethane type epoxy resin and an epoxy resin other than the triphenylmethane type epoxy resin.

  Epoxy resins other than triphenylmethane type epoxy resins include biphenyl type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins, sulfur atom-containing epoxy resins, novolac type epoxy resins, dicyclopentadiene type epoxy resins, and naphthalene type epoxy resins. At least one selected from the group consisting of a resin, a biphenylene type epoxy resin and a dihydroanthracene type epoxy resin is preferable.

  It is also preferable that the epoxy resin does not contain a triphenylmethane type epoxy resin and contains an epoxy resin other than the triphenylmethane type epoxy resin. In this case, it contains at least one selected from the group consisting of biphenyl type epoxy resins, sulfur atom-containing epoxy resins, novolac type epoxy resins, dicyclopentadiene type epoxy resins, biphenylene type epoxy resins and dihydroanthracene type epoxy resins. More preferred.

  From the viewpoint of filling property and reflow resistance, the epoxy resin is composed of triphenylmethane type epoxy resin, biphenyl type epoxy resin that is diglycidyl ether of alkyl-substituted or unsubstituted biphenol, and bisphenol that is diglycidyl ether of bisphenol F. At least one selected from the group consisting of an F-type epoxy resin, a stilbene-type epoxy resin, and a sulfur atom-containing epoxy resin, and a triphenylmethane-type epoxy resin, a biphenyl-type epoxy resin, and a sulfur atom-containing epoxy resin And at least one selected from the group consisting of:

  The above-mentioned biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin and sulfur atom-containing epoxy resin may be used singly or in combination of two or more.

  At least one selected from the group consisting of a biphenyl type epoxy resin, a bisphenol F type epoxy resin, a stilbene type epoxy resin, and a sulfur atom-containing epoxy resin has a content ratio in the entire epoxy resin in order to fully exhibit its performance. It is preferably 40% by mass or more, more preferably 60% by mass or more, and further preferably 80% by mass or more.

  It is also preferable that the epoxy resin contains at least one selected from the group consisting of a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, and a naphthalene type epoxy resin.

  A novolak type epoxy resin is preferable from the viewpoint of curability, a dicyclopentadiene type epoxy resin is preferable from the viewpoint of low hygroscopicity, and a naphthalene type epoxy resin is preferable from the viewpoint of heat resistance and low warpage.

  It is also preferable that the epoxy resin contains at least one selected from the group consisting of an epoxidized aralkyl type phenol resin and a dihydroanthracene type epoxy resin.

  From the viewpoint of adhesiveness, an epoxidized product of an aralkyl type phenol resin is preferable, and from the viewpoint of curability and adhesion, a dihydroanthracene type epoxy resin is preferable.

  The content rate of the epoxy resin contained in the sealing material is not particularly limited. For example, it is preferable that it is 3 mass%-15 mass% of the whole sealing material, and it is more preferable that it is 5 mass%-10 mass%.

  The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of stabilization of the warping behavior, 150 g / mol to 300 g / mol is preferable, and 155 g / mol to 280 g / mol is more preferable.

Hereinafter, specific examples of the epoxy resin will be described.
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), the 3, 3 ′, 5, 5 ′ positions when the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 ′ positions are methyl groups. There, YX-4000H (manufactured by Mitsubishi Chemical Corporation, trade name) other ^{R 8} is a hydrogen atom, all the ^{R 8} are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl, When all R ⁸ are hydrogen atoms, and the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 ′ positions, the 3, 3 ′, 5, 5 ′ positions are methyl groups, and the other R YL-6121H (Mitsubishi Chemical Corporation, trade name), which is a mixed product when ⁸ is a hydrogen atom, is commercially available.

In the 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 may be the same or different. n is an average value and shows the number of 0-10.

The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferable. Among the epoxy resins represented by the following general formula (III), 3, ⁹ ′, 5, 5 ′ positions are methyl groups when R ⁹ is substituted with oxygen atoms at positions 4 and 4 ′. And R ⁹ other than that is a hydrogen atom, and all of R ¹⁰ are hydrogen atoms, and three of the 3, ⁹ ′, 5, 5 ′ positions of R ⁹ are methyl groups, ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), etc., which is a mixture of the case where one is a t-butyl group, the other R ⁹ is a hydrogen atom, and all R ¹⁰ are hydrogen atoms It is available as a commercial product.

In formula (III), R ⁹ and R ^{10 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. n is an average value and shows the number of 0-10.

The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferable. Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and 3, 3 when the positions where oxygen atoms are substituted in R ¹² are the 4 and 4 ′ positions. YSLV-80XY (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which the ', 5,5' position is a methyl group and the other R ¹² is a hydrogen atom is commercially available.

In formula (IV), R ¹¹ and R ^{12 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. n is an average value and shows the number of 0-10.

The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, the epoxy resin represented with the following general formula (V) is mentioned. Among the epoxy resins represented by the following general formula (V), the 3 and 3 'positions when the positions where oxygen atoms are substituted in R ¹³ are the 4 and 4' positions are t-butyl groups, YSLV-120TE (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which the 6,6′-position is a methyl group and the other R ¹³ is a hydrogen atom is commercially available.

In the formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all may be the same or different. n is an average value and shows the number of 0-10.

The novolac type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac type phenol resin. For example, an epoxy resin obtained by epoxidizing a novolak-type phenol resin such as a phenol novolak resin, a cresol novolak resin, or a naphthol novolak resin using a method such as glycyridyl etherification is preferable, and is represented by the following general formula (VI) An epoxy resin is more preferable. Among the epoxy resins represented by the following general formula (VI), all of R ¹⁴ are hydrogen atoms, R ¹⁵ is a methyl group, and i = 1, ESCN-190, ESCN-195 (Sumitomo Chemical Co., Ltd.) , Trade names) etc. are available as commercial products.

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

  The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material. For example, an epoxy resin represented by the following general formula (VII) is preferable. Among epoxy resins represented by the following general formula (VII), HP-7200 (DIC Corporation, trade name) where i = 0 is available as a commercial product.

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

  The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton. For example, an epoxy resin obtained by glycidyl etherification of a triphenylmethane type phenol resin such as a novolak type phenol resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferable, and is represented by the following general formula (VIII). An epoxy resin is more preferable. Among epoxy resins represented by the following general formula (VIII), i is 0 and k is 0, 1032H60 (Mitsubishi Chemical Corporation, trade name), EPPN-502H (Nippon Kayaku Co., trade name) EPPN-501HY (Nippon Kayaku Co., Ltd., trade name) etc. are commercially available.

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

The copolymerization type epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton. . For example, an epoxy resin obtained by glycidyl etherification of a novolac type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and an epoxy resin represented by the following general formula (IX) is more preferable. Among the epoxy resins represented by the following general formula (IX), NC-7300 (Nippon Kayaku Co., Ltd., trade name) in which R ²¹ is a methyl group, i is 1, j is 0, and k is 0. ) Etc. are available as commercial products.

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

  Examples of the epoxy resin represented by the general formula (IX) include a random copolymer containing l constituent units and m constituent units at random, an alternating copolymer containing alternating units, and a copolymer containing regular units. And a block copolymer contained in a block form. Any one of these may be used alone, or two or more may be used in combination.

  The aralkyl type epoxy resin is synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, or derivatives thereof. If it is an epoxy resin which uses a phenol resin as a raw material, it will not be specifically limited. For example, 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 dimethoxyparaxylene, bis (methoxymethyl) biphenyl, or derivatives thereof An epoxy resin obtained by glycidyl etherification is preferable, and an epoxy resin represented by the following general formulas (X) and (XI) is more preferable.

Among epoxy resins represented by the following general formula (X), i is 0, R- ³⁸ is a hydrogen atom, NC-3000S (Nippon Kayaku Co., Ltd., trade name), i is 0, and R ³⁸ CER-3000 (Nippon Kayaku Co., Ltd., trade name) in which an epoxy resin in which R ⁸ is a hydrogen atom and an epoxy resin in which all R ^{8 in} the general formula (II) are hydrogen atoms are mixed at a mass ratio of 80:20 is commercially available. It is available as a product. Among epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which i is 0, j is 0, and k is 0 is commercially available. It is available as a product.

In the formulas (X) and (XI), R ³⁸ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. R ³⁷ and R ^{39 to} R ⁴¹ each represent a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. i is each independently an integer from 0 to 3, j is each independently an integer from 0 to 2, k is each independently an integer from 0 to 4, and l is each independently an integer from 0 to 6. Show. n is an average value and is a number of 0-10 each independently.

Regarding R ^{8 to} R ²¹ and R ^{37 to} R ^{41 in the} general formulas (II) to (XI), “all may be the same or different” means, for example, 8 to 8 in the formula (II) It means that all 88 R ⁸ may be the same or different. It means that all of R ^{9 to} R ²¹ and R ^{37 to} R ⁴¹ may be the same or different with respect to the respective numbers included in the formula. R ^{8 to} R ²¹ and R ^{37 to} R ⁴¹ may be the same as or different from each other. For example, all of R ⁹ and R ¹⁰ may be the same or different.
Moreover, it is preferable that the C1-C18 organic group in general formula (III)-(XI) is an alkyl group or an aryl group.

  N in the above general formulas (II) to (XI) is an average value, and is preferably in the range of 0 to 10 independently. When n is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity at the time of melt molding of the curable resin composition decreases, filling failure, deformation of the bonding wire (gold wire connecting the element and the lead) Etc. tend to be suppressed. More preferably, n is set in the range of 0-4.

(B) Curing agent The curing agent is not particularly limited, and can be selected from those generally used as a material for a sealing material.
Specifically, polyphenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc. And at least one phenolic compound selected from the group consisting of naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde Novolac-type phenol resin obtained by condensation or co-condensation under a catalyst; the above phenolic compound, dimethoxyparaxylene, bis (methoxy Aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from methyl) biphenyl, etc .; phenol resins modified with at least one of paraxylylene and metaxylylene; melamine modified phenol resins; terpene modified phenol resins; And dicyclopentadiene and dicyclopentadiene-type phenol resin and dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; And a triphenylmethane type phenol resin obtained by condensing or cocondensing an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde with an acidic catalyst; Phenol resins obtained by copolymerization of two or more these can be cited. These phenol curing agents may be used alone or in combination of two or more.

  It is preferable that a hardening | curing agent contains a triphenylmethane type phenol resin. By including a triphenylmethane type phenol resin as a curing agent, the glass transition temperature of the cured product of the sealing material is increased, and the stability of the warping behavior tends to be further improved. In addition, by including triphenylmethane type epoxy resin as an epoxy resin and triphenylmethane type phenol resin as a curing agent, the glass transition temperature of the cured product of the sealing material becomes higher and the heat resistance is further improved. The stability of the warping behavior tends to be further improved.

  When the curing agent contains a triphenylmethane type phenol resin, the content is preferably 20% by mass or more, more preferably 30% by mass or more, and 50% by mass or more of the entire curing agent. Is more preferable.

The curing agent may include a triphenylmethane type phenol resin and a curing agent other than the triphenylmethane type phenol resin. The curing agent other than the triphenylmethane type phenol resin is preferably at least one selected from the group consisting of a biphenyl type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, and a novolac type phenol resin. The resin is more preferable, and it is more preferable that the resin includes at least one selected from the group consisting of a phenol novolak resin, a cresol novolak resin, and a naphthol novolak resin (naphthalene type phenol resin).
When the curing agent uses a novolac type phenol resin, the content is preferably 30% by mass or more, more preferably 50% by mass or more based on the entire curing agent in order to exhibit its performance.
It is preferable that the curing agent contains a biphenyl type phenol resin or an aralkyl type phenol resin because the contact angle can be reduced.

  It is also preferable that the curing agent does not include a triphenylmethane type phenol resin and includes a curing agent other than the triphenylmethane type phenol resin. In this case, it is preferable to include at least one selected from the group consisting of a biphenyl type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin and a novolac type phenol resin.

  The hydroxyl equivalent of the curing agent is not particularly limited. From the viewpoint of stabilization of the warping behavior, it is preferably 50 g / mol to 150 g / mol, and more preferably 75 g / mol to 125 g / mol.

  The ratio between the epoxy resin and the curing agent is not particularly limited. In order to suppress each unreacted component to be small, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (number of hydroxyl groups in the curing agent / number of epoxy groups in the epoxy resin) is in the range of 0.5 to 2. It is preferable that it is the ratio which becomes, and it is more preferable that it is a ratio which becomes the range of 0.6-1.3. From the viewpoint of moldability and reflow resistance of the sealing material, the ratio is more preferably in the range of 0.8 to 1.2.

Hereinafter, specific examples of the curing agent will be described.
Examples of the aralkyl type phenol resin include a phenol aralkyl resin and a naphthol aralkyl resin synthesized from a phenolic compound, dimethoxyparaxylene, bis (methoxymethyl) biphenyl and the like. The aralkyl type phenol resin may be further copolymerized with another phenol resin. Examples of the copolymerized aralkyl type phenol resin include a copolymer type phenol resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, a copolymer type phenol resin of a salicylaldehyde type phenol resin and an aralkyl type phenol resin, and a novolac type phenol resin. Examples thereof include copolymer type phenol resins with aralkyl type phenol resins.

  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 a phenol compound and a naphthol compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, or a derivative thereof. . For example, phenol resins represented by the following general formulas (XII) to (XIV) are preferable.

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

Among the phenol resins represented by the above general formula (XII), MEH-7851 (Maywa Kasei Co., Ltd., trade name) in which i is 0 and all R ²³ are hydrogen atoms is commercially available. .

  Among the phenolic resins represented by the general formula (XIII), XL-225, XLC (Mitsui Chemicals, trade name), iH is 0, and k is 0, MEH-7800 (Maywa Kasei Co., Ltd., (Trade name) etc. are commercially available.

Among the phenol resins represented by the above general formula (XIV), j is 0, k is 0, p is 0, SN-170 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name), j is 0 Yes, SN-395 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name) in which k is 1, R ²⁷ is a hydroxyl group, and p is 0 is available as a commercial product.

  The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin obtained using a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (Shin Nippon Petrochemical Co., Ltd., trade name) in which i is 0 is available as a commercial product.

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

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

  Among phenol resins represented by the following general formula (XVI), MEH-7500 (Maywa Kasei Co., Ltd., trade name), HE910-10 (Air Water Co., Ltd.), etc., where i is 0 and k is 0 Is commercially available.

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

  The copolymerization type phenol resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin is not particularly limited as long as it is a copolymer type phenol resin of a phenol resin obtained from a compound having a benzaldehyde skeleton and an aralkyl type phenol resin. For example, a phenol resin represented by the following general formula (XVII) is preferable.

  Among phenol resins represented by the following general formula (XVII), HE-510 (Air Water Chemical Co., Ltd., trade name) in which i is 0, k is 0, and q is 0 is commercially available. It is available as a product.

In the formula (XVII), R ^{32 to} R ³⁴ represent a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. i is an integer of 0-3 independently, k is an integer of 0-4 each independently, and q is an integer of 0-5 each independently. Each of l and m is an average value and is independently a number from 0 to 11. However, the sum of l and m is a number from 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 a phenol compound and a naphthol compound and an aldehyde compound under an acidic catalyst. . For example, a phenol resin represented by the following general formula (XVIII) is preferable.

Among the phenolic resins represented by the following general formula (XVIII), Tamanols 758 and 759 (Arakawa Chemical Industries, Ltd., trade name) in which i is 0 and all R ³⁵ are hydrogen atoms, HP-850N (Hitachi Chemical) Co., Ltd., trade name) etc. are available as commercial products.

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

“All may be the same or different” described for R ^{22 to} R ³⁶ in the above general formulas (XII) to (XVIII) is, for example, that all i R ^{22s in} formula (XII) are the same. But it means they can be different from each other. For the other R ^{23 to} R ³⁶ , it means that all the numbers contained in the formula may be the same or different from each other. R ^{22 to} R ³⁶ may be the same as or different from each other. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

  N in the general formulas (XII) to (XVIII) is preferably in the range of 0 to 10.

(C) Inorganic filler A sealing material contains an inorganic filler for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement, and intensity | strength improvement. Inorganic fillers include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Examples thereof include powders such as spinel, mullite, titania, beads formed by spheroidizing these, and glass fibers.
Among these, silica is preferable and fused silica is more preferable from the viewpoint of reduction in filling properties and linear expansion coefficient. Alumina is preferred from the viewpoint of high thermal conductivity. An inorganic filler may be used individually by 1 type, or may use 2 or more types together. The shape of the inorganic filler is preferably a spherical shape from the viewpoints of fillability and mold wear.

  It is preferable that the content rate of an inorganic filler is 80 mass% or more of the whole sealing material from a viewpoint of a filling property and reliability. When the content of the inorganic filler is 80% by mass, the warp tends to be more effectively suppressed as compared with the case where the content of the inorganic filler is less than 80% by mass. From the viewpoint of filling properties and ease of preparation of the sealing material, the content of the inorganic filler is preferably 95% by mass or less.

  In the present disclosure, the content of the inorganic filler in the sealing material is measured as follows. First, the total mass of the sealing material is measured, and this sealing material is baked at 400 ° C. for 2 hours and then at 700 ° C. for 3 hours to remove components other than the inorganic filler such as resin and solvent. Next, the mass of the remaining inorganic filler is measured, and the ratio of the mass of the inorganic filler to the total mass of the sealing material is calculated from the obtained value.

  The sealing material may have an opening formed by a laser or the like in the state of a molded product. Therefore, it is preferable that the inorganic filler is controlled to have a predetermined particle size by classification treatment from the viewpoint of ease of forming the opening by laser. For example, it is preferable that the mesh can pass through a sieve having an opening of 75 μm or less. The inorganic filler classification treatment can be performed using a commonly used sieving machine, classification apparatus, or the like, regardless of whether it is wet or dry. Examples of the apparatus to be used include an air classifier, an electrostatic classifier, a sonic vibration classifier, and an electromagnetic vibration classifier.

  From the viewpoint of filling properties, the inorganic filler is preferably one that can pass through a sieve having a sieve opening of 75 μm or less (with coarse particles removed). Considering the case where the above-described opening has been made finer, it is more preferable that the opening can pass through a sieve having a finer mesh (for example, 20 μm). It is desirable that the classification accuracy is less than 1% when a certain opening is passed through and then the opening is passed again.

(Curing accelerator)
The sealing material may include a curing accelerator from the viewpoint of curability. The curing accelerator is not particularly limited as long as it is generally used for a sealing material.
Specifically, 1,8-diaza-bicyclo [5.4.0] undec-7-ene, 1,5-diaza-bicyclo [4.3.0] nonene, 5,6-dibutylamino-1, Cycloamidine compounds such as 8-diaza-bicyclo [5.4.0] undec-7-ene; these cycloamidine compounds include 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- Compounds having intramolecular polarization formed by adding a quinone compound such as benzoquinone, diazophenylmethane, a compound having a π bond such as a phenol resin; benzyldimethylamine, Tertiary amines such as tanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and derivatives thereof; Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and the like Derivatives; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine; maleic anhydride, quinone compounds, diazophenylmethane, Phosphorus compounds having intramolecular polarization formed by adding a compound having a π bond such as phenol resin; tetraphenylphosphonium tetraphenylborate, triphenylphosphinetetraphenylbore DOO, 2-ethyl-4-methylimidazole tetraphenyl borate, tetraphenyl boron salts such as N- methylmorpholine tetraphenylborate; and derivatives thereof. These curing accelerators may be used alone or in combination of two or more. Among these, an adduct of an organic phosphine and a quinone compound is preferable from the viewpoint of filling property and reflow resistance.

  When the sealing material contains a curing accelerator, the content is not particularly limited. For example, it is preferable that it is 0.005 mass%-2 mass% of the whole sealing material, and it is more preferable that it is 0.01 mass%-0.5 mass%. When the content of the curing accelerator is 0.005% by mass or more, the curability in a short time tends to be excellent. When the content of the curing accelerator is 2% by mass or less, a good curing rate can be maintained and a good molded product can be obtained.

(Coupling agent)
The sealing material may contain a coupling agent in order to enhance the adhesiveness between the resin component contained in the sealing material or a member in contact with the sealing material such as a frame and the inorganic filler. The coupling agent is not particularly limited as long as it is generally used for a sealing material.
Specifically, silane compounds having at least one amino group selected from primary, secondary and tertiary amino groups, various silane compounds such as epoxy silane, mercapto silane, alkyl silane, ureido silane and vinyl silane, titanium Compounds, aluminum chelates, aluminum / zirconium compounds, and the like.

  Illustrative examples include silane coupling agents having unsaturated bonds such as vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, β- Silane coupling agents having an epoxy group such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-mercaptopropyltrimethoxysilane Γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ- Nilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxysilane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxy Silane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N-ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) aminopropyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltri Ethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N Diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropylmethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxy Silane coupling agents such as silane and γ-mercaptopropylmethyldimethoxysilane; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) , Isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis ( Dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) Titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl Ruphosphite) titanium coupling agents such as titanate; These coupling agents may be used alone or in combination of two or more. Among these, from the viewpoint of filling properties, a silane coupling agent is preferable, and a silane coupling agent having an epoxy group is more preferable.

  When the sealing material includes a coupling agent, the content is preferably 0.037% by mass to 4.75% by mass of the entire sealing material, and 0.05% by mass to 3% by mass. Is more preferable, and it is further more preferable that it is 0.1 mass%-2.5 mass%. When the content of the coupling agent is 0.037% by mass or more, the adhesiveness to the resin component or the frame tends to be improved. There exists a tendency for the moldability of a package to improve that the content rate of a coupling agent is 4.75 mass% or less.

  When the sealing material contains a coupling agent, the coupling agent is preferably in a state of covering the surface of the inorganic filler. In this case, the coverage of the inorganic filler with the coupling agent (hereinafter also referred to as the coverage) is preferably 0.3 to 1.0, more preferably 0.4 to 0.9, More preferably, it is in the range of 0.5 to 0.8. When the coverage is 1.0 or less, bubbles due to volatile components generated during molding tend to decrease, and the generation of voids particularly in a portion where the thickness of the sealing material is small tends to be suppressed. When the coverage is 0.3 or more, the adhesive strength between the resin component and the inorganic filler is increased, and the strength of the molded product tends to be further improved.

  In the present disclosure, the coverage X of the inorganic filler with the coupling agent is defined as in the following formula (A). In formula (A), Sc and Sf represent the total minimum covering area of all coupling agents and the total surface area of all fillers in the encapsulant, respectively, and are defined by formulas (B) and (C), respectively. .

Formula (A): X (%) = (Sc / Sf) × 100
Formula (B): Sc = A1 * W1 + A2 + * W2 + ... + An * Mn
Formula (C): Sf = B1 × W1 + B2 × W2 +... + Bl × Wl

  In the formula (B), n represents the number of types of coupling agents to be used, and in the formula (C), l represents the number of types of inorganic fillers to be used. A and M represent the minimum coating area of each coupling agent and the amount of use thereof, and B and W represent the specific surface area of each inorganic filler and the amount of use thereof, respectively. The minimum coating area of the coupling agent is an area per unit weight of the coupling agent on the assumption that the coupling agent covers the filler as a monomolecular film, and is represented by the following equation (D).

Formula (D): Minimum covering area (m ² /g)=(6.02×1023×13×10−20)/molecular weight of coupling agent

  In the above formula, if the minimum coating area and specific surface area of each coupling agent and inorganic filler used are known, the desired coverage can be obtained from formula (A), formula (B) and formula (C). The amount of coupling agent and inorganic filler used can be calculated.

(Flame retardants)
The sealing material may contain a flame retardant. The flame retardant is not particularly limited because it is generally used for semiconductor encapsulating resin materials. For example, brominated epoxy resins such as dibromocidyl etherified product of tetrabromobisphenol A, brominated phenol novolac epoxy resin; phosphorus compounds such as antimony oxide, red phosphorus, phosphate ester; melamine, melamine cyanurate, melamine modified phenolic resin, Nitrogen-containing compounds such as guanamine-modified phenol resins; phosphorus / nitrogen-containing compounds such as cyclophosphazenes; metal compounds such as zinc oxide, iron oxide, molybdenum oxide, ferrocene, aluminum hydroxide, magnesium hydroxide, and composite metal hydroxides; Is mentioned. Non-halogen and non-antimony flame retardants are preferred from the viewpoint of environmental problems in recent years and high temperature storage properties. Among these, phosphate esters are preferable from the viewpoint of filling properties, and composite metal hydroxides are preferable from the viewpoints of safety and moisture resistance.

The composite metal hydroxide is preferably a compound represented by the following composition formula (XX).
_{p (M1 a O b) ·} q (M2 c O d) · r (M3 c O d) · m (H 2 O) (XX)
Here, M1, M2, and M3 represent different metal elements, a, b, c, d, p, q, and m represent positive numbers, and r represents 0 or a positive number.
Among these, a compound where r in the composition formula (XX) is 0, that is, a compound represented by the following composition formula (XXa) is more preferable.
_{m (M1 a O b) ·} n (M2 c O d) · l (H 2 O) (XXa)
Here, M1 and M2 represent different metal elements, and a, b, c, d, m, n, and l represent positive numbers.

  M1 and M2 in the composition formulas (XX) and (XXa) are not particularly limited as long as they are different metal elements. From the viewpoint of flame retardancy, M1 is a third-period metal element, Group IIA alkaline earth metal element, Group IVB, Group IIB, Group VIII, Group IB, Group IIIA and M1 so that M1 and M2 are not the same. It is preferably selected from metal elements belonging to group IVA, M2 is preferably selected from IIIB to IIB group transition metal elements, and M1 is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc. More preferably, M2 is selected from iron, cobalt, nickel, copper and zinc. From the viewpoint of fluidity, it is preferable that M1 is magnesium, M2 is zinc or nickel, M1 is magnesium, and M2 is zinc.

The molar ratio of p, q, and r in the composition formula (XX) is not particularly limited, but r is 0, and the molar ratio of p and q (p / q) is 99/1 to 50/50. Is preferred. That is, the molar ratio (m / n) of m and n in the composition formula (XXa) is preferably 99/1 to 50/50.
The metal element is classified into a long-period type periodic table in which a typical element is a subgroup A and a transition element is a subgroup B (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4” February 15, 1987) This is performed based on the 30th edition of the daily reduction plate.

  The shape of the composite metal hydroxide is not particularly limited. From the viewpoint of fluidity and filling properties, a polyhedral shape having an appropriate thickness is preferable to a flat plate shape. The composite metal hydroxide is more likely to obtain polyhedral crystals than the metal hydroxide.

  When the sealing material contains a flame retardant, the content is not particularly limited. For example, it is preferable that it is 0.5 mass%-20 mass% of the whole sealing material, It is more preferable that it is 0.7 mass%-15 mass%, 1.4 mass%-12 mass% are still more preferable . When the content of the flame retardant is 0.5% by mass or more, sufficient flame retardancy tends to be obtained, and when it is 20% by mass or less, the filling property and reflow resistance tend to be improved.

(Anion exchanger)
The sealing material may contain an anion exchanger from the viewpoint of improving the moisture resistance and high temperature storage characteristics of the semiconductor element. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. Examples thereof include hydrotalcites and hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, bismuth and the like. An anion exchanger may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, hydrotalcite represented by the following composition formula (XXI) is preferable.
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XXI)
(0 <X ≦ 0.5, m is a positive number)

(Other ingredients)
The sealing material may contain components other than the components described above as necessary. For example, higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, release agents such as polyethylene and polyethylene oxide, colorants such as carbon black, stress relaxation agents such as silicone oil and silicone rubber powder (however, specified Etc. except those corresponding to silicone compounds) can be contained as required.

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

  The curable resin composition is preferably a solid at normal temperature and pressure (for example, 25 ° C. and atmospheric pressure). The shape in particular when a curable resin composition is solid is not restrict | limited, A powder form, granular form, tablet shape, etc. are mentioned. When the curable resin composition is in the form of a tablet, the size and mass should be adjusted so as to match the molding conditions of the package.

  The method for molding the sealing material is not particularly limited. For example, a method of melt extrusion at a predetermined heating temperature using a commonly used molding machine, a method of injection molding while heating, and the like can be mentioned. In the molding, conditions such as heating temperature are not particularly limited. For example, the molding temperature (mold temperature) is preferably in the range of 100 ° C. to 175 ° C., and more preferably 150 ° C. or less from the viewpoint of low warpage. Further, after molding, the cured product of the obtained sealing material may be further subjected to post-molding heat treatment (after cure).

(Glass-transition temperature)
From the viewpoint of suppressing warpage, the sealing material preferably has a glass transition temperature of 150 ° C. or higher when cured at a molding temperature of 175 ° C. or lower and a heat treatment temperature after molding of 150 ° C. or lower, and 160 ° C. More preferably.

  Examples of a method for causing the glass transition temperature of the cured material of the sealing material to satisfy the above conditions include, for example, a triphenylmethane type epoxy resin (preferably a compound represented by the general formula (VIII)) as the epoxy resin of the sealing material ) And at least one triphenylmethane type phenol resin (preferably a compound represented by the general formula (XVI)) as a curing agent.

  As a method for measuring the glass transition temperature of the cured product of the sealing material, a TMA method (differential expansion method) can be used. For example, a linear expansion curve of a test piece having a size of 19 mm × 3 mm × 3 mm cut out from each cured product before and after after-curing is measured by a method of measuring under a condition of a heating rate of 5 ° C./min. The glass transition temperature is determined based on the inflection point of the linear expansion coefficient. Furthermore, the linear expansion coefficient at a predetermined temperature in the temperature region (glass region) below the glass transition temperature is read from the linear expansion curve. Usually, the linear expansion coefficient at 40 ° C. is the linear expansion coefficient in the glass region. The linear expansion curve is measured using, for example, a TASS6000 manufactured by Seiko Instruments Inc.

(Preparation and use of encapsulant)
The sealing material can be prepared by any method as long as the raw materials can be sufficiently dispersed and mixed. As a general method, a raw material of a predetermined blending amount is sufficiently mixed by a mixer, etc., then mixed or melt-kneaded by a mixing roll, an extruder, a raking machine, a planetary mixer, etc., then cooled and removed as necessary. Examples include foaming and pulverization.

<Method for Manufacturing Semiconductor Device>
The method for manufacturing a semiconductor device according to this embodiment includes a step of placing a semiconductor chip on a support, a step of placing the above-described sealing material on the support on which the semiconductor chip is placed, Curing the sealing material disposed on the semiconductor chip and sealing the semiconductor chip.

  The method includes a step of arranging a plurality of semiconductor chips on a support, a step of arranging the sealing material of the above-described embodiment on the support on which the semiconductor chips are arranged, and an arrangement on the support. The method may include a step of curing the sealing material formed to seal the semiconductor chip, and a step of separating the support.

  The method for sealing the semiconductor chip by curing the sealing material is not particularly limited, and can be performed by a general compression molding method. Further, the types of the support and the semiconductor chip used for manufacturing the semiconductor device are not particularly limited, and those generally used for manufacturing the semiconductor device can be used.

<Semiconductor device>
The semiconductor device of this embodiment includes a support, a semiconductor chip disposed on the support, and a cured product of the sealing material of the above-described embodiment that seals the semiconductor chip.

  The method for manufacturing the semiconductor device is not particularly limited. For example, the semiconductor device can be manufactured by the method for manufacturing the semiconductor device according to the above-described embodiment. Moreover, the kind in particular of the support body and semiconductor chip which are used for a semiconductor device is not restrict | limited, What is generally used for manufacture of a semiconductor device can be used.

  Hereinafter, although the said embodiment is described concretely by an Example, the said embodiment is not limited to these Examples. Note that the sealing material and the semiconductor device were evaluated based on an evaluation method described later unless otherwise specified.

  The materials shown in Table 1 are premixed (dry blended) so as to have the composition shown in Table 1, and further kneaded for 15 minutes with a biaxial roll whose roll surface temperature is set to 90 ° C. to 110 ° C. Prepared. Subsequently, the sealing material was cooled and pulverized, and a tablet (pellet shape) having a thickness of 5.5 mm was formed at a molding temperature of 25 ° C. with a mold having a diameter of 43 mm. A cured product of the stop material was produced.

  The details of each material shown in Table 1 are as follows. The numerical values in Table 1 indicate the blending amount (parts by mass) of each material, and the blank indicates that it is not blended.

Epoxy resin 1: triphenylmethane type epoxy resin (Nippon Kayaku Co., Ltd., trade name: EPPN-501HY, epoxy equivalent: 169 g / mol, softening point: 60 ° C.)
Epoxy resin 2: biphenyl type epoxy resin (Mitsubishi Chemical Corporation, trade name: YX-4000, epoxy equivalent: 280 g / mol, melting point: 105 ° C.)
Epoxy resin 3: Silicone compound represented by the general formula (2) (Shin-Etsu Chemical Co., Ltd., trade name: KF-1001, epoxy equivalent: 3500 g / mol)
Epoxy resin 4: Silicone compound represented by general formula (4) (Toray Dow Corning Co., Ltd., trade name: BY16-876, epoxy equivalent: 2800 g / mol)
Epoxy resin 5: silicone compound represented by the general formula (3) (Shin-Etsu Chemical Co., Ltd., trade name: X-22-9002, epoxy equivalent: 5000 g / mol)
Curing agent 1: triphenylmethane type phenol resin (Air Water Co., Ltd., trade name: HE910-10, hydroxyl group equivalent: 83 g / mol)

Inorganic filler 1: spherical fused silica passed through a sieve having an opening of 20 μm (volume average particle diameter: 11.2 μm, specific surface area: 3.1 m ² / g)
Inorganic filler 2: spherical fused silica that passed through a sieve having an opening of 75 μm (volume average particle size: 0.6 μm, specific surface area: 7.0 m ² / g)
Curing accelerator: adduct of triisobutylphosphine and 1,4-benzoquinoneCoupling agent: Silane coupling agent (Shin-Etsu Chemical Co., Ltd., product name: KBM-403)
Colorant: Carbon black (Mitsubishi Chemical Corporation, product name: MA-600MJ-S)
Additive 1: Both-end modified silicone oil (Shin-Etsu Chemical Co., Ltd., trade name: X-22-4952
Additive 2: Polysiloxane having a softening point of 80 ° C. (Toray Dow Corning Co., Ltd., trade name: AY42-119)

  The produced semiconductor sealing resin materials of Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated by the following tests. The evaluation results are shown in Table 1. "-" In Table 1 indicates that it has not been evaluated.

<Measurement of physical properties>
About the produced hardened | cured material of the sealing material, the glass transition temperature (Tg, ° C) was measured by the above-described method by the TMA method (differential expansion method). The results are shown in Table 1.

  About the produced molded object of the sealing material, the coefficient of thermal expansion (CTE, ppm / ° C.) was measured. The measurement is performed using a thermomechanical analyzer TMA8140 (trade name, manufactured by Rigaku Corporation), measuring the amount of thermal expansion at a temperature rising rate of 3 ° C./min and a measuring temperature range of 0 to 250 ° C. The point of intersection with the tangent of the straight line on the high temperature side was the glass transition temperature, and the gradient of the straight line on the low temperature side was expressed as the coefficient of thermal expansion. Table 1 shows the case of the glass transition temperature or lower as CTE1 (<Tg) and the case of the glass transition temperature or higher as CTE2 (> Tg).

  Bending at 25 ° C. in a three-point support bending test in accordance with JIS-K-6911, using Tensilon manufactured by A & D Co., Ltd. The elastic modulus (GPa) was determined. The results are shown in Table 1.

The molding shrinkage ratio (%) of the molded article of the sealing material thus produced was measured under the conditions described below. Specifically, the molding shrinkage percentage (%) was obtained from the following formula from the length of the mold at the molding temperature (175 ° C.) measured in advance and the length of the test piece at room temperature (25 ° C.). The results are shown in Table 1.
Mold shrinkage (%) = [(D−d) / D] × 100
D: Mold cavity length d: Specimen length

<Evaluation of warpage>
Warpage was evaluated using a 6-inch silicon wafer (thickness: 650 μm). Specifically, the sealing material was disposed on the entire surface of one side of the silicon wafer so that the thickness after curing was 500 μm, the molding temperature was 130 ° C., and the sealing material was molded under conditions of 600 seconds. Then, it heat-processed on the conditions of 175 degreeC and 6 hours, and was hardened. Next, the silicon wafer was placed on a flat table so that the surface on which the cured product of the sealing material of the silicon wafer was placed, and the height (mm) of the silicon wafer from the table was measured with a ruler. The measurement was performed at two points, and the average value is shown in Table 1. Further, the measurement of warpage using a 12-inch silicon wafer (thickness: 750 μm) was performed in the same manner as described above. The results are shown in Table 1.

<Examination results>
In Examples 1 to 6 using the specific silicone compound as the epoxy resin, the effect of reducing warpage of the silicon wafer was significantly improved as compared with Comparative Examples 1 and 2 in which the specific silicone compound was not used as the epoxy resin.
Furthermore, it was found that even in Example 3 using 10 parts by mass of the specific silicone compound as the epoxy resin, a sufficient warp reduction effect can be obtained. Moreover, it turned out that the reduction effect of curvature increases as the ratio of the specific silicone compound in an epoxy resin is increased from the comparison between Example 3 and Examples 4 and 5.

Claims (9)

  A solid sealing material for compression molding containing an epoxy resin, a curing agent, and an inorganic filler, wherein the epoxy resin contains an epoxy-modified silicone compound having an epoxy equivalent of 1000 g / mol or more. The solid sealing material for compression molding according to claim 1, wherein the epoxy-modified silicone compound includes a compound represented by any one of the following general formulas (1) to (4).

[In General Formula (1), l represents an integer of 1 or more. R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ² each independently represents a monovalent organic group having an epoxy group or a carbon number. 1 to 18 substituted or unsubstituted monovalent hydrocarbon groups (wherein at least one of R ² is a monovalent organic group having an epoxy group). ]

[In General Formula (2), m represents an integer of 0 or 1 or more, and n represents an integer of 1 or more. R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ² independently represents a monovalent organic group having an epoxy group. ]

[In General Formula (3), p represents 0 or an integer of 1 or more, q represents an integer of 1 or more, and r represents an integer of 1 or more. In addition, each R ¹ independently represents a monovalent substituted or unsubstituted hydrocarbon group having 1 to 18 carbon atoms, each R ² independently represents a monovalent organic group having an epoxy group, R ³ each independently represents an alkyloxy, phenyl group, aralkyl group or phenol group. ]

[In the general formula (4), s represents 0 or an integer of 1 or more, and t represents an integer of 1 or more. R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ² independently represents a monovalent organic group having an epoxy group. ]   The solid sealing material for compression molding according to claim 1 or 2, wherein a ratio of the epoxy-modified silicone compound in the epoxy resin is 5% by mass to 100% by mass.   The solid sealing material for compression molding according to any one of claims 1 to 3, wherein the epoxy resin further includes a triphenylmethane type epoxy resin.   The solid sealing material for compression molding according to any one of claims 1 to 4, wherein the curing agent contains a triphenylmethane type phenol resin.   The compression molding according to any one of claims 1 to 5, wherein the glass transition temperature when cured at a molding temperature of 175 ° C or lower and a heat treatment temperature after molding of 150 ° C or lower is 150 ° C or higher. Solid sealing material.   The solid sealing material for compression molding according to any one of claims 1 to 6, wherein the inorganic filler can pass through a sieve having an opening of 75 µm or less.   The process of arrange | positioning a semiconductor chip on a support body, The process of arrange | positioning the solid sealing material for compression molding of any one of Claims 1-7 on the said support body on which the said semiconductor chip is arrange | positioned. And a step of curing the solid molding material for compression molding disposed on the support and sealing the semiconductor chip.   The hardened | cured material of the solid sealing material for compression molding of any one of Claims 1-7 which has sealed the support body, the semiconductor chip arrange | positioned on the said support body, and the said semiconductor chip. A semiconductor device comprising: