Epoxy resin composition, electronic component, and semiconductor device

Abstract

To prevent generation of discomfort smell in heating and curing an epoxy resin composition.SOLUTION: An epoxy resin composition contains epoxy resin and curing accelerator. When gas in a sealed space after heating the epoxy resin composition arranged in the sealed space at 150°C for 10 minutes is measured as a measurement chart indicating changes of signal intensity to retention time by gas chromatography mass spectrometry, smell caused by a peak at which the retention time is positioned between 13.0 minutes and 13.2 minutes is not detected.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an epoxy resin composition, an electronic component, and a semiconductor device.

Background Art

[0002] Many semiconductor elements such as integrated circuits constituting semiconductor devices are encapsulated using an epoxy resin composition. When performing an encapsulation process using this epoxy resin, odors may be generated, which may cause discomfort to workers. For this reason, technologies for suppressing the odors generated during the encapsulation process are in demand. As such a technology, for example, for the purpose of reducing the discomfort of workers caused by the unique odor emitted during transfer molding, a fragrance component (such as carboxylic acid like spearmint oil or pinene) is further blended with the main components (epoxy resin, curing agent, inorganic filler) constituting the epoxy resin composition, and an epoxy resin composition has been proposed (Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] On the other hand, as a typical molding method used for the encapsulation process using an epoxy resin composition, in addition to the above-described transfer molding, compression molding is also known. Since this compression molding is suitable for manufacturing large molded products, the opportunities for its use have increased in recent years. This is due to the spread of wafer-level chip size package technology.

[0005] Also, when performing a sealing process using compression molding, unpleasant odors may be generated during compression molding (pre-curing) or during post-curing (main curing) performed thereafter. This is considered to be due to the use of a large amount of an epoxy resin composition that can be a source of odor when performing compression molding at the wafer level, or due to performing heat treatment in a closed space where odors generated using an oven or the like during post-curing are likely to be trapped. When heat-curing such a large amount of epoxy resin composition, odors may become a problem. On the other hand, in the epoxy resin compositions exemplified in Patent Documents 1 and 2, they only mask the unpleasant odors generated during heat-curing with the odor of the fragrance component, and do not fundamentally prevent the generation of unpleasant odors. In addition to this, the fragrance component itself not only does not contribute to improving the basic properties such as adhesiveness required for the epoxy resin composition, but may also have an adverse effect in some cases. Considering these points, it is considered important to fundamentally prevent the generation of unpleasant odors without using a fragrance component.

[0006] The present invention has been made in view of the above circumstances, and an object thereof is to provide an epoxy resin composition that prevents the generation of unpleasant odors generated during heat-curing, as well as an electronic component and a semiconductor device manufactured using the same.

Means for Solving the Problems

[0007] The above problems are achieved by the following present invention. That is, The epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin and a curing accelerator, and when the gas in the sealed space after heat-treating the epoxy resin composition disposed in the sealed space at 150°C for 10 minutes is measured as a measurement chart showing the change in signal intensity with respect to the retention time by gas chromatography-mass spectrometry, no odor caused by a peak located between a retention time of 13.0 minutes and 13.2 minutes is detected.

[0008] In one embodiment of the epoxy resin composition of the present invention, it is preferable that no peak is observed in the measurement chart where the retention time is between 13.0 minutes and 13.2 minutes.

[0009] In another embodiment of the epoxy resin composition of the present invention, in the measurement chart, a peak is observed where the retention time is between 13.0 minutes and 13.2 minutes, and the intensity of the observed peak is preferably 1.0×10 3 as follows.

[0010] In another embodiment of the epoxy resin composition of the present invention, the compounding amount of the curing accelerator is preferably 1 phr to 10 phr.

[0011] In another embodiment of the epoxy resin composition of the present invention, it is preferable that the curing accelerator contains an imidazole-based curing accelerator.

[0012] In another embodiment of the epoxy resin composition of the present invention, it is preferable that the curing accelerator does not contain 2-phenyl-4-methylimidazole.

[0013] In another embodiment of the epoxy resin composition of the present invention, the curing accelerator contains 2-phenyl-4-methylimidazole, and the compounding amount of 2-phenyl-4-methylimidazole is preferably more than 0 phr and 1.5 phr or less.

[0014] In another embodiment of the epoxy resin composition of the present invention, it is preferable to contain a coupling agent.

[0015] In another embodiment of the epoxy resin composition of the present invention, it is preferably an epoxy resin composition for compression molding.

[0016] The electronic component of the present invention includes a cured product of the epoxy resin composition of the present invention.

[0017] The semiconductor device of the present invention includes at least a plurality of stacked semiconductor elements and a cured product of the epoxy resin composition of the present invention that seals the plurality of semiconductor elements.

Advantages of the Invention

[0018] According to the present invention, it is possible to provide an epoxy resin composition that prevents the generation of unpleasant odors during heat curing, and an electronic component and a semiconductor device manufactured using the same.

Brief Description of the Drawings

[0019]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0020] The epoxy resin composition of the present embodiment is an epoxy resin composition containing an epoxy resin and a curing accelerator. When the gas in the sealed space after heat-treating the epoxy resin composition arranged in the sealed space at 150°C for 10 minutes is measured as a measurement chart showing the change in signal intensity with respect to the retention time by gas chromatography mass spectrometry, no odor caused by the peak located between a retention time of 13.0 minutes and 13.2 minutes is detected. Thereby, when the epoxy resin composition of the present embodiment is heat-cured, it is possible to prevent the generation of unpleasant odors for the operator. The reason for obtaining such an effect is as follows.

[0021] First, the inventors carried out gas chromatography mass spectrometry on the epoxy resin composition when it was heat-cured at the typical lowest heating temperature (i.e., 150°C) generally assumed in these curing processes, based on the fact that the unpleasant odor generated when the epoxy resin composition was heat-cured occurs during compression molding (pre-curing) and during post-curing (main curing). In this case, the correspondence between the odor that the worker finds unpleasant and the measurement chart (chart showing the change in signal intensity with respect to retention time) obtained by gas chromatography mass spectrometry was examined. As a result, it was found that although various types of gas components are released from the epoxy resin composition during heat curing, only a specific gas component (a component caused by a peak observed between retention times of 13.0 minutes and 13.2 minutes) is recognized as an unpleasant odor by the worker.

[0022] The inventors therefore carried out the same tests as above for the various raw material components (epoxy resin, curing accelerator, and other components blended as necessary) used in the preparation of the epoxy resin composition in which a peak was observed between retention times of 13.0 and 13.2 minutes. As a result, no peaks were observed between retention times of 13.0 and 13.2 minutes for any of the raw material components. In light of these facts, it is speculated that the gas components that cause unpleasant odors to workers are not derived from the raw material components themselves used in the preparation of the epoxy resin composition, but from reaction components generated by chemical reactions between the raw material components during the heat curing of the epoxy resin composition.

[0023] Based on the above findings, in order not to generate an unpleasant odor during the heat curing of the epoxy resin composition, it is necessary that "the odor caused by the peak located between a retention time of 13.0 minutes and 13.2 minutes is not detected". Here, "the odor caused by the peak located between a retention time of 13.0 minutes and 13.2 minutes is not detected" means (1) the peak located between a retention time of 13.0 minutes and 13.2 minutes is not observed (in other words, the gas component itself that causes the unpleasant odor is not generated), or (2) although a peak is observed between a retention time of 13.0 minutes and 13.2 minutes, the peak intensity is so small that it is not recognized as an unpleasant odor (in other words, although the gas component that causes the unpleasant odor is generated, its generation amount is too small to be perceived as an unpleasant odor by the operator). In the case of (2) above, the peak intensity required for the operator not to perceive an unpleasant odor is 1.0×10 3 The following is preferable, 5.0×10 2 The following is more preferable, 1.0×10 2 The following is even more preferable.

[0024] Next, the details of each component constituting the epoxy resin composition of this embodiment will be described.

[0025] (A) Epoxy resin The epoxy resin may be various epoxy resins generally used for semiconductor encapsulation, and can be used without particular limitation. As the epoxy resin, only one type of epoxy resin may be used, or two or more types of epoxy resins may be used in combination.

[0026] Specific examples of epoxy resins typically include aromatic epoxy resins and aliphatic epoxy resins. Examples of aromatic epoxy resins include bisphenol A type epoxy resins such as p-glycidyloxyphenyldimethyltris(bisphenol A diglycidyl ether); bisphenol F type epoxy resins; novolac type epoxy resins; fluorene type epoxy resins; biphenyl aralkyl epoxy resins; diepoxy resins such as p-tert-butylphenyl glycidyl ether and 1,4-phenyldimethanol diglycidyl ether; biphenyl type epoxy resins such as 3,3’,5,5’-tetramethyl-4,4’-diglycidyloxybiphenyl; aminophenol type epoxy resins such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, and tetraglycidyl-m-xylylenediamine; naphthalene type epoxy resins; and epoxy resins having a plant-derived skeleton.

[0027] Examples of aliphatic epoxy resins include monofunctional aliphatic epoxy compounds having one epoxy group in the molecule, such as alkyl alcohol glycidyl ethers [butyl glycidyl ether, 2-ethylhexyl glycidyl ether, etc.] and alkenyl alcohol glycidyl ethers [vinyl glycidyl ether, allyl glycidyl ether, etc.]; difunctional aliphatic epoxy compounds having two epoxy groups in the molecule, such as polyalkylene glycol diglycidyl ethers like alkylene glycol diglycidyl ether and polytetramethylene glycol diglycidyl ether, and alkenylene glycol diglycidyl ether; and polyfunctional aliphatic epoxy compounds having three or more epoxy groups in the molecule, such as polyglycidyl ethers of trifunctional or higher alcohols like trimethylolpropane, pentaerythritol, and dipentaerythritol [trimethylolpropane triglycidyl ether, pentaerythritol (tri or tetra) glycidyl ether, dipentaerythritol (tri, tetra, penta or hexa) glycidyl ether, etc.].

[0028] Among the various epoxy resins listed above, bisphenol type epoxy resins, polytetramethylene glycol diglycidyl ether, and aminophenol type epoxy are preferred.

[0029] (B) Curing accelerator The curing accelerator can be used without particular limitation as long as it is a known curing accelerator. For example, amine-based curing accelerators such as imidazole-based curing accelerators, tertiary amine-based curing accelerators, and amine adduct-based curing accelerators can be mentioned, but it is preferable to use an imidazole-based curing accelerator. Further, as the curing accelerator, only one type of epoxy resin may be used, or two or more types of epoxy resins may be used in combination.

[0030] Examples of the imidazole-based curing accelerator include 2-phenyl-4-methylimidazole, 2,4-diamino-6-[2’-methylimidazolyl-(1’)]-ethyl-s-triazine, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2,4-diamino-6-(2´-undecyl-imidazolyl)-ethyl-s-triazine, 2,4-diamino-6-[2’-ethyl-4’-methylimidazolyl-(1’)]-ethyl-s-triazine isocyanuric acid adduct, 1-(2-cyanoethyl)-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like.

[0031] The blending amount of the curable resin composition is not particularly limited, but from the viewpoint of easily obtaining a viscosity and adhesiveness suitable for encapsulation treatment, particularly encapsulation treatment using compression molding, it is preferably 1 phr to 10 phr (1 part by mass to 10 parts by mass with respect to 100 parts by mass of the epoxy resin), more preferably 2 phr to 10 phr, and even more preferably 4 phr to 8 phr.

[0032] Incidentally, as described above, in the gas chromatography-mass spectrometry of the curing accelerator alone, which is a raw material component of the epoxy resin composition, no peak has been observed between the retention times of 13.0 minutes and 13.2 minutes. However, the present inventors have found that a peak is observed between the retention times of 13.0 minutes and 13.2 minutes in the epoxy resin composition containing an appropriate amount of 2-phenyl-4-methylimidazole with respect to the epoxy resin. From these facts, it is presumed that the reaction component generated by the reaction of the epoxy resin and 2-phenyl-4-methylimidazole during heat curing is one of the causes of the unpleasant odor.

[0033] Based on the above findings, it is preferable not to use 2-phenyl-4-methylimidazole as the curing accelerator blended in the epoxy resin composition. Further, when 2-phenyl-4-methylimidazole is used as the curing accelerator, from the viewpoint of suppressing the generation of an unpleasant odor, its blending amount is preferably more than 0 phr and 1.5 phr or less, and more preferably more than 0 phr and 1.0 phr. However, using only 2-phenyl-4-methylimidazole with a blending amount of 1.5 phr or less as the curing accelerator tends to result in insufficient adhesiveness and curability of the epoxy resin composition. Therefore, when using 2-phenyl-4-methylimidazole with a blending amount of 1.5 phr or less as the curing accelerator, it is particularly preferable to use it in combination with other curing accelerators.

[0034] (C) Filler In the epoxy resin composition of this embodiment, a filler may be further blended as necessary. The filler is not particularly limited as long as it has the effect of reducing the coefficient of thermal expansion of the cured product of the epoxy resin composition. Examples of the filler material include silica, alumina, aluminum, aluminum nitride, silicon carbide, silicon nitride, and the like. As the filler, silica or alumina is particularly preferable from the viewpoint of being able to increase the blending amount (filling amount) of the filler with respect to the epoxy resin composition. Further, the filler may be surface-treated with a surface treatment agent such as a silane coupling agent. Further, as the filler blended in the epoxy resin composition, only one type of filler may be used, or two or more types of fillers may be used in combination.

[0035] The shape of the filler is not particularly limited and may be any form such as spherical, amorphous, flaky, etc. Further, the average particle size of the filler is preferably from 0.001 μm to 20 μm, more preferably from 0.5 μm to 20 μm, and even more preferably from 1 μm to 15 μm. The average particle size means the volume average particle size D50 (the particle size at which the cumulative percentage from the small diameter side of the particle size distribution based on volume reaches 50%) measured using a laser diffraction particle size distribution measuring device.

[0036] The blending ratio (filling rate) of the filler contained in the epoxy resin composition can be appropriately selected according to the intended use of the epoxy resin composition. For example, when the epoxy resin composition is used for compression molding, 50% by mass to 95% by mass is preferable, 55% by mass to 90% by mass is more preferable, and 60% by mass to 85% by mass is particularly preferable.

[0037] (D) Coupling agent In the epoxy resin composition of the present embodiment, a coupling agent may be further blended as necessary. As long as the coupling agent can improve and enhance the adhesiveness to the adhesion target (such as a semiconductor element, a wiring board, etc.), a known coupling agent can be used without particular limitation. Further, as the coupling agent blended in the epoxy resin composition, only one type of coupling agent may be used, or two or more types of coupling agents may be used in combination.

[0038] Specific examples of the coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyltrimethoxysilane, 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)anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N,Silane coupling agents such as (N-dibutyl) aminopropylmethyldimethoxysilane, γ-(N-methyl) anilinopropylmethyldimethoxysilane, γ-(N-ethyl) anilinopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl) ethylenediamine, N-(dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.; titanate coupling agents such as isopropyltriisostearoyl titanate, isopropyltris(dioctylpyrophosphate) titanate, isopropyltri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecyl phosphite) 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, isopropylisostearyldiacryl titanate, isopropyltri(dioctyl phosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis(dioctyl phosphite) titanate, etc. can be mentioned.,

[0039] (E) Other components In the epoxy resin composition, other components other than the components listed above can also be appropriately blended. Examples of such other components include ion trap agents, leveling agents, antioxidants, defoaming agents, flame retardants, colorants, reactive diluents, elastomers, etc. The types and blending amounts of each blending agent are as per conventional methods.,

[0040] The epoxy resin composition of this embodiment is prepared by mixing and stirring a mixture obtained by mixing each component constituting the epoxy resin composition. When mixing and stirring, known mixing and stirring means such as a roll mill or a planetary mixer can be appropriately used. When the (A) epoxy resin used in the preparation of the epoxy resin composition is in a solid state, it is preferable to liquefy or fluidize the epoxy resin by heating or the like and then mix it with the remaining components. Further, the procedure of mixing and stirring is not particularly limited. For example, all the components constituting the epoxy resin composition may be mixed simultaneously, or after preparing a preliminary mixture by mixing only some of the components first, the remaining components may be further mixed with this preliminary mixture later. For example, when it is difficult to uniformly disperse the (C) filler with respect to the (A) epoxy resin, a preliminary mixture obtained by mixing the (A) epoxy resin and the (C) filler first may be prepared, and the remaining components may be further mixed with this preliminary mixture later.

[0041] The epoxy resin composition of this embodiment can be widely used as an adhesive or a sealing material, but it is preferably used for the encapsulation treatment of electronic elements such as semiconductor elements. In particular, it is preferably used for the encapsulation treatment using compression molding in which a relatively larger amount of the epoxy resin composition is used compared with other molding methods during the encapsulation treatment. That is, the epoxy resin composition of this embodiment is particularly preferably used as an epoxy resin composition for compression molding. In such applications, unpleasant odors tend to be generated due to the use of a large amount of the epoxy resin composition inherently, but the epoxy resin composition of this embodiment can surely prevent this.

[0042] Also, by encapsulating an electronic device (e.g., a wafer-shaped semiconductor device) using the epoxy resin composition of the present embodiment, an electronic component (e.g., a semiconductor device) including a cured product of the epoxy resin composition can be obtained. However, the electronic component of the present embodiment is particularly preferably a semiconductor device including at least a plurality of stacked semiconductor devices and a cured product of the epoxy resin composition of the present embodiment that encapsulates the plurality of semiconductor devices. In manufacturing a semiconductor device having such a three-dimensional structure, a large amount of the epoxy resin composition is used. Therefore, originally, an unpleasant odor is likely to be generated due to the use of a large amount of the epoxy resin composition. However, if the epoxy resin composition of the present embodiment is used, this can be surely prevented.

Examples

[0043] Specific examples of the present invention will be described below with reference to examples, but the present invention is not limited only to the examples described below.

[0044] 1. Preparation of epoxy resin composition The epoxy resin composition used for various evaluations and measurements was prepared by mixing and stirring raw material components using a roll mill so as to have the compounding compositions shown in Tables 1 to 5.

[0045] 2. Raw material components used for preparing the epoxy resin composition The following shows the material names, manufacturers, etc. together with the trade names of the raw material components used for preparing the epoxy resin composition.

[0046] (A) Epoxy resin · YDF8170 (bisphenol F type liquid epoxy resin, manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 158 g / eq) · Epogose PT (general grade) (diglycidyl ether of polytetramethylene glycol, manufactured by Yokkaichi Gosei Co., Ltd., epoxy equivalent 440 g / eq) · jER630 (aminophenol type liquid epoxy resin, epoxy equivalent 98 g / eq)

[0047] (B) Imidazole-based curing accelerator · 2P4MZ (2-phenyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · 2MZA (2,4-diamino-6-[2‘-methylimidazolyl-(1’)]-ethyl-s-triazine, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · C11Z (2-undecylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · C17Z (2-heptadecylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · 2E4MZ-A (2,4-diamino-6-[2-ethyl-4methylimidazolyl-(1)]-ethyl-s-triazine, Shikoku Kasei Kogyo Co., Ltd.) · 2PZ (2-phenylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · 1B2PZ (1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · 2E4MZ-CN (1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · C11Z-A (2,4-diamino-6-(2´-undecyl-imidazolyl)-ethyl-s-triazine, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · 2MAOK (2,4-diamino-6-[2’-ethyl-4’-methylimidazolyl-(1’)]-ethyl-s-triazine isocyanurate adduct, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · 2PZ-CN (1-(2-cyanoethyl)-2-phenylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · 2P4MHZ (2-phenyl-4-methyl-5-hydroxymethylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · C11Z-CN (1-cyanoethyl-2-undecylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.) · 2PHZ (2-phenyl-4,5-dihydroxymethylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd.)

[0048] (C) Filler · SE605H-SMG (Silica filler (average particle size 1.8 μm, maximum particle size 5.0 μm), manufactured by Admatechs Co., Ltd.) · STW7010-20 (Silica filler (average particle size 10.0 μm, maximum particle size 20.0 μm), manufactured by Micron Co., Ltd.)

[0049] (D) Coupling agent · KBE9007N (3-isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.) · KBM-403 (3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.)

[0050] 3. Evaluation results Table 1 shows the results of odor evaluation, as well as the measurement results of viscosity and adhesive strength, together with the compounding amount of the curing accelerator, for an epoxy resin composition composed of an epoxy resin and a curing accelerator. The epoxy resin used in the preparation of the epoxy resin composition shown in Table 1 is a mixture of YDF8170, Epogose PT, and jER630 blended at a mass ratio of 1:1:1. As shown in Table 1, odor evaluation was carried out by greatly varying the compounding amount of the curing accelerator in the range of 4 phr to 20 phr. However, an unpleasant odor was observed only when 2P4MZ was used as the curing accelerator at a compounding amount of 2 phr or more. And at this time, it was found that the gas component determined as an unpleasant odor was the peak observed at a retention time of around 13.1 min in the CG-MS measurement chart. Note that in Table 1, only the evaluation results for 2MZA, 2E4MZ-CN, and 2P4MZ as the curing accelerator are shown. However, when similar evaluations were carried out for other imidazole-based curing accelerators other than these three types of curing accelerators, for odor evaluation, evaluation results similar to those of 2MZA and 2E4MZ-CN were obtained, and for viscosity and adhesive strength, evaluation results generally equivalent to those of 2E4MZ-CN were obtained.

[0051] Also, Tables 2 to 5 show the results of odor evaluation for epoxy resin compositions in which, based on the results shown in Table 1, the compounding composition was varied in various ways except that the compounding amount of the curing accelerator blended in the epoxy resin composition was fixed at 4 phr or 2 phr (i.e., the compounding amount with the potential to generate an unpleasant odor).

[0052]

Table 1

[0053]

Table 2

[0054]

Table 3

[0055]

Table 4

[0056]

Table 5

[0057] 4. Various measurement and evaluation methods 4.1 Odor evaluation The odor evaluation shown in Tables 1 to 5 was carried out using the headspace gas chromatograph mass spectrometer (HS-GC / MS device; gas chromatograph (8890GC, manufactured by Agilent Technologies), mass spectrometer (5977MSD, manufactured by Agilent Technologies), autosampler (MPS robotic PRO, manufactured by Agilent Technologies)) shown in FIG. 1. The headspace gas chromatograph mass spectrometer 10 shown in FIG. 1 has its main part composed of a gas chromatograph device 20 and a mass spectrometer 30. A needle 50 is provided at the tip of a conduit 40 connected to the gas inlet side of a column (not shown in FIG. 1) disposed inside the gas chromatograph device 20. During measurement, the needle 50 is fixed in a state of piercing the cap 72 of a vial 70 (a bottle forming a sealed space) in which an analysis sample 60 (epoxy resin composition) is disposed inside. Further, a branch pipe 44 is connected in the middle of a conduit 42 connecting the gas outlet side of the column disposed inside the gas chromatograph device 20 and the mass spectrometer 30. Therefore, among various components contained in the gas generated from the analysis sample 60, one component separated by the column is released from the outlet side of the column, and a part of the component is introduced into the mass spectrometer 30. At the same time, the remainder is released from the outlet side of the branch pipe 44. Thus, the subject 100 can directly smell the odor of the gas derived from the above component released from the outlet side of the branch pipe 44.

[0058] When measuring odor, based on the data measured by the mass spectrometer 30, a measurement chart (GC-MS chart) is obtained that displays the change in the signal intensity of various components contained in the gas emitted from the analysis sample 60 with respect to the retention time. Here, in the GC-MS chart, regardless of whether the subject 100 feels an odor, the signal intensities derived from various components contained in the gas generated from the analysis sample 60 are recorded with respect to the retention time. Also, when the subject 100 who smells the odor of the gas emitted from the outlet side of the branch pipe 44 feels an unpleasant odor, by pressing a button that is electrically linked to the recorder by the subject 100, an odor discrimination chart is obtained that records at which point in time on the retention time the unpleasant odor was felt. Here, the degree of intensity of the unpleasant odor felt by the subject 100 can be reflected as the intensity on the odor discrimination chart by the time of continuously pressing the button.

[0059] Figure 2 is a schematic diagram for explaining the method of interpreting the measurement results obtained by odor measurement. The upper part of Figure 2 shows the GC-MS chart, and the lower part of Figure 2 shows the odor determination chart obtained by measuring in synchronization with the GC-MS chart shown in the upper part. Here, in the GC-MS chart 200 shown in Figure 2, six peaks A1 to F1 resulting from six components contained in the gas generated from the analysis sample 60 are observed. Here, when the subject 100 smells the odors of the components corresponding to peaks B1, D1, and E1 among the six peaks and feels that these odors are unpleasant, peaks B2, D2, and E2 corresponding to each of peaks B1, D1, and E1 are displayed on the odor determination chart 300. And the degree of intensity of the unpleasant odor felt by the subject 100 is reflected as the difference in the intensity of peaks B2, D2, and E2 in the odor determination chart 300. Also, from the comparison result between the GC-MS chart 200 and the odor determination chart 300, it can be understood that among the six peaks A1 to F1 shown in the GC-MS chart 200, the components corresponding to peaks A1, C1, and F1 were not determined as unpleasant odors by the subject 100.

[0060] Therefore, by performing the odor measurement described above and interpreting the measurement results obtained thereby (GC-MS chart 200 and odor determination chart 300), it is possible to determine which component causing the peak detected at which position in the retention time is the cause of the unpleasant odor.

[0061] The measurement conditions for the odor measurement using the headspace gas chromatograph mass spectrometer 10 are as follows. Note that the starting point (0 minutes) of the retention time is the point in time when the needle 50 is pierced into the cap 72 after the temperature of the headspace (the space above the inside of the vial 70) reaches 150°C (in other words, the point in time when the gas generated inside the vial 70 can be introduced into the gas chromatograph device 20). (1) Analytical sample 60 and its treatment conditions · Sampling amount: 5 mg · Heating conditions of vial 70: 150°C, 10 minutes · Temperature of headspace: 150°C (2) Injection port of gas chromatograph device 20 · Heating desorption temperature: 270°C · CIS temperature: 10°C (1.5 min) → temperature increase at 12°C / min → 270°C (3) Gas chromatograph device 20 · Carrier gas: He (120 kPa) · Oven temperature: 40°C (3.0 min) → temperature increase at 10°C / min → 320°C (5 min) (4) Mass spectrometer 30 · Ion source temperature: 250°C · Quadrupole temperature: 150°C (5) Gas injection conditions · Injection volume: 1000 μL · Injection speed: 200 μL / s (6) Column Model number: G3540A

[0062] Note that the odor evaluations shown in Tables 1 to 5 were carried out in the range where the retention time was 0 to 20 min. The maximum value of the retention time was set to 20 min because no peaks were detected or the detected peaks were extremely weak when the retention time was 20 min or more. Also, regarding whether the gas components causing the peaks observed at a specific retention time generate an unpleasant odor (the presence or absence of an unpleasant odor), when two or more out of 100 subjects judged it to be an unpleasant odor, it was determined that an unpleasant odor was generated. Note that the 100 subjects were selected from among the technicians involved in the development of the epoxy resin composition.

[0063] Also, the criteria for judging the "intensity of the unpleasant odor caused by the peak observed during the retention time of 13.0 to 13.2 min" shown in Tables 2 to 5 are as follows. 0: No peak was observed during the retention time of 13.0 to 13.2 min (that is, the gas components that are the sources of the unpleasant odor were not detected). 1: Two or more out of 100 subjects felt a weak but unpleasant odor. 2: Two or more out of 100 subjects felt a significantly unpleasant odor.

[0064] 4.2 Adhesive strength The adhesive strength of the epoxy resin composition was measured according to the procedure described below. First, a silicon chip (10 mm in length × 10 mm in width, 0.625 mm in thickness) was fixed to the center in the width direction of a ceramic plate made of SiN (15 mm in width × 60 mm in length × 0.500 mm in thickness) using a commercially available instant adhesive (Aron Alpha, manufactured by Toagosei Co., Ltd.). Next, a silicone rubber mold (10 mm in width × 15 mm in length × 7 mm in thickness; the shape and dimensions of the hole provided in the center of the mold were frustum-shaped, 3 mm in diameter on the upper surface side of the mold, and 5 mm in diameter on the bottom surface side (the side in contact with the ceramic plate)) was placed on the ceramic plate so as to surround the silicon chip. At this time, three silicon chips and the mold were arranged at substantially equal intervals along the longitudinal direction of the ceramic plate. Then, a washer (M6 stainless steel washer) was placed on the mold so that the center of the hole in the mold and the center of the hole in the washer substantially coincided, thereby forming a laminate in which the ceramic plate, the mold, and the washer were laminated in this order, and further fixing both surfaces of this laminate with metal clips. In this state, after filling the epoxy resin composition into the mold at room temperature, it was heat-cured at 150°C for 2 hours. Then, by removing the clips, washers, and mold from the sample after heat curing, a measurement sample was obtained in which three frustum-shaped cured products covering the three silicon chips fixed on the ceramic plate were formed. Note that for the evaluation of the adhesive strength of the same epoxy resin composition, two measurement samples in which three frustum-shaped cured products were formed on the ceramic plate were prepared.

[0065] Next, at room temperature, using a universal bond tester (manufactured by Nordson Advanced Technology, tool width: 6 mm), a shearing force was applied in a direction parallel to the surface of the ceramic plate to the cured product formed on the ceramic plate, thereby flicking off the cured product from the ceramic plate. At this time, the strength A immediately before the cured product was flicked off was measured. Also, the area of the fracture surface (fracture cross-sectional area B) formed after the cured product was flicked off was measured using a CCD camera (observation magnification: 30 times). Then, the adhesive strength S was determined based on the following formula. · Adhesive strength S (MPa) = Strength A (kg) × 9.8 / Fracture cross-sectional area B (mm 2 )

[0066] Then, the average value of each adhesive strength S obtained by conducting the above-described test on six cured products was taken as the adhesive strength shown in Table 1. Note that if the adhesive strength is 4.0 MPa or more, it is judged to be suitable as the epoxy resin composition used for the sealing treatment.

Explanation of Signs

[0067] 10: Headspace gas chromatograph mass spectrometer 20: Gas chromatograph 30: Mass spectrometer 40: Conduit 42: Duct 44: Branch pipe 50: Needle 60: Analytical sample 70: Vial 72: Cap 100: Subject 200: GC-MS chart 300: Odor judgment chart

Claims

1. Epoxy resin and A hardening accelerator, An epoxy resin composition comprising, When the epoxy resin composition placed in a sealed space is heated at 150°C for 10 minutes, and the gas in the sealed space is measured by gas chromatography-mass spectrometry as a measurement chart showing the change in signal intensity with respect to retention time, no odor is detected at the peak located between 13.0 and 13.2 minutes of retention time. Epoxy resin composition.

2. The epoxy resin composition according to claim 1, wherein no peak is observed in the measurement chart where the retention time is between 13.0 minutes and 13.2 minutes.

3. In the measurement chart, a peak was observed where the retention time was between 13.0 minutes and 13.2 minutes, and the intensity of the observed peak was 1.0 × 10⁻⁶. ３ The epoxy resin composition according to claim 1, which is as follows:

4. The epoxy resin composition according to any one of claims 1 to 3, wherein the amount of the curing accelerator is 1 phr to 10 phr.

5. The epoxy resin composition according to any one of claims 1 to 3, wherein the curing accelerator comprises an imidazole-based curing accelerator.

6. The epoxy resin composition according to any one of claims 1 to 3, wherein the curing accelerator does not contain 2-phenyl-4-methylimidazole.

7. The epoxy resin composition according to any one of claims 1 to 3, wherein the curing accelerator contains 2-phenyl-4-methylimidazole, and the amount of 2-phenyl-4-methylimidazole is greater than 0 phr and 1.5 phr or less.

8. An epoxy resin composition according to any one of claims 1 to 3, comprising a coupling agent.

9. The epoxy resin composition according to any one of claims 1 to 3, which is an epoxy resin composition for compression molding.

10. An electronic component comprising a cured product of the epoxy resin composition according to any one of claims 1 to 3.

11. Multiple stacked semiconductor elements, A semiconductor device comprising at least a cured epoxy resin composition according to any one of claims 1 to 3 for encapsulating the plurality of semiconductor elements.

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