JP2019052246A - Epoxy resin composition - Google Patents

Abstract

The present invention provides an epoxy resin composition that provides a cured product having excellent workability, high adhesion to a base material, and high adhesion retention after storage under high temperature and high humidity. (A) An epoxy resin, (B) an aromatic amine-based curing agent, and (C) an organosilicon compound represented by the formula (1), and (A) with respect to 1 equivalent of all epoxy groups in the epoxy resin. (B) The epoxy resin composition whose ratio of the equivalent of all the amino groups in an aromatic amine type hardening | curing agent is 0.7-1.5. (R is a hydrolyzable group; R ′ is an alkyl group; A is an alkylene group; X is O or S; Z is NH, O or S; M is N or CH; R1 to R4 are each independently H, an alkyl group, An alkoxy group, a fluoroalkyl group, or an amino group; R1 and R2, and R3 and R4 are each bonded to C and a cycloalkyl group or an aryl group; m is an integer of 1 to 3; n is an integer of 0 to 3) ] None

Description

  The present invention relates to an epoxy resin composition, and more particularly, to an epoxy resin composition used for sealing semiconductor devices such as diodes, transistors, ICs, LSIs, and super LSIs.

In a semiconductor device, a process of sealing a semiconductor element such as a semiconductor device such as a diode, a transistor, an IC, an LSI, or a super LSI is one of important processes that affects the reliability of the semiconductor device.
In response to the reduction in size and weight and the increase in functionality of electronic devices, semiconductor devices tend to be thinner and larger while semiconductor devices are becoming smaller, thinner, and narrower in pitch. From the viewpoint of ensuring reliability, it is required to maintain adhesion with a lead frame after moisture absorption treatment and adhesion after high-temperature storage. In addition, a sealing resin having low elasticity and a low coefficient of thermal expansion is required for the purpose of reducing stress between the sealing resin and the lead frame.

So far, a liquid epoxy resin has been proposed in which the reliability of a semiconductor element is improved by adding thermoplastic rubber powder for the purpose of reducing the elasticity of the sealing resin (Patent Document 1). Moreover, the resin composition for semiconductor adhesion which processed the filler surface with the specific silane coupling agent and improved adhesive strength is proposed (patent document 2).
However, the reduction in elasticity with thermoplastic rubber powder has a problem that workability is remarkably deteriorated due to an increase in viscosity. In addition, there is a problem that wettability with the resin is deteriorated although the adhesive strength is increased by applying the treatment with a specific silane coupling agent to the filler.

JP 2014-152310 A JP 2006-089992 A

  Accordingly, an object of the present invention is to provide an epoxy resin composition that is excellent in workability and further excellent in adhesiveness and adhesive retention.

  As a result of intensive studies to solve the above problems, the present inventors have found that (A) an epoxy resin, (B) an aromatic amine-based curing agent, and (C) an epoxy resin containing an organosilicon compound. The present inventors have found that the composition can solve the above problems and have completed the present invention.

  Accordingly, the present invention provides the following epoxy resin composition.

（一般式（１）中、
Ｒは加水分解性基であり、
Ｒ’は炭素数１〜４のアルキル基であり、
Ａは直鎖状又は分岐鎖状の炭素数１〜６のアルキレン基であり、
Ｘは酸素原子又は硫黄原子であり、
ＺはＮＨ、酸素原子又は硫黄原子であり、
Ｍは窒素原子又はＣＨであり、
Ｒ^１〜Ｒ^４はそれぞれ独立に水素原子、炭素数１〜６のアルキル基、アルコキシ基、フルオロアルキル基、又はアミノ基であり、Ｒ^１及びＲ^２が結合する炭素原子とＲ^３及びＲ^４が結合する炭素原子間で二重結合を形成してもよく、Ｒ^１又はＲ^２とＲ^３又はＲ^４が結合してこれらが結合する炭素原子と共に脂肪族環又は芳香族環を形成してもよい。
ｍは１〜３の整数であり、ｎは０〜３の整数である。） [1]
(A) epoxy resin,
(B) an aromatic amine-based curing agent, and (C) an organosilicon compound represented by the following general formula (1), and the above (B) with respect to 1 equivalent of all epoxy groups in the (A) epoxy resin An epoxy resin composition, wherein the ratio of equivalents of all amino groups in the aromatic amine-based curing agent is 0.7 to 1.5.

(In general formula (1),
R is a hydrolyzable group,
R ′ is an alkyl group having 1 to 4 carbon atoms,
A is a linear or branched alkylene group having 1 to 6 carbon atoms,
X is an oxygen atom or a sulfur atom,
Z is NH, an oxygen atom or a sulfur atom,
M is a nitrogen atom or CH,
R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a fluoroalkyl group, or an amino group, and the carbon atom to which R ¹ and R ² are bonded to R ³ and R ^4. A double bond may be formed between carbon atoms to which R ¹ or R ² is bonded, and R ¹ or R ² and R ³ or R ⁴ are bonded to form an aliphatic ring or an aromatic ring together with the carbon atom to which they are bonded. Also good.
m is an integer of 1 to 3, and n is an integer of 0 to 3. )

（式（２）〜（５）中、Ｒ^５〜Ｒ^８は、それぞれ独立して、同一又は異種の炭素数１〜６の１価炭化水素基、ＣＨ_３Ｓ−及びＣＨ_３ＣＨ_２Ｓ−から選ばれる基である。ｐは０〜４の整数である。） [2]
The aromatic amine curing agent of component (B) is one or more selected from aromatic amine compounds represented by the following formulas (2), (3), (4) and (5). [1] The epoxy resin composition according to [1].

(In formulas (2) to (5), R ^{5 to} R ⁸ are each independently the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms, CH ₃ S— and CH ₃ CH ₂ S—. (P is an integer of 0 to 4).

[3]
The epoxy resin composition according to [1] or [2], wherein the amount of component (C) is 0.1 to 10% by mass relative to 100 parts by mass of the total of component (A) and component (B). .

[4]
The epoxy resin composition according to any one of [1] to [3], wherein the epoxy resin as the component (A) is a liquid epoxy resin.

[5]
The epoxy resin composition according to any one of [1] to [4], further comprising (D) an inorganic filler.

[6]
The epoxy resin composition according to any one of [1] to [5], which is liquid at 25 ° C.

  The epoxy resin composition of the present invention is excellent in workability with little change in viscosity over time. Further, the cured product of the epoxy resin composition of the present invention is excellent in adhesion to substrates, particularly copper and silver, and can maintain high adhesion to these substrates even after being stored under high temperature and high humidity. Therefore, since the epoxy resin composition of the present invention becomes a cured product excellent in heat resistance and moisture resistance, it is useful as a sealing material for semiconductor devices.

Hereinafter, the present invention will be described in detail.
The epoxy resin composition of the present invention comprises the following components (A) epoxy resin,
(B) contains an aromatic amine curing agent, and (C) an organosilicon compound.

(A) Epoxy resin The epoxy resin which is a component (A) is not specifically limited, A well-known epoxy resin can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin , Triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, trisphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, aminophenol Type epoxy resin, alicyclic epoxy resin and the like. Moreover, the polyglycerides and diglycidyl ether compounds of polycyclic aromatics such as anthracene are also included. Furthermore, the phosphorus containing epoxy resin etc. which introduce | transduced the phosphorus compound into the epoxy resin of the (A) component illustrated above are mentioned. These may be used alone or in combination of two or more.

  The component (A) is preferably a liquid epoxy resin having a viscosity at 25 ° C. of preferably 0.01 to 100,000 mPa · s, more preferably 0.1 to 10,000 mPa · s. Based on the description of JIS Z 8803: 2011, this viscosity is a viscosity obtained by setting a sample using a conical plate type rotational viscometer (E type viscometer) at a measurement temperature of 25 ° C. and measuring a value after 2 minutes. is there.

  As content of (A) component, it is preferable to make it contain 10-95 mass% in a resin composition, More preferably, it is 15-85 mass%, More preferably, it is 15-80 mass%.

(B) Aromatic amine-based curing agent The aromatic amine-based curing agent as component (B) is a curing agent for the above-mentioned component (A), and in particular, an amine-based one having an aromatic ring excellent in heat resistance and storage stability. Compounds. Specific examples include aromatic amine compounds represented by the following formulas (2) to (5).

In general formulas (2) to (5), R ^{5 to} R ⁸ are each independently the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms, CH ₃ S— and CH ₃ CH ₂ S—. Is a group selected from p is an integer of 0-4.

Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms represented by R ^{5 to} R ⁸ in the general formulas (2) to (5) include methyl group, ethyl group, n-propyl group, isopropyl group, n- Alkyl group such as butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group; cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; vinyl group, 1-propenyl Groups, allyl groups, isopropenyl groups, 1-butenyl groups, 2-butenyl groups, 1-pentenyl groups and the like alkenyl groups; phenyl groups and the like aryl groups. Especially, a C1-C6 alkyl group is preferable.

  Among the aromatic amine curing agents represented by the general formulas (2), (3), (4) and (5), for example, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3, Fragrances represented by general formula (3) such as 3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane 2,4-diaminotoluene, 1,4-diaminobenzene, 1,3-diaminobenzene, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6- Aromatic diamine compounds represented by the general formula (2) such as diamine are preferred. These may be used alone or in combination of two or more.

  Among the aromatic amine-based curing agents, those that are liquid at normal temperature (20 to 30 ° C.) may be blended into the composition as they are, but if solid ones are blended into the composition as they are, the viscosity of the composition increases. Since the workability is remarkably deteriorated, it is preferable to melt and mix with the epoxy resin of the component (A) in advance, and melt and mix at a specific blending ratio described later at a temperature range of 70 to 150 ° C. for 1 to 2 hours. Is more preferable. If the melt mixing temperature is less than 70 ° C, the aromatic amine curing agent may not be sufficiently compatible with the component (A) epoxy resin, and if the temperature exceeds 150 ° C, the component (A) epoxy resin and There is a risk that the viscosity will increase upon reaction. Also, if the melt mixing time is less than 1 hour, the aromatic amine-based curing agent is not sufficiently compatible with the component (A) epoxy resin, and may increase the viscosity, and if it exceeds 2 hours (A) It may react with the component epoxy resin to increase the viscosity.

  The blending amount of the aromatic amine curing agent is such that the ratio of the equivalent of all amino groups in the aromatic amine curing agent to 1 equivalent of all epoxy groups in the component (A) is 0.7 to 1.5. The amount is preferably 0.7 to 1.2, more preferably 0.7 to 1.1, and still more preferably 0.85 to 1.05. If the ratio of the above equivalents is less than 0.7, unreacted epoxy groups remain, the glass transition temperature of the cured product of the epoxy resin composition may be lowered, and the adhesion may be lowered. On the other hand, when the above equivalent ratio exceeds 1.5, the cured product of the epoxy resin composition becomes hard and brittle, and cracks may occur during reflow or a temperature cycle test.

(C) Organosilicon compound (C) The organosilicon compound is represented by the following general formula (1).

In general formula (1),
R is a hydrolyzable group,
R ′ is an alkyl group having 1 to 4 carbon atoms,
A is a linear or branched alkylene group having 1 to 6 carbon atoms,
X is an oxygen atom or a sulfur atom,
Z is NH, an oxygen atom or a sulfur atom,
M is a nitrogen atom or CH,
R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a fluoroalkyl group, or an amino group, and the carbon atom to which R ¹ and R ² are bonded to R ³ and R ^4. A double bond may be formed between carbon atoms to which R ¹ or R ² is bonded, and R ¹ or R ² and R ³ or R ⁴ are bonded to form an aliphatic ring or an aromatic ring together with the carbon atom to which they are bonded. Also good. m is an integer of 1 to 3, and n is an integer of 0 to 3.

  Here, in the general formula (1), the hydrolyzable group represented by R specifically includes halogen atoms such as chlorine and bromine; alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group. Etc.

  Examples of the alkyl group having 1 to 4 carbon atoms represented by R ′ include a methyl group, an ethyl group, and a propyl group.

  Examples of the linear alkylene group having 1 to 6 carbon atoms represented by A include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and the like, and a branched chain having 1 to 6 carbon atoms represented by A. Examples of the alkylene group include, but are not limited to, a propylene group, a methylethylene group, and a 1,1-dimethylethylene group.

^The alkyl group having 1 to 6 carbon atoms represented by R 1 to R ^4, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, s- butyl, t -A butyl group, a pentyl group, a hexyl group, etc. are mentioned.

Examples of the alkoxy group represented by R ^{1 to} R ⁴ include a methoxy group, an ethoxy group, and a propoxy group.

Examples of the fluoroalkyl group represented by R ^{1 to} R ⁴ include groups in which some or all of the hydrogen atoms of the above-described alkyl group having 1 to 6 carbon atoms have been substituted with fluorine atoms.

The case where a double bond is formed between the carbon atom to which R ¹ and R ² are bonded and the carbon atom to which R ³ and R ⁴ are bonded is specifically represented by the following structural formula (in the following structural formula, the ^{R 1} of R ¹ and ^{R 2,} showed ^{R 3} of ^{R 3} and ^{R 4,} may be ^R 2, ^{R 4} which are respectively). As a result of forming a double bond between the carbon atom to which R ¹ and R ² are bonded and the carbon atom to which R ³ and R ⁴ are bonded, the carbon atom to which R ¹ (R ² ) is bonded and R ³ (R ⁴ 6-membered ring having a carbon atom to which) is bonded (hereinafter simply referred to as a heterocyclic ring) has a resonance structure in the following structure. Therefore, the specific structure in the case where a double bond is formed between the carbon atom to which R ¹ and R ² are bonded and the carbon atom to which R ³ and R ⁴ are bonded includes a resonance structure having the following structural formula.

Examples of the aliphatic ring that forms a condensed ring with the heterocyclic ring together with the carbon atom to which R ¹ or R ² and R ³ or R ⁴ are bonded include a cycloheptane ring, a cyclohexane ring, and the like. The hydrogen atom of the group ring may be substituted with an alkyl group or the like.
The aromatic ring that forms a condensed ring with the heterocyclic ring together with the carbon atom to which R ¹ or R ² and R ³ or R ⁴ are bonded includes a monocyclic benzene ring; a condensed polycyclic naphthalene A ring, a fluorene ring, a phenanthrene ring, an anthracene ring, and the like. The hydrogen atom of these aromatic rings may be substituted with an alkyl group or the like.

  The compounding amount of the organosilicon compound (C) is preferably 0.1 to 10% by mass with respect to 100 parts by mass in total of the component (A) and the component (B), and 0.2 to 5 mass. % Is more preferable.

  In addition to the components (A) to (C), (D) an inorganic filler and / or (E) other additives can be appropriately blended in the epoxy resin composition of the present invention.

(D) Inorganic filler (D) The inorganic filler is appropriately added as necessary to reduce the thermal expansion coefficient and improve the moisture resistance reliability of the epoxy resin composition. Examples of the inorganic filler include: Examples thereof include silicas such as fused silica, crystalline silica, and cristobalite, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, and magnesium oxide. The average particle diameter and shape of these inorganic fillers can be selected according to the application. Of these, spherical alumina, spherical fused silica, glass fiber and the like are preferable.
(D) It is preferable that the compounding quantity of an inorganic filler shall be 20-1,500 mass% with respect to a total of 100 mass parts of (A)-(C) component, More preferably, it is 50-1,000 mass%. It is.

(E) Other Additives The epoxy resin composition of the present invention may contain the component (E) as other additives, as necessary, within a range that does not impair the objects and effects of the present invention. Examples of the additive include a curing accelerator, a release agent, a flame retardant, an ion trap agent, an antioxidant, an adhesion imparting agent, a low stress agent, and a colorant.

  The curing accelerator is not particularly limited as long as it accelerates the reaction between the epoxy resin and the amine curing agent, and a conventionally known curing accelerator can be used. Examples of the curing accelerator include basic organic compounds selected from tetraphenylphosphine, imidazole, and tertiary amine. Examples of tetraphenylphosphine include tetraphenylphosphine and tetraphenylborate derivatives. Examples of imidazole include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxy Examples thereof include triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo [5,4,0, and the like. ] Undecene-7 etc. are mentioned.

  It is preferable that the addition amount of a hardening accelerator is 0-20 mass parts with respect to a total of 100 mass parts of (A) and (B) component. When there are more hardening accelerators than an upper limit, there exists a possibility that the preservability of an epoxy resin composition may be impaired.

  The curing accelerator is preferably in the form of a powder having an average particle size of 1 to 5 μm and a maximum particle size of 20 μm or less. More preferably, the average particle size is 2 to 5 μm and the maximum particle size is 15 μm or less. When the average particle size is smaller than the lower limit, the specific surface area increases, and the viscosity of the composition may increase when mixed with the composition. When the average particle size exceeds the upper limit, dispersion with the epoxy resin becomes non-uniform, which may cause a decrease in reliability.

  Moreover, the purity of this hardening accelerator becomes like this. Preferably it is 90% or more, More preferably, it is 93% or more. If the purity is less than 90%, the reactivity may vary and the curability may vary.

  The release agent is added for the purpose of improving the release property from the mold. Examples of the mold release agent include carnauba wax, rice wax, candelilla wax, polyethylene, polyethylene oxide, polypropylene, montanic acid, montan wax (montanic acid, saturated alcohol, 2- (2-hydroxyethylamino) ethanol, Examples thereof include all known compounds such as ester compounds with ethylene glycol or glycerin), stearic acid, stearic acid esters, and stearic acid amides.

  The flame retardant is added for the purpose of imparting flame retardancy. The flame retardant is not particularly limited, and all known ones can be used. For example, phosphazene compounds, silicone compounds, zinc molybdate-supported talc, zinc molybdate-supported zinc oxide, aluminum hydroxide, magnesium hydroxide, Examples thereof include molybdenum oxide.

The ion trapping agent is added for the purpose of capturing ionic impurities contained in the resin composition and preventing thermal deterioration and moisture absorption deterioration.
The ion trapping agent is not particularly limited, and all known ones can be used, and examples thereof include hydrotalcites, bismuth hydroxide compounds, rare earth oxides, and the like.

  The stress reducing agent is added for the purpose of suppressing resin cracking and reducing elasticity. Examples of the low stress agent include liquid silicone resin, liquid acrylic resin, liquid butadiene rubber, solid silicone resin, solid acrylic resin, and solid butadiene rubber.

  The compounding amount of the component (E) other than the curing accelerator varies depending on the purpose of use of the epoxy resin composition, but can usually be 10% by mass or less of the entire epoxy resin composition. (E) When mix | blending a component, it is preferable that it is 5 mass% or more.

  The epoxy resin composition of the present invention can be prepared by the following method. For example, (A) an epoxy resin, (B) an aromatic amine-based curing agent, and (C) an organosilicon compound are mixed, stirred, dissolved and / or dispersed while performing heat treatment simultaneously or separately as necessary. Thus, a resin mixture of components (A) to (C) can be obtained. There is also a method of obtaining a resin mixture of components (A) to (D) by adding, stirring, dissolving and / or dispersing (D) inorganic filler to a mixture of components (A) to (C). Further, depending on the application, the mixture of the components (A) to (C) or the mixture of the components (A) to (D) may be added with a curing accelerator, a release agent, a flame retardant, an ion trap agent and a low stress agent ( E) At least one additive may be added and mixed. Each component of (A) to (E) may be used alone or in combination of two or more.

  There are no particular limitations on the method for preparing the resin mixture and the apparatus for mixing, stirring and dispersing. Specifically, for example, a raikai machine equipped with a stirring and heating device, a two-roll mill, a three-roll mill, a ball mill, a planetary mixer, a mass collider, or the like can be used, and these devices are used in appropriate combinations. Also good.

  When the epoxy resin composition of the present invention is also used as a sealing material for semiconductor devices, it is preferably liquid at 25 ° C. In this case, the viscosity of the liquid epoxy resin composition is 1 at a viscosity of 25 ° C. measured at a rotation speed of 1 rpm using an E-type rotational viscometer by appropriately selecting the types and blending amounts of the components described above. 000 Pa · s or less, and particularly preferably 500 Pa · s or less. The lower limit is not particularly limited, but is usually 1 Pa · s or more.

  Moreover, although the shaping | molding method and shaping | molding conditions of the epoxy resin composition of this invention can be made into a conventional method, Preferably it post-cure at 150-180 degreeC for 1-3 hours after shaping | molding hardening at 40-100 degreeC. For example, it is more preferable to post-cure in a heat oven at 150 ° C. for 1 hour or longer. If the post cure is less than 1 hour at 150 ° C., sufficient cured product properties may not be obtained.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Examples 1 to 12 and Comparative Examples 1 to 11]
About Examples 1-12 and Comparative Examples 1-11, each component shown below was mix | blended with the composition shown in Table 1, 2, and the epoxy resin composition was prepared. In Tables 1 and 2, the amount of each component indicates parts by mass. “(B) / (A) molar ratio” in Tables 1 and 2 indicates the equivalent of all amino groups in component (B) to 1 equivalent of all epoxy groups in component (A).

(A) Epoxy resin (1) Epoxy resin (A1): Bisphenol A type epoxy resin (Epicoat 828: manufactured by Mitsubishi Chemical Corporation)
(2) Epoxy resin (A2): aminophenol type trifunctional epoxy resin (jER630: manufactured by Mitsubishi Chemical Corporation)

(B) Aromatic amine curing agent (1) Aromatic amine curing agent (B1): 3,3′-diethyl-4,4′-diaminodiphenylmethane (Kayahard AA, manufactured by Nippon Kayaku Co., Ltd.)
(2) Aromatic amine curing agent (B2): Diethyltoluenediamine (Etacure 100, manufactured by Albemarle Corporation)
Non-aromatic amine curing agent (for comparative example)
(3) Alicyclic amine-based curing agent (B3): 1,3-bisaminomethylcyclohexane (1,3-BAC, manufactured by Mitsubishi Gas Chemical Company)

有機ケイ素化合物（比較例用）
（２）有機ケイ素化合物（Ｃ２）（３−グリシドキシプロピルトリメトキシシラン：信越化学工業社製）
（３）有機ケイ素化合物（Ｃ３）（３−メルカプトプロピルトリメトキシシラン：信越化学工業社製）
（４）有機ケイ素化合物（Ｃ４）（下記式（７）：信越化学工業社製）

（５）有機ケイ素化合物（Ｃ５）（下記式（８）：信越化学工業社製）

（６）有機ケイ素化合物（Ｃ６）（３−グリシドキシプロピルトリメトキシシランとイミダゾールとの付加物（下記式（９））：信越化学工業製）

(C) Organosilicon compound (1) Organosilicon compound (C1) (Formula (6) below: manufactured by Shin-Etsu Chemical Co., Ltd.)

Organosilicon compound (for comparative example)
(2) Organosilicon compound (C2) (3-glycidoxypropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd.)
(3) Organosilicon compound (C3) (3-mercaptopropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd.)
(4) Organosilicon compound (C4) (following formula (7): manufactured by Shin-Etsu Chemical Co., Ltd.)

(5) Organosilicon compound (C5) (Formula (8) below: manufactured by Shin-Etsu Chemical Co., Ltd.)

(6) Organosilicon compound (C6) (addition product of 3-glycidoxypropyltrimethoxysilane and imidazole (the following formula (9)): manufactured by Shin-Etsu Chemical Co., Ltd.)

(D) Inorganic filler (1) Fused spherical silica having an average particle size of 13 μm (Product name: CS-6103 53C, manufactured by Tatsumori)

  About each obtained composition, the test was done by the evaluation method shown below. The results are shown in Tables 1 and 2.

上記式の粘度増加率が１００〜２００％未満の範囲の場合には「○」と評価し、２００％以上の場合には「×」と評価し、その結果を表１，２に記載した。 [Viscosity increase rate]
About the viscosity (henceforth an initial viscosity, unit: mPa * s) of the resin composition immediately after producing in Examples 1-12 and Comparative Examples 1-11, according to JISZ8803: 2011 at 25 degreeC measurement temperature. The resin composition (sample) of each example was set using a conical plate type rotational viscometer (E type viscometer), and the value after 2 minutes was measured.
Further, the viscosity after holding the resin composition of each example at 25 ° C. for 24 hours (hereinafter referred to as viscosity after 24 hours; unit: mPa · s) was also measured in the same manner, and the rate of increase in viscosity (unit:%) was measured. It was calculated by the following formula.

When the viscosity increase rate of the above formula was in the range of 100 to less than 200%, it was evaluated as “◯”, and when it was 200% or more, it was evaluated as “x”, and the results are shown in Tables 1 and 2.

(Curing sample preparation conditions)
About the epoxy resin composition of each example of Examples 1-12 and Comparative Examples 1-11, since the composition before hardening is liquid at 25 degreeC, the epoxy resin composition of each example is 0.5 at 120 degreeC. After heating for a period of time, molding was performed at 165 ° C. for 3 hours to prepare a test piece for use in the following test.

[Cu adhesion test 1]
An epoxy resin composition of the present invention is applied onto a Cu lead frame having a size of 10 × 10 mm so as to have a coating area of 4 mm ^2, and a silicon chip is placed thereon, and then the epoxy resin is cured under the above curing conditions. A test piece for Cu adhesion test was prepared by curing the composition. Using this test piece, a bond tester DAGE-SERIES-4000PXY (manufactured by DAGE) was used to measure a shear adhesive force at 150 ° C. (hereinafter referred to as initial shear adhesive force) as an adhesive evaluation. The bonding area between the frame of the test piece and the resin is 4 mm ² . The results are shown in Tables 1 and 2.

[Cu adhesion test 2]
Similarly to the Cu adhesion test 1, a test piece for a Cu adhesion test was produced. The test piece for Cu adhesion test was stored at 180 ° C. for 500 hours, then cooled to room temperature, and the shear adhesion was measured in the same manner as the above-described method for measuring the initial shear adhesion. The adhesive strength retention (%) after high temperature storage was calculated by the following formula. Tables 1 and 2 show the adhesive strength retention of each test piece after high-temperature storage.

[Cu adhesion test 3]
Similarly to the Cu adhesion test 1, a test piece for a Cu adhesion test was produced. After storing the test piece for Cu adhesion test at 85 ° C./85% RH (relative humidity) for 168 hours, the test piece was cooled to room temperature, and the shear adhesion force was measured in the same manner as the above-described method for measuring the initial shear adhesion force. It was measured. The adhesion retention (%) after storage at high temperature and high humidity was calculated by the following formula. Tables 1 and 2 show the adhesive strength retention of each test piece after storage at high temperature and high humidity.

[Ag adhesion test 1]
An epoxy resin composition of the present invention is applied on an Ag lead frame having a size of 10 × 10 mm so as to have a coating area of 4 mm ^2, and a silicon chip is placed on the epoxy resin composition. A test piece for an Ag adhesion test was prepared by curing the composition. Using this test piece, a bond tester DAGE-SERIES-4000PXY (manufactured by DAGE) was used to measure a shear adhesive force at 150 ° C. (hereinafter referred to as initial shear adhesive force) as an adhesive evaluation. The bonding area between the frame of the test piece and the resin is 4 mm ² . The results are shown in Tables 1 and 2.

[Ag adhesion test 2]
Similarly to the Ag adhesion test 1, a test piece for Ag adhesion test was prepared. The test piece for Ag adhesion test was stored at 180 ° C. for 500 hours, cooled to room temperature, and the shear adhesion was measured in the same manner as the above-described method for measuring the initial shear adhesion. The adhesive strength retention (%) after high temperature storage was calculated by the following formula. Tables 1 and 2 show the adhesive strength retention of each test piece after high-temperature storage.

[Ag adhesion test 3]
Similarly to the Ag adhesion test 1, a test piece for Ag adhesion test was prepared. The Ag adhesion test test piece was stored at 85 ° C./85% RH for 168 hours, then cooled to room temperature, and the shear adhesive strength was measured in the same manner as the above-described initial shear adhesive strength measurement method. The adhesion retention (%) after storage at high temperature and high humidity was calculated by the following formula. Tables 1 and 2 show the adhesive strength retention of each test piece after storage at high temperature and high humidity.

Claims (6)

(A) epoxy resin,
(B) an aromatic amine-based curing agent, and (C) an organosilicon compound represented by the following general formula (1), and the above (B) with respect to 1 equivalent of all epoxy groups in the (A) epoxy resin An epoxy resin composition, wherein the ratio of equivalents of all amino groups in the aromatic amine-based curing agent is 0.7 to 1.5.

(In general formula (1),
R is a hydrolyzable group,
R ′ is an alkyl group having 1 to 4 carbon atoms,
A is a linear or branched alkylene group having 1 to 6 carbon atoms,
X is an oxygen atom or a sulfur atom,
Z is NH, an oxygen atom or a sulfur atom,
M is a nitrogen atom or CH,
R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group , a fluoroalkyl group, or an amino group, and the carbon atom to which R ¹ and R ² are bonded to R ³ and R ^4. A double bond may be formed between carbon atoms to which R ¹ or R ² is bonded, and R ¹ or R ² and R ³ or R ⁴ are bonded to form an aliphatic ring or an aromatic ring together with the carbon atom to which they are bonded. Also good.
m is an integer of 1 to 3, and n is an integer of 0 to 3. ) The aromatic amine curing agent of component (B) is one or more selected from aromatic amine compounds represented by the following formulas (2), (3), (4) and (5). The epoxy resin composition according to claim 1.

(In formulas (2) to (5), R ^{5 to} R ⁸ are each independently the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms, CH ₃ S— and CH ₃ CH ₂ S—. (P is an integer of 0 to 4).   The compounding quantity of (C) component is 0.1-10 mass% with respect to a total of 100 mass parts of the said (A) component and (B) component, The epoxy resin composition of Claim 1 or 2.   The epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin (A) is a liquid epoxy resin.   Furthermore, the epoxy resin composition of any one of Claims 1-4 containing (D) inorganic filler. The epoxy resin composition according to any one of claims 1 to 5, which is liquid at 25 ° C.