JPWO2012147874A1 - RESIN COMPOSITION FOR ELECTRONIC COMPONENT AND ELECTRONIC COMPONENT DEVICE - Google Patents

Abstract

The present invention contains an epoxy resin, an aromatic amine compound, and at least one compound selected from the group of compounds having a structural moiety represented by the following general formula (I) as a curing accelerator. A resin composition for electronic parts is provided. In formula, L1 shows the bivalent group comprised from a carbon atom, a hydrogen atom, and an oxygen atom, or a bivalent hydrocarbon group. R1 to R3 each independently represents a monovalent group, a monovalent hydrocarbon group, or a hydrogen atom composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, and a sulfur atom. Show. R4 to R7 are each independently a monovalent group, a monovalent hydrocarbon group, a hydroxyl group, or hydrogen composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, and a sulfur atom. Indicates an atom. Two groups selected from R4 to R7 may be bonded to each other to form a ring.

Description

  The present invention relates to a resin composition for electronic components and an electronic component device.

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin compositions have been widely used. This is because the epoxy resin is balanced in various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. Liquid resin compositions for electronic components are widely used as sealing materials in semiconductor devices mounted on bare chips such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package). Further, in a semiconductor device (flip chip) in which a semiconductor element is directly bump-connected to a wiring board having a ceramic, glass / epoxy resin, glass / imide resin, or polyimide film as a substrate, the bump-connected semiconductor element and the wiring board A liquid resin composition for electronic parts is used as an underfill material for filling the gap. These liquid resin compositions for electronic parts play an important role in protecting electronic parts from temperature and humidity and mechanical external force.

  When flip chip mounting is performed, the element and the substrate have different coefficients of thermal expansion, and thermal stress is generated at the joint. Therefore, ensuring connection reliability is an important issue. In addition, since the circuit forming surface of the bare chip is not sufficiently protected, moisture and ionic impurities are liable to enter, and ensuring moisture resistance reliability is also an important issue. In order to protect the chip, fillets are formed on the side of the chip, but the thermal stress caused by the difference in thermal expansion between the underfill material and the chip causes cracks in the resin, resulting in the worst case destroying the chip. There is a fear. Furthermore, depending on the selection of the underfill material, the joint may not be sufficiently protected when subjected to repeated thermal shocks in a temperature cycle test or the like, and the joint may be fatigued at low cycles. Further, if voids are present in the underfill material, the bumps are not sufficiently protected, and the joint portion may be similarly fatigued at low cycles.

  Under the above circumstances, an epoxy resin composition for sealing excellent in moisture-resistant adhesive strength and low stress resistance, and an electronic component device having high reliability (moisture resistance and thermal shock resistance) provided with an element sealed thereby In order to provide, (A) a liquid epoxy resin, (B) a curing agent containing a liquid aromatic amine, (C) an elastomer, (D) an epoxy resin composition for sealing containing a surfactant, and this sealing An electronic component device including an element sealed with a stopping epoxy resin composition is disclosed (for example, see Japanese Patent No. 3716237).

  While the chip size has increased with the recent increase in the degree of integration and functionality of the device, the bump diameter has been reduced, the pitch has been reduced, and the gap has been reduced due to the increase in the number of pins. Furthermore, chip thickness has been reduced with the miniaturization of on-board equipment, and it has become increasingly difficult to ensure high reliability of electronic component devices only by adding an elastomer and a surfactant.

  The present invention has been made in view of such circumstances, and has a long pot life, a fast gel time, and a resin composition for electronic components capable of lowering the curing temperature, as well as being sealed with moisture resistance and temperature resistance. It is an object of the present invention to provide an electronic component device that is excellent in reliability such as cycle performance.

  As a result of intensive studies, the present inventors have found a resin composition for electronic parts containing a specific curing agent and a curing accelerator. The present invention includes the following aspects.

<1> An electron containing an epoxy resin, an aromatic amine compound, and a curing accelerator containing at least one compound selected from the group of compounds having a structural moiety represented by the following general formula (I) It is a resin composition for parts.

(Wherein, L ¹ represents a carbon atom, a divalent group having 1 to 18 carbon atoms comprised of hydrogen atoms and oxygen atoms, or a divalent hydrocarbon group having 1 to 18 carbon atoms.
R ^{1 to} R ³ are each independently a monovalent group having 1 to 18 carbon atoms composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom; -18 monovalent hydrocarbon groups or hydrogen atoms.
R ^{4 to} R ⁷ are each independently a monovalent group having 1 to 18 carbon atoms composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom; -18 monovalent hydrocarbon groups, hydroxyl groups, or hydrogen atoms. Two adjacent groups selected from R ^{4 to} R ⁷ may be bonded to each other to form a ring. )

<2> The said hardening accelerator is a resin composition for electronic components as described in said <1> containing the compound represented by either of the following general formula (IIa), (IIb), and (IIc).

^{(Wherein, L 21} is a carbon atom, a divalent group having from 1 to 18 hydrogen atoms and carbon atoms composed of an oxygen atom, or ^{.R 21} ~ for a divalent hydrocarbon group having 1 to 18 carbon atoms R ²⁶ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, Ar represents an m-valent aromatic hydrocarbon group having 6 to 18 carbon atoms, or at least two carbon atoms having 6 carbon atoms. -18 aromatic hydrocarbon groups are linked by a linking group consisting of at least one selected from the group consisting of a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms, a carbonyl group and an oxygen atom. And m represents an integer of 2 to 8, m represents an integer of 2 to 8, and n represents an integer of 0 to 20.)

<3> The said hardening accelerator is a resin composition for electronic components as described in said <1> containing the compound represented by the following general formula (III).

^{(Wherein, L 21} is a carbon atom, a divalent group having from 1 to 18 hydrogen atoms and carbon atoms composed of an oxygen atom, or ^{.R 21} ~ for a divalent hydrocarbon group having 1 to 18 carbon atoms R ²³ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ²⁷ represents a hydrogen atom or a group represented by the following general formula (IIIa) or general formula (IIIb). Show.

Ar represents an m-valent aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 2 or more carbon atoms having a single bond or an alkylene group having 1 to 12 carbon atoms, a carbonyl group, and oxygen. A group which is linked by at least one linking group selected from the group consisting of atoms and becomes m-valent as a whole is shown.
m represents an integer of 1 to 8, p represents an integer of 1 to 8, and m ≧ p. )

<4> The curing accelerator is any one of the above <1> to <3>, which is an addition reaction product of at least one compound having a phenolic hydroxyl group and at least one compound having a vinyl ether group. It is a resin composition for electronic components as described in one.

<5> The resin composition for electronic components according to any one of <1> to <4>, wherein the epoxy resin is a liquid epoxy resin.

<6> The resin composition for electronic components according to any one of <1> to <5>, wherein the aromatic amine compound is a liquid aromatic amine compound.

<7> The above <1> to <6>, further containing an inorganic filler, wherein the content of the inorganic filler is in the range of 50% by mass to 80% by mass in the total mass of the resin composition for electronic components. It is the resin composition for electronic components as described in any one of these.

<8> Any of the above <1> to <7>, wherein the aromatic amine compound contains at least one selected from the group consisting of 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine. It is the resin composition for electronic components as described in any one.

<9> A semiconductor element, an inorganic or organic substrate having a circuit on a surface opposite to a surface on which the electrode of the semiconductor element is formed, and the semiconductor element and the substrate are sandwiched between the electrode and the electrode A bump for electrically connecting a circuit; and a cured product of the resin composition for electronic components according to any one of <1> to <8>, which is filled in a gap between the semiconductor element and the substrate. , An electronic component device.

  According to the present invention, a resin composition for electronic parts that has a long pot life, a fast gel time, and a low curing temperature, and an electron that is sealed by this and has excellent reliability such as moisture resistance and temperature cycle resistance. A component device can be provided.

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Further, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

<Resin composition for electronic parts>
The resin composition for electronic parts of the present invention comprises (A) at least one epoxy resin, (B) at least one aromatic amine compound, and a compound group having a structural moiety represented by the following general formula (I) And (C) a curing accelerator containing at least one compound selected from the above (hereinafter also referred to as “specific curing accelerating compound”).

Wherein, L ¹ represents a carbon atom, a divalent group having 1 to 18 carbon atoms comprised of hydrogen atoms and oxygen atoms, or a divalent hydrocarbon group having 1 to 18 carbon atoms. R ^{1 to} R ³ are each independently a monovalent group having 1 to 18 carbon atoms composed of at least one selected from a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom, and a monovalent group having 1 to 18 carbon atoms. Represents a hydrocarbon group or a hydrogen atom. R ^{4 to} R ⁷ are each independently a monovalent group having 1 to 18 carbon atoms composed of at least one selected from a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom, and a monovalent group having 1 to 18 carbon atoms. Represents a hydrocarbon group, a hydroxyl group, or a hydrogen atom.
Two adjacent groups selected from R ^{4 to} R ⁷ may be bonded to each other to form a ring structure.

  By containing a curing accelerator containing a compound having a specific structure, the resin composition for electronic parts has excellent pot life and fluidity in a narrow gap, suppresses the generation of voids during molding, and shortens the gel time. This makes it possible to lower the curing temperature. Moreover, the cured | curing material formed has the small fall of the adhesive force with various base materials by moisture absorption, and the adhesive strength with various base materials is high after moisture absorption. Furthermore, the thermal stress applied to the chip is reduced. Therefore, if an electronic component is sealed using this resin composition for electronic components, an electronic component device with high moldability and reliability can be obtained, and its industrial value is extremely high.

  This can be considered as follows, for example. The specific curing accelerating compound is considered to be excellent in storage stability and various reliability because it is blocked by adding a vinyl group to a phenolic hydroxyl group having a curing accelerating action. Further, since the vinyl group is rapidly desorbed by heating at the time of curing, it can be considered that the gel time is shortened and the curing temperature can be lowered.

The resin composition for electronic parts is preferably liquid. In this specification, liquid means liquid at normal temperature (25 ° C.). Specifically, it means that the viscosity measured with an E-type viscometer is 1000 Pa · s or less at 25 ° C. However, when the resin composition for electronic parts of the present invention is cured by reaction or the like, it may become a solid even at room temperature. In addition, the viscosity is assumed to be a sample using an E-type viscometer EHD type (cone angle 3 °, cone diameter 28 mm), measurement temperature: 25 ° C., sample volume: 0.7 ml, and referring to the following. The value after one minute has elapsed from the start of measurement is set as the measured value.
(1) When the assumed viscosity is 100 Pa · s or more and 1000 Pa · s or less: Rotational speed: 0.5 rpm
(2) When the assumed viscosity is less than 100 Pa · s: 5 rpm

(A) Epoxy resin The resin composition for electronic components of the present invention contains at least one epoxy resin. The epoxy resin is not particularly limited and can be appropriately selected from conventionally used epoxy resins. Among them, those having two or more epoxy groups in one molecule are preferable, and liquid epoxy resins having two or more epoxy groups in one molecule and liquid at normal temperature are more preferable.

As an epoxy resin, the epoxy resin generally used with the resin composition for electronic components can be used. Examples of the epoxy resin include bisphenol-type epoxy resins that are diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A; Epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or co-condensation of alcohols; glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin; Glycidylamine-type epoxy resin obtained by reaction of amine compounds such as isocyanuric acid and epichlorohydrin; linear aliphatic epoxy obtained by oxidizing olefinic bonds with peracids such as peracetic acid Fat, such as alicyclic epoxy resins. These may be used alone or in combination of two or more.
Among these, from the viewpoint of fluidity, a liquid bisphenol type epoxy resin is preferable. From the viewpoint of heat resistance, adhesiveness and fluidity, liquid glycidylamine type epoxy resins are preferred.

  The liquid epoxy resin (preferably at least one selected from the group consisting of a liquid bisphenol-type epoxy resin and a liquid glycidylamine-type epoxy resin) may be used alone or in combination of two or more. May be used. The content of the liquid epoxy resin is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 70% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. More preferably.

  Moreover, the said resin composition for electronic components may contain the solid epoxy resin if it is in the range with which the effect of this invention is achieved. When the resin composition for electronic parts contains a solid epoxy resin, the content of the solid epoxy resin is preferably 70% by mass or less and 50% by mass or less in the total amount of the epoxy resin from the viewpoint of fluidity during molding. It is more preferable that it is 30% by mass or less. In addition, a solid epoxy resin means that it is a solid epoxy resin at normal temperature (25 degreeC).

  The epoxy equivalent of the epoxy resin is not particularly limited. Especially, it is preferable that it is 50-5000, More preferably, it is 70-1000, More preferably, it is 70-500.

  The purity of the epoxy resin, particularly the amount of hydrolyzable chlorine, is preferably less because it relates to corrosion of aluminum wiring on the IC and other elements, and is 500 ppm or less in order to obtain a resin composition for electronic parts having excellent moisture resistance. It is preferable. Here, the amount of hydrolyzable chlorine is a value obtained by dissolving 1 g of the epoxy resin of the sample in 30 ml of dioxane, adding 5 ml of 1M-KOH methanol solution, refluxing for 30 minutes and then potentiometric titration. It is.

  The content of the epoxy resin in the resin composition for electronic parts is not particularly limited. For example, from the viewpoint of viscosity and strength, it is preferably 5% by mass to 90% by mass, and more preferably 10% by mass to 70% by mass.

(B) Aromatic amine compound The resin composition for electronic parts contains at least one aromatic amine compound. The aromatic amine compound is not particularly limited as long as it includes an amine compound having an aromatic ring group. Among them, an aromatic amine compound that is liquid at room temperature is preferable. In the resin composition for electronic parts, the aromatic amine compound functions as a curing agent, for example.

  As aromatic amine compounds, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5 -Triethyl-2,6-diaminobenzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,5,3 ′, 5′-tetramethyl-4,4′-diaminodiphenylmethane and the like.

These aromatic amine compounds are, for example, commercially available products such as jER Cure W (trade name, manufactured by Mitsubishi Chemical Corporation), Kayahard A-A, Kayahard AB, Kayahard AS (manufactured by Nippon Kayaku Co., Ltd., Product name), Totoamine HM-205 (trade name, manufactured by Toto Kasei Co., Ltd.), Adeka Hardener EH-101 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), Epomic Q-640, Epomic Q-643 (Mitsui Chemicals, Inc.) Company name, product name), DETDA80 (Lonza company name, product name) and the like are available.
These aromatic amine compounds may be used alone or in combination of two or more.

  Among the aromatic amine compounds, from the viewpoint of storage stability, at least one selected from the group consisting of 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine is preferable. It is more preferable to contain 20% by mass or more of at least one selected from the group consisting of 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine, and in the wholly aromatic amine compound, It is more preferable to contain 30% by mass or more of at least one selected from the group consisting of 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine.

Examples of the diethyltoluenediamine include 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine. These may be used alone or in a mixture.
In particular, it is preferable that 60% by mass or more of 3,5-diethyltoluene-2,4-diamine is contained in the wholly aromatic amine compound.

  The active hydrogen equivalent of the aromatic amine compound is not particularly limited. Among these, it is preferably 30 or more and 1000 or less, more preferably 30 or more and 500 or less, and further preferably 30 or more and 200 or less.

In the electronic component resin composition, in addition to the aromatic amine compound, an amine-based curing agent other than the aromatic amine compound, a phenolic curing agent, an acid anhydride, as long as the effects of the present invention are achieved. The other hardening | curing agent generally used with the resin composition for electronic components, such as a thing, can be used together. The other curing agent may be a liquid curing agent or a solid curing agent.
When other curing agents are used in combination, the content of the aromatic amine compound is preferably 60% by mass or more in the total amount of the curing agent in order to exhibit its performance.

  There is no particular limitation on the equivalent ratio of (A) the epoxy resin and (B) the curing agent containing the aromatic amine compound contained in the resin composition for electronic parts. In order to reduce the amount of each unreacted component, it is preferable to set the curing agent in the range of 0.7 equivalents or more and 1.8 equivalents or less with respect to 1.0 equivalent of the epoxy resin, and 0.8 equivalents or more and 1.6 equivalents or less. An equivalent or less is more preferable, and 1.0 or more and 1.5 equivalents or less are still more preferable.

(C) Curing accelerator The resin composition for an electronic component includes at least one compound (specific curing accelerating compound) selected from the group of compounds having a structural moiety represented by the following general formula (I). Contains an accelerator.

In the formula, L ¹ represents “a divalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and an oxygen atom” or “a divalent hydrocarbon group having 1 to 18 carbon atoms”. R ^{1 to} R ³ each independently represents “a monovalent group having 1 to 18 carbon atoms composed of at least one selected from carbon atoms, hydrogen atoms, oxygen atoms and sulfur atoms”, “1 to 18 monovalent hydrocarbon group "or" hydrogen atom ". R ^{4 to} R ⁷ are each independently a “monovalent group having 1 to 18 carbon atoms composed of at least one selected from a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom”, and “1 to 18 carbon atoms”. A monovalent hydrocarbon group ”,“ hydroxyl group ”, or“ hydrogen atom ”.
Two adjacent groups selected from R ^{4 to} R ⁷ may be connected to each other to form a saturated ring or an unsaturated ring.

  It can be confirmed that the specific curing accelerating compound has a structural moiety represented by the general formula (I) by using a commonly used analysis method. Specifically, it can be confirmed using a nuclear magnetic resonance (NMR) spectrum, an infrared absorption (IR) spectrum, or the like.

Specific examples of the “divalent hydrocarbon group having 1 to 18 carbon atoms” include a linear or branched alkylene group having 1 to 18 carbon atoms; a cycloalkylene group having 3 to 18 carbon atoms; A linear or branched alkenylene group having 18 to 18 carbon atoms; a cycloalkenylene group having 3 to 18 carbon atoms; an arylene group having 6 to 18 carbon atoms such as a phenylene group, a biphenylene group, or a naphthylene group.
Among these, from the viewpoint of pot life, a linear or branched alkylene group having 1 to 12 carbon atoms; a cycloalkylene group having 3 to 12 carbon atoms; a linear or branched alkenylene having 2 to 12 carbon atoms. Group: a C3-C12 cycloalkenylene group; a C6-C12 arylene group is preferable, a C1-C8 linear or branched alkylene group; a phenylene group, a biphenylene group, a naphthylene group, etc. An arylene group having 6 to 12 carbon atoms is more preferable, and a linear or branched alkylene group having 1 to 8 carbon atoms is more preferable.

Specific examples of the “C1-C18 divalent group composed of carbon atom, hydrogen atom and oxygen atom” include methyleneoxy group, ethyleneoxy group, propyleneoxy group, diethyleneoxy group, dipropyleneoxy group. A linear or branched alkyleneoxy group having 1 to 18 carbon atoms such as a group, a triethyleneoxy group or a tripropyleneoxy group, and a linear or branched oligoalkyleneoxy group.
Among these, from the viewpoint of pot life, a linear or branched alkyleneoxy group having 1 to 12 carbon atoms and a linear or branched oligoalkyleneoxy group having 2 to 12 carbon atoms are preferable, and the carbon number is 1 -8 linear or branched alkyleneoxy groups and 2 to 8 carbon linear or branched oligoalkyleneoxy groups are more preferred, linear or branched C1-8 linear or branched More preferred is an alkyleneoxy group.

Specific examples of the “monovalent hydrocarbon group having 1 to 18 carbon atoms” include a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, and 2 carbon atoms. -18 linear or branched alkenyl group, C3-C18 cycloalkenyl group, C6-C18 aryl group, etc. are mentioned.
Among these, from the viewpoint of pot life, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, and a linear or branched alkenyl group having 2 to 18 carbon atoms. Group, a C3-C18 cycloalkenyl group and a C6-C18 aryl group are preferred, a C1-C12 linear or branched alkyl group, a C3-C12 cycloalkyl group, A linear or branched alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms are more preferable, and a linear or branched chain having 1 to 6 carbon atoms. A chain alkyl group is more preferable.

Specific examples of “monovalent group having 1 to 18 carbon atoms composed of at least one atom selected from the group consisting of carbon atom, hydrogen atom, oxygen atom and sulfur atom” include a methoxy group, an ethyloxy group, C1-C18 linear or branched alkoxy groups such as propyloxy group and 2-propyloxy group; methoxymethyl group, phenoxymethyl group, methoxyphenyl group, dimethoxyphenyl group, benzoylphenyl group, acetylphenyl Group, 2-hydroxyphenyl group, 2-hydroxyphenylmethyl group, 2-hydroxyphenyloxy group, 2-hydroxyphenylmethylmethyl group, 2-hydroxyphenylethylmethyl group, 2-hydroxyphenylthio group, 2-hydroxyphenylsulfonyl Group, 3-hydroxyphenyl group, 3-hydroxyphenylmethyl Group, 3-hydroxyphenyloxy group, 3-hydroxyphenylmethylmethyl group, 3-hydroxyphenylethylmethyl group, 3-hydroxyphenylthio group, 3-hydroxyphenylsulfonyl group, 4-hydroxyphenyl group, 4-hydroxyphenyl Carbon atom such as methyl group, 4-hydroxyphenyloxy group, 4-hydroxyphenylmethylmethyl group, 4-hydroxyphenylethylmethyl group, 4-hydroxyphenylthio group, 4-hydroxyphenylsulfonyl group, hydrogen atom, oxygen atom and Examples thereof include an alkyl group and an aryl group substituted with a substituent composed of at least one atom selected from the group consisting of sulfur atoms.
Among these, from the viewpoint of pot life and rapid curing, methoxy group, methoxymethyl group, phenoxymethyl group, 2-hydroxyphenyl group, 2-hydroxyphenylmethyl group, 2-hydroxyphenyloxy group, 2-hydroxyphenylmethylmethyl group 2-hydroxyphenylethylmethyl group, 2-hydroxyphenylthio group and 2-hydroxyphenylsulfonyl group are preferred, methoxy group, phenoxymethyl group, 2-hydroxyphenyl group, 2-hydroxyphenylmethyl group, 2-hydroxyphenyloxy And a 2-hydroxyphenylmethylmethyl group is more preferred.

L ¹ is a divalent hydrocarbon group having 1 to 12 carbon atoms and a divalent group having 1 to 12 carbon atoms composed of a carbon atom, a hydrogen atom, and an oxygen atom from the viewpoint of pot life and rapid curing. Preferably, it is a C1-C8 linear or branched alkylene group, phenylene group, biphenylene group, naphthylene group, and a C1-C8 divalent group composed of a carbon atom, a hydrogen atom and an oxygen atom. Are more preferable, a linear or branched alkylene group having 1 to 8 carbon atoms and a linear or branched alkyleneoxy group having 1 to 8 carbon atoms are more preferable, and a linear chain having 1 to 4 carbon atoms. Particularly preferred is a linear or branched alkylene group.

R ^{1 to} R ³ are each independently preferably a hydrogen atom and a monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms. Further, a hydrogen atom and a linear or branched alkyl group having 1 to 3 carbon atoms are more preferable, and a hydrogen atom and a methyl group are particularly preferable.

R ^{4 to} R ⁷ are each independently at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 12 carbon atoms, and a carbon atom, a hydrogen atom, an oxygen atom, and a sulfur atom. C1-C12 monovalent group comprised from an atom is preferable, The carbon number which may have a hydrogen atom, a hydroxyl group, a C1-C6 linear or branched alkyl group, and a substituent It may have a 6-12 aryl group, a C1-C6 linear or branched alkoxy group, a C6-C12 aryloxy group which may have a substituent, and a substituent. An arylalkyl group having 6 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms which may have a substituent and an arylsulfonyl group having 6 to 12 carbon atoms which may have a substituent are more preferable, and a hydrogen atom , Hydroxyl group, linear or branched chain having 1 to 4 carbon atoms An alkyl group, an aryl group having 6 to 9 carbon atoms which may have a hydroxyl group, a linear or branched alkoxy group having 1 to 4 carbon atoms, and an aryl having 6 to 9 carbon atoms which may have a hydroxyl group An oxy group, an arylalkyl group having 6 to 9 carbon atoms which may have a hydroxyl group, an arylthio group having 6 to 9 carbon atoms which may have a hydroxyl group, and an aryl having 6 to 9 carbon atoms which may have a hydroxyl group A sulfonyl group is more preferable, and a hydrogen atom, hydroxyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, methoxy group, ethoxy group, phenyl group, tolyl group, phenoxy group, 2-hydroxyphenyl. Group, 2-hydroxyphenylmethyl group, 2-hydroxyphenyloxy group, 2-hydroxyphenylmethylmethyl group, 2-hydroxyphenylethylmethyl group, 2-hydroxyphenyl group Niruchio group, and 2-hydroxyphenyl sulfonyl group are particularly preferred.

In addition, among R ^{4 to} R ⁷ in the structural moiety represented by the general formula (I), the group located in the ortho position with respect to the oxygen atom is selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom. A monovalent group having 1 to 18 carbon atoms or a hydroxyl group composed of at least one kind of atom, a linear or branched alkoxy group having 1 to 18 carbon atoms, 2-hydroxyphenyl group, 2 A -hydroxyphenylmethyl group, 2-hydroxyphenyloxy group, 2-hydroxyphenylmethylmethyl group, 2-hydroxyphenylthio group, 2-hydroxyphenylsulfonyl group, or hydroxyl group is more preferable.
By having a specific substituent at the ortho position of the oxygen atom, the curing acceleration tends to be further improved.

  The specific curing accelerating compound is preferably a compound represented by any one of the following general formula (IIa), general formula (IIb), and general formula (IIc) from the viewpoint of curing acceleration.

In General Formula (IIa), General Formula (IIb), and General Formula (IIc), L ²¹ represents “a divalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom, and an oxygen atom”, or “ A divalent hydrocarbon group having 1 to 18 carbon atoms. R ^{21 to} R ²⁶ each independently represent a “hydrogen atom” or “a monovalent hydrocarbon group having 1 to 18 carbon atoms”.
Ar is an “m-valent aromatic hydrocarbon group having 6 to 18 carbon atoms” or “at least two aromatic hydrocarbon groups having 6 to 18 carbon atoms are a single bond or a straight chain having 1 to 12 carbon atoms, or A group that is linked by at least one linking group selected from the group consisting of a branched alkylene group, a carbonyl group, and an oxygen atom to be m-valent as a whole.
m represents an integer of 2 to 8, and n represents an integer of 0 to 20.

  A divalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and an oxygen atom in general formula (IIa), general formula (IIb) and general formula (IIc); The details of the hydrocarbon group and the monovalent hydrocarbon group having 1 to 18 carbon atoms are the same as described above.

L ²¹ is a divalent hydrocarbon group having 1 to 12 carbon atoms, and a divalent group having 1 to 12 carbon atoms composed of a carbon atom, a hydrogen atom, and an oxygen atom, from the viewpoint of pot life and rapid curability. C1-C8 linear or branched alkylene group, phenylene group, biphenylene group, naphthylene group, and C1-C8 divalent composed of carbon atom, hydrogen atom and oxygen atom Group is more preferable, linear or branched alkylene group having 1 to 8 carbon atoms and linear or branched alkyleneoxy group having 1 to 8 carbon atoms are more preferable, and straight chain having 1 to 4 carbon atoms. A chain or branched alkylene group is particularly preferable.

R ^{21 to} R ²⁶ are each independently preferably a hydrogen atom and a monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms. Further, a hydrogen atom and a linear or branched alkyl group having 1 to 3 carbon atoms are more preferable, and a hydrogen atom and a methyl group are particularly preferable.

When Ar represents an m-valent aromatic hydrocarbon group, Ar is a group formed by removing m hydrogen atoms from an aromatic hydrocarbon compound, and the position at which the hydrogen atom is removed is not particularly limited.
The aromatic hydrocarbon compound constituting the m-valent aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 15 carbon atoms, from the viewpoint of pot life and fast curability. More preferably, it has 6 to 12 carbon atoms.

Specific examples of the aromatic hydrocarbon compound constituting the m-valent aromatic hydrocarbon group include benzene, naphthalene, anthracene, and phenanthrene.
The aromatic hydrocarbon may have a substituent. Specific examples of the substituent include a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 1 to 18 carbon atoms, a hydroxyl group, and a straight chain having 1 to 18 carbon atoms. Examples thereof include a linear or branched alkoxy group and a linear or branched alkenyloxy group having 1 to 18 carbon atoms. Among these, a hydroxyl group is preferable as the substituent.

The two or more aromatic hydrocarbon groups in Ar are a single bond or a linking group consisting of at least one selected from the group consisting of a linear or branched alkylene group having 1 to 12 carbon atoms, a carbonyl group and an oxygen atom. An m-valent group (hereinafter also referred to as “m-valent aromatic-containing linking group”) in which the aromatic hydrocarbon group becomes a bonding position with an oxygen atom is connected to two or more aromatic hydrocarbon compounds. This is a group constituted by removing m hydrogen atoms from an aromatic hydrocarbon group of an aromatic ring-containing compound connected by a bond or the linking group, and the position at which the hydrogen atom is removed is not particularly limited.
The aromatic hydrocarbon compound constituting the aromatic ring-containing compound is the same as the aromatic hydrocarbon compound in the m-valent aromatic hydrocarbon group.

Specific examples of the linking group for linking two or more aromatic hydrocarbon groups include a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms such as a methylene group, an ethylene group, and a propylene group; ethylene C2-C12 linear or branched alkyleneoxy groups such as oxy group, propyleneoxy group and diethyleneoxy group and polymers thereof; oxygen atom; carbonyloxy group; carbonyl group; and combinations thereof be able to.
Among these, from the viewpoint of pot life and fast curing, at least selected from the group consisting of a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, an oxygen atom, a carbonyloxy group, and a carbonyl group. One type is preferable.

  Although the specific example of the aromatic ring containing compound which comprises the aromatic containing coupling group in Ar below is shown, this invention is not limited to these.

  The bonding position in the m-valent aromatic-containing linking group represented by Ar is on the aromatic hydrocarbon group. Although the specific example of the aromatic containing coupling group represented by Ar below is shown, this invention is not limited to these. In the following chemical formula, “*” represents a bonding position.

  The aromatic-containing linking group in Ar may have a substituent. Specific examples of the substituent include a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 2 to 18 carbon atoms, a hydroxyl group, and a straight chain having 1 to 18 carbon atoms. Examples thereof include a linear or branched alkoxy group and a linear or branched alkenyloxy group having 2 to 18 carbon atoms. Among the substituents, at least one selected from the group consisting of a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 1 to 6 carbon atoms, and a hydroxyl group. It is preferable that

In General Formula (IIa), General Formula (IIb), and General Formula (IIc), m is an integer of 2 to 4 and n is 0 to 10 from the viewpoint of fast curability, low viscosity, and pot life. It is preferably an integer.
Moreover, when any one or more of L ²¹ , R ^{21 to} R ²⁶ and Ar are present in the general formula (IIa), the general formula (IIb) and the general formula (IIc), two or more L ²¹ and R ^{21 to} R are present. ²⁶ and Ar may be the same or different.

  The specific curing accelerating compound is also preferably a compound represented by the general formula (III) from the viewpoint of curing acceleration.

^{L 21, R} 21 ^{~R 23} in formula (III), and Ar have the general formula (IIa), ^L 21 in the general formula (IIb) and formula ^{(IIc), R 21 ~R 23} , and Ar respectively It is synonymous and a preferable aspect is also the same.
R ²⁷ represents “hydrogen atom” or “group represented by the following general formula (IIIa) or general formula (IIIb)”.

Formula (IIIa) and formula (IIIb) in ^R 21 ^{to R 23} and Ar are respectively the same meanings as ^R 21 ^{to R 23} and Ar in formula (III), preferable embodiments thereof are also the same. m represents an integer of 1 to 8, p represents an integer of 1 to 8, and m ≧ p. From the viewpoint of fast curability and quick life, m is an integer of 1 to 5, p is an integer of 1 to 5, and preferably m ≧ p.
In the general formula ^{(III), L 21, R} 21 ~R 23, when any one of ^{R 27} and Ar are present 2 or more, ^L 21 present 2 or ^{more, R 21 ~R 23,} R ²⁷ and Ar are each identical Or different.

The weight average molecular weight of the specific curing accelerating compound is not particularly limited. From the viewpoint of obtaining a resin composition for electronic parts having a viscosity excellent in handleability, it is preferably 200 to 20,000, more preferably 300 to 10,000, and further preferably 300 to 5,000.
In addition, the weight average molecular weight of a specific hardening acceleration | stimulation compound can be measured by the normal method using a mass spectrometer or GPC method.

  The compound having a structural site represented by the general formula (I) (specific curing accelerating compound) can be obtained, for example, by subjecting a compound having a phenolic hydroxyl group and a compound having a vinyl ether group to an addition reaction. The reaction conditions for the addition reaction are not particularly limited. For example, it can be obtained by reacting in the temperature range of 50 ° C. to 150 ° C. for about 10 minutes to 24 hours. The addition reaction can also be performed in a nitrogen atmosphere.

  Further, a solvent such as xylene may be used for the addition reaction. The addition reaction can also be promoted by an acid catalyst such as an acidic phosphate ester. The end point of the addition reaction can be determined by titrating the remaining phenolic hydroxyl group with, for example, an ethanol solution of potassium hydroxide.

The charged molar ratio when the compound having a phenolic hydroxyl group and the compound having a vinyl ether group are subjected to addition reaction can be appropriately selected according to the structures of the compound having a phenolic hydroxyl group and the compound having a vinyl ether group.
For example, when the specific curing accelerating compound is a compound represented by any one of the general formula (IIa), the general formula (IIb), and the general formula (IIc), the compound having a phenolic hydroxyl group is replaced with a compound having a vinyl ether group. By addition reaction of at least one selected from the group consisting of a divinyl ether compound having two vinyl ether groups and a vinyl alkyl ether compound having one vinyl ether group, general formula (IIa), general formula (IIb) and general formula A compound represented by any of (IIc) can be obtained. As the compound having a vinyl ether group, it is preferable to use a divinyl ether compound having two vinyl ether groups.
The charging amount ratio between the compound having a phenolic hydroxyl group and the vinyl ether compound can be appropriately selected according to the total number m of phenolic hydroxyl groups possessed by the compound having a phenolic hydroxyl group. For example, it is preferable that it is 0.55 times mole or more with respect to the total number of phenolic hydroxyl groups, and it is more preferable that it is 0.75-4 times mole.

When the specific curing accelerating compound is a compound represented by the general formula (III), the compound having a phenolic hydroxyl group is composed of a divinyl ether compound having two vinyl ether groups and a vinyl alkyl ether compound having one vinyl ether group. A compound represented by the general formula (III) can be obtained by addition reaction of at least one selected from the group. As the compound having a vinyl ether group, it is preferable to use a vinyl alkyl ether compound having one vinyl ether group.
The charging ratio of the compound having a phenolic hydroxyl group and the compound having a vinyl ether group can be appropriately selected according to the total number of phenolic hydroxyl groups possessed by the compound having a phenolic hydroxyl group. For example, it should just exceed 1 time mole with respect to the total number of phenolic hydroxyl groups. Among these, 1.1 to 4 times mol is preferable, 1.2 to 3 times mol is more preferable, and 1.2 to 2 times mol is more preferable.

  Furthermore, when the vinyl ether compound is excessively contained with respect to the compound having a phenolic hydroxyl group, even if the vinyl ether compound is eliminated, the phenolic hydroxyl group is blocked by an equilibrium reaction, so that the storage stability is excellent. Further, since the polymerization reaction is stopped at an appropriate molecular weight due to an excess vinyl ether compound, the viscosity can be set within a desired range.

Examples of the compound having a phenolic hydroxyl group include phenol, cresol, xylenol, resorcin, catechol, 4-tert-butylcatechol, 3-methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3,5-di- Phenol compounds such as tert-butylcatechol, pyrogallol, phloroglucinol, 2,2′-biphenol, 4,4′-biphenol, bisphenol A, bisphenol F, phenylphenol, aminophenol; α-naphthol, β-naphthol, 1 , 2-dihydroxynaphthalene, naphthol compounds such as 2,3-dihydroxynaphthalene; and at least one of the above phenolic compounds and naphthol compounds, formaldehyde, acetaldehyde, propionaldehyde, A novolak-type phenol resin obtained by condensation or co-condensation with an aldehyde compound such as benzaldehyde and salicylaldehyde in the presence of an acidic catalyst; at least one of the phenol compound and the naphthol compound, dimethoxyparaxylene and bis (methoxymethyl) Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from biphenyl; at least one of paraxylylene-modified phenol resin and metaxylylene-modified phenol resin; melamine-modified phenol resin; terpene-modified phenol resin; at least of phenol compound and naphthol compound A dicyclopentadiene type phenolic resin and a dicyclopentadiene type naphthol resin synthesized by copolymerization from one kind and dicyclopentadiene; Ropentajien modified phenol resin; polycyclic aromatic ring-modified phenolic resins; biphenyl type phenolic resins; triphenylmethane type phenol resins; etc. as well as phenolic resins obtained by copolymerizing two or more of these and the like.
The compounds having a phenolic hydroxyl group may be used singly or in combination of two or more.

Among these, from the viewpoint of low viscosity, phenol, cresol, xylenol, resorcin, catechol, 4-tert-butylcatechol, 3-methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3,5-di-tert -Phenolic compounds such as butylcatechol, pyrogallol, phloroglucinol, 2,2'-biphenol, 4,4'-biphenol, bisphenol A, bisphenol F, phenylphenol and aminophenol, and α-naphthol, β-naphthol and At least one selected from the group consisting of naphthol compounds such as 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene is preferred.
From the viewpoint of curing acceleration, catechol, 4-tert-butylcatechol, 3-methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3,5-di-tert-butylcatechol, 2,2′-biphenol , 1,2-dihydroxynaphthalene, and at least one selected from the group consisting of 2,3-dihydroxynaphthalene are preferable.

  Examples of the compound having a vinyl ether group include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, 1-propenyl vinyl ether, 1,2-dimethylpropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 1,3-dimethylbutyl. Vinyl ether, 2-ethylbutyl vinyl ether, vinyl hexyl ether, isohexyl vinyl ether, 2-ethylhexyl vinyl ether, 5-methylhexyl vinyl ether, 1-pentylhexyl vinyl ether, n-heptyl vinyl ether, 1-methylheptyl vinyl ether, octyl vinyl ether, 4-ethyl -1-methyloctyl vinyl ether, 2-methyloctyl vinyl ether, n- Nil vinyl ether, n-decyl vinyl ether, undecyl vinyl ether, dodecyl vinyl ether, tridecyl vinyl ether, tetradecyl vinyl ether, pentadecyl vinyl ether, hexadecyl vinyl ether, heptadecyl vinyl ether, n-eicosyl vinyl ether, henicosyl vinyl ether, n-docosyl Vinyl ether, tricosyl vinyl ether, tetracosyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, octadecyl vinyl ether, 6-methylheptyl vinyl ether, sec-butyl vinyl ether, triethylene glycol methyl vinyl ether, (1,5-dimethyl-1-vinyl -4-hexenyl) vinyl ether, vinyl (1-methylethenyl) ether 1-methylallyl vinyl ether, 2-methylallyl vinyl ether, vinyl 2-butenyl ether, 2-pentenyl vinyl ether, cis-1-methyl-2-butenyl vinyl ether, trans-1-methyl-2-butenyl vinyl ether, 1- Ethyl allyl vinyl ether, 1,3-dimethyl-2-butenyl vinyl ether, 1-methyl-2-hexenyl vinyl ether, phenyl vinyl ether, (6-phenyl-2-hexenyl) vinyl ether, (2,2-dimethylpropyl) vinyl ether, ( 1-ethylpropyl) vinyl ether, (1-isopropyl-2-methylpropyl) vinyl ether, p-phenylbenzyl vinyl ether, vinyl (α-methylbenzyl) ether, phenethyl vinyl ether, 2-phenylpropyl Pyrvinyl ether, 3-phenylpropyl vinyl ether, α, α-dimethylbenzyl vinyl ether, vinylbenzhydryl ether, 2-phenylallyl vinyl ether, 1-methyl-2-phenylallyl vinyl ether, glycidyl vinyl ether, allyl vinyl ether, 3-hexenyl vinyl ether, 4 -Hexenyl vinyl ether, 5-hexenyl vinyl ether, 1-heptenyl vinyl ether, 2-heptenyl vinyl ether, 3-heptenyl vinyl ether, 4-heptenyl vinyl ether, 5-heptenyl vinyl ether, 6-heptenyl vinyl ether, 1-octenyl vinyl ether 2-octenyl vinyl ether, 3-octenyl vinyl ether, 4-octenyl vinyl ether, 5-octenyl vinyl ether Ter, 6-octenyl vinyl ether, 7-octenyl vinyl ether, 1-nonenyl vinyl ether, 2-nonenyl vinyl ether, 3-nonenyl vinyl ether, 4-nonenyl vinyl ether, 5-nonenyl vinyl ether, 6-nonenyl vinyl ether, 7-nonenyl vinyl ether, 8-nonenyl vinyl ether, 1-decenyl vinyl ether, 2-decenyl vinyl ether, 3-decenyl vinyl ether, 4-decenyl vinyl ether, 5-decenyl vinyl ether, 6-decenyl Cenyl vinyl ether, 7-decenyl vinyl ether, 8-decenyl vinyl ether, 9-decenyl vinyl ether, 1-undecenyl vinyl ether, 2-undecenyl vinyl ether, 3-undecenyl vinyl ether, 4-undece Nilvinyl A 5-undecenyl vinyl ether, 6-undecenyl vinyl ether, 7-undecenyl vinyl ether, 8-undecenyl vinyl ether, 9-undecenyl vinyl ether, 10-undecenyl vinyl ether, 3,6-dioxa- 1-decene, 1-naphthyl vinyl ether, 2-naphthyl vinyl ether, o-tolyl vinyl ether, m-tolyl vinyl ether, p-tolyl vinyl ether, 2,3-xylyl vinyl ether, 2,4-xylyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether 4-n-butylcyclohexyl vinyl ether, vinyl (2-cyclohexylideneethyl) ether, 4- [3- (2,2,4-trimethyl) pentyl] -cyclohexyl vinyl ether, 4-n-dodecyl Cyclohexyl vinyl ether, 4-cyclohexyl cyclohexyl vinyl ether, vinyl (cyclohexyl methyl) ether, 1-cyclohexyl ethyl vinyl ether, 2-cyclohexyl ethyl vinyl ether, 2-decahydronaphthyl vinyl ether, 2-cyclopentenyl vinyl ether, 2-cyclohexenyl vinyl ether, 1-cyclo Pentenylmethyl vinyl ether, 1-cyclopentenylethyl vinyl ether, (1-cyclohexenylmethyl) vinyl ether, [1- (1-cyclohexenyl) ethyl] vinyl ether, (3-methyl-1-cyclohexenyl) methyl vinyl ether, [(3 4-dimethyl-1-cyclohexenyl) methyl] vinyl ether, [(3-methyl-4-ethoxy-1-cyclohexenyl) ) Methyl] vinyl ether, cycloheptenyl methyl vinyl ether, cyclooctenyl methyl vinyl ether, 2-cyclobutylidene ethyl vinyl ether, 2-cyclopentylidene ethyl vinyl ether, 2-cyclohexylidene-1-methylethyl vinyl ether, 2-cycloheptyl Ridenethyl vinyl ether, 2-cyclooctylidene ethyl vinyl ether, terpineyl vinyl ether, menthyl vinyl ether, norbornyl vinyl ether, 2-furyl vinyl ether, 3-furyl vinyl ether, furfuryl vinyl ether, tetrahydrofurfuryl vinyl ether, 2-thienyl vinyl ether, 3- Thienyl vinyl ether, 2-tenyl vinyl ether, 2-pyridyl vinyl ether, 3-pyridyl vinyl ether, -Pyridyl vinyl ether, 2,6,8-trimethylnonyl vinyl ether, 2- (vinyloxy) ethyl acetate, 3-methyl-2-butenyl vinyl ether, vinyl (3,3-diphenyl-2-propenyl) ether, N, N- Dimethyl-2- (vinyloxy) ethanamine, [2- (2-ethoxyethoxy) ethyl] vinyl ether, divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, heptaethylene glycol di Vinyl ether, 1,3-propanediol divinyl ether, propylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,3-butanediol divinyl Ether, 1,2-butanediol divinyl ether, 2,3-butanediol divinyl ether, 1-methyl-1,3-propanediol divinyl ether, 2-methyl-1,3-propanediol divinyl ether, 2-methyl- 1,2-propanediol divinyl ether, 1,5-pentanediol divinyl ether, 1,6-hexanediol divinyl ether, cyclohexane-1,4-diol divinyl ether, cyclohexane-1,4-dimethanol divinyl ether, p- Xylene glycol divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol divinyl ether, polypropylene glycol divinyl ether, 3-vinyloxypropyl vinyl ether, 3,9-dioxa , 10-undecadiene, 10-vinyloxydecyl vinyl ether, 12-vinyloxyoctadecyl vinyl ether, dipropylene glycol divinyl ether, resorcinol divinyl ether, m-phenylene bis (ethylene glycol) divinyl ether, bisphenol A divinyl ether, etc. And alicyclic vinyl ether compounds and aromatic vinyl ether compounds.

  Among these, from the viewpoint of storage stability, divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, heptaethylene glycol divinyl ether, 1,3-propanediol divinyl ether, propylene glycol Divinyl ether, 1,4-butanediol divinyl ether, 1,3-butanediol divinyl ether, 1,2-butanediol divinyl ether, 2,3-butanediol divinyl ether, 1-methyl-1,3-propanediol di Vinyl ether, 2-methyl-1,3-propanediol divinyl ether, 2-methyl-1,2-propanediol divinyl ether, 1,5-pentane All divinyl ether, 1,6-hexanediol divinyl ether, cyclohexane-1,4-diol divinyl ether, cyclohexane-1,4-dimethanol divinyl ether, p-xylene glycol divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol A divinyl ether compound having two vinyl ether groups such as divinyl ether and polypropylene glycol divinyl ether is preferred, and 1,4-butanediol divinyl ether is more preferred.

  From the viewpoint of handling after synthesis, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, 1-propenyl vinyl ether, 1,2-dimethylpropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 1,3-dimethylbutyl vinyl ether, 2-ethylbutyl vinyl ether, vinylhexyl ether, isohexyl vinyl ether, 2-ethylhexyl vinyl ether, 5-methylhexyl vinyl ether, 1-pentylhexyl vinyl ether, n-heptyl vinyl ether, 1-methylheptyl vinyl ether, octyl vinyl ether, 4-ethyl-1 -Methyl octyl vinyl ether, 2-methyl octyl vinyl ether, n-nonyl vinyl ether N-decyl vinyl ether, undecyl vinyl ether, dodecyl vinyl ether, tridecyl vinyl ether, tetradecyl vinyl ether, pentadecyl vinyl ether, vinyl hexadecyl ether, heptadecyl vinyl ether, n-eicosyl vinyl ether, henicosyl vinyl ether, n-docosyl Vinyl ether, tricosyl vinyl ether, tetracosyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, octadecyl vinyl ether, vinyl (6-methylheptyl) ether, vinyl sec-butyl ether, triethylene glycol methyl vinyl ether, (1,5-dimethyl- 1-vinyl-4-hexenyl) vinyl ether, vinyl (1-methylethenyl) ether, 1-methyl Ryl vinyl ether, 2-methylallyl vinyl ether, vinyl 2-butenyl ether, 2-pentenyl vinyl ether, cis-1-methyl-2-butenyl vinyl ether, trans-1-methyl-2-butenyl vinyl ether, 1-ethylallyl vinyl ether 1,3-dimethyl-2-butenyl vinyl ether, 1-methyl-2-hexenyl vinyl ether, phenyl vinyl ether, (6-phenyl-2-hexenyl) vinyl ether, (2,2-dimethylpropyl) vinyl ether, (1-ethyl) Propyl) vinyl ether (1-isopropyl-2-methylpropyl) vinyl ether, p-phenylbenzyl vinyl ether, vinyl (α-methylbenzyl) ether, phenethyl vinyl ether, 2-phenylpropyl vinyl ether Ter, 3-phenylpropyl vinyl ether, α, α-dimethylbenzyl vinyl ether, vinyl benzhydryl ether, 2-phenylallyl vinyl ether, 1-methyl-2-phenylallyl vinyl ether, glycidyl vinyl ether, allyl vinyl ether, 3-hexenyl vinyl ether, 4- Hexenyl vinyl ether, 5-hexenyl vinyl ether, 1-heptenyl vinyl ether, 2-heptenyl vinyl ether, 3-heptenyl vinyl ether, 4-heptenyl vinyl ether, 5-heptenyl vinyl ether, 6-heptenyl vinyl ether, 1-octenyl vinyl ether, 2-octenyl vinyl ether, 3-octenyl vinyl ether, 4-octenyl vinyl ether, 5-octenyl vinyl ether, 6-o Tenenyl vinyl ether, 7-octenyl vinyl ether, 1-nonenyl vinyl ether, 2-nonenyl vinyl ether, 3-nonenyl vinyl ether, 4-nonenyl vinyl ether, 5-nonenyl vinyl ether, 6-nonenyl vinyl ether, 7-nonenyl vinyl ether 8-nonenyl vinyl ether, 1-decenyl vinyl ether, 2-decenyl vinyl ether, 3-decenyl vinyl ether, 4-decenyl vinyl ether, 5-decenyl vinyl ether, 6-decenyl vinyl ether, 7 -Decenyl vinyl ether, 8-decenyl vinyl ether, 9-decenyl vinyl ether, 1-undecenyl vinyl ether, 2-undecenyl vinyl ether, 3-undecenyl vinyl ether, 4-undecenyl vinyl ether, 5- Eun Senyl vinyl ether, 6-undecenyl vinyl ether, 7-undecenyl vinyl ether, 8-undecenyl vinyl ether, 9-undecenyl vinyl ether, 10-undecenyl vinyl ether, 3,6-dioxa-1-decene, 1, -Naphtyl vinyl ether, 2-naphthyl vinyl ether, o-tolyl vinyl ether, m-tolyl vinyl ether, p-tolyl vinyl ether, 2,3-xylyl vinyl ether, 2,4-xylyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, 4-n- Butyl cyclohexyl vinyl ether, 2-cyclohexylidene ethyl vinyl ether, 4- [3- (2,2,4-trimethyl) pentyl] -cyclohexyl vinyl ether, 4-n-dodecyl cyclohexyl vinyl Ether, 4-cyclohexylcyclohexyl vinyl ether, vinyl (cyclohexylmethyl) ether, 1-cyclohexylethyl vinyl ether, 2-cyclohexylethyl vinyl ether, 2-decahydronaphthyl vinyl ether, 2-cyclopentenyl vinyl ether, 2-cyclohexenyl vinyl ether, 1-cyclopentenyl Methyl vinyl ether, 1-cyclopentenylethyl vinyl ether, (1-cyclohexenylmethyl) vinyl ether, [1- (1-cyclohexenyl) ethyl] vinyl ether, (3-methyl-1-cyclohexenyl) methyl vinyl ether, [(3,4 -Dimethyl-1-cyclohexenyl) methyl] vinyl ether, [(3-methyl-4-ethoxy-1-cyclohexenyl) methyl] vinyl Ether, cycloheptenyl methyl vinyl ether, cyclooctenyl methyl vinyl ether, 2-cyclobutylidene ethyl vinyl ether, 2-cyclopentylidene ethyl vinyl ether, 2-cyclohexylidene-1-methyl ethyl vinyl ether, 2-cycloheptylidene ethyl vinyl ether 2-cyclooctylidene ethyl vinyl ether, terpineyl vinyl ether, menthyl vinyl ether, norbornyl vinyl ether, 2-furyl vinyl ether, 3-furyl vinyl ether, furfuryl vinyl ether, tetrahydrofurfuryl vinyl ether, 2-thienyl vinyl ether, 3-thienyl vinyl ether, 2-Tenyl vinyl ether, 2-pyridyl vinyl ether, 3-pyridyl vinyl ether, 4-pyridyl vinyl Ether, 2,6,8-trimethylnonyl vinyl ether, 2- (vinyloxy) ethyl acetate, 3-methyl-2-butenyl vinyl ether, vinyl (3,3-diphenyl-2-propenyl) ether, N, N-dimethyl- Vinyl ether compounds having one vinyl ether group such as 2- (vinyloxy) ethanamine, [2- (2-ethoxyethoxy) ethyl] vinyl ether, and glycidyl vinyl ether are preferred, and are selected from the group consisting of propyl vinyl ether, 2-ethylhexyl vinyl ether, and glycidyl vinyl ether. More preferred are vinyl ether compounds having one vinyl ether group.

The specific curing accelerating compound is phenol, cresol, xylenol, resorcin, catechol, 4-tert-butylcatechol, 3-methylcatechol, 4-methylcatechol from the viewpoint of low viscosity and storage stability of the resin composition for electronic parts. , 3-methoxycatechol, 3,5-di-tert-butylcatechol, pyrogallol, phloroglucinol, 2,2′-biphenol, 4,4′-biphenol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc. A phenol compound, a compound having at least one phenolic hydroxyl group selected from the group consisting of naphthol compounds such as α-naphthol, β-naphthol and 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and vinyl ether The is preferably an addition product of divinyl ether compounds having two,
The divinyl ether compound having two vinyl ether groups is divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, heptaethylene glycol divinyl ether, 1,3-propanediol divinyl ether. , Propylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,3-butanediol divinyl ether, 1,2-butanediol divinyl ether, 2,3-butanediol divinyl ether, 1-methyl-1,3- Propanediol divinyl ether, 2-methyl-1,3-propanediol divinyl ether, 2-methyl-1,2-propanediol divinyl Ether, 1,5-pentanediol divinyl ether, 1,6-hexanediol divinyl ether, cyclohexane-1,4-diol divinyl ether, cyclohexane-1,4-dimethanol divinyl ether, p-xylene glycol divinyl ether, tripropylene More preferably, it is at least one selected from the group consisting of glycol divinyl ether, tetrapropylene glycol divinyl ether, and polypropylene glycol divinyl ether,
Furthermore, from the viewpoint of curing acceleration, catechol, 4-tert-butylcatechol, 3-methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3,5-di-tert-butylcatechol, 2,2′-biphenol, A compound having at least one phenolic hydroxyl group selected from the group consisting of 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene, divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, Tetraethylene glycol divinyl ether, heptaethylene glycol divinyl ether, 1,3-propanediol divinyl ether, propylene glycol divinyl ether, 1,4-butanediol divinyl Ether, 1,3-butanediol divinyl ether, 1,2-butanediol divinyl ether, 2,3-butanediol divinyl ether, 1-methyl-1,3-propanediol divinyl ether, 2-methyl-1,3- Propanediol divinyl ether, 2-methyl-1,2-propanediol divinyl ether, 1,5-pentanediol divinyl ether, 1,6-hexanediol divinyl ether, cyclohexane-1,4-diol divinyl ether, cyclohexane-1, From the group consisting of 4-dimethanol divinyl ether, p-xylene glycol divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol divinyl ether, and polypropylene glycol divinyl ether And more preferably an addition reaction product of divinyl ether compound two having at least one vinyl ether group barrel.

The specific curing accelerating compounds are phenol, cresol, xylenol, resorcin, catechol, 4-tert-butylcatechol, 3-methylcatechol, 4-methylcatechol from the viewpoint of low viscosity and handling properties of the resin composition for electronic parts. , 3-methoxycatechol, 3,5-di-tert-butylcatechol, pyrogallol, phloroglucinol, 2,2′-biphenol, 4,4′-biphenol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc. A phenol compound, a compound having at least one phenolic hydroxyl group selected from the group consisting of naphthol compounds such as α-naphthol, β-naphthol and 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and vinyl Is preferably an addition product of a vinyl ether compound having the ether group only one
From the viewpoint of curing acceleration, catechol, 4-tert-butylcatechol, 3-methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3,5-di-tert-butylcatechol, 2,2′-biphenol, 1 More preferably, it is an addition reaction product of a compound having at least one phenolic hydroxyl group selected from the group consisting of 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene and a vinyl ether compound having only one vinyl ether group. .

In the resin composition for electronic parts, from the viewpoint of low viscosity and storage stability, the specific curing accelerating compound is phenol, cresol, xylenol, resorcin, catechol, 4-tert-butylcatechol, 3-methylcatechol, 4- Methyl catechol, 3-methoxy catechol, 3,5-di-tert-butyl catechol, pyrogallol, phloroglucinol, 2,2'-biphenol, 4,4'-biphenol, bisphenol A, bisphenol F, phenylphenol and aminophenol And a compound having at least one phenolic hydroxyl group selected from the group consisting of naphthol compounds such as α-naphthol, β-naphthol and 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and the like, Vinylue Is an addition reaction product of divinyl ether compound having two ether groups, preferably has a content of from 0.2% to 30% by weight based on the total weight of the epoxy resin,
The specific curing accelerator compound is phenol, cresol, xylenol, resorcin, catechol, 4-tert-butylcatechol, 3-methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3,5-di-tert-butylcatechol, Pyrogallol, phloroglucinol, 2,2′-biphenol, 4,4′-biphenol, phenolic compounds such as bisphenol A, bisphenol F, phenylphenol and aminophenol, and α-naphthol, β-naphthol and 1,2- A compound having at least one phenolic hydroxyl group selected from the group consisting of naphthol compounds such as dihydroxynaphthalene and 2,3-dihydroxynaphthalene, divinyl ether, ethylene glycol divinyl ether, diethylene group Coal divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, heptaethylene glycol divinyl ether, 1,3-propanediol divinyl ether, propylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,3-butane Diol divinyl ether, 1,2-butanediol divinyl ether, 2,3-butanediol divinyl ether, 1-methyl-1,3-propanediol divinyl ether, 2-methyl-1,3-propanediol divinyl ether, 2- Methyl-1,2-propanediol divinyl ether, 1,5-pentanediol divinyl ether, 1,6-hexanediol divinyl ether, cyclohexane-1,4-dioe Vinyl ether that is at least one selected from the group consisting of divinyl ether, cyclohexane-1,4-dimethanol divinyl ether, p-xylene glycol divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol divinyl ether, and polypropylene glycol divinyl ether It is an addition reaction product of a divinyl ether compound having two groups, and the content is more preferably 0.6% by mass to 20% by mass with respect to the total mass of the epoxy resin.

  Furthermore, in the resin composition for electronic parts, from the viewpoint of low viscosity and handling properties, the specific curing accelerating compound may be phenol, cresol, xylenol, resorcin, catechol, 4-tert-butylcatechol, 3-methylcatechol, 4- Methyl catechol, 3-methoxy catechol, 3,5-di-tert-butyl catechol, pyrogallol, phloroglucinol, 2,2'-biphenol, 4,4'-biphenol, bisphenol A, bisphenol F, phenylphenol and aminophenol A compound having at least one phenolic hydroxyl group selected from the group consisting of naphthol compounds such as α-naphthol, β-naphthol and 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, etc. Is an addition reaction product of a vinyl ether compound having a vinyl ether group only one, it is also preferable that content is 0.2% to 30% by weight based on the total weight of the epoxy resin.

  If the said resin composition for electronic components is in the range with which the effect of this invention is achieved, in addition to a specific hardening acceleration | stimulation compound, another conventionally well-known hardening accelerator can be used together. Other curing accelerators include 1,8-diaza-bicyclo [5.4.0] undecene-7, 1,5-diaza-bicyclo [4.3.0] nonene, 5,6-dibutylamino-1. , 8-diaza-bicyclo [5.4.0] undecene-7 and other cycloamidine compounds; triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and other tertiary amine compounds 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-hydroxyimidazole, 1-benzyl-2-phenylimidazole, 1 -Benzyl-2-methylimidazole, 2-phenyl-4,5-dihydride Ximethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, 2-heptadecylimidazole Imidazole compounds such as tributylphosphine, dialkylarylphosphine such as dimethylphenylphosphine, alkyldiarylphosphine such as methyldiphenylphosphine, triphenylphosphine, and organic phosphines such as triphenylphosphine substituted with an alkyl group; these compounds Maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1, -Intramolecular polarization formed by adding a quinone compound such as benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, or a compound having a π bond such as diazophenylmethane or phenol resin. Compounds; and derivatives thereof. Furthermore, phenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate are exemplified. Other potential curing accelerators include core-shell particles in which a normal temperature solid amino group-containing compound is used as a core and a normal temperature solid epoxy compound shell is coated. Amicure (Ajinomoto Co., Inc.) is a commercially available product. Novacure (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.) in which a microencapsulated amine is dispersed in a bisphenol A type epoxy resin or a bisphenol F type epoxy resin can be used.

  The content of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved. The range of 0.2% by mass to 30% by mass is preferable with respect to the total mass of the epoxy resin, the range of 0.5% by mass to 25% by mass is more preferable, and the range of 6% by mass to 20% by mass is more preferable. . When the content is 0.2% by mass or more, the effect of adding the curing accelerator can be sufficiently exerted, and as a result, the generation of voids during molding and the effect of reducing warpage can be sufficiently obtained. It is more excellent in storage stability when it is 30% by mass or less.

(D) Inorganic filler It is preferable that the said resin composition for electronic components contains at least 1 sort (s) of an inorganic filler further from viewpoints, such as reduction of a thermal expansion coefficient. Examples of inorganic fillers include silica such as fused silica and crystalline silica, calcium carbonate, clay, alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, phosphor. There are stellite, steatite, spinel, mullite, titania, and the like. In addition to these powders or beads obtained by spheroidizing these, glass fibers and the like can be mentioned. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. Among these, fused silica is preferable, and spherical silica is more preferable from the viewpoint of fluidity and permeability into the fine gap of the resin composition for electronic components. These inorganic fillers may be used alone or in combination of two or more.

The volume average particle diameter of the inorganic filler is preferably in the range of 0.1 μm to 10 μm, more preferably in the range of 0.3 μm to 5 μm, and more preferably in the range of 0.5 μm to 3 μm, particularly in the case of spherical silica. A range is further preferred. When the volume average particle size is 0.1 μm or more, the dispersibility in the liquid resin is excellent, and thixotropic properties are hardly imparted to the resin composition for electronic parts, and an effect of excellent flow characteristics is obtained. By setting it to 10 μm or less, sedimentation of the inorganic filler in the resin composition for electronic parts can be reduced, and the permeability and fluidity to the fine gap as the resin composition for electronic parts are improved, resulting in voids / unfilled There is a tendency to be able to prevent.
The volume average particle diameter can be measured with a laser scattering diffraction particle size distribution analyzer.

  The content of the inorganic filler is preferably set in the range of 50% by mass to 80% by mass in the total mass of the resin composition for electronic components. The content of the inorganic filler is preferably set in the range of 55% by mass to 75% by mass, and more preferably 60% by mass to 70% by mass. When the content of the inorganic filler is 50% by mass or more, an effect of reducing the thermal expansion coefficient is easily obtained. When the content of the inorganic filler is 80% by mass or less, the viscosity of the resin composition for electronic parts is prevented from increasing, and fluidity / penetration and dispensing properties are improved.

(E) Other additives The resin composition for electronic components can contain various flexible agents from the viewpoint of improving thermal shock resistance and reducing stress on the semiconductor element. Although there is no restriction | limiting in particular as a flexible agent, A rubber particle is preferable. Examples of the flexible agent include rubber particles such as styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), and acrylic rubber (AR). Among these, rubber particles made of acrylic rubber are preferable from the viewpoint of heat resistance and moisture resistance, and core-shell type acrylic polymers, that is, core-shell type acrylic rubber particles are more preferable.

  Silicone rubber particles can also be suitably used as rubber particles other than those described above. Silicone rubber particles include silicone rubber particles obtained by crosslinking polyorganosiloxanes such as linear polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane, silicone rubber particles whose surfaces are coated with a silicone resin, and surfaces that are epoxy groups. And core-shell polymer particles comprising a core of solid silicone particles obtained by emulsion polymerization and a shell of an organic polymer such as an acrylic resin.

  These silicone rubber particles can be used in an amorphous or spherical shape, but in order to keep the viscosity related to the moldability of the resin composition for electronic parts low, use a spherical one. Is preferred. These silicone rubber particles are commercially available from Toray Dow Corning Silicone Co., Ltd. and Shin-Etsu Chemical Co., Ltd.

  The volume average particle size of the silicone rubber particles is preferably 0.001 μm or more and 100 μm or less, more preferably 0.01 μm or more and 50 μm or less, from the viewpoint of improving thermal shock resistance and reducing stress on the semiconductor element. And more preferably 0.05 μm or more and 10 μm or less.

  Moreover, the said resin composition for electronic components may contain a silicone modified epoxy resin as needed. For example, the silicone-modified epoxy resin has an effect as a surfactant. The silicone-modified epoxy resin can be obtained as a reaction product of an organosiloxane having a functional group that reacts with an epoxy group and an epoxy resin. This silicone-modified epoxy resin is preferably liquid at normal temperature. Examples of the organosiloxane having a functional group that reacts with an epoxy group include dimethylsiloxane, diphenylsiloxane, and methylphenylsiloxane having one or more functional groups such as amino group, carboxyl group, hydroxyl group, phenolic hydroxyl group, and mercapto group in one molecule. Etc. The weight average molecular weight of the organosiloxane is preferably in the range of 500 or more and 5000 or less. This is because when the weight average molecular weight is 500 or more and 5000 or less, the compatibility with the epoxy resin is appropriate. That is, when the weight average molecular weight is 500 or more, it is appropriately compatible with the epoxy resin, and the effect as an additive is appropriately exhibited. When the weight average molecular weight is 5,000 or less, incompatibility with the epoxy resin is suppressed, the silicone-modified epoxy resin is prevented from being separated or exuded during molding, and the adhesiveness and appearance are excellent.

  The epoxy resin for obtaining the silicone-modified epoxy resin is not particularly limited as long as it is compatible with the epoxy resin contained in the resin composition for electronic components, and is an epoxy generally used for the resin composition for electronic components. Resin can be used. For example, glycidyl ether type epoxy resins obtained by reaction of phenol compounds such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and epichlorohydrin; phenol compounds including orthocresol novolac type epoxy resins A novolak-type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or co-condensation of aldehyde with an aldehyde compound; a glycidyl ester-type epoxy resin obtained by reaction of a polybasic acid such as phthalic acid or dimer acid and epichlorohydrin; diaminodiphenylmethane; Glycidylamine-type epoxy resin obtained by reaction of polyamines such as isocyanuric acid and epichlorohydrin; obtained by oxidizing olefinic bonds with peracids such as peracetic acid Linear aliphatic epoxy resin, an alicyclic epoxy resin. These may be used alone or in combination of two or more. These epoxy resins are preferably liquid at room temperature.

  The content of the silicone-modified epoxy resin is preferably 0.01% by mass or more and 1.5% by mass or less, and 0.05% by mass or more and 1% by mass or less in the total mass of the resin composition for electronic components. More preferably. When the content of the silicone-modified epoxy resin is 0.01% by mass or more, a sufficient addition effect tends to be obtained. Further, when the content of the silicone-modified epoxy resin is 1.5% by mass or less, there is a tendency that it is possible to prevent exudation from the surface of the cured product at the time of curing and to prevent a decrease in adhesive force. As long as the effect of the present invention is obtained, an additive having an effect as a surfactant can be contained in addition to the silicone-modified epoxy resin.

  The resin composition for electronic parts may further contain a coupling agent as necessary. By containing the coupling agent, it is possible to further strengthen the interfacial adhesion between the epoxy resin and the inorganic filler, or between the epoxy resin and the component of the electronic component. There is no restriction | limiting in particular in these coupling agents, A conventionally well-known thing can be used. Examples of coupling agents include various silanes such as silane compounds having at least one selected from primary amino groups, secondary amino groups, and tertiary amino groups, epoxy silanes, mercapto silanes, alkyl silanes, ureido silanes, vinyl silanes, and the like. Compounds, titanium compounds, aluminum chelates, aluminum / zirconium compounds, and the like. Specific examples thereof 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) aminopropylto Methoxysilane, 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, N-dibutyl) amino Nopropylmethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilyl) Isopropyl) silane coupling agents such as ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane; Isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (N-aminoethyl-aminoethyl) titanate, Traoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene Titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tris (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) ) Titanate coupling agents such as titanate The These may be used alone or in combination of two or more.

Moreover, it is preferable that the resin composition for electronic parts of this invention further contains the ion trap agent represented by the following general formula (1) or (2) as needed. By further containing an ion trapping agent, it is possible to further improve the migration resistance, moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC.
Mg _(1-x) Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (1)
(0 <x ≦ 0.5, m is a positive number)
BiO _x (OH) _y (NO ₃ ) _z (2)
(0.9 ≦ x ≦ 1.1, 0.6 ≦ y ≦ 0.8, 0.2 ≦ z ≦ 0.4)

  The content of these ion trapping agents is preferably 0.1% by mass or more and 3.0% by mass or less, more preferably 0.3% by mass or more and 1.5% by mass in the total mass of the resin composition for electronic parts. % Or less. The volume average particle size of the ion trapping agent is preferably 0.1 μm or more and 3.0 μm or less, and the maximum particle size is preferably 10 μm or less. In addition, the compound of General formula (1) is available as Kyowa Chemical Industry Co., Ltd. brand name DHT-4A as a commercial item. Moreover, the compound of General formula (2) is available as IXE500 (Toagosei product name) as a commercial item. Further, other anion exchangers can be added as necessary. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. Examples thereof include hydrated oxides such as magnesium, aluminum, titanium, zirconium, and antimony, and these can be used alone or in combination of two or more.

  The resin composition for electronic parts may contain a colorant such as a dye and carbon black, a diluent, a leveling agent, an antifoaming agent, and the like as other additives.

  The resin composition for electronic parts can be prepared by any method as long as the above various components can be uniformly dispersed and mixed. As a general method, it can be obtained by weighing components of a predetermined blending amount, mixing and kneading using a raking machine, mixing roll, planetary mixer, etc., and defoaming treatment as necessary.

The resin composition for electronic parts of the present invention has a viscosity at 25 ° C. of preferably 0.01 Pa · s to 1000 Pa · s, more preferably 0.1 Pa · s to 200 Pa · s, and 1 Pa · s. More preferably, it is ˜50 Pa · s.
The viscosity at 25 ° C. of the resin composition for electronic parts is measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm).

  The resin composition for electronic parts can be used to seal a gap between a semiconductor element and a substrate. Examples of a method for sealing an element using the resin composition for electronic parts include a dispensing method, a casting method, and a printing method.

<Electronic component device>
An electronic component device of the present invention is sandwiched between a semiconductor element, an inorganic or organic substrate having a circuit on a surface opposite to a surface on which the electrode of the semiconductor element is formed, and the semiconductor element and the substrate. The resin composition for an electronic component according to any one of claims 1 to 8, which is filled in a gap between the bump that electrically connects the electrode and the circuit, and the gap between the semiconductor element and the substrate. And a cured product.
Specifically, in the electronic component device, the surface on which the electrode of the semiconductor element is disposed and the surface on which the circuit of the inorganic or organic substrate is disposed are opposed to each other, and the electrode of the semiconductor element and the circuit of the substrate are disposed. It can be obtained by electrically connecting via bumps and sealing the resin composition for electronic components in the gap between the semiconductor element and the substrate.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

In preparing the resin composition for electronic parts, the following materials were prepared. Moreover, the hardening accelerators 1-13 which are specific hardening acceleration | stimulation compounds were prepared as shown below.
(Epoxy resin)
Epoxy 1: Liquid epoxy resin having an epoxy equivalent of 160 obtained by epoxidizing bisphenol F (trade name jER806, manufactured by Mitsubishi Chemical Corporation)
Epoxy 2: Trifunctional liquid epoxy resin with an epoxy equivalent of 95 obtained by epoxidizing aminophenol (Mitsubishi Chemical Corporation, trade name jER630)

(Curing agent)
Aromatic amine 1: Diethyltoluenediamine having an active hydrogen equivalent of 45 (liquid aromatic amine compound; manufactured by Mitsubishi Chemical Corporation, trade name jER Cure W)
Aromatic amine 2: diethyldiaminodiphenylmethane having an active hydrogen equivalent of 63 (liquid aromatic amine compound; manufactured by Nippon Kayaku Co., Ltd., trade name Kayahard AA)
Aliphatic amine: Jefferamine T-403 having an active hydrogen equivalent of 160 (liquid aliphatic amine; manufactured by Mitsui Chemicals Fine Co., Ltd.)
Acid anhydride: acid anhydride equivalent 168 liquid acid anhydride (manufactured by Hitachi Chemical Co., Ltd., trade name HN5500)
Phenol resin: Allylated phenol novolak resin having a hydroxyl group equivalent of 141 (liquid phenol resin; product name MEH-8000H, manufactured by Meiwa Kasei Co., Ltd.)

(Other curing accelerators)
Curing accelerator 14: 2-phenyl-4-methyl-hydroxyimidazole Curing accelerator 15: Catechol (CAT)
Curing accelerator 16: 2,2′-biphenol (OBP)
(Inorganic filler)
Silica: spherical fused silica (additive) with a volume average particle diameter of 1 μm
Silicone rubber particles: Spherical silicone rubber particles having a volume average particle diameter of 2 μm in which the surface of dimethyl type solid silicone rubber particles is modified with an epoxy group,
Silane coupling agent: γ-glycidoxypropyltrimethoxysilane Colorant: Carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation)
-Ion trap agent: Bismuth ion trap agent (manufactured by Toagosei Co., Ltd., trade name IXE-500)

The weight average molecular weight (Mw) of the curing accelerator synthesized below is as shown below. Here, the weight average molecular weight (Mw) is determined by GPC method using tetrahydrofuran as a solvent, and details of GPC method are as follows.
Device name (pump): Hitachi L-6200
Column: TSKgelG2000H _XL + TSKgelG5000H _XL
Detector: RI Hitachi L-3300 (differential refractometer detector)
Column temperature: 30 ° C
Eluent: Tetrahydrofuran Flow rate: 1 ml / min Standard substance: Polystyrene

(Preparation of curing accelerator 1)
A flask is charged with 12.9 g of catechol and 25.0 g of 1,4-butanediol divinyl ether (molar ratio of catechol to 1,4-butanediol divinyl ether is 1: 1.5) and reacted at 100 ° C. for 2 hours. By doing so, a curing accelerator 1 having a structural site represented by the general formula (I) was obtained. The weight average molecular weight of the curing accelerator 1 was 526 in terms of polystyrene.

(Preparation of curing accelerator 2)
A flask is charged with 12.9 g of resorcinol and 25.0 g of 1,4-butanediol divinyl ether (molar ratio of resorcinol to 1,4-butanediol divinyl ether is 1: 1.5) and reacted at 100 ° C. for 2 hours. As a result, a curing accelerator 2 having a structural portion represented by the general formula (I) was obtained. The weight average molecular weight of the curing accelerator 2 was 2399 in terms of polystyrene.

(Preparation of curing accelerator 3)
The flask was charged with 21.8 g of 2,2′-biphenol and 25.0 g of 1,4-butanediol divinyl ether (the molar ratio of 2,2′-biphenol to 1,4-butanediol divinyl ether was 1: 1). .5), by causing a reaction at 100 ° C. for 2 hours, a curing accelerator 3 having a structural portion represented by the general formula (I) was obtained. The weight average molecular weight of the curing accelerator 3 was 816 in terms of polystyrene.

(Preparation of curing accelerator 4)
A flask was charged with 19.7 g of pyrogallol and 50.0 g of 1,4-butanediol divinyl ether (molar ratio of pyrogallol to 1,4-butanediol divinyl ether was 1: 2.25) and reacted at 120 ° C. for 8 hours. As a result, a curing accelerator 4 having a structural portion represented by the general formula (I) was obtained. The weight average molecular weight of the curing accelerator 4 was 1685 in terms of polystyrene.

(Preparation of curing accelerator 5)
The flask was charged with 13.3 g of resorcinol and 25.0 g of n-propyl vinyl ether (molar ratio of resorcinol to n-propyl vinyl ether was 1: 2.4) and raised from room temperature to 70 ° C. over 30 minutes. The reaction was carried out at 70 ° C. for 10 hours. Thereafter, using a rotary evaporator, unreacted n-propyl vinyl ether is distilled off from the mixed solution, and then vacuum-dried by a vacuum pump, whereby the curing accelerator 5 having a structural portion represented by the general formula (I) is obtained. Got. The weight average molecular weight of the curing accelerator 5 was 448 in terms of polystyrene.

(Preparation of curing accelerator 6)
A flask was charged with 31.0 g of catechol and 30.0 g of 1,4-butanediol divinyl ether (molar ratio of catechol to 1,4-butanediol divinyl ether was 1: 0.75) and reacted at 110 ° C. for 2 hours. By doing so, a curing accelerator 6 having a structural portion represented by the general formula (I) was obtained. The weight average molecular weight of the curing accelerator 6 was 1445 in terms of polystyrene.

(Preparation of curing accelerator 7)
A flask is charged with 38.7 g of catechol and 50.0 g of 1,4-butanediol divinyl ether (molar ratio of catechol to 1,4-butanediol divinyl ether is 1: 1) and allowed to react at 100 ° C. for 2 hours. Thereby, the hardening accelerator 7 which has a structure site | part represented by general formula (I) was obtained. The weight average molecular weight of the curing accelerator 7 was 934 in terms of polystyrene.

(Preparation of curing accelerator 8)
The flask was charged with 24.5 g of 4-tert-butylcatechol and 21.0 g of 1,4-butanediol divinyl ether (the molar ratio of 4-tert-butylcatechol and 1,4-butanediol divinyl ether was 1: 1). ) And 3 hours of reaction at 120 ° C. to obtain a curing accelerator 8 having a structural portion represented by the general formula (I). The weight average molecular weight of the curing accelerator 8 was 1016 in terms of polystyrene.

(Preparation of curing accelerator 9)
A flask was charged with 21.8 g of 3-methylcatechol and 25.0 g of 1,4-butanediol divinyl ether (molar ratio of 3-methylcatechol to 1,4-butanediol divinyl ether was 1: 1), 120 ° C. Was allowed to react for 2 hours to obtain a curing accelerator 9 having a structural moiety represented by the general formula (I). The weight average molecular weight of the curing accelerator 9 was 1132 in terms of polystyrene.

(Preparation of curing accelerator 10)
A flask is charged with 24.6 g of 3-methoxycatechol and 25.0 g of 1,4-butanediol divinyl ether (molar ratio of 3-methoxycatechol to 1,4-butanediol divinyl ether is 1: 1), 120 ° C. Was allowed to react for 24 hours to obtain a curing accelerator 10 having a structural moiety represented by the general formula (I). The weight average molecular weight of the curing accelerator 10 was 1203 in terms of polystyrene.

(Preparation of curing accelerator 11)
A flask was charged with 20.8 g of 3,5-di-tert-butylcatechol and 20.0 g of 1,4-butanediol divinyl ether (3,5-di-tert-butylcatechol and 1,4-butanediol divinyl ether). The molar ratio of vinyl ether was 1: 1.5), and the reaction was carried out at 120 ° C. for 2 hours to obtain a curing accelerator 11 having a structural site represented by the general formula (I). The weight average molecular weight of the curing accelerator 11 was 489 in terms of polystyrene.

(Preparation of curing accelerator 12)
The flask was charged with 22.5 g of 2,3-dihydroxynaphthalene and 30.0 g of 1,4-butanediol divinyl ether (the molar ratio of 2,3-dihydroxynaphthalene to 1,4-butanediol divinyl ether was 1: 1. .5), by causing a reaction at 90 ° C. for 2 hours, a curing accelerator 12 having a structural portion represented by the general formula (I) was obtained. The weight average molecular weight of the curing accelerator 12 was 963 in terms of polystyrene.

(Preparation of curing accelerator 13)
A structure represented by the general formula (I) is prepared by charging 9.6 g of catechol and 30.0 g of glycidyl vinyl ether into a flask (molar ratio of catechol to glycidyl vinyl ether is 1: 2) and reacting at 120 ° C. for 12 hours. The hardening accelerator 13 which has a site | part was obtained. The weight average molecular weight of the curing accelerator 13 was 202 in terms of polystyrene.

<Examples 1 to 25 and Comparative Examples 1 to 9>
After mixing each component so that it may become a composition shown in the following Table 1-Table 3, it knead | mixes and disperses with a three roll and a vacuum crusher, Resin for electronic components of Examples 1-25 and Comparative Examples 1-9 A composition was prepared. The blending units in the table are parts by weight unless otherwise specified. "-" Indicates unsigned.

  It shows in Table 4-Table 6 about the evaluation result of the obtained resin composition for electronic components. The test method of the characteristic test will be described below. The characteristics and impregnation time, void observation, and various reliability evaluations of the used resin composition for electronic parts were performed by the following methods and conditions.

  The specifications of the semiconductor device before resin sealing used for the evaluation of reliability are as follows: chip size 20 × 20 × 0.55 tmm (circuit: daisy chain connection of aluminum, passivation: polyimide film HD4000, manufactured by Hitachi Chemical DuPont Microsystems, (Trade name), bump: solder ball (Sn-Ag-Cu, diameter 80 μm, 7,744 pin), bump pitch: 190 μm, substrate: FR-5 (solder resist SR7200, manufactured by Hitachi Chemical Co., Ltd., trade name, 60 × 60) × 0.8 tmm), chip / substrate gap: 50 μm.

  The semiconductor device was produced by underfilling a resin composition for electronic components by a dispense method and curing at a curing temperature of 130 ° C. or 165 ° C. for 2 hours. The curing conditions for various test pieces were also the same.

(1) Viscosity (initial viscosity)
Within 2 hours after preparing the resin composition for electronic parts, the viscosity (Pa · s) at 25 ° C. is measured by the E type viscometer EHD type manufactured by Tokimec Co., Ltd. (currently Tokyo Keiki Co., Ltd.) Measurement was performed at a sample volume of 0.7 ml using a cone angle of 3 °, a cone diameter of 30 mm, and a rotation speed of 5 rpm. The value after 1 minute from the start of measurement was taken as the measured value.

(2) Pot life After leaving the resin composition for electronic parts obtained above at 25 ° C. for 24 hours, the viscosity at 25 ° C. was measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm). (Viscosity after standing). The pot life (%) was calculated by ((viscosity after standing) − (initial viscosity)) / (initial viscosity) × 100.
In addition, when it was gelled after being left for 24 hours, measurement was impossible.

(3) Gel time Gel time was evaluated as follows using a gelation tester. After a suitable amount (about 3 ml) of the resin composition for electronic parts obtained above was dropped on a hot plate at 165 ° C. or 130 ° C., it was observed visually, and the time until it lost fluidity and became a gel state was gel time. (Sec.).

(4) Glass transition temperature (Tg)
A test piece (3 mm × 3 mm × 20 mm) obtained by curing the resin composition for electronic parts obtained above under a predetermined condition is used with a thermomechanical analyzer TMAQ400 (manufactured by TA Instruments), and a load of 15 g. The glass transition temperature (Tg) was measured under the conditions of a measurement temperature of 0 ° C. to 200 ° C. and a heating rate of 10 ° C./min.

(5) Adhesive strength The adhesive strength of the resin composition for electronic parts obtained above to the polyimide resin (PI) and silicon nitride was evaluated as follows.
-SiN adhesive strength 3mm in diameter and 3mm in height formed on the surface of a wafer with P-SiN (p-type silicon wafer with silicon nitride film, manufactured by Sumitomo Corporation Kyushu Co., Ltd.) using a resin composition for electronic components A test piece on which an object was formed was prepared, and a bond tester DS100 type (manufactured by DAGE) was used to apply a shear stress under the conditions of a head speed of 50 μm / sec and 25 ° C., and the cured product was peeled from the wafer with P-SiN. The strength was measured. This measurement was performed both immediately after molding of the test piece and after treatment for 200 h under the condition of 130 ° C. and 85% RH HAST (Highly Accelerated Temperature and Humidity Stress Test).
-PI adhesive force A test piece in which a cured product having a diameter of 3 mm and a height of 3 mm formed using a resin composition for electronic parts was formed on the surface of photosensitive polyimide HD4100 (product name, manufactured by Hitachi Chemical DuPont Microsystems). A bond tester DS100 type (manufactured by DAGE) was used to apply shear stress under the conditions of a head speed of 50 μm / sec and 25 ° C., and the strength at which the cured product peeled from the photosensitive polyimide was measured. This measurement was performed both immediately after the test piece molding and after 200 h treatment under HAST conditions of 130 ° C. and 85% RH.

(6) Impregnation time The semiconductor device before resin sealing is placed on a hot plate heated to 110 ° C., and a predetermined amount (about 1 ml) of the resin composition for electronic components is applied to the side surface (one side) of the chip using a dispenser. The time (sec.) Until the resin composition penetrated into the opposite side surfaces was measured.

(7) Void Observation The inside of the semiconductor device produced by underfilling and curing the resin composition for electronic components was observed with an ultrasonic flaw detector AT-5500 (manufactured by Hitachi Construction Machinery), and the presence or absence of voids was examined.

(8) Chip warpage The amount of warpage (μm) on the chip diagonal line of a semiconductor device produced by underfilling and curing a resin composition for electronic components was measured at room temperature using a surface roughness measuring device Surfcoder SE-2300 (Kosaka Research). ).

(9) Temperature cycle resistance The semiconductor device produced by underfilling and curing the resin composition for electronic parts was subjected to 2000 cycles at −55 ° C. to 125 ° C. for 30 minutes in each heat cycle. Conductivity test was conducted every 1000 cycles to check for disconnection defects of aluminum wiring and pads, and evaluated by the number of defective packages / number of evaluation packages.

(10) Moisture resistance reliability After a semiconductor device manufactured by underfilling and curing a resin composition for electronic components under a HAST condition of 130 ° C. and 85% RH for 200 hours, the presence or absence of disconnection of aluminum wiring and pads is determined from a continuity test. The number of defective packages / the number of evaluation packages was evaluated.

In Comparative Examples 1 to 3 not containing the curing accelerator (C) component in the present invention, the gel time was long and voids were generated. Furthermore, in 130 degreeC hardening, since the adhesive force of hardened | cured material is low, it was inferior to temperature cycling resistance and moisture-proof reliability, and especially temperature cycling resistance was remarkably inferior.
Further, in Comparative Example 4 in which the component (B) is an aliphatic amine, the pot life is inferior even when the curing accelerator is not contained, and the evaluation cannot be performed because the semiconductor device cannot be filled and cannot be evaluated. There was an item.
Moreover, the comparative example 8 whose (B) component is an acid anhydride, and the comparative example 9 which is a phenol resin did not harden | cure.
Moreover, in Comparative Example 5 in which the component (C) is the curing accelerator 6, although the gel time was shortened, the adhesive strength after the Tg and HAST treatment of the cured product was reduced, and the moisture resistance was remarkably reduced. In addition, there are evaluation items that cannot be filled and evaluated when a semiconductor device is manufactured.
Moreover, in Comparative Examples 6 and 7 in which the component (C) is the curing accelerators 7 and 8, although the gel time was shortened, the pot life was deteriorated.
On the other hand, in Examples 1 to 25, the gel time is shortened compared to Comparative Examples 1 to 3, no voids are generated, the adhesive strength of the cured product is improved, and temperature cycle resistance and moisture resistance are improved. Improved. In particular, the adhesive strength at 130 ° C. curing has been improved, and the temperature cycle resistance and moisture resistance have been improved, and it has become possible to reduce the chip warpage by setting the curing temperature low. Further, when compared with Comparative Example 5, the adhesive strength after HAST treatment was improved, and a semiconductor device excellent in moisture resistance was obtained. Moreover, when compared with Comparative Examples 6 and 7, the pot life was improved. Furthermore, compared with Comparative Examples 1-9, the semiconductor device which was excellent in the balance of a moldability and reliability was obtained.

The entire disclosure of Japanese Patent Application No. 2011-102355 is incorporated herein by reference.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims (9)

Resin for electronic parts containing an epoxy resin, an aromatic amine compound, and a curing accelerator containing at least one compound selected from the group of compounds having a structural moiety represented by the following general formula (I) Composition.

(Wherein, L ¹ represents a carbon atom, a divalent group having 1 to 18 carbon atoms comprised of hydrogen atoms and oxygen atoms, or a divalent hydrocarbon group having 1 to 18 carbon atoms.
R ^{1 to} R ³ are each independently a monovalent group having 1 to 18 carbon atoms composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom; -18 monovalent hydrocarbon groups or hydrogen atoms.
R ^{4 to} R ⁷ are each independently a monovalent group having 1 to 18 carbon atoms composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom; -18 monovalent hydrocarbon groups, hydroxyl groups, or hydrogen atoms. Two adjacent groups selected from R ^{4 to} R ⁷ may be bonded to each other to form a ring. ) The resin composition for electronic components according to claim 1, wherein the curing accelerator includes a compound represented by any one of the following general formulas (IIa), (IIb), and (IIc).

^{(Wherein, L 21} represents a carbon atom, a divalent group having 1 to 18 carbon atoms comprised of hydrogen atoms and oxygen atoms, or a divalent hydrocarbon group having 1 to 18 carbon atoms.
R ^{21 to} R ²⁶ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms.
Ar is an m-valent aromatic hydrocarbon group having 6 to 18 carbon atoms, or at least two aromatic hydrocarbon groups having 6 to 18 carbon atoms are a single bond or a linear or branched chain having 1 to 12 carbon atoms. A group that is connected to at least one linking group selected from the group consisting of an alkylene group, a carbonyl group, and an oxygen atom to be m-valent as a whole.
m represents an integer of 2 to 8, and n represents an integer of 0 to 20. ) The resin composition for electronic components according to claim 1, wherein the curing accelerator includes a compound represented by the following general formula (III).

^{(Wherein, L 21} represents a carbon atom, a divalent group having 1 to 18 carbon atoms comprised of hydrogen atoms and oxygen atoms, or a divalent hydrocarbon group having 1 to 18 carbon atoms.
R ^{21 to} R ²³ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms.
R ²⁷ represents a hydrogen atom or a group represented by the following general formula (IIIa) or general formula (IIIb).

Ar represents an m-valent aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic hydrocarbon group having 2 or more carbon atoms having a single bond or an alkylene group having 1 to 12 carbon atoms, a carbonyl group, and oxygen. A group which is linked by at least one linking group selected from the group consisting of atoms and becomes m-valent as a whole is shown.
m represents an integer of 1 to 8, p represents an integer of 1 to 8, and m ≧ p. )   The said hardening accelerator is an addition reaction product of at least 1 sort (s) of the compound which has a phenolic hydroxyl group, and at least 1 sort (s) of the compound which has a vinyl ether group, The any one of Claims 1-3. Resin composition for electronic parts.   The said epoxy resin is a liquid epoxy resin, The resin composition for electronic components of any one of Claims 1-4.   The resin composition for electronic parts according to any one of claims 1 to 5, wherein the aromatic amine compound is a liquid aromatic amine compound.   Furthermore, an inorganic filler is contained, The content rate of the said inorganic filler is the range of 50 to 80 mass% in the total mass of the resin composition for electronic components, The any one of Claims 1-6 The resin composition for electronic parts as described in the paragraph.   The said aromatic amine compound contains at least one chosen from the group which consists of 3,3'-diethyl-4,4'-diaminodiphenylmethane and diethyltoluenediamine in any one of Claims 1-7. The resin composition for electronic components as described. A semiconductor element;
An inorganic or organic substrate having a circuit on a surface facing the surface on which the electrodes of the semiconductor element are formed;
A bump sandwiched between the semiconductor element and the substrate and electrically connecting the electrode and the circuit;
The cured product of the resin composition for electronic components according to any one of claims 1 to 8, which is filled in a gap between the semiconductor element and the substrate.
An electronic component device.