JP2013001811A - Resin composition for electronic component and electronic component device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for electronic components, which has excellent fluidity in a narrow gap, the gel time of which is quickened to be cured at low temperature, and which allows the thermal stress imposed on a chip to be reduced and void generation to be suppressed when molded.SOLUTION: The resin composition for electronic components contains an epoxy resin, an aromatic amine compound and at least one compound which is used as a curing promotor and selected from the group comprising the compounds represented by general formula (I) (wherein Lis an m-valent group comprising a carbon atom, a hydrogen atom and an oxygen atom or an m-valent hydrocarbon group; Rto Rare each a hydrogen atom or a monovalent hydrocarbon group independently; Ris a monovalent group comprising a carbon atom, a hydrogen atom and an oxygen atom, a monovalent group comprising a carbon atom, a hydrogen atom and a nitrogen atom, or a monovalent hydrocarbon group; m is an integer of 2-6).

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 thermal expansion coefficient is different between the element and the substrate, so that 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 addition, a fillet is formed on the side of the chip to protect the chip, but the resin cracks due to the thermal stress caused by the difference in thermal expansion between the underfill material and the chip. As a result, in the worst case, the chip is destroyed. There is a fear. 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 joints 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 an epoxy resin composition for fastening is disclosed (for example, see Patent Document 1).

Japanese Patent No. 3716237

  The chip size has increased with the recent high integration and multi-functionality of the elements, but with the increase in the number of pins, the bump diameter has been reduced, the pitch and the gap have been reduced, and the mounting equipment has also been reduced in size. Accordingly, the chip thickness has been reduced, 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 was made in view of such circumstances, the fluidity in a narrow gap is good, the gel temperature is accelerated, the curing temperature can be lowered, and the thermal stress applied to the chip is reduced. It is another object of the present invention to provide a liquid resin composition for electronic components in which the generation of voids during molding is suppressed, and an electronic component device having high reliability (moisture resistance and temperature cycle resistance) sealed thereby.

As a result of intensive studies, the present inventors have found a liquid resin composition for electronic parts containing a specific curing agent and a curing accelerator. More specifically, the present invention relates to the following.
<1> Liquid resin for electronic parts containing an epoxy resin, an aromatic amine compound, and at least one compound selected from the group of compounds represented by the following general formula (I) as a curing accelerator Composition.

(Wherein, ^{L m} is a carbon atom, m-valent group having from 1 to 18 hydrogen atoms and carbon atoms composed of an oxygen atom, or ^.R 1 ~ indicating the m-valent hydrocarbon group having 1 to 18 carbon atoms R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ⁴ is a monovalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and an oxygen atom. , A monovalent group having 1 to 18 carbon atoms or a monovalent hydrocarbon group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and a nitrogen atom, m represents an integer of 2 to 6)

<2> The liquid resin composition for electronic components according to <1>, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II).

^{(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, and R ²⁷ and R ²⁸ each independently represents 1 carbon atom composed of a carbon atom, a hydrogen atom and an oxygen atom. A monovalent group having 1 to 18 carbon atoms, or a monovalent hydrocarbon group having 1 to 18 carbon atoms, which is composed of a monovalent group having 18 to 18 carbon atoms, a hydrogen atom and a nitrogen atom)

<3> The curing accelerator is a reaction product obtained by addition reaction of at least one compound having only one carboxy group and at least one compound having at least two vinyl ether groups. <1> or the liquid resin composition for electronic components as described in <2>.

<4> The liquid resin composition for electronic components according to any one of <1> to <3>, wherein the epoxy resin is a liquid epoxy resin.

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

<6> Further, an inorganic filler is contained, and the content of the inorganic filler is in the range of 50% by mass or more and 80% by mass or less of the entire liquid resin composition for electronic parts, according to the items <1> to <5>. The liquid resin composition for electronic components of any one of Claims 1.

<7> The aromatic amine compound includes at least one selected from 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine, and any one of the above <1> to <6> Liquid resin composition for electronic parts as described in 2.

<8> The circuit formation surface of the semiconductor element and the circuit formation surface of the inorganic or organic substrate are opposed to each other, and the electrode of the semiconductor element and the circuit of the substrate are electrically connected via a bump, and the semiconductor element and the circuit The electronic component apparatus formed by sealing the liquid resin composition for electronic components of any one of said <1>-<7> in the clearance gap with a board | substrate.

  According to the present invention, the fluidity in a narrow gap is good, the gel time is accelerated, the curing temperature can be lowered, the thermal stress applied to the chip is reduced, and the generation of voids during molding is suppressed. In addition, it is possible to provide a liquid resin composition for electronic components and an electronic component device having high reliability (moisture resistance and temperature cycle resistance) sealed by the liquid resin composition.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action 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, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, the total amount of the plurality of substances present in the composition unless otherwise specified. Means.

  The liquid resin composition for electronic parts of the present invention comprises (A) at least one epoxy resin, (B) at least one aromatic amine compound, and (C) a curing accelerator represented by the following general formula (I): And at least one compound selected from the group of compounds represented.

Wherein, L ^m represents carbon atom, m-valent group having 1 to 18 carbon atoms comprised of hydrogen atoms and oxygen atoms, or an m-valent hydrocarbon group having 1 to 18 carbon atoms. R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms. R ⁴ is a monovalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and an oxygen atom, a monovalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and a nitrogen atom, or A monovalent hydrocarbon group having 1 to 18 carbon atoms is shown. m shows the integer of 2-12.

  By using a curing accelerator having a specific structure, generation of voids during molding is suppressed, gel time is shortened, and curing temperature can be lowered. 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. Therefore, if an electronic component is sealed using this liquid resin composition for electronic components, an electronic component device with high moldability and reliability can be obtained, and its industrial value is great.

  This can be considered as follows, for example. The specific curing accelerating compound is excellent in storage stability and various reliability because it is blocked by adding a vinyl group to a carboxy 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.

In addition, the liquid state in this invention means that it is liquid state at normal temperature (25 degreeC). Specifically, it means that the viscosity measured with an E-type viscometer is 1000 Pa · s or less at 25 ° C.
However, when the liquid 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.

(A) Epoxy resin The epoxy resin used in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule. Especially, it is preferable that it is a liquid epoxy resin which is liquid at normal temperature.
As an epoxy resin, the epoxy resin generally used with the liquid resin composition for electronic components can be used. Examples of epoxy resins that can be used in the present invention include diglycidyl ether type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, hydrogenated bisphenol A, and phenols typified by orthocresol novolac type epoxy resins. Epoxidized aldehyde novolak resin, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, amine compound such as p-aminophenol, diaminodiphenylmethane, isocyanuric acid and epichlorohydrin A glycidylamine type epoxy resin obtained by a reaction obtained by condensation or cocondensation of olefin, a linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peracid such as peracetic acid, an alicyclic ester Such as carboxymethyl resins. These may be used alone or in combination of two or more.
Among these, a liquid bisphenol type epoxy resin is preferable from the viewpoint of fluidity, and a liquid glycidylamine type epoxy resin is preferable from the viewpoint of heat resistance, adhesiveness, and fluidity.

  The liquid epoxy resin (preferably at least one selected from liquid bisphenol type epoxy resin and liquid glycidylamine type epoxy resin) may be used alone or in combination of two or more. . The content of the liquid epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. preferable.

  Moreover, the said liquid resin composition for electronic components may contain the solid epoxy resin, if it exists in the range with which the effect of this invention is achieved. The content of the solid epoxy resin is preferably 20% by mass or less in the total amount of the epoxy resin from the viewpoint of fluidity at the time of molding.

  The content of the epoxy resin in the total amount of the liquid resin composition for electronic parts is not particularly limited. For example, it is preferably 20% by mass or more and 50% by mass or less, more preferably 25% by mass or more and 75% by mass or less, and further preferably 30% by mass or more and 70% by mass or less.

  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.

  Further, the purity of these epoxy resins, particularly the amount of hydrolyzable chlorine, is preferably less because it relates to the corrosion of aluminum wiring on ICs and other elements. In order to obtain a liquid resin composition for electronic parts having excellent moisture resistance, 500 ppm. The following 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, heating and refluxing for 30 minutes, and then by potentiometric titration. It is.

(B) Aromatic amine compound If the aromatic amine compound used for this invention contains the amine which has an aromatic ring, there will be no restriction | limiting in particular. Among them, an aromatic amine compound that is liquid at room temperature is preferable. In the liquid resin composition for electronic parts, the aromatic amine compound functions as a curing agent, for example.
Examples of aromatic amine compounds include 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. It is done.
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 these, 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine are preferable from the viewpoint of storage stability, and any one of these or a mixture thereof is contained as a main component as an aromatic amine compound. It is preferable.
Examples of 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 addition, the liquid resin composition for electronic parts of the present invention is not limited to the above aromatic amine compound, but may be an amine curing agent other than the aromatic amine compound, phenolic curing, as long as the effects of the present invention are achieved. Curing agents generally used in liquid resin compositions for electronic parts such as an agent and acid anhydride can be used in combination, and a solid curing agent can also be used in combination.
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 the performance.

  The equivalent ratio of the epoxy resin and the curing agent containing the aromatic amine compound is not particularly limited. However, in order to suppress each unreacted component to a small amount, the curing agent is added to 0.7 equivalent of the epoxy resin. It is preferably set in the range of not less than the equivalent and not more than 1.8 equivalent, more preferably not less than 0.8 and not more than 1.6 equivalent, and still more preferably not less than 1.0 and not more than 1.5 equivalent.

(C) Curing Accelerator The curing accelerator in the present invention contains at least one compound selected from the group of compounds represented by the following general formula (I) (hereinafter also referred to as “specific curing accelerating compound”). To do.

Wherein, L ^m represents carbon atom, m-valent group having 1 to 18 carbon atoms comprised of hydrogen atoms and oxygen atoms, or an m-valent hydrocarbon group having 1 to 18 carbon atoms. R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms. R ⁴ is a monovalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and an oxygen atom, a monovalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and a nitrogen atom, or A monovalent hydrocarbon group having 1 to 18 carbon atoms is shown. m shows the integer of 2-12.
Here, the monovalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and an oxygen atom represented by R ⁴ is derived from a carboxy group such as a carboxy group and an ester or amide as a substituent. It preferably has no substituent.

  The m-valent hydrocarbon group having 1 to 18 carbon atoms is an m-valent group configured by removing m hydrogen atoms from a hydrocarbon compound having 1 to 18 carbon atoms. Examples of the hydrocarbon compound having 1 to 18 carbon atoms include a linear or branched alkane having 1 to 18 carbon atoms, a cycloalkane having 3 to 18 carbon atoms, and a linear or branched chain having 2 to 18 carbon atoms. And alkenes of 5 to 18 carbon atoms, cycloalkenes having 5 to 18 carbon atoms, and aromatic hydrocarbons having 6 to 18 carbon atoms. Among them, a linear or branched alkane having 1 to 12 carbon atoms, a cycloalkane having 5 to 12 carbon atoms, a linear alkane having 5 to 12 carbon atoms, a complex of a branched alkane and a cycloalkane, It is preferably at least one selected from the group consisting of a linear or branched alkene having 2 to 12 carbon atoms, a cycloalkene having 5 to 12 carbon atoms and an aromatic hydrocarbon having 6 to 15 carbon atoms.

Specific examples of the linear or branched alkane having 1 to 18 carbon atoms include ethane, propane, butane, pentane, 2,2-dimethylpropane, hexane, 2-ethylhexane, octane, decane, dodecane, and octadecane. And so on.
Examples of the cycloalkane having 3 to 18 carbon atoms include cyclopropane, cyclopentane, cyclohexane, cyclooctane, and bicyclo [4.4.0] decane.
Examples of the linear or branched alkene having 2 to 18 carbon atoms include ethylene, propylene, and butene.
Examples of the cycloalkene having 5 to 18 carbon atoms include cyclopentene and cyclohexene.
Examples of the aromatic hydrocarbon having 6 to 18 carbon atoms include benzene, naphthalene, anthracene, and phenanthrene.

  Among these, as the hydrocarbon compound constituting the m-valent hydrocarbon group having 1 to 18 carbon atoms, from the viewpoint of curing acceleration and storage stability (pot life), A branched alkane, a cycloalkane, a complex of a linear alkane and a cycloalkane, a linear or branched alkene, a cycloalkene, benzene, and naphthalene are preferable, and a linear chain having 1 to 8 carbon atoms or More preferred are branched alkanes, cycloalkanes, and complexes of linear alkanes and cycloalkanes.

Specific examples of the C1-C18 m-valent group composed of carbon atom, hydrogen atom and oxygen atom include methyleneoxy group, ethyleneoxy group, propyleneoxy group, diethyleneoxy group, dipropyleneoxy group, C1-C18 alkyleneoxy group such as triethyleneoxy group and tripropyleneoxy group, and bivalent group such as oligoalkyleneoxy group, glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Examples thereof include m-valent groups constituted by removing m hydroxyl groups from a polyhydric alcohol.
Among these, from the viewpoint of pot life, an alkyleneoxy group and an oligoalkyleneoxy group having 2 to 12 carbon atoms are preferable, and an alkyleneoxy group and an oligoalkyleneoxy group having 2 to 8 carbon atoms are more preferable.

Specific examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms include an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, and an aryl group.
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 the monovalent group having 1 to 18 carbon atoms composed of carbon atom, hydrogen atom and oxygen atom include methoxy group, ethoxy group, methoxymethyl group, phenoxy group, phenoxymethyl group, methoxyphenyl group, dimethoxy Examples thereof include an alkyl group and an aryl group substituted with a substituent composed of a carbon atom such as a phenyl group, a benzoylphenyl group, and an acetylphenyl group, a hydrogen atom, and an oxygen atom.
Among these, from the viewpoint of pot life, methoxy group, ethoxy group, methoxymethyl group, phenoxymethyl group, phenoxy group, methoxyphenyl group, dimethoxyphenyl group and acetylphenyl group are preferable, and methoxy group, ethoxy group, methoxymethyl group, phenoxy group are preferable. A methyl group, a phenoxy group, a methoxyphenyl group, and an acetylphenyl group are more preferable, and a methoxy group, an ethoxy group, and a phenoxy group are particularly preferable.

  Specific examples of the monovalent group having 1 to 18 carbon atoms composed of carbon atom, hydrogen atom and nitrogen atom include nitrogen such as cyanomethyl group, cyanophenyl group, aminomethyl group, aminophenyl group and diaminophenyl group. Examples thereof include an alkyl group and an aryl group substituted by a group to be contained.

L ^m is a divalent or trivalent structure formed by removing 2 or 3 hydrogen atoms from a linear or branched alkane having 1 to 18 carbon atoms from the viewpoint of curing acceleration and stability. A hydrocarbon group and an alkyleneoxy group or oligoalkyleneoxy group having 2 to 18 carbon atoms are preferred, and is constituted by removing 2 or 3 hydrogen atoms from a linear or branched alkane having 1 to 12 carbon atoms. A divalent or trivalent hydrocarbon group is more preferable, and a divalent hydrocarbon group constituted by removing two hydrogen atoms from a linear or branched alkane having 1 to 8 carbon atoms is more preferable. .

R ^{1 to} R ³ are each independently preferably a hydrogen atom or 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 is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or 3 carbon atoms from the viewpoint of curing acceleration. -18 cycloalkenyl group, C6-C18 aryl group, methoxymethyl group, phenoxymethyl group, methoxyphenyl group, dimethoxyphenyl group, benzoylphenyl group, acetylphenyl group, cyanomethyl group, cyanophenyl group, aminomethyl group , An aminophenyl group, and a diaminophenyl group are preferable, and an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a methoxymethyl group, an acetylphenyl group, a cyanomethyl group, and a cyanophenyl group are more preferable. .

Although m shows the integer of 2-12, it is preferable that it is an integer of 2-6, and it is more preferable that it is an integer of 2-4.
When m is 2, the compound represented by the general formula (I) is represented by the following general formula (II).

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. R ²⁷ and R ²⁸ are each independently a C 1-18 monovalent group composed of a carbon atom, a hydrogen atom and an oxygen atom, a C 1-18 composed of a carbon atom, a hydrogen atom and a nitrogen atom. Or a monovalent hydrocarbon group having 1 to 18 carbon atoms.

  A divalent group having 1 to 18 carbon atoms, a divalent hydrocarbon group having 1 to 18 carbon atoms, a carbon atom, a hydrogen atom, and an oxygen atom composed of a carbon atom, a hydrogen atom, and an oxygen atom in the general formula (II) A monovalent group having 1 to 18 carbon atoms, a monovalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and a nitrogen atom, and a monovalent hydrocarbon having 1 to 18 carbon atoms The groups have the same meanings as those in formula (I), and preferred embodiments are also the same.

L ²¹ in the general formula (II) is a linear or branched alkylene group having 1 to 18 carbon atoms or an alkyleneoxy group having 2 to 18 carbon atoms and oligoalkylene from the viewpoints of curing acceleration and storage stability. An oxy group is preferable, and a linear or branched alkylene group having 1 to 12 carbon atoms is more preferable.

R ^{21 to} R ²⁶ are each independently preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom or 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 ²⁷ and R ²⁸ are each an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkenyl group having 3 to 18 carbon atoms, from the viewpoint of curing acceleration. Group, aryl group having 6 to 18 carbon atoms, methoxymethyl group, phenoxymethyl group, methoxyphenyl group, dimethoxyphenyl group, benzoylphenyl group, acetylphenyl group, cyanomethyl group, cyanophenyl group, aminomethyl group, aminophenyl group, And a diaminophenyl group are preferable, and an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a methoxymethyl group, an acetylphenyl group, a cyanomethyl group, and a cyanophenyl group are more preferable.

The weight average molecular weight of the specific curing accelerating compound is not particularly limited. From the viewpoint of obtaining a viscosity excellent in handleability, the viscosity is preferably 100 to 5000, more preferably 150 to 2000, and still more preferably 200 to 1000.
The weight average molecular weight can be measured by a normal method using a mass spectrometer or GPC.

The curing accelerator may contain a compound having a free carboxy group.
The content of free carboxy groups in the specific curing accelerating compound is preferably 5 mol% or less, more preferably 2 mol% or less, and even more preferably 0.5 mol% or less.
The content rate of a free carboxy group can be measured using ¹³ C-NMR. Specifically, for example, about 100 mg of a sample is dissolved in 0.5 ml of heavy acetone or the like, placed in a sample tube, and measured using a highly quantitative inverse gate decoupling method with a repetition time of 30 seconds or more. And the content rate of a free carboxy group can be evaluated by calculating the integral ratio of the carbon of an unreacted carboxy group and the carbon of the carboxy group which has formed the ester bond by reaction.

Moreover, the said hardening accelerator may contain the compound represented by the following general formula (IIa). The compound represented by the following general formula (IIa) is a by-product when a specific curing accelerator is produced from a compound having one carboxy group and a divinyl ether compound in the method for producing a specific curing acceleration compound as described later. An example of a possible compound.
By further including such a compound having a vinyl ether group, the storage stability may be further improved.

Formula (IIa) ^{L 21} and ^R 21 in ^{to R 27} are the same meaning as ^{L 21} and ^R 21 ^{to R 27} in the general formula (II).

  The content rate of the compound represented by general formula (IIa) contained in a hardening accelerator is not restrict | limited in particular. From the viewpoints of curing acceleration and storage stability, the total amount of the curing accelerator is preferably 75% by mass or less, and more preferably 50% by mass or less.

The compound represented by the general formula (I) (specific curing accelerating compound) includes, for example, a compound having only one carboxy group and a compound having at least two vinyl ether groups (hereinafter also simply referred to as “vinyl ether compound”). It can be obtained by 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 carboxy group with, for example, an ethanol solution of potassium hydroxide.

The charged molar ratio in the addition reaction of the compound having a carboxy group and the vinyl ether compound can be appropriately selected according to the structures of the compound having a carboxy group and the vinyl ether compound.
Specifically, the compound represented by the general formula (I) is obtained by subjecting a compound having one carboxy group to a compound having m vinyl ether groups. The charging ratio of the compound having one carboxy group to the compound having m vinyl ether groups (compound having one carboxy group / compound having m vinyl ether groups) may be m times mol or less. Especially, it is preferable that it is 0.25m-m times mole, and it is more preferable that it is 0.40m-0.95m times mole.

  When the specific curing accelerating compound is a compound represented by the general formula (II), a compound having one carboxy group and a compound having two vinyl ether groups as a compound having a vinyl ether group (hereinafter referred to as “bisvinyl ether compound”). The compound represented by general formula (II) can be obtained by addition reaction. The charge ratio of the compound having one carboxy group to the bisvinyl ether compound (compound having one / bisvinyl ether compound carboxy group) may be, for example, 2.0 times mol or less. Among these, 0.5 to 2.0 times mol is preferable, 0.8 to 1.9 times mol is more preferable, and 1.0 to 1.8 times mol is more preferable.

  Furthermore, by containing an excessive amount of the vinyl ether compound, the carboxy group is blocked by an equilibrium reaction even when the vinyl ether compound is eliminated, and 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. Moreover, in order to reduce the residual carboxylic acid ratio, it is preferable that the reaction is performed for a sufficient reaction time so that the dicarboxylic acid and the vinyl ether compound can sufficiently react.

  Examples of the compound having one carboxy group include acetic acid, phenylacetic acid, diphenylacetic acid, triphenylacetic acid, methoxyacetic acid, phenoxyacetic acid, pyruvic acid, benzoic acid, toluic acid, methoxybenzoic acid, dimethoxybenzoic acid, and benzoylbenzoic acid. Acetylbenzoic acid, cyanobenzoic acid, acetylsalicylic acid and the like. Of these, methoxyacetic acid, benzoic acid, diphenylbenzoic acid, toluic acid, acetylbenzoic acid, benzoylbenzoic acid, and acetylsalicylic acid are preferred from the viewpoints of curing acceleration and storage stability.

  Examples of the compound having two vinyl ether groups include 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, and 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-pe Tandiol 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-1,10-undecadiene, 10-vinyloxydecyl vinyl ether, 12-vinyloxyoctadecyl vinyl ether, dipropylene glycol divinyl ether, resorcinol di Vinyl ether, m-phenylene bis (ethylene glycol) divinyl ether, bisphenol A divinyl ether Aliphatic vinyl ether compounds having two vinyl ether groups, such as ether, and the like alicyclic vinyl ether compound and an aromatic vinyl compound.

  Examples of the compound having three or more vinyl ether groups include glycerol trivinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, diglycerol tetravinyl ether, dipentaerythritol hexavinyl ether, and the like.

  Among these, from the viewpoint of storage stability, 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 glycol divinyl ether, tetrapropylene glycol divinyl ether Polypropylene glycol divinyl ether is preferred, and 1,4-butanediol divinyl ether is most preferred.

  Further, in the liquid resin composition for electronic parts of the present invention, the component (C) can be used in combination with a conventionally known curing accelerator as long as the effect of the present invention is achieved. For example, 1,8-diaza-bicyclo [5.4.0] undecene-7, 1,5-diaza-bicyclo [4.3.0] nonene, 5,6-dibutylamino-1,8- Cycloamidine compounds such as diaza-bicyclo [5.4.0] undecene-7, tertiary amine compounds such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 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-dihydroxymethy Such as imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, 2-heptadecylimidazole, etc. Organic compounds such as imidazole compounds, trialkyl phosphines such as tributyl phosphine, dialkyl aryl phosphines such as dimethyl phenyl phosphine, alkyl diaryl phosphines such as methyl diphenyl phosphine, triphenyl phosphine, alkyl group-substituted triphenyl phosphine Maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4- Compound having intramolecular polarization formed by adding a quinone compound such as nzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, etc., a compound having a π bond such as diazophenylmethane, phenol resin, etc. , And derivatives thereof, and further, phenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. Moreover, as a curing accelerator having a potential, core-shell particles formed by coating a shell having a normal temperature solid amino group as a core and a shell of a normal temperature solid epoxy compound are listed. Company name, product name), NovaCure (trade name, manufactured by Asahi Kasei Chemicals Corporation) 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, but a range of 0.2% by mass to 30% by mass with respect to the mass of all epoxy resins is preferable. The range of 0.5 mass%-25 mass% is more preferable, and the range of 6 mass%-20 mass% is further more preferable. By containing 0.2% by mass or more, the effect of adding a curing accelerator can be sufficiently exerted, and as a result, generation of voids during molding can be sufficiently suppressed, and a warp reduction effect can be sufficiently obtained. It is excellent in storage stability by being 30 mass% or less.

(D) Inorganic filler It is preferable that the liquid resin composition for electronic components of the present invention further contains at least one inorganic filler from the viewpoint of reducing the 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. These inorganic fillers may be used alone or in combination of two or more. Of these, fused silica is preferred, and spherical silica is more preferred from the viewpoint of fluidity and permeability into the fine gaps of the liquid resin composition for electronic components.

  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, the thixotropic property is hardly imparted to the liquid resin composition for electronic parts, and the effect of excellent flow characteristics is obtained. By setting the thickness to 10 μm or less, the sedimentation of the inorganic filler in the liquid resin composition for electronic parts can be reduced, and the permeability and fluidity to the fine gap as the liquid resin composition for electronic parts can be improved. There is a tendency to prevent unfilling.

  The content of the inorganic filler is preferably set in the range of 50% by mass to 80% by mass of the entire liquid 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 is 50% by mass or more, the effect of reducing the thermal expansion coefficient can be easily obtained, and when the content is 80% by mass or less, the viscosity of the liquid resin composition for electronic parts is prevented from increasing, and the fluidity and permeability In addition, the dispensing property is improved.

(E) Other Additives Various flexible agents can be blended in the liquid resin composition for electronic components of the present invention from the viewpoints of improving thermal shock resistance and reducing stress on semiconductor elements. The flexible agent is not particularly limited, but rubber particles are preferable. Examples thereof include styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), and acrylic. Examples thereof include rubber particles such as 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 the rubber particles other than those described above. For example, silicones obtained by crosslinking polyorganosiloxanes such as linear polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, etc. Rubber particle, silicone rubber particle surface coated with silicone resin, silicone rubber particle surface modified with epoxy group, solid silicone particle core obtained by emulsion polymerization and organic polymer shell such as acrylic resin And core-shell polymer particles.

  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 liquid resin composition for electronic parts low, use a spherical one. It is preferable. 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, it is preferable to add a silicone-modified epoxy resin having an effect as a surfactant as required. 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 organosiloxanes having functional groups that react with epoxy groups include dimethylsiloxane, diphenylsiloxane, methyl having at least one functional group such as amino group, carboxyl group, hydroxyl group, phenolic hydroxyl group, and mercapto group in one molecule. Examples include phenylsiloxane. The weight average molecular weight of the organosiloxane is preferably in the range of 500 or more and 5000 or less. The reason for this is that the compatibility with the resin system is moderate by setting it to 500 or more and 5000 or less. When the weight average molecular weight is 500 or more, the resin system is appropriately compatible with the resin, and the effect as an additive is appropriately exhibited. This is because when the weight average molecular weight is 5000 or less, incompatibility with the resin system is suppressed, and the silicone-modified epoxy resin is prevented from separating or exuding at the time of molding and excellent in adhesiveness and appearance. .

  The epoxy resin for obtaining the silicone-modified epoxy resin is not particularly limited as long as it is compatible with the resin system of the liquid resin composition for electronic parts, and is an epoxy generally used for liquid resin compositions for electronic parts. For example, glycidyl ether type epoxy resin obtained by reaction of phenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and epichlorohydrin, orthocresol novolac type epoxy A novolak epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of phenols such as resins and aldehydes, or a group obtained by reaction of a polybasic acid such as phthalic acid or dimer acid with epichlorohydrin. Sidyl ester type epoxy resin, diaminodiphenylmethane, isocyanuric acid and other polyamines obtained by the reaction of epichlorohydrin and glycidylamine type epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, fat Examples thereof include cyclic epoxy resins, and these may be used alone or in combination of two or more, but those at room temperature are preferred.

  The addition amount of the silicone-modified epoxy resin is preferably 0.01% by mass or more and 1.5% by mass or less, and more preferably 0.05% by mass or more and 1% by mass or less with respect to the entire liquid resin composition for electronic components. A sufficient addition effect can be obtained by setting the content to 0.01% by mass or more. By setting the content to 1.5% by mass or less, occurrence of bleeding from the surface of the cured product at the time of curing can be prevented, and a decrease in adhesive strength can be prevented. . As long as the effect of the present invention is obtained, an additive having an effect as a surfactant can be added in addition to the silicone-modified epoxy resin.

  In the liquid resin composition for electronic components of the present invention, a coupling agent is preferably used for the purpose of strengthening the interfacial adhesion between the resin and the inorganic filler or between the resin and the component of the electronic component, if necessary. These coupling agents are not particularly limited and conventionally known ones can be used. For example, silane compounds having primary and / or secondary and / or tertiary amino groups, epoxy silane, mercaptosilane, Examples thereof include various silane compounds such as alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Silane, 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) amino Propyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropy Rumethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ) 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, tetrao Tilbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltris (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate And titanate coupling agents such as These may be used alone or in combination of two or more.

In addition, in the liquid resin composition for electronic components of the present invention, an ion trap agent represented by the following general formula (1) or (2) is added to the migration resistance, moisture resistance, and the like of a semiconductor element such as an IC as necessary. It is preferably contained from the viewpoint of improving the high temperature storage characteristics.
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 addition amount 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 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 of elements such as magnesium, aluminum, titanium, zirconium, and antimony, and these can be used alone or in combination of two or more.

  In the liquid resin composition for electronic parts of the present invention, as other additives, coloring agents such as dyes and carbon black, diluents, leveling agents, antifoaming agents and the like can be blended as necessary.

  The liquid resin composition for electronic parts of the present invention can be prepared by any method as long as the above various components can be uniformly dispersed and mixed. However, as a general method, a component having a predetermined blending amount is weighed. It can be obtained by mixing, kneading using a raking machine, mixing roll, planetary mixer or the like, and defoaming as necessary.

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

  The liquid resin composition for electronic components of the present invention can be used to seal a gap between a semiconductor element and a substrate. Specifically, in an electronic component device using the liquid resin composition for electronic components of the present invention, a circuit forming surface of a semiconductor element and a circuit forming surface of an inorganic or organic substrate are opposed to each other, The circuit of the board is electrically connected via bumps, and the liquid resin composition for electronic parts of the present invention is sealed in the gap between the semiconductor element and the board.

  Examples of the method for sealing an element using the liquid resin composition for electronic parts of the present invention include a dispensing method, a casting method, and a printing method.

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

(Examples 1-16, Comparative Examples 1-7)
As a liquid epoxy resin, a liquid diepoxy resin having an epoxy equivalent of 160 obtained by epoxidizing bisphenol F (liquid epoxy 1; manufactured by Mitsubishi Chemical Co., Ltd., trade name jER806), a trifunctional having an epoxy equivalent of 95 obtained by epoxidizing aminophenol. Liquid epoxy resin (liquid epoxy 2; manufactured by Mitsubishi Chemical Corporation, trade name jER630), diethyltoluenediamine having an active hydrogen equivalent of 45 as a curing agent (liquid amine 1; trade name jER Cure W manufactured by Mitsubishi Chemical Corporation), active hydrogen Equivalent 63 diethyldiaminodiphenylmethane (liquid amine 2; Nippon Kayaku Co., Ltd., trade name Kayahard A-A), active hydrogen equivalent 63 tetramethyldiaminodiphenylmethane (solid amine; Nippon Kayaku Co., Ltd., trade name Kayabond C) -200S), acid anhydride equivalent 168 Liquid acid anhydride (acid anhydride; manufactured by Hitachi Chemical Co., Ltd., trade name HN5500), allylated phenol novolak resin having a hydroxyl equivalent weight of 141 (phenol resin; trade name MEH-8000H, manufactured by Meiwa Kasei Co., Ltd.), curing accelerator 2-phenyl-4-methyl-hydroxyimidazole (curing accelerator 5), spherical fused silica (silica) having a volume average particle diameter of 1 μm as an inorganic filler, and in addition, the surface of dimethyl type solid silicone rubber particles is an epoxy group Spherical silicone particles having a volume average particle size of 2 μm modified with γ-glycidoxypropyltrimethoxysilane, carbon black (Mitsubishi Chemical, trade name MA-100), bismuth ion trapping agent (product of Toagosei, product) No. IXE-500) was prepared.

(Preparation of curing accelerator 1)
A flask was charged with 34.3 g of benzoic acid and 24.0 g of 1,4-butanediol divinyl ether (molar ratio of benzoic acid to 1,4-butanediol divinyl ether was 5: 3) and reacted at 100 ° C. for 2 hours. By doing this, the curing accelerator 1 represented by the general formula (I) was obtained.

(Preparation of curing accelerator 2)
A flask was charged with 25.3 g of methoxyacetic acid and 24.0 g of 1,4-butanediol divinyl ether (molar ratio of methoxyacetic acid to 1,4-butanediol divinyl ether was 5: 3) and reacted at 100 ° C. for 2 hours. Thus, a curing accelerator 2 represented by the general formula (I) was obtained.

(Preparation of curing accelerator 3)
A flask was charged with 50.7 g of acetylsalicylic acid and 24.0 g of 1,4-butanediol divinyl ether (molar ratio of acetylsalicylic acid to 1,4-butanediol divinyl ether was 5: 3) and reacted at 100 ° C. for 2 hours. By doing this, the curing accelerator 3 represented by the general formula (I) was obtained.

(Preparation of curing accelerator 4)
A flask was charged with 41.4 g of 4-cyanobenzoic acid and 24.0 g of 1,4-butanediol divinyl ether (molar ratio of 4-cyanobenzoic acid to 1,4-butanediol divinyl ether was 5: 3). By making it react at 100 degreeC for 2 hours, the hardening accelerator 4 represented by general formula (I) was obtained.

  After mixing each component so that it may become a composition shown in following Table 1, it knead | mixes and disperses with a 3 roll and a vacuum crusher, The liquid resin composition for electronic components of Examples 1-16 and Comparative Examples 1-7 Was made. The blending units in Table 1 are parts by mass unless otherwise specified.

The evaluation results of the obtained liquid resin composition for electronic parts are shown in Table 2. The test method of the characteristic test will be described below. In addition, various characteristics and impregnation time of the used liquid resin composition for electronic components, observation of a void, and evaluation of various reliability were performed with the following method and conditions.
The specifications of the semiconductor device used for the evaluation of the reliability are as follows: chip size 20 × 20 × 0.55 tmm (circuit: daisy chain connection of aluminum, passivation: polyimide film HD4000, product name, manufactured by Hitachi Chemical DuPont Microsystems), bump : Solder balls (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 liquid resin composition for electronic components by a dispense method and curing at 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 liquid resin composition for electronic parts, the viscosity at 25 ° C. was measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm).

(2) Pot life After leaving the liquid resin composition for electronic parts 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.

(3) Gel time Using a gelation tester, an appropriate amount (about 3 ml) of the blended liquid resin composition for electronic parts was dropped on a hot plate at 165 ° C. or 130 ° C., and then visually observed to lose fluidity. The time until the gel state was reached was measured.

(4) Glass transition temperature (Tg)
Using a thermomechanical analyzer TMAQ400 (manufactured by TA Instruments), a test piece (3 mm × 3 mm × 20 mm) cured under predetermined conditions was loaded with a load of 15 g, a measurement temperature of 0 ° C. to 200 ° C., and a temperature increase rate of 10 ° C. / The measurement was performed under the condition of minutes.

(5) Adhesive strength / SiN adhesive strength A test piece was prepared by molding a liquid resin composition for electronic parts to a diameter of 3 mm and a height of 3 mm on the surface of a wafer with P-SiN (manufactured by Sumitomo Corporation Kyushu Co., Ltd.). Using a mold (manufactured by DAGE), a shear stress was applied under the conditions of a head speed of 50 μm / sec and 25 ° C., and the strength at which the molded product peeled from the wafer with P-SiN was measured. This measurement was performed immediately after molding the test piece and after 200 h treatment at 130 ° C. and 85% RH HAST (Highly Accelerated Temperature and Humidity Stress Test) conditions.
-PI adhesive strength A test piece was prepared by molding a liquid resin composition for electronic parts to a surface of photosensitive polyimide HD4100 (product name, manufactured by Hitachi Chemical DuPont Microsystems Co., Ltd.) to a diameter of 3 mm and a height of 3 mm, and bond tester DS100 type (DAGE) The strength at which the molded product peels from the photosensitive polyimide was measured by applying a shear stress under the conditions of a head speed of 50 μm / sec and 25 ° C. This measurement was performed immediately after the test piece was molded and after 200 h treatment under HAST conditions of 130 ° C. and 85% RH.

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

(7) Void observation The inside of the semiconductor device produced by underfilling the liquid resin composition for electronic components was observed with an ultrasonic flaw detector AT-5500 (manufactured by Hitachi Construction Machinery Co., Ltd.), 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 a liquid resin composition for electronic components was measured at room temperature using a surface roughness measuring device Surfcoder SE-2300 (manufactured by Kosaka Laboratory). ).

(9) Temperature resistance cycle resistance A semiconductor device prepared by underfilling a liquid resin composition for electronic components was treated for 2000 cycles at a heat cycle of −55 ° C. to 125 ° C. for 30 minutes each, and a continuity test was conducted every 1000 cycles. The disconnection defect of the aluminum wiring and the pad was examined, and the evaluation was performed by the number of defective packages / the number of evaluation packages.

(10) Moisture resistance reliability After a semiconductor device manufactured by underfilling a liquid 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 confirmed by 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.
In Comparative Example 4 where the component (B) is a solid amine, the viscosity was high, and a semiconductor device could not be produced without filling.
In Comparative Example 6 in which the component (B) is an acid anhydride, the gel time was shortened, but the adhesive strength after the HAST treatment was lowered and the moisture resistance was significantly lowered. In Comparative Example 7, which is a phenol resin whose component (B) is an acid anhydride, although the gel time is similarly shortened, Tg was lowered, so that the temperature cycle performance was significantly lowered.
Moreover, in Comparative Example 5 in which the component (C) is the curing accelerator 5, although the gel time was shortened, the adhesive strength after the Tg and HAST treatment of the cured product was lowered, and the moisture resistance was significantly lowered.
In contrast, in Examples 1 to 16, the gel time was shortened compared to Comparative Examples 1 to 3, no void was generated, the adhesive strength of the cured product was improved, and the temperature cycle resistance and moisture resistance were 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. Moreover, compared with the comparative example 5, the adhesive force after HAST processing has improved, and the semiconductor device excellent in moisture resistance has been obtained. Compared with the comparative examples 1 to 7, the balance in formability and reliability is improved. A good semiconductor device was obtained.

Claims (8)

A liquid resin composition for electronic parts, comprising an epoxy resin, an aromatic amine compound, and at least one compound selected from the group of compounds represented by the following general formula (I) as a curing accelerator.

(Wherein, ^{L m} is a carbon atom, m-valent group having from 1 to 18 hydrogen atoms and carbon atoms composed of an oxygen atom, or ^.R 1 ~ indicating the m-valent hydrocarbon group having 1 to 18 carbon atoms R ³ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ⁴ is a monovalent group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and an oxygen atom. , A monovalent group having 1 to 18 carbon atoms or a monovalent hydrocarbon group having 1 to 18 carbon atoms composed of a carbon atom, a hydrogen atom and a nitrogen atom, m represents an integer of 2 to 6) The liquid resin composition for electronic components according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II).


^{(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, and R ²⁷ and R ²⁸ each independently represents 1 carbon atom composed of a carbon atom, a hydrogen atom and an oxygen atom. A monovalent group having 1 to 18 carbon atoms, or a monovalent hydrocarbon group having 1 to 18 carbon atoms, which is composed of a monovalent group having 18 to 18 carbon atoms, a hydrogen atom and a nitrogen atom)   The curing accelerator is a reaction product obtained by addition reaction of at least one compound having only one carboxy group and at least one compound having at least two vinyl ether groups. The liquid resin composition for electronic components according to claim 2.   The liquid resin composition for electronic components according to any one of claims 1 to 3, wherein the epoxy resin is a liquid epoxy resin.   The liquid resin composition for electronic components according to any one of claims 1 to 4, wherein the aromatic amine compound is a liquid aromatic amine compound.   Furthermore, an inorganic filler is contained, The content of the said inorganic filler is the range of 50 to 80 mass% of the whole liquid resin composition for electronic components, The any one of Claims 1-5. Liquid resin composition for electronic parts as described in 2.   The electron according to any one of claims 1 to 6, wherein the aromatic amine compound contains at least one selected from 3,3'-diethyl-4,4'-diaminodiphenylmethane and diethyltoluenediamine. Liquid resin composition for parts. The circuit formation surface of the semiconductor element and the circuit formation surface of the inorganic or organic substrate are opposed to each other, and the electrode of the semiconductor element and the circuit of the substrate are electrically connected via bumps, and the semiconductor element and the substrate The electronic component apparatus formed by sealing the liquid resin composition for electronic components of any one of Claims 1-7 in a clearance gap.