JP6298786B2 - Liquid resin composition for electronic components and electronic component device - Google Patents

Description

  The present invention relates to a liquid resin composition for electronic components and an electronic component device. More specifically, the present invention relates to a liquid resin composition for electronic components that is particularly suitable for sealing electronic component devices that require strict reliability, and an electronic component device that includes an element sealed with the composition.

  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 adhesiveness with 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 on a wiring board using ceramic, glass / epoxy resin, glass / imide resin or polyimide film as a substrate, the bump-connected semiconductor element and 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 a stopping epoxy resin composition 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 has been 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, 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 that does not generate voids during molding, 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) (A) liquid epoxy resin, (B) liquid aromatic amine, and (C) a compound having a structure represented by the following general formula (I) in the molecule as a curing accelerator, The compound having a structure represented by (I) in the molecule is one or more carboxylic acids selected from the group consisting of aliphatic carboxylic acids, alicyclic carboxylic acids, and aromatic carboxylic acids; A liquid resin composition for electronic parts, which is a reaction product obtained by addition reaction of a compound having a vinyl ether group with a molar ratio (carboxylic acids: compound having a vinyl ether group) 1: 1.1 to 1: 4.

(R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ^{2 to} R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon having 1 to 18 carbon atoms. Group.)

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

(R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ^{2 to} R ⁴ and R ^{6 to} R ⁸ are each independently a hydrogen atom or 1 to 18 carbon atoms. A monovalent hydrocarbon group, and n represents an integer of 1 or more.)

  (3) The liquid for electronic components according to the above (1) or (2), wherein the compound having a structure represented by the general formula (I) in the molecule is a compound represented by the following general formula (VII) Resin composition.

(R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ^{2 to} R ⁴ and R ^{6 to} R ⁸ are each independently a hydrogen atom or 1 to 18 carbon atoms. A monovalent hydrocarbon group, and n represents an integer of 1 or more.)

  (4) Any of (1) to (3) above, wherein the liquid aromatic amine (B) contains at least one of 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine. 2. A liquid resin composition for electronic parts as set forth in claim 1.

  (5) Further, (E) an inorganic filler is contained, and the blending amount of the (E) inorganic filler is in the range of 50% by mass to 80% by mass of the whole liquid resin composition for electronic parts (1) The liquid resin composition for electronic parts of any one of (4)-(4).

  (6) 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 electrodes of the semiconductor element and the circuit of the substrate are electrically connected via bumps, The electronic component apparatus formed by sealing the liquid resin composition for electronic components of any one of said (1)-(5) in the clearance gap between the said board | substrates.

  The liquid resin composition for sealing an electronic component of the present invention suppresses the generation of voids during molding and enables the curing temperature to be lowered. Further, the cured product has a small decrease in adhesive strength with various substrates due to moisture absorption, and has high adhesive strength with various substrates even after moisture absorption. Therefore, if an electronic component is sealed using this liquid resin composition for sealing an electronic component, an electronic component device having high moldability and reliability (moisture resistance, temperature cycle resistance) can be obtained. Industrial value is great.

  The present invention relates to a liquid resin composition used for sealing an electronic component containing a liquid epoxy resin, a liquid aromatic amine, and a curing accelerator. By using a specific curing accelerator, the gel time can be shortened. The effect of is obtained. The liquid in the present invention is a liquid at normal temperature (25 ° C.), and when cured by reaction or the like, it may become a solid even at normal temperature. Details of the present invention are described below.

(A) Liquid epoxy resin The (A) liquid epoxy resin used in the present invention has two or more epoxy groups in one molecule and is not limited as long as it is liquid at room temperature, and is a liquid resin composition for electronic components. The liquid epoxy resin generally used 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 novolak resin obtained by condensation or co-condensation of aldehydes, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, p-aminophenol, diaminodiphenylmethane, Glycidylamine type epoxy resins obtained by reaction of amine compounds such as isocyanuric acid and epichlorohydrin, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, and alicyclic ethers. Carboxymethyl resins and the like, may be used in combination of two or more even with these alone. 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 above two liquid epoxy resins (liquid bisphenol type epoxy resin and liquid glycidylamine type epoxy resin) may be used alone or in combination of two or more. In order to exhibit the performance, it is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, based on the total amount of the liquid epoxy resin.

  The epoxy equivalent of the liquid epoxy resin is preferably 50 or more and 5000 or less, more preferably 70 or more and 1000 or less, and still more preferably 70 or more and 500 or less.

  Further, in the liquid resin composition for electronic parts of the present invention, a solid epoxy resin can be used in combination as long as the effect of the present invention is achieved, but the solid resin used in combination from the viewpoint of fluidity during molding. The epoxy resin is preferably 20% by mass or less based on the total amount of the epoxy resin.

  Furthermore, the purity of these epoxy resins, particularly the amount of hydrolyzable chlorine, is preferable because it is related to corrosion of aluminum wiring on elements such as ICs, and in order to obtain a liquid resin composition for electronic parts having excellent moisture resistance. It is preferably 500 ppm or less. Here, the hydrolyzable chlorine amount was obtained by dissolving 1 g of the epoxy resin of the sample in 30 ml of dioxane, adding 5 ml of 1 mol / L-KOH methanol solution and refluxing for 30 minutes, and then using the value obtained by potentiometric titration as a scale. Is.

(B) Liquid aromatic amine (B) The liquid aromatic amine used in the present invention is not particularly limited as long as it contains an amine having a liquid aromatic ring at room temperature, and examples thereof 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 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,5,3 ′, 5′-tetramethyl-4,4′-diaminodiphenylmethane, and the like. These liquid aromatic amine compounds are, for example, jER Cure W (trade name, manufactured by Mitsubishi Chemical Corporation (former Japan Epoxy Resin Co., Ltd.), Kayahard AA, Kayahard AB, Kayahard AS, as commercially available products. (Nippon Kayaku Co., Ltd. trade name), Totoamine HM-205 (Toto Kasei Co., Ltd. trade name), Adeka Hardener EH-101 (Asahi Denka Kogyo Co., Ltd. trade name), Epomic Q-640, Epomic Q- 643 (trade name, manufactured by Mitsui Chemicals, Inc.), DETDA 80 (trade name, manufactured by Lonza) and the like are available, and these may be used alone or in combination of two or more.

  Among these, from the viewpoint of storage stability, 3,3′-diethyl-4,4′-diaminodiphenylmethane or diethyltoluenediamine is preferable, and (B) any one of these or a mixture thereof as a liquid aromatic amine is a main component. It is preferable to contain as. 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, and it is preferable that 3,5-diethyltoluene-2,4-diamine is contained in 60% by mass or more in the total (B) liquid aromatic amine.

  (B) The active hydrogen equivalent of the liquid aromatic amine is preferably 30 or more and 1000 or less, more preferably 30 or more and 500 or less, and still more preferably 30 or more and 200 or less.

  In addition, the liquid resin composition for electronic parts of the present invention includes, in addition to the above liquid aromatic amine, an amine curing agent other than the liquid aromatic amine, phenol, as long as the effects of the present invention are achieved. Curing agents generally used in liquid resin compositions for electronic parts, such as basic curing agents and acid anhydrides, can be used in combination, and solid curing agents can also be used in combination. When other curing agents are used in combination, the blending amount of component (B) is preferably 60% by mass or more with respect to the total amount of the curing agent in order to exhibit its performance.

  The equivalent ratio of the epoxy resin containing the component (A) and the curing agent containing the component (B) is not particularly limited, but the curing agent is used with respect to 1.0 equivalent of the epoxy resin in order to reduce each unreacted component. Is preferably set in the range of 0.7 equivalents to 1.8 equivalents, more preferably 0.8 equivalents to 1.6 equivalents, and even more preferably 1.0 to 1.5 equivalents.

(C) Curing accelerator The (C) curing accelerator used in the present invention contains a curing accelerator having a structure represented by the following general formula (I) in the molecule.

(R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ^{2 to} R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon having 1 to 18 carbon atoms. Group.)

  Examples of the group represented by the general formula (I) include structures represented by the following general formula (III).

(R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms.)

  Specific examples of the curing accelerator having a structure represented by the general formula (I) in the molecule include compounds represented by the following general formula (II) and the following general formula (IV). The compounds represented by the general formula (II) are more preferable from the viewpoints of curing acceleration, storage stability, and various reliability.

(R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ^{2 to} R ⁴ and R ^{6 to} R ⁸ are each independently a hydrogen atom or 1 to 18 carbon atoms. A monovalent hydrocarbon group, and n represents an integer of 1 or more.)

^{(R 1} is a divalent hydrocarbon group having 1 to 18 carbon ^atoms, each R 2 to R ⁴ and ^R 11 ^{to R 13} are independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms R ⁹ and R ¹⁰ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms.)

  The compound represented by the general formula (II) includes a compound represented by the following general formula (V), and the compound represented by the general formula (V) is represented by the following general formula (VI). Compounds.

(R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, and n represents an integer of 1 or more.)

(R ¹ is a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ⁹ and R ¹⁰ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms.)

Specific examples of R ¹ and R ⁵ in the general formulas (I) to (VI) include an alkylene group having 1 to 18 carbon atoms, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, a phenylene group, a biphenylene group, and a naphthylene group. Can be mentioned.

R ¹ is preferably an alkylene group having 1 to 18 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 2 to 8 carbon atoms, and an alkylene group having 3 to 5 carbon atoms. Further preferred is a propylene group.

R ⁵ is preferably an alkylene group having 1 to 18 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 2 to 8 carbon atoms, and an alkylene group having 3 to 5 carbon atoms. More preferred is a propylene group or butylene group.

R ^{2 to} R ⁴ , R ^{6 to} R ⁸ , and R ^{11 to} R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a phenyl group, A biphenyl group, a naphthyl group, etc. are mentioned, A hydrogen atom or a C1-C18 alkyl group is preferable, A hydrogen atom or a C1-C10 alkyl group is more preferable, A hydrogen atom or a methyl group is still more preferable, A hydrogen atom Is particularly preferred.

R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a phenyl group, a biphenyl group, a naphthyl group, or the like. An alkyl group or an alkenyl group is preferable, and an alkyl group or alkenyl group having 1 to 10 carbon atoms is more preferable. When R ⁹ and R ¹⁰ have an ethylenic double bond, each of R ⁹ and R ¹⁰ is preferably independently an alkenyloxyalkyl group having 1 to 18 carbon atoms, and vinyloxy having 1 to 18 carbon atoms. More preferably, it is an alkyl group.

  The n is an integer of 1 or more, preferably an integer of 1 to 30, more preferably an integer of 1 to 20, and still more preferably an integer of 1 to 10.

  Of the compounds having a structure represented by the general formula (II) in the molecule, a compound represented by the following general formula (VII) is preferable. The compound represented by the following general formula (VII) is excellent in terms of storage stability and various reliability because both ends are blocked with carboxylic acid groups by vinyl groups.

(R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ^{2 to} R ⁴ and R ^{6 to} R ⁸ are each independently a hydrogen atom or 1 to 18 carbon atoms. A monovalent hydrocarbon group, and n represents an integer of 1 or more.)

^R 1 to R ⁸ in the general formula (VII) is the same as ^R 1 to R ⁸ described above, the same applies to the preferred range. N in the general formula (VII) is the same as n described above, and the same applies to the preferred range.

  Examples of the compound represented by the general formula (VII) include a compound represented by the following general formula (VIII).

In the general formula (VIII), R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, and are the same as R ¹ and R ⁵ described above. It is the same. In the general formula (VIII), n is an integer of 1 or more, is the same as n described above, and the same applies to the preferred range.

  The weight average molecular weight of the compound having the structure represented by the general formula (I) is preferably 300 to 20000, more preferably 500 to 10,000, from the viewpoint of a viscosity excellent in handleability. More preferably, it is 500-5000.

  The residual carboxylic acid ratio in the compound having the structure represented by the general formula (I) is preferably 5% or less, more preferably 2% or less, and further preferably 0.5% or less. . The residual carboxylic acid ratio can be measured using 13C NMR. For example, about 100 mg of a sample is dissolved in 0.5 ml of heavy acetone, put into a sample tube, and measured using a highly quantitative inverse gate decoupling method, for example, with a repetition time of 30 seconds or more. It can be calculated by comparing the integral ratio between the carbonyl carbon of the unreacted carboxylic acid and the carbonyl carbon produced by the reaction.

  The compound having the structure represented by the general formula (I) used in the present invention is not limited to this, but is a reaction product obtained by addition reaction of a carboxylic acid and a vinyl ether compound. For example, it can be obtained by reacting in the temperature range of 50 ° C. to 150 ° C. for about 3 to 6 hours. The reaction can be performed in a nitrogen atmosphere, and a solvent such as xylene may be used. The reaction can be accelerated by an acid catalyst such as an acidic phosphate ester. The reaction end point can be determined by titrating the remaining carboxylic acid with an ethanol solution of potassium hydroxide.

  The compound represented by the general formula (VII) can be obtained by addition reaction of dicarboxylic acids and divinyl ether compounds. By making the charged molar amount of the divinyl ether compound larger than the charged molar amount of the dicarboxylic acids, a compound represented by the above general formula (VII) in which both ends are vinyl groups and the carboxylic acid groups are blocked is obtained, The residual carboxylic acid ratio can be lowered. In order to reduce the residual carboxylic acid ratio, the charged molar amount of the divinyl ether compound should be more than 1 times the charged molar amount of the dicarboxylic acid, and the charged molar ratio of dicarboxylic acid: divinyl ether compound is 1: It is preferably 1.1 to 1: 4, more preferably 1: 1.2 to 1: 3, and still more preferably 1: 1.2 to 1: 2.

  Further, by containing an excessive amount of the vinyl ether compound, even if the vinyl ether compound is eliminated, the carboxylic acid group is blocked by the equilibrium reaction, 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 carboxylic acid and the vinyl ether compound can sufficiently react. For example, when the reaction temperature is 100 ° C. and the charged molar ratio of carboxylic acid: vinyl ether compound is 1: 1.1 to 1: 1.4, the reaction time is 4 hours or more. It is preferable to make it react, and when it is 1: 1.5-1: 4, it is preferable to make it react in 2 hours or more.

  Said carboxylic acid should just be a compound which has two or more carboxyl groups in 1 molecule, and is 1 type selected from the carboxylic acid group which consists of aliphatic carboxylic acid, alicyclic carboxylic acid, and aromatic carboxylic acid Or 2 or more types are mentioned. Examples of carboxylic acids include aliphatic polycarboxylic acids such as malonic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, octanedioic acid, nonanedioic acid, decanedioic acid, acetylenedicarboxylic acid, fumaric acid, and maleic acid; Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, meritic acid, benzenepentacarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3- Aromatic polycarboxylic acids such as naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,2-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid; tetrahydrophthal Acid, hexahydrophthalic acid, methylhexaphthalic acid, 1,3-cyclohex Alicyclic polycarboxylic acids such as carboxylic acid, 1,4-cyclohexanedicarboxylic acid; and polyester resins, acrylic resins, polyether resins, polyamide resins, silicone resins, polyamideimide resins having two or more carboxyl groups in one molecule Etc.

  Among these, from the viewpoint of curing acceleration and storage stability, the carboxylic acids include malonic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, octanedioic acid, nonanedioic acid, decanedioic acid, and acetylenedicarboxylic acid. , Fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, meritic acid, benzenepentacarboxylic acid, 1,4-naphthalene Dicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,2-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid are preferred, Malonic acid, succinic acid, adipic acid, glutaric acid from the viewpoint of handling after synthesis Pimelic acid, octanedioic acid, nonanedioic acid, decanedioic acid, acetylenedicarboxylic acid, fumaric acid, and maleic acid are more preferred, and adipic acid, glutaric acid, and pimelic acid are more preferred for ease of synthesis, and glutaric acid is particularly preferred. preferable.

  Examples of the vinyl ether compound 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- 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, 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, vinyl tetradecyl 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 Ruallyl 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- Ethylpropyl) vinyl ether, (1-isopropyl-2-methylpropyl) vinyl ether, p-phenylbenzyl vinyl ether, vinyl (α-methylbenzyl) ether, phenethyl vinyl ether, 2-phenylpropyl vinyl 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, -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-none Nyl 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 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-dodecylcyclohexyl Xyl 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-cyclopenten-1-yl vinyl ether, 2-cyclohex-1- Nyl vinyl ether, 1- (cyclopenten-1-yl) methyl vinyl ether, 1- (cyclopenten-1-yl) ethyl vinyl ether, (1-cyclohexenylmethyl) vinyl ether, [1- (1-cyclohexenyl) ethyl] vinyl ether, ( 3-methyl-1-cyclohexenyl) methyl vinyl ether, [(3,4-dimethyl-1-cyclohexen-1-yl) methyl] vinyl ether, [(3-mes -4-ethyl-1-cyclohexen-1-yl) methyl] vinyl ether, cyclohept-1-nylmethyl vinyl ether, cyclooct-1-nylmethyl vinyl ether, 2-cyclobutylidene ethyl vinyl ether, 2-cyclopentylidene ethyl vinyl ether, 2-cyclohexylidene-1-methylethyl 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-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 divinyl ether, 1,3-propanediol divinyl ether, propylene glycol divinyl ether, 1,4-butyl Tandiol 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-1,10-undecadiene, 10-vinyloxydecyl vinyl ether, 12-vinyloxyoctadecyl vinyl ether, dipropylene glycol divinyl ether, resorcinol divinyl ether, m-phenylenebis (ethylene glycol) ) Aliphatic vinyl ether compounds such as divinyl ether and bisphenol A divinyl ether, 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 vinyl 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, 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, vinyl tetradecyl 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, 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, 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 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 -U Decenyl 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-dodecylcyclohexyl 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-cyclopenten-1-yl vinyl ether, 2-cyclohex-1- Nyl vinyl ether, 1- (cyclopenten-1-yl) methyl vinyl ether, 1- (cyclopenten-1-yl) ethyl vinyl ether, (1-cyclohexenylmethyl) vinyl ether, [1- (1-cyclohexenyl) ethyl] vinyl ether, ( 3-methyl-1-cyclohexenyl) methyl vinyl ether, [(3,4-dimethyl-1-cyclohexen-1-yl) methyl] vinyl ether, [(3-methyl 4-ethoxy-1-cyclohexen-1-yl) methyl] vinyl ether, cyclohept-1-nylmethyl vinyl ether, cyclooct-1-nylmethyl 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, full Furyl vinyl ether, tetrahydrofurfuryl vinyl ether, 2-thienyl vinyl ether, 3-thienyl vinyl ether, 2-thenyl 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-2- (vinyloxy) ethanamine, and [2- (2-ethoxyethoxy) ethyl] vinyl ether are preferably one vinyl ether group, more preferably propyl vinyl ether and 2-ethylhexyl vinyl ether. preferable.

  In the compound having the structure represented by the general formula (I), a site derived from a carboxylic acid has a role as a curing accelerator, a site derived from a vinyl ether blocks a carboxylic acid, and plays a role of improving storage stability. Expected to play. At the time of storage of the liquid resin composition for electronic parts, the carboxyl group is blocked by the vinyl ether group, so that the effect as a curing accelerator is not exhibited, while when the liquid resin composition for electronic parts is cured, It is considered that the block is removed by heating, and an effect as a curing accelerator is obtained.

  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-dihydroxymethyl Imidazole compounds such as imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2′-methylimidazolyl-1 ′)-ethyl-s-triazine, 2-heptadecylimidazole, etc. , Trialkylphosphine such as tributylphosphine, dialkylarylphosphine such as dimethylphenylphosphine, alkyldiarylphosphine such as methyldiphenylphosphine, organic phosphines such as triphenylphosphine and alkyl-substituted triphenylphosphine, and anhydrous maleic compounds thereof Acid, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzo Compound having intramolecular polarization formed by adding a quinone compound such as non, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, a compound having a π bond such as diazophenylmethane and phenol resin , 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 can be cited. Amicure (Ajinomoto Co., Inc.) is commercially available. 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.

  (C) Although the compounding quantity of a hardening accelerator will not be restrict | limited especially if the hardening acceleration effect is achieved, it is the range of 0.2 mass%-20 mass% with respect to the mass of all the epoxy resins. Is preferable, the range of 0.5% by mass to 17% by mass is more preferable, and the range of 6% by mass to 16% by mass is still 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 excellent in storage stability by being 20 mass% or less.

(E) Inorganic filler Furthermore, it is preferable that (E) inorganic filler is included 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. 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 more 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 blending amount of the inorganic filler is preferably set in the range of 50% by mass or more and 80% by mass or less of the entire liquid resin composition for electronic parts. The blending amount of the inorganic filler is preferably limited to 55% by mass to 75% by mass, and more preferably 60% by mass to 70% by mass. When the blending amount is 50% by mass or more, an effect of reducing the thermal expansion coefficient is easily obtained, and when the blending amount 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.

(F) Other Additives Various flexible agents can be blended in the liquid resin composition for electronic parts of the present invention from the viewpoint 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 polymer 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 properly compatible with the resin, and the effect as an additive is appropriately exhibited. 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 being separated or exuded at the time of 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 resin system of the liquid resin composition for electronic parts, and is generally used for the liquid resin composition for electronic parts. Epoxy resin can be used. For example, phenols such as glycidyl ether type epoxy resins and orthocresol novolak type epoxy resins obtained by reaction of phenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and epichlorohydrin. A novolak type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or co-condensation with aldehydes, 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, linear fat obtained by oxidizing olefinic bonds with peracids such as peracetic acid Family epoxy resin, alicyclic epoxy resin. These may be used alone or in combination of two or more, and 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 tri (N-aminoethyl-aminoethyl) titanate, tetraoctane Rubis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate And titanate coupling agents such as A seed may be used independently or may be used in combination of 2 or more types.

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, and more preferably 0.3% by mass or more and 1.5% by mass or less. The 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 a 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 Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.

(Examples 1-30, Comparative Examples 1-7)
As a liquid epoxy resin, an epoxy equivalent 160 liquid diepoxy resin obtained by epoxidizing bisphenol F (liquid epoxy 1; manufactured by Mitsubishi Chemical Corporation (formerly Japan Epoxy Resin Co., Ltd.), trade name jER806), aminophenol is epoxidized Trifunctional liquid epoxy resin having an epoxy equivalent of 95 (liquid epoxy 2; manufactured by Mitsubishi Chemical Corporation (former Japan Epoxy Resin Co., Ltd.), trade name: jER630), diethyltoluenediamine (liquid amine) having an active hydrogen equivalent of 45 as a curing agent 1; manufactured by Mitsubishi Chemical Corporation (formerly Japan Epoxy Resin Co., Ltd., trade name: jER Cure W), 3,3′-diethyl-4,4′-diamino-diphenylmethane having an active hydrogen equivalent of 63 (liquid amine 2; Nippon Kayaku) Yakuhin brand name Kayahard AA), active hydrogen Amount of tetramethyl-diamino-diphenylmethane (solid amine; Nippon Kayaku Co., Ltd. trade name Kayabond C-200S), acid anhydride equivalent 168 liquid acid anhydride (acid anhydride; Hitachi Chemical Co., Ltd. trade name HN5500) ), An allylated phenol novolak resin having a hydroxyl group equivalent of 141 (phenol resin; trade name MEH-8000H, manufactured by Meiwa Kasei Co., Ltd.), 2-phenyl-4-methyl-hydroxyimidazole (curing accelerator 3), inorganic as a curing accelerator As a filler, spherical fused silica (silica) having a volume average particle diameter of 1 μm, spherical silicone particles having a volume average particle diameter of 2 μm whose surface of dimethyl type solid silicone rubber particles is modified with an epoxy group, γ-glycid Xylpropyltrimethoxysilane, carbon black (trade name MA-10 manufactured by Mitsubishi Chemical Corporation) 0) and a bismuth-based ion trap agent (trade name IXE-500 manufactured by Toagosei Co., Ltd.) were prepared.

The curing accelerator 1 was charged with 48.2 g of glutaric acid and 51.8 g of 1,4-butanediol divinyl ether in a flask (the molar ratio of glutaric acid and 4-butanediol divinyl ether was 1: 0.6. The compound represented by the general formula (V) in which R ¹ is a propylene group and R ⁵ is a butylene group was obtained by reacting at 100 ° C. for 2 hours. From 13C NMR, the ratio of carboxylic acid reacted with vinyl ether to unreacted carboxylic acid was 96: 4, ie, the residual carboxylic acid was 4%.

The curing accelerator 2 was charged with 60.5 g of glutaric acid and 47.3 g of n-propyl vinyl ether in a flask, raised from room temperature to 70 ° C. over 30 minutes, and then reacted at 70 ° C. for 4 hours. Then, using a rotary evaporator, unreacted vinyl ether is distilled off from the mixed solution, and then vacuum-dried by a vacuum pump, so that R ¹ is a propylene group and R ⁵ is a propylene group, and corresponds to the general formula (III) Was obtained.

The curing accelerator 4 was charged with 48.2 g of glutaric acid and 77.8 g of 1,4-butanediol divinyl ether in a flask (the molar ratio of glutaric acid and 4-butanediol divinyl ether was 1: 1.5. The compound corresponding to the general formulas (V) and (VIII) in which R ¹ is a propylene group and R ⁵ is a butylene group was obtained by reacting at 100 ° C. for 2 hours. From 13C NMR, no residual carboxylic acid was detected.

The curing accelerator 5 is charged with 60.5 g of glutaric acid and 94.7 g of n-propyl vinyl ether in a flask (molar ratio of glutaric acid and n-propyl vinyl ether is 1: 2.4), and 30 minutes. The temperature was raised from room temperature to 70 ° C., and then reacted at 70 ° C. for 4 hours. Then, using a rotary evaporator, unreacted vinyl ether is distilled off from the mixed solution, and then vacuum-dried by a vacuum pump, whereby R ¹ is a propylene group and R ⁹ and R ¹⁰ are propyl groups. ) Was obtained.

The curing accelerator 6 is charged with 48.2 g of glutaric acid and 103.8 g of 1,4-butanediol divinyl ether in a flask (the molar ratio of glutaric acid and 4-butanediol divinyl ether is 1: 2. And by reacting at 100 ° C. for 2 hours, compounds corresponding to the general formulas (V) and (VIII) in which R ¹ is a propylene group and R ⁵ is a butylene group were obtained. From 13C NMR, no residual carboxylic acid was detected.

The curing accelerator 7 was charged with 48.2 g of glutaric acid and 62.8 g of 1,4-butanediol divinyl ether in a flask (the molar ratio of glutaric acid and 4-butanediol divinyl ether was 1: 1.2. The compound corresponding to the general formulas (V) and (VIII) in which R ¹ is a propylene group and R ⁵ is a butylene group was obtained by reacting at 100 ° C. for 4 hours. From 13C NMR, no residual carboxylic acid was detected.

The curing accelerator 8 was charged with 48.2 g of glutaric acid and 62.8 g of 1,4-butanediol divinyl ether in a flask (the molar ratio of glutaric acid and 4-butanediol divinyl ether was 1: 1.2. By reacting at 100 ° C. for 1 hour, compounds corresponding to the general formulas (V) and (VIII) in which R ¹ is a propylene group and R ⁵ is a butylene group were obtained. From 13C NMR, the ratio of carboxylic acid reacted with vinyl ether to unreacted carboxylic acid was 98: 2, that is, the residual carboxylic acid was 2%.

The curing accelerator 9 is charged with 48.2 g of glutaric acid and 51.9 g of 1,4-butanediol divinyl ether in a flask (the molar ratio of glutaric acid and 4-butanediol divinyl ether is 1: 1). And by reacting at 100 ° C. for 1 hour, compounds corresponding to the general formulas (V) and (VIII) in which R ¹ is a propylene group and R ⁵ is a butylene group were obtained. From 13C NMR, the ratio of carboxylic acid reacted with vinyl ether to unreacted carboxylic acid was 95: 5, ie, the residual carboxylic acid was 5%.

  After compounding with the composition shown in the following Tables 1 and 2 and kneading and dispersing with a three roll and vacuum crusher, liquid resin compositions for electronic parts of Examples 1 to 30 and Comparative Examples 1 to 7 were prepared. The blending unit in the table is part by mass unless otherwise specified, and the blank represents no blending.

  The evaluation results of the obtained liquid resin composition for electronic parts are shown in Tables 3 and 4. 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 reliability evaluation 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 ball (Sn—Ag—Cu, diameter 80 μm, 7,744 pin), bump pitch: 190 μm, substrate: FR-5 (solder resist SR7200, trade name, manufactured by Hitachi Chemical Co., Ltd., 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)
The viscosity at 25 ° C. of the liquid resin composition for electronic parts was measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm). However, for samples with high viscosity that cannot be measured at 5 rpm, the measurement was performed at 2.5 rpm.

(2-1) Pot life 1
The liquid resin composition for electronic components was allowed to stand at 25 ° C. for 24 hours, and the viscosity at 25 ° C. was measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm) (viscosity after standing). However, for samples with high viscosity that cannot be measured at 5 rpm, the measurement was performed at 2.5 rpm. The pot life (%) was calculated by ((viscosity after standing) − (initial viscosity)) / (initial viscosity) × 100.

(2-2) Pot life 2
The liquid resin composition for electronic parts was allowed to stand at 35 ° C. for 24 hours, and the viscosity at 25 ° C. was measured using an E-type viscometer (cone angle 3 °, rotation speed 5 rpm) (viscosity after standing). However, for samples with high viscosity that cannot be measured at 5 rpm, the measurement was performed at 2.5 rpm. 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 components was placed on a hot plate at 165 ° C or 130 ° C, and then the time until gelation was started 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 of 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 force A test piece was prepared by molding a liquid resin composition for electronic parts on a surface of photosensitive polyimide HD4100 (trade name, manufactured by Hitachi Chemical DuPont Microsystems Co., Ltd.) to a diameter of 3 mm and a height of 3 mm. 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.) to examine the presence or absence of voids.

(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 instrument Surfcoder SE-2300 (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, 2, and 3 not containing the component (C) 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 inferior.
Moreover, in the comparative example 4 whose (B) component is a solid amine, the viscosity was high and the semiconductor device could not be produced without filling.

Moreover, although the gel time became short in the comparative example 6 whose (B) component is an acid anhydride, the adhesive force after HAST processing fell and moisture resistance fell remarkably.
In Comparative Example 7 in which the component (B) is a phenol resin, the gel time was shortened as in Comparative Example 6, but Tg was lowered, so that the temperature cycle performance was significantly lowered.

  Further, in Comparative Example 5 in which the component (C) is the curing accelerator 3, the gel time was shortened, but the adhesive strength after the Tg and HAST treatment of the cured product was reduced, and the moisture resistance was remarkably reduced.

  On the other hand, Examples 1-30 shortened gel time compared with Comparative Examples 1-3, a void did not generate | occur | produce, the adhesive force of hardened | cured material also improved, and temperature cycle resistance and moisture resistance 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.

Furthermore, the following comparative examination was performed in the Example.
When Example 2 (65% by mass), Example 14 (55% by mass), and Example 15 (75% by mass) are compared with respect to the blending amount of the inorganic filler, Example 15 having a large blending amount of the inorganic filler is In Example 14, the viscosity increases and the impregnation time is slightly inferior, but the chip warpage is reduced, the temperature cycle resistance is improved, and the amount of the inorganic filler is small, the humidity cycle resistance is slightly lowered. However, it was excellent in fluidity.

  About Example 1 and 2 (liquid amine 1), Example 5 and 6 (liquid amine 2), and Example 8 and 9 (combined use of liquid amine 1 and 2) about a hardening | curing agent, when liquid amine 1 is contained, Excellent fluidity and pot life, and when liquid amine 2 was contained, the adhesive strength of the cured product was improved and the temperature cycle resistance was improved. By using these two kinds of liquid amines in combination, these properties were excellent in a well-balanced manner, and chip warpage and temperature cycle resistance were excellent.

  As for the equivalent ratio of the epoxy resin and the curing agent, when Examples 9, 11, 12 and 13 are compared, when the amount of the curing agent increases (the equivalent ratio of the epoxy resin and the curing agent increases), the fluidity is excellent and less As a result, Tg increased upon curing at 165 ° C. In the curing at 130 ° C., the Tg increased when the amount of the curing agent increased, but the Tg decreased when the amount of the curing agent increased excessively.

About a hardening accelerator, when Example 1 and 2 (hardening accelerator 1) and Example 3 and 4 (hardening accelerator 2) are compared, when it contains hardening accelerator 1, it is excellent in pot life, and hardening accelerator 2 However, the pot life was slightly deteriorated, but the fluidity was excellent.
Further, when Examples 2, 16, 18 and 19 were compared, when the equivalent ratio of the vinyl ether compound in the curing accelerator was increased, the gel time was slightly reduced, but the pot life was excellent. Further, when Examples 2, 19, 20 and 21 were compared, although the gel time was slightly reduced when the amount of residual carboxylic acid in the curing accelerator was reduced, the pot life was excellent.

  About the compounding quantity of a hardening accelerator, Example 7 (1% of the compounding quantity of an epoxy resin), Example 8 (5% of the compounding quantity of an epoxy resin), Example 9 (10% of the compounding quantity of an epoxy resin), and implementation When Example 10 (20% of the amount of the epoxy resin compounded) is compared, the smaller amount is preferable from the viewpoint of pot life, and the larger amount is shorter in gel time, reducing the adhesiveness of the cured product and chip warpage. Excellent temperature cycle resistance. The blending amount of the curing accelerator had a great influence on the adhesive strength and moisture resistance reliability of the cured product particularly when cured at 130 ° C.

  In particular, in Examples 1 to 30, the curing accelerator 4 is contained, the equivalent ratio of the epoxy resin and the curing agent is appropriately balanced, the curing agent 1 and the curing agent 2 are used in combination, and the inorganic filler is further used. Example 16 having a blending amount in the range of 60% by mass to 70% by mass had the most excellent balance of properties.

Claims (4)

(A) liquid epoxy resin contains a compound having the structure represented in the the molecule with (B) a liquid aromatic amine, and (C) the following general formula as a curing accelerator (I), prior to following general formula (I The liquid resin composition for electronic components, wherein the compound having a structure represented by) in the molecule is a compound represented by the following general formula (VII).


(R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ^{2 to} R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon having 1 to 18 carbon atoms. Group.)

(R ¹ and R ⁵ are each independently a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ^{2 to} R ⁴ and R ^{6 to} R ⁸ are each independently a hydrogen atom or 1 to 18 carbon atoms. A monovalent hydrocarbon group, and n represents an integer of 1 or more.)   2. The liquid resin composition for electronic components according to claim 1, wherein the liquid aromatic amine (B) contains at least one of 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine. .   Furthermore, (E) inorganic filler is contained, The compounding quantity of this (E) inorganic filler exists in the range of 50 to 80 mass% of the whole liquid resin composition for electronic components. 2. A liquid resin composition for electronic parts according to 2.   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 1-3 in a clearance gap.