JP5886051B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition, and more particularly, to a resin composition that seals a semiconductor element mounted on a circuit board and a copper wire that electrically connects the circuit board and the semiconductor element.

  2. Description of the Related Art Conventionally, semiconductor elements such as diodes and transistors use gold wires for electrical connection with a circuit board, and these semiconductor elements and gold wires are sealed with a sealing resin.

  In recent years, in order to cope with the downsizing, weight reduction, and high performance of electronic devices, the integration of semiconductor elements has been advanced, and the surface mounting of semiconductor devices has been promoted. The demand for the resin composition used is becoming more and more severe. Furthermore, the demand for reducing the cost of semiconductor devices is severe, and the price of gold is soaring. Since the cost of conventional gold wire connection is high, bonding with a copper wire is being studied.

However, since copper wires are more easily corroded than gold wires (gold wires), migration between copper wires is a concern. Migration is a phenomenon in which copper in a copper wire is eluted by an electrochemical reaction, resulting in a decrease in resistance value. The copper wire acts as an electrode when the semiconductor device is activated. In FIG. 1, the schematic diagram explaining the migration of copper wires is shown. Migration starts with the anode 2, Cu is eluted by the reaction formula: Cu + (OH ⁻ ) → Cu (OH), and Cu (OH) moves on the substrate 1 in the direction of the solid arrow, that is, toward the cathode 3, In the cathode 3, Cu is deposited on the substrate 1 in the direction of the broken line arrow, that is, in the direction of the anode 2 by the reaction formula: CuOH + H ₃ O ⁺ → Cu + 2H ₂ O. Usually, copper wires are sealed with an epoxy resin-based resin composition, but migration occurs due to OH ⁻ or H ₃ O ⁺ derived from H ₂ O absorbed in the epoxy resin. Furthermore, in the atmosphere Cl ^- when there is an ion migration is accelerated dramatically. This Cl ⁻ ion is usually present as an impurity of the epoxy resin. When migration occurs, the resistance value between the anode and the cathode of the copper wire decreases, and when migration proceeds, the anode and cathode are short-circuited. In addition, Cu (OH) may be Cu (OH) ₂ or Cu (OH) ⁺ precisely, and in the case of Cu (OH) ₂ , it moves to the cathode side due to the concentration difference. In the case of Cu (OH) ⁺ , it moves electrically.

  In order to prevent this migration, a resin composition containing at least one possible substance selected from benzotriazoles, triazines, and these isocyanurs has been reported as an ion binder (Patent Document 1).

  However, when benzotriazoles and the like are dispersed in an epoxy resin, the curing reaction between the epoxy resin and the benzotriazoles proceeds at room temperature, and the viscosity increases remarkably. In addition, benzotriazoles have an effect of preventing migration, but there is a problem that corrosion of copper in the electrode portion cannot be prevented.

JP 2008-98646 A

  The present invention prevents migration of the copper wire in the cured resin composition and suppresses the curing reaction during storage of the resin composition, specifically, when the resin composition is used in liquid form. It is an object to suppress thickening during storage. Accordingly, it is an object of the present invention to provide a highly reliable resin composition having excellent storage characteristics and excellent migration resistance after curing.

This invention relates to the resin composition which solved the said problem by having the following structures.
[1] (A) epoxy resin,
(B) a curing agent,
(C) filler, and (D) general formula (1):

(Wherein R ₁ , R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms), xanthines represented by the general formula (2):

(Wherein, R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, and m is an integer of 1 to 5). And general formula (3):

(Wherein R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 5). A resin composition comprising at least one selected from the group consisting of compounds.
[2] The component (D) is caffeine, theophylline, theobromine, paraxanthine, 5,8-dimethyltocol, 7,8-dimethyltocol, 8-methyltocol, 5,7,8-trimethyltocotrienol, 5,8 The resin composition according to the above [1], which is at least one selected from the group consisting of dimethyltocotrienol, 7,8-dimethyltocotrienol, 8-methyltocotrienol and 5,7,8-trimethyltocol.
[3] The resin composition according to [1] or [2] above, wherein the component (C) is 50 to 92 parts by mass with respect to 100 parts by mass of the resin composition.
[4] The resin composition according to any one of [1] to [3], wherein the average particle size of the component (C) is 0.6 to 20 μm.
[5] The above (4), wherein the component (C) comprises a first filler having an average particle diameter of 0.5 to 3 μm and a second filler having an average particle diameter of 8 to 20 μm. Resin composition.
[6] The resin composition according to any one of [1] to [5], further including (E) a curing accelerator.
[7] The resin composition according to any one of [1] to [6], further comprising (F) a coupling agent.
[8] The resin composition according to any one of [1] to [7], further comprising (G) a rubber component.
[9] The resin composition according to any one of [1] to [8], further comprising (H) an ion exchanger.
[10] The resin composition according to any one of [1] to [9], wherein the component (D) is 0.01 to 12 parts by mass with respect to 100 parts by mass of the resin composition.
[11] The resin composition according to any one of [1] to [10]. Semiconductor encapsulant.
[12] A semiconductor device having a semiconductor element sealed with the resin composition according to any one of [1] to [11].

  According to the present invention [1], a resin composition having excellent storage characteristics, specifically, a thickening during storage when the resin composition is used in a liquid state, and having excellent migration resistance after curing. Can be provided.

  According to the present invention [10], a highly reliable semiconductor device excellent in migration resistance can be easily provided.

It is a mimetic diagram explaining migration of a copper wire. It is a schematic diagram explaining the evaluation method of the injectability of a resin composition.

The resin composition of the present invention comprises (A) an epoxy resin,
(B) a curing agent,
(C) filler, and (D) general formula (1):

(Wherein R ₁ , R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms), xanthines represented by the general formula (2):

(Wherein, R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, and m is an integer of 1 to 5). And general formula (3):

(Wherein R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 5). It contains at least one selected from the group consisting of compounds.

  As the component (A), when the resin composition is used as an underfill material, a liquid epoxy resin is preferable, a liquid bisphenol A type epoxy resin, a liquid bisphenol F type epoxy resin, a liquid naphthalene type epoxy resin, a liquid aminophenol. Type epoxy resin, liquid hydrogenated bisphenol type epoxy resin, liquid alicyclic epoxy resin, liquid alcohol ether type epoxy resin, liquid cyclic aliphatic type epoxy resin, liquid fluorene type epoxy resin, liquid siloxane type epoxy resin, etc. Liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid aminophenol type epoxy resin, and liquid siloxane type epoxy resin are preferable from the viewpoints of curability, heat resistance, adhesiveness, and durability. In addition, when using a resin composition by solid, such as a film form, (A) component is preferable in it being a solid epoxy resin, and the solid of what was mentioned as a liquid epoxy resin as a solid epoxy resin is mentioned. From the viewpoint of film moldability, a phenoxy resin is preferable. The epoxy equivalent is preferably 80 to 250 g / eq from the viewpoint of adjusting the viscosity. Commercially available products include Nippon Steel Chemical's bisphenol F type epoxy resin (product name: YDF8170), Nippon Steel Chemical's bisphenol F type epoxy resin (product name: YDF870GS), Mitsubishi Chemical's aminophenol type epoxy resin (grade: JER630, JER630LSD), DIC naphthalene type epoxy resin (product name: HP4032D), Momentive Performance siloxane epoxy resin (product name: TSL9906), Nippon Steel Chemical Co., Ltd. 1,4-cyclohexanedimethanol diglycidyl ether (product name: ZX1658GS) ) And the like. (A) A component may be individual or may use 2 or more types together.

  Examples of the component (B) include acid anhydrides, amine-based curing agents, and phenol-based curing agents. Acid anhydrides include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, Methylcyclohexene tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (anhydro trimellitate) mono Substituted with acetate, dodecenyl succinic anhydride, aliphatic dibasic polyanhydride, chlorendic anhydride, methylbutenyl tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, methyl hymic anhydride, alkenyl group Succinic anhydride was, glutaric anhydride and the like, methyl butenyl tetrahydrophthalic acid anhydride are preferred. Examples of amine-based curing agents include chain aliphatic amines, cycloaliphatic amines, aliphatic aromatic amines, aromatic amines, and the like, and aromatic amines are preferred. Examples of the phenolic curing agent include phenol novolak and cresol novolak, and phenol novolak is preferable. Commercially available products include Mitsubishi Chemical acid anhydrides (grade: YH306, YH307), Hitachi Chemical 3 or 4-methyl-hexahydrophthalic anhydride (product name: HN-5500), Nippon Kayaku amine curing agent (product name). : Kayahard A-A), Meiwa Kasei phenol curing agent (product name: MEH8005), and the like. (B) A component may be individual or may use 2 or more types together.

  Examples of the component (C) include silica such as colloidal silica, hydrophobic silica, fine silica, and nano silica, acrylic beads, glass beads, urethane beads, bentonite, acetylene black, and ketjen black. Moreover, the average particle diameter of the component (C) (if it is not granular, the average maximum diameter) is not particularly limited, but is 0.01 to 50 μm to uniformly disperse the filler in the resin composition. Moreover, it is preferable for reasons such as excellent injectability when the resin composition is used as an underfill material. When it is less than 0.01 μm, the viscosity of the resin composition increases, and the injectability may deteriorate when used as an underfill material. If it exceeds 50 μm, it may be difficult to uniformly disperse the filler in the resin composition. Moreover, from a viewpoint of protecting a copper wire from the heat stress of the cured resin composition, the average particle size of the component (C) is more preferably 0.6 to 10 μm. Commercially available products include high purity synthetic spherical silica manufactured by Admatechs (product name: SO-E5, average particle size: 2 μm; product name: SE-2300, average particle size: 0.6 μm), silica manufactured by Tatsumori (product name: FB7SDX, Average particle size: 10 μm), Micron silica (product name: TS-10-034P, average particle size: 20 μm), and the like. Here, the average particle diameter of the filler is measured by a dynamic light scattering nanotrack particle size analyzer. (C) A component may be individual or may use 2 or more types together.

  In addition, when the component (C) includes a first filler having an average particle diameter of 0.5 to 3 μm and a second filler having an average particle diameter of 8 to 20 μm, from the viewpoint of fluidity, preferable. Moreover, it is more preferable from a fluid viewpoint that a 1st filler is 10-80 mass parts with respect to the sum total: 100 mass parts of a 1st filler and a 2nd filler.

  The component (D) suppresses the curing reaction during storage of the resin composition, specifically, suppresses thickening during storage when the resin composition is used in a liquid state, and improves the migration resistance after curing. Improve. The component (D) is represented by the general formula (1):

When X 1 is represented by the formula (wherein R ₁ , R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms), it is usually a solid. When the component (D) is represented by the general formula (1), the reason for improving the migration resistance of the cured resin composition is that there are two carbonyl group oxygens and carbon in the imidazole ring. It is thought that this is because nitrogen having a double bond is coordinated to Cu ions such as metallic copper and Cu (OH).

As the component (D) represented by the general formula (1), R ₁ , R ₂ and R ₃ are preferably each independently hydrogen or an alkyl group having 1 carbon atom, and the formula (4):

Caffeine, formula (5):

Theophylline of formula (6):

Theobromine and formula (7):

It is more preferable that it is at least one selected from the group consisting of paraxanthines.

  The component (D) is represented by the general formula (2):

(Wherein R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, preferably hydrogen or an alkyl group having 1 carbon atom, A compound represented by an integer of 5, preferably 3, or a general formula (3):

(Wherein R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, preferably hydrogen or an alkyl group having 1 carbon atom, and n is 1 In the case of a compound represented by an integer of ˜5, preferably 3, it is usually a liquid. When the component (D) is represented by the general formula (2) or the general formula (3), the reason why the migration resistance of the cured resin composition is improved is the general formula (2) or the general formula (3). It is considered that the oxane ring (tetrahydropyran ring) in () is coordinated to Cu ions such as metallic copper and Cu (OH). In addition, since an oxan ring does not have a large electron donating property, for example, unlike a compound containing a cyclic structure containing an azo group or an azide group, it suppresses thickening due to a curing reaction during storage of the resin composition. Can do. Moreover, it is thought that the hydrocarbon couple | bonded with an oxane ring (in the parenthesis of General formula (2) or General formula (3)) has contributed to liquefaction of (D) component.

  Furthermore, since the component (D) represented by the general formula (2) or the general formula (3) is a liquid, the component (A) can contain a desired amount. If it demonstrates in detail, generally when manufacturing a resin composition, after mixing (A) component and (D) component, (B) component is mixed. Here, in the case of mixing a solid powder material with the component (A), it is difficult to obtain a uniform resin composition unless a master batch is prepared by previously mixing the component (A) and the powder material. For this reason, a master batch production step is required, and the ratio of the component (A) and the powder material that can obtain a uniform master batch is limited. On the other hand, since the component (D) is a liquid, it is not necessary to prepare a master batch, and the component (A) can contain a desired amount.

  The component (D) is more preferably a tocol having m of 3 in the general formula (2) or a tocotrienol having n of 3 in the general formula (3). Tocols include 5,7,8-trimethyltocol (α-tocopherol), 5,8-dimethyltocol (β-tocopherol), 7,8-dimethyltocol (γ-tocopherol), 8-methyltocol (δ- Tocopherols include 5,7,8-trimethyltocotrienol (α-tocotrienol), 5,8-dimethyltocotrienol (β-tocotrienol), 7,8-dimethyltocotrienol (γ-tocotrienol), 8-methyl as tocotrienols. Tocotrienol (δ-tocotrienol) is preferable from the viewpoint of the storage characteristics of the resin composition and the migration resistance of the resin composition after curing.

  From the viewpoint of good reactivity and reliability, the resin composition has an acid anhydride equivalent of component (B) preferably 0.6 to 1.2 with respect to epoxy equivalent of component (A): 1. More preferably, it is 0.65-1.1. When it is 0.6 or more, reactivity, moisture resistance reliability and migration resistance in the PCT test (Pressure Cooker Test; durability test at 121 ° C., 2 atm, humidity: 100%) of the cured resin composition On the other hand, when it is 1.2 or less, the thickening factor does not become too high, and the generation of voids is suppressed.

  The component (C) is preferably contained in an amount of 50 to 92 parts by mass, more preferably 70 to 80 parts by mass with respect to 100 parts by mass of the resin composition. A linear expansion coefficient can be lowered | hung as it is 50-92 mass parts, and deterioration of injectability can be avoided.

  Moreover, (C) component is 50-92 mass parts preferably with respect to 100 mass parts of hardened | cured materials of a resin composition, More preferably, 70-90 mass parts is contained. A linear expansion coefficient can be lowered | hung as it is 50-92 mass parts, and deterioration of injectability can be avoided. Here, since the resin composition has a small mass loss of about 1 to 2% by mass when cured, the content of the preferred component (C) in the cured product is the same as the content in the resin composition. is there. Here, the quantitative analysis of the component (C) is performed by mass spectrometry.

  The component (D) is preferably contained in an amount of 0.01 to 12 parts by mass, more preferably 0.05 to 10.71 parts by mass, and 0.99 to 7.41 parts by mass with respect to 100 parts by mass of the resin composition. It is more preferable to include a part. Lead corrosion resistance is favorable as it is 0.01 mass part or more, and the raise of the viscosity increase rate of a resin composition can be suppressed as it is 12 mass parts or less. As the component (D), for example, a reagent commercially available from Wako Pure Chemical Industries may be used.

  Moreover, (D) component is preferable when it contains 0.01-12 mass parts with respect to 100 mass parts of hardened | cured materials of a resin composition, It is more preferable when 0.05-10.71 mass parts is contained, More preferably, 99 to 7.41 parts by mass are included. Here, the quantitative analysis of the component (D) is performed by mass spectrometry.

  When the resin composition further contains a curing accelerator as the component (E), an appropriate curability is obtained, and the curing accelerator is not particularly limited as long as the curing accelerator is an epoxy resin curing accelerator, A well-known thing can be used. For example, an amine hardening accelerator, a phosphorus hardening accelerator, etc. are mentioned.

  Examples of amine-based curing accelerators include imidazoles such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Compounds, triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) And tertiary amine compounds such as triethylenediamine, benzyldimethylamine, and triethanolamine. Of these, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine and 2-phenyl-4-methylimidazole are preferable. Examples of the phosphorus curing accelerator include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, and the like. (E) A component may be individual or may use 2 or more types together. In addition, when using an acid anhydride type hardening | curing agent for (B) component, it is preferable to use an amine hardening accelerator from the point of sclerosis | hardenability and storage stability.

  The component (E) may be an adduct type adducted with an epoxy resin or the like, or may be a microcapsule type. As a microcapsule type commercial product, a microencapsulated latent curing agent (product name: NovaCure HX3088) manufactured by Asahi Kasei E-Materials can be used.

  When the resin composition further contains a coupling agent as component (F), it is preferable from the viewpoint of adhesion, and as component (F), 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxy are preferable. Silane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (Triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane and the like can be mentioned, and 3-glycidoxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane are preferable from the viewpoint of adhesion. Examples of commercially available products include KBM403, KBE903, and KBE9103 manufactured by Shin-Etsu Chemical. (F) A component may be individual or may use 2 or more types together.

  When the resin composition further contains a rubber component as component (G), it is preferable from the viewpoint of stress relaxation of the cured product of the resin composition. As component (G), acrylic rubber, urethane rubber, silicone rubber, butadiene Rubber. (G) A solid thing can be used for a component. The form is not particularly limited, and for example, particles, powders, pellets can be used, and in the case of particles, for example, the average particle diameter is 10 to 750 nm, preferably 30 to 500 nm, more preferably, 50-300 nm. The component (G) can also be used at room temperature, and examples thereof include polybutadiene, butadiene / acrylonitrile copolymer, polyisoprene, polypropylene oxide, and polydiorganosiloxane having a relatively low average molecular weight. Moreover, what has a group which reacts with an epoxy group at the terminal can be used for (G) component, These may be a solid or liquid form. Examples of commercially available products include ATBN 1300-16, CTBN1008-SP, etc., manufactured by Ube Industries. (G) A component may be individual or may use 2 or more types together.

  When the resin composition further contains an ion exchanger which is component (H), it is preferable from the viewpoint of reducing the amount of ionic impurities extracted into the resin composition. As the ion exchanger, an inorganic ion exchanger is used. More preferable. As the component (H), an inorganic ion exchanger (product name: IXE-500) manufactured by Toagosei Co., Ltd. may be mentioned.

  Component (E) is preferably more than 0.1 parts by mass and less than 5 parts by mass, more preferably 0.2-4 parts by mass, and even more preferably 0.3-3 parts per 100 parts by mass of the resin composition. 0.0 part by mass is contained. When it is 0.1 parts by mass or more, the reactivity is good, and when it is 5 parts by mass or less, the moisture resistance reliability is good, and the thickening ratio is stable.

  The component (F) is preferably contained in an amount of 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition. Adhesiveness improves that it is 0.05 mass part or more, moisture resistance reliability in a PCT test becomes more favorable, and foaming of a resin composition is suppressed as it is 15 mass parts or less.

  The component (G) is preferably contained in an amount of 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, and further preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin composition. When it is 0.1 part by mass or more, the stress of the cured product of the resin composition is relieved, and when it is 30 parts by mass or less, moisture resistance reliability does not decrease.

  The component (H) is preferably contained in an amount of 0.1 to 3.0 parts by mass, more preferably 0.6 to 1.1 parts by mass with respect to 100 parts by mass of the resin composition. This is because if 3.0 parts by mass or more, the flow characteristics are impaired, and if it is 0.1 parts by mass or less, the effect of suppressing the extraction amount of ionic impurities is small.

  In the resin composition of the present invention, a pigment such as carbon black, a dye, an antifoaming agent, an antioxidant, a stress relaxation agent, other additives, etc., as necessary, within a range that does not impair the purpose of the present invention. Can be blended.

  The resin composition of the present invention is obtained, for example, by stirring, melting, mixing, and dispersing the components (A) to (D) and other additives simultaneously or separately, with heat treatment as necessary. Can do. The mixing, stirring, dispersing and the like devices are not particularly limited, and a raikai machine equipped with a stirring and heating device, a three-roll mill, a ball mill, a planetary mixer, a bead mill and the like can be used. . Moreover, you may use combining these apparatuses suitably.

  The viscosity of the resin composition of the present invention at a temperature of 25 ° C. is preferably 50 to 2000 mPa · s from the viewpoint of injectability. Here, the viscosity is measured with an E-type viscometer (model number: TVE-22H) manufactured by Toki Sangyo Co., Ltd.

  The resin composition of the present invention is formed and applied at a desired position on the substrate by a dispenser, printing or the like. Here, the resin composition is formed between a substrate such as a flexible wiring substrate and the semiconductor element so that at least a part thereof is in contact with the wiring of the substrate.

  As for hardening of the resin composition of this invention, 80-300 degreeC is preferable, and when it hardens within 200 second, it is preferable from a viewpoint of productivity improvement.

  In addition, although a semiconductor element and a board | substrate can use a desired thing, the combination of the semiconductor element and board | substrate suitable for the wire bonding by a copper wire is preferable.

  Thus, the resin composition of the present invention is very suitable for a liquid semiconductor encapsulant, and a semiconductor device having a semiconductor element encapsulated with this liquid semiconductor encapsulant has migration resistance, and Excellent lead corrosion resistance and high reliability.

  The present invention will be described with reference to examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and mass% unless otherwise specified.

[Examples 1 to 16, Comparative Example 1]
Resin compositions were prepared with the formulations shown in Tables 1 to 3. The prepared resin compositions were all liquid. Further, [acid anhydride of component (B), phenol or amine equivalent] / [epoxy equivalent of component (A)] was set to 0.82 in all of Examples 1 to 27 and Comparative Examples 1 and 2.

[Evaluation of viscosity]
The viscosity (unit: mPa · s) of the resin composition immediately after production was measured under the condition of 50 revolutions per minute using an E-type viscometer (model number: TVE-22H) manufactured by Toki Sangyo Co., Ltd. Tables 1 to 3 show the measurement results.

[Evaluation of gel time]
The gel time of the resin composition is when the resin composition: 5 ± 1 mg is supplied on a hot plate heated to 150 ° C., and the stirring bar is lifted and pulled away while stirring in a circle with the stirring bar. It was obtained by measuring the time until the stringing became 5 mm or less. The proper range of gel time is 10 to 100 seconds. Tables 1 to 3 show the measurement results.

[Evaluation of tremor index]
The variation index of the resin composition was measured using an E-type viscometer (model number: TVE-22H) manufactured by Toki Sangyo Co., Ltd. The tremor index is a ratio obtained by dividing the measured value obtained under the condition of 5 revolutions per minute by the measured value obtained under the condition of 50 revolutions per minute, that is, (viscosity at 5 revolutions per minute) / (every time. (Viscosity at 50 rpm). An appropriate range of the thymometric index is 0.8 to 3.0. Tables 1 to 3 show the measurement results.

[Evaluation of thermal expansion coefficient]
Each resin composition was cured at 150 ° C. for 30 minutes so that the dimension after curing was 5 mmφ × 3 mm. This was measured in the TMA method compression mode using a thermomechanical analyzer (model number: TMA4000SA series) manufactured by Bruker ASX, and the thermal expansion coefficient was determined. An appropriate range of the thermal expansion coefficient is 3 to 20 ppm / ° C.

[THB test (Thermal Humidity Bias test)]
In order to evaluate the migration characteristics of the resin composition, a THB test was conducted. Here, in the pattern using a copper wire, since the wire pitch was about 100 μm, a comb electrode having a line pitch of 10 μm was used as an acceleration test. Each resin composition was applied onto a comb-like electrode (line / space = 10 μm / 10 μm, Sn-plated Cu electrode) formed on a polyimide (Kapton made by Toray DuPont) substrate and cured (150 ° C. × 30 minutes) To prepare an evaluation sample (n = 3). The evaluation sample was put into a constant temperature layer having a temperature of 85 ° C. and a humidity of 85%, and the resistance value was measured while applying a voltage of 60 V to the comb electrode, and the time until it became 10 ⁹ Ω or less was evaluated. The THB test was evaluated for up to 500 hours. The THB test is preferably 80 hours or longer, and more preferably 500 hours or longer. Tables 1 to 3 show the measurement results.

[Temperature cycle test]
A temperature cycle test (−55 ° C./125° C. (30 minutes / 30 minutes)) was performed, and the change in resistance value after the temperature cycle test was evaluated. In the temperature cycle test, the state where the resistance value does not change is preferably 100 times or more, and more preferably 500 times or more.

  As can be seen from Tables 1 to 3, in all of Examples 1 to 27, the gel time of the resin composition was long, that is, the rate of increase in the viscosity of the resin composition was low, and the variation index was within an appropriate range. Moreover, since the coefficient of thermal expansion was within the proper range, the results of the temperature cycle test were good. Furthermore, the result of the THB test was also good, and it was found that no copper migration occurred. On the other hand, in Comparative Example 1 containing no component (D), the result of the THB test was less than 50 hours, and copper migration occurred. Moreover, the comparative example 2 which does not contain (C) component had a large thermal expansion coefficient, and the result of the temperature cycle test was as few as 100 times.

  As mentioned above, the resin composition of this invention can suppress the viscosity increase at the time of the preservation | save of a resin composition, and can make the migration resistance of the resin composition after hardening high.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Cathode 10, 11 Resin composition 20 Substrate 30 Glass plate 40 Gap

Claims (12)

(A) epoxy resin,
(B) a curing agent,
(C) filler, and (D) general formula (1):
(Wherein R ₁ , R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms), xanthines represented by the general formula (2):
(Wherein, R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, and m is an integer of 1 to 5). And general formula (3):
(Wherein R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 5). A liquid resin composition comprising at least one selected from the group consisting of compounds and containing no phenol resin . (D) component is caffeine, theophylline, theobromine, paraxanthine, 5,8-dimethyltocol, 7,8-dimethyltocol, 8-methyltocol, 5,7,8-trimethyltocotrienol, 5,8-dimethyltocotrienol 2. The liquid resin composition according to claim 1, which is at least one selected from the group consisting of 7,8-dimethyltocotrienol, 8-methyltocotrienol and 5,7,8-trimethyltocol. (C) The liquid resin composition of Claim 1 or 2 whose component is 50-92 mass parts with respect to 100 mass parts of resin compositions. The liquid resin composition of any one of Claims 1-3 whose average particle diameter of (C) component is 0.6-20 micrometers. The liquid resin composition according to claim 4, wherein the component (C) includes a first filler having an average particle diameter of 0.5 to 3 μm and a second filler having an average particle diameter of 8 to 20 μm. . Furthermore, (E) Liquid resin composition of any one of Claims 1-5 containing a hardening accelerator. Furthermore, the liquid resin composition of any one of Claims 1-6 containing a coupling agent (F). Furthermore, (G) The liquid resin composition of any one of Claims 1-7 containing a rubber component. Furthermore, the liquid resin composition of any one of Claims 1-8 containing (H) ion exchanger. (D) The liquid resin composition of any one of Claims 1-9 whose component is 0.01-12 mass parts with respect to 100 mass parts of resin compositions. The liquid resin composition of any one of Claims 1-10 is included. Semiconductor encapsulant. The semiconductor device which has a semiconductor element sealed with the liquid resin composition of any one of Claims 1-11.