JP2017039846A - Electrically conductive adhesive and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrically conductive adhesive that provides a low connection resistance value after being cured and that has a high adhesion strength with both metal and resin.SOLUTION: The electrically conductive adhesive is provided that contains (A) an epoxy resin, (B) an amine-based curing agent and/or a phenolic curing agent, (C) a morpholine reducing agent and/or 8-quinolinol, (D) an electrically conductive filler and (E) an additive comprising acid group and amino group. Preferably, the component (C) is at least one kind selected from the group consisting of morpholine, 2,6-dimethyl morpholine, 4-(3-hydroxypropyl)morpholine, 4-methylmorpholine, 4-(4-amino-phenyl)morpholine, thiomorpholine and 1,1-di-oxo-thiomorpholine.SELECTED DRAWING: None

Description

  The present invention relates to a conductive adhesive, and more particularly to a conductive adhesive that can connect a metal that easily forms an oxide film with low resistance.

  A semiconductor device in which an electrode portion of a semiconductor element and a conductive portion of a resin substrate are bonded is very widely used, and a conductive adhesive is used for bonding the electrode portion of the semiconductor element and the conductive portion of the resin substrate. Or solder is used. The conductive adhesive has an advantage that it can be bonded at a lower temperature than the solder. However, since the bulk resistance is higher than that of the solder, a reduction in the resistance of the conductive adhesive is being studied.

  As a technique for reducing the bulk resistance of a conductive adhesive, high filling of a conductive filler in the conductive adhesive is widely known. However, when the conductive part of the resin substrate is a metal (nickel, copper, aluminum, tin, etc.) that is easy to form an oxide film on the outermost surface, if it is joined with a conductive adhesive, oxidation (corrosion) of this metal causes The interface resistance value increases. For this reason, the increase in the connection resistance value cannot be prevented by increasing the amount of the conductive filler in the conductive adhesive.

  As a known technique for reducing the connection resistance when using a conductive adhesive as described above, a conductive adhesive is used when joining a metal that easily forms an oxide film with a conductive adhesive. It is known to add 8-hydroxyquinoline (8-quinolinol) to the agent as a corrosion inhibitor.

  Known techniques for adding 8-hydroxyquinoline as a corrosion inhibitor in a conductive adhesive include (a) a polymer resin, (b) a conductive filler, (c) an anticorrosive, and (d) reactive as desired. Or a composition for use in a microelectronic device comprising a non-reactive diluent, (e) optionally an inert filler, and (f) optionally an adhesion promoter, wherein the anticorrosive is 8-hydroxyquinoline. There is a known composition (Patent Document 1).

JP 2002-348486 A

  In addition to the adhesion between the electrode portion of the semiconductor element and the conductive portion of the resin substrate, the conductive adhesive is formed with a lid (LID (lid)) that is an electromagnetic wave shielding material for the IC chip and a metal electrode for grounding. Used for bonding various parts such as bonding to a resin substrate. That is, the conductive adhesive has applications that require not only a metal-metal bond but also a metal-resin adhesive force.

  By adding a silane coupling agent, which is often used for the purpose of improving the adhesive strength, to the composition using 8-hydroxyquinoline as an anticorrosive agent, the adhesive strength between the metal and the conductive adhesive is improved. However, there is a problem that the adhesive force between the conductive adhesive and the resin cannot be improved. Accordingly, an object of the present invention is to provide a conductive adhesive having a low connection resistance value after curing and a high adhesive strength for both metal and resin.

The present invention relates to a conductive adhesive and a semiconductor device that have solved the above problems by having the following configuration.
[1] (A) epoxy resin,
(B) a phenolic curing agent and / or an amine curing agent,
(C) a morpholine reducing agent and / or 8-quinolinol,
A conductive adhesive comprising (D) a conductive filler and (E) an additive containing an acid group and an amino group.
[2] The component (C) is morpholine, 2,6-dimethylmorpholine, 4- (3-hydroxypropyl) morpholine, 4-methylmorpholine, 4- (4-aminophenyl) morpholine, thiomorpholine and 1,1- The conductive adhesive according to [1] above, which is at least one selected from the group consisting of dioxothiomorpholine.
[3] The conductivity according to [1] or [2], wherein the component (C) is 0.05 to 1.00 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). adhesive.
[4] The conductive adhesive according to any one of [1] to [3], wherein the acid value and amine value of the component (E) are 20 to 200 mgKOH / g, respectively.
[5] Powder in which component (D) contains at least one metal or alloy selected from the group consisting of silver, nickel, copper, tin, aluminum, silver alloy, nickel alloy, copper alloy, tin alloy and aluminum alloy The conductive adhesive according to any one of [1] to [4] above.
[6] A resin substrate having a conductive portion and a semiconductor element having an electrode portion,
A semiconductor device in which a conductive part of a resin substrate and an electrode part of a semiconductor element are bonded with a cured product of the conductive adhesive according to any one of [1] to [5].
[7] The semiconductor device according to [6], wherein the conductive portion of the resin substrate is nickel, aluminum, copper, or tin.
[8] A lid that is an electromagnetic wave shielding material for an IC chip, and a resin substrate on which a metal electrode for grounding is formed,
A semiconductor device comprising a cured product of the conductive adhesive according to any one of [1] to [5], wherein a lid is bonded to a metal electrode and / or a resin substrate.
[9] The semiconductor device according to [8] above, wherein the lid has nickel, aluminum, copper, or tin at least on the surface thereof.

  According to the present invention [1], it is possible to provide a conductive adhesive having a low connection resistance value after curing, and having a high adhesive strength for both metal and resin.

  According to the present invention [6], a highly reliable semiconductor can be obtained by a conductive adhesive having a small connection resistance value between the electrode portion of the semiconductor element and the conductive portion of the resin substrate and having high adhesive strength for both the metal and the resin. A device can be obtained. According to the present invention [8], a highly reliable semiconductor device can be obtained by using a conductive adhesive having a low connection resistance value between the lid and the resin substrate and having a high adhesive strength for both the metal and the resin.

The conductive adhesive of the present invention is
(A) epoxy resin,
(B) a phenolic curing agent and / or an amine curing agent,
(C) a morpholine reducing agent and / or 8-quinolinol,
(D) A conductive filler and (E) an additive containing an acid group and an amino group are contained.

  The component (A) imparts adhesiveness and curability to the conductive adhesive, and imparts durability and heat resistance to the cured conductive adhesive. As component (A), liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid naphthalene type epoxy resin, liquid aminophenol type epoxy resin, liquid hydrogenated bisphenol type epoxy resin, liquid alicyclic epoxy resin, liquid Examples include alcohol ether type epoxy resin, liquid cycloaliphatic 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 naphthalene type epoxy resin From the viewpoints of adhesiveness, curability, durability, and heat resistance. The epoxy equivalent is preferably 80 to 250 g / eq from the viewpoint of adjusting the viscosity. As commercial products, bisphenol F type epoxy resin (product name: YDF8170) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type epoxy resin (product name: EXA-850CRP) manufactured by DIC, bisphenol F type epoxy resin (product name: YDF870GS) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., DIC bisphenol A type / bisphenol F type mixed epoxy resin (product name: EXA835LV), DIC naphthalene type epoxy resin (product name: HP4032D), Mitsubishi Chemical aminophenol type epoxy resin (grade: JER630, JER630LSD), Momentive Performance Examples thereof include siloxane-based epoxy resins (product name: TSL9906), 1,4-cyclohexanedimethanol diglycidyl ether (product name: ZX1658GS) manufactured by Nippon Steel & Sumikin Chemical. (A) A component may be individual or may use 2 or more types together.

  The component (B) cures the conductive adhesive. (B) As a phenol type hardening | curing agent of a component, a phenol novolak, a cresol novolak, etc. are mentioned, A phenol novolak is preferable. The phenol-based curing agent can reduce the resistance of the conductive adhesive after curing as compared with the amine-based curing agent. In addition, the phenolic curing agent is less reactive than the amine curing agent, so that the pot life of the conductive adhesive can be lengthened. If 80% or more of the component (B) is a phenolic curing agent, these effects can be obtained.

  The amine-based curing agent as the component (B) is not particularly limited as long as it has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule. Examples of amine-based curing agents include aliphatic amine compounds such as dicyandiamide, diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4′-diamino-dicyclohexylmethane; Aromatic amine compounds such as' -diaminodiphenylmethane, 2-methylaniline; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole; imidazoline, 2-methylimidazoline, 2-ethylimidazoline, etc. Examples include imidazoline compounds.

  Commercially available products of component (B) include Gunei Chemical's allylphenol type phenolic resin (product name: XPL-4437E), Meiwa Kasei's phenol curing agent (product names: MEH8000, MEH8005), and ADEKA curing agent (product name: EH-). 3842) and the like, but the component (B) is not limited to these product names. (B) A component may be individual or may use 2 or more types together.

  The component (C) serves to remove the oxide film on the surface of the component (D) and reduce the connection resistance value of the conductive adhesive after curing. In addition, since (C) component is basic, (B) component which is a hardening | curing agent of (A) component is also basic. As the component (C), a morpholine reducing agent is preferable because it has a reducing power stronger than 8-quinolinol, and can reduce the resistance of the conductive adhesive after curing. Moreover, a morpholine reducing agent is preferable from the viewpoint of suppressing generation of voids in the conductive adhesive. The morpholines used for the reducing agent of component (C) refer to morpholine and compounds having a morpholine structure. (C) component can reduce the connection resistance value of the conductive adhesive after hardening. As the component (C), morpholine, 2,6-dimethylmorpholine, 4- (3-hydroxypropyl) morpholine, 4-methylmorpholine, 4- (4-aminophenyl) morpholine, thiomorpholine, 1,1-dioxo Examples include thiomorpholine.

The component (C) is preferably at least one selected from the group consisting of morpholines represented by the following chemical formulas (1) to (7) because the connection resistance value can be reduced.
Morpholine represented by chemical formula (1):

2,6-dimethylmorpholine represented by the chemical formula (2):

4- (3-hydroxypropyl) morpholine represented by the chemical formula (3):

4-methylmorpholine represented by chemical formula (4):

4- (4-aminophenyl) morpholine represented by the chemical formula (5):

Thiomorpholine represented by the chemical formula (6):

1,1-dioxothiomorpholine (thiomorpholine 1,1-dioxide) represented by chemical formula (7):

  As the component (C), for example, a reagent commercially available from Wako Pure Chemical Industries, Nippon Emulsifier, Tokyo Chemical Industry may be used. (C) A component may be individual or may use 2 or more types together.

  The conductive filler of the component (D) is not particularly limited. Examples of the component (D) include silver, nickel, copper, gold, palladium, platinum, bismuth, tin, and alloys thereof (particularly bismuth-tin). Alloy), carbon fiber, graphite, carbon black, aluminum, indium tin oxide, silver-coated copper, silver-coated aluminum, metal-coated glass sphere, silver-coated fiber, silver-coated resin, antimony-doped tin oxide, and mixtures thereof Can be mentioned. The component (D) is a powder containing at least one metal or alloy selected from the group consisting of silver, nickel, copper, tin, aluminum, silver alloy, nickel alloy, copper alloy, tin alloy, and aluminum alloy. The effect of the present invention that suppresses an increase in the connection resistance value is easily exhibited, which is preferable. When the conductive portion of the resin substrate is a metal that is easily corroded, such as nickel, aluminum, copper, or tin, the component (C) also acts as a corrosion inhibitor for the conductive portion of the resin substrate. It is preferable to use a metal having a small bulk resistance, such as gold, palladium, or platinum, as the component, because the connection resistance value can be reduced. (D) The average particle diameter of a component is 0.1-50 micrometers from a viewpoint of workability | operativity and viscosity reduction, and is more preferable. Here, the average particle diameter of the component (D) is a volume-based median diameter measured by a laser diffraction method. In addition, the shape of the component (D) is more preferably a flake shape from the viewpoint of reducing resistance. Commercially available products include DOWA electronics silver powder (product name: FA618) and Mitsui Mining & Smelting silver powder (product name: SL02). (D) A component may be individual or may use 2 or more types together.

  The acid group in the additive containing the acid group and amino group of the component (E) can improve the adhesion to the resin, and the amino group can improve the adhesion to the metal. As the component (E), any of an additive containing an acid group and an amino group in one molecule and a mixture of a molecule containing an acid group and a molecule containing an amino group can be used. From the viewpoint of stability, an additive containing an acid group and an amino group in one molecule is preferable. Here, the additive containing an acid group and an amino group in one molecule is more preferably a polymer from the viewpoint of low volatility. Here, in the polymer additive containing an acid group and an amino group in one molecule, the bonding position of the acid group and amino group to the polymer main body is not particularly limited, and may be a main chain or a side chain. It may be located in the main chain and the side chain. The acid group and amino group may be directly bonded to the polymer main body or may be bonded via a linking group. Examples of the linking group include lower alkylene groups such as ethylene group to octylene group, phenylene group, low intermediate alkylene group having an ether bond in the chain, low intermediate alkylene group having a carboxylic ester bond in the chain, and a carboxylic acid in the chain. And low intermediate alkylene groups having an amide bond. The lower alkylene group preferably has 1 to 8 carbon atoms, and the lower intermediate alkylene group having an ether bond in the chain preferably has 2 to 12 carbon atoms in total. The weight average molecular weight of the polymer additive containing an acid group and an amino group in one molecule is preferably in the range of 2,000 to 150,000, and more preferably in the range of 3,000 to 100,000. . Here, the weight average molecular weight (Mw) is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran). As the additive containing an acid group and an amino group in one molecule, a synthetic product or a commercially available product may be used.

  The acid value and amine value of the component (E) are each preferably 20 to 200 mgKOH / g, more preferably 50 to 100 mgKOH / g, from the viewpoint of adhesion to metals and resins. When the acid value and amine value of the component (E) are less than 20 mgKOH / g, the adhesive strength with a metal or resin tends to be insufficient, and when it exceeds 200 mgKOH / g, the viscosity tends to increase. . Here, the acid value represents mg of potassium hydroxide required to neutralize free fatty acid, resin acid and the like contained in 1 g of component (E), and a potassium hydroxide ethanol solution according to JIS K0070. Determined by potentiometric titration using The amine value represents the amine value in 1 g of component (E), and a value obtained by potentiometric titration using a 0.1N hydrochloric acid aqueous solution is converted to an equivalent of potassium hydroxide.

  As a commercial product of an additive containing an acid group and an amino group in one molecule, a polymer additive manufactured by Big Chemie (Product name: BYK-106 (acid value: 132 mgKOH / g, amine value: 74 mgKOH / g), BYK-130 (Acid value: 2 mgKOH / g, amine value: 190 mgKOH / g), BYK-140 (acid value: 73 mgKOH / g, amine value: 76 mgKOH / g), BYK-142 (acid value: 46 mgKOH / g, amine value: 43 mgKOH) / G), BYK-145 (acid value: 76 mgKOH / g, amine value: 71 mgKOH / g), BYK-180 (acid value: 94 mgKOH / g, amine value: 94 mgKOH / g), BYK-187 (acid value: 35 mgKOH) / G, amine value: 35 mgKOH / g), BYK-191 (acid value: 30 mgKOH / g, amine value: 2) mgKOH / g), BYK-2001 (acid value: 19 mgKOH / g, amine value: 29 mgKOH / g), BYK-2010 (acid value: 20 mgKOH / g, amine value: 20 mgKOH / g), BYK-2020 (acid value: 37 mgKOH / g, amine value: 36 mgKOH / g), BYK-2020N (acid value: 36 mgKOH / g, amine value: 36 mgKOH / g), BYK-2025 (acid value: 38 mgKOH / g, amine value: 37 mgKOH / g) BYK -9076 (acid value: 38 mg KOH / g, amine value: 44 mg KOH / g), ANTI-TERRA-U (acid value: 24 mg KOH / g, amine value: 19 mg KOH / g)) Lubrizol polymer additive (product name: SOLPERSE24000) (Acid value: 24 mg KOH / g, amine value: 47 gKOH / g), SOLPERSE 32000 (acid value: 15 mgKOH / g, amine value: 180 mgKOH / g)), Enomoto Kasei Polymer Additive (Product name: Disparon DA-234 (acid value: 16 mgKOH / g, amine value: 20 mgKOH / g), Disparon DA-325 (acid value: 14 mg KOH / g, amine value: 20 mg KOH / g), Ajinomoto Fine-Techno polymer additive (product name: Ajisper PB-821 (acid value: 17 mg KOH / g, amine value: 10 mg KOH) / G), Azisper PB-822 (acid value: 14 mg KOH / g, amine value: 17 mg KOH / g), Azisper PB-881 (acid value: 17 mg KOH / g, amine value: 17 mg KOH / g)) and the like. E) Ingredients are big chemi from the viewpoint of pot life and workability -Polymer additives (Product names: BYK-140 and BYK-180 are preferred, and BYK-180 is more preferred from the viewpoint of low content of volatile components. In the case of a mixture of a molecule containing an acid group and a molecule containing an amino group, an example of a commercially available molecule containing an acid group is oleic acid, and an example of a commercially available molecule containing an amino group is a polymer manufactured by BYK Chemie. Additives (Product name: BYK-116 (acid value: 0 mg KOH / g, amine value: 76 mg KOH / g) are included. (E) Component is not limited to these product names. However, you may use 2 or more types together.

  (A) A component is preferable in it being 6-24 mass parts with respect to a total of 100 mass parts of (A)-(E) component, and more preferable in it being 8-21 mass parts.

  The component (B) is preferably 1 to 10 parts by mass, and 1 to 5 parts by mass with respect to 100 parts by mass in total of the components (A) to (E), from the viewpoint of good reactivity and reliability. More preferably.

  (C) It is preferable that it is 0.05-1.00 mass part with respect to a total of 100 mass parts of (A)-(E) component, and is 0.1-1.00 mass part, More preferred. When the component (C) is less than 0.05 parts by mass with respect to 100 parts by mass of the conductive adhesive, the connection resistance value is likely to increase. The pot life of the agent tends to be shortened.

  In addition, the component (C) is preferably 0.05 to 1.00 parts by mass with respect to 100 parts by mass in total of the components (A) to (E) also in the case of the cured product of the conductive adhesive. It is more preferable in it being 0.1-1.00 mass part. Here, when the conductive adhesive does not contain a solvent (including the case where the solvent is volatilized from the conductive adhesive), the mass loss upon curing is less than 1%, which is preferable in the cured product. The content of the component (C) is the same as the content in the components (A) to (E) before curing. Here, the quantitative analysis of the component (C) is performed by an ion chromatograph-mass spectrometer. In addition, the mass reduction | decrease at the time of hardening of a conductive adhesive in case a conductive adhesive contains a solvent is 3-5 mass%, for example.

  (D) It is preferable that it is 19-47 volume% from a viewpoint of the electrical resistance value of conductive adhesive itself, and, as for (D) component, it is more preferable that it is 22-38 volume%. In addition, when volume% is converted into a mass part, when using silver as (D) component, (D) component is 70- with respect to a total of 100 mass parts of (A)-(E) component. 90 parts by mass is preferable, and 74 to 86 parts by mass is more preferable.

  In addition, the component (D) is preferably 19 to 47% by volume, and more preferably 22 to 38% by volume in the case of a cured product of the conductive adhesive. In addition, when volume% is converted into a mass part, when using silver as (D) component, (D) component is 70- with respect to a total of 100 mass parts of (A)-(E) component. 90 parts by mass is preferable, and 74 to 86 parts by mass is more preferable. Here, the quantitative analysis of the component (D) is performed by mass spectrometry.

  The component (E) is preferably contained in an amount of 0.05 to 5 parts by mass, more preferably 0.1 to 0.8 parts by mass with respect to a total of 100 parts by mass of the components (A) to (E). Adhesive strength becomes it high that it is 0.05 mass part or more, and the bridge | crosslinking inhibition at the time of hardening of a conductive adhesive is suppressed as it is 5 mass parts or less.

  The conductive adhesive of the present invention can further contain a curing accelerator as the component (F) from the viewpoint of acceleration of curing. The curing accelerator is preferably an imidazole compound. Examples of the imidazole compound include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl -4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole and the like can be mentioned, and 2-phenyl-4,5-dihydroxymethylimidazole is cured. It is preferable from the viewpoint of speed and workability.

  In the conductive adhesive of the present invention, a leveling agent, a colorant, an ion trapping agent, an antifoaming agent, a flame retardant, and the like can be further blended as necessary without departing from the object of the present invention.

  The conductive adhesive of the present invention can be obtained, for example, by stirring, melting, mixing, and dispersing the components (A) to (E) and other components simultaneously or separately, with heat treatment as necessary. it can. 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 conductive adhesive of the present invention is formed and applied to a desired position of an electronic component such as a conductive portion of a resin substrate or an electrode portion of a semiconductor element by a dispenser, printing or the like.

  As for hardening of the conductive adhesive of this invention, 120-200 degreeC is preferable.

  The conductive adhesive of the present invention is suitable as an adhesive for electronic parts such as an electrode part of a semiconductor element and a conductive part of a resin substrate.

[Semiconductor device]
The semiconductor device of the present invention includes a resin substrate having a conductive portion and a semiconductor element having an electrode portion, and the conductive portion of the resin substrate and the electrode portion of the semiconductor element are connected by a cured product of the conductive adhesive. The

  In this semiconductor device, the conductive portion of the resin substrate is preferably nickel, aluminum, copper, or tin from the viewpoint of easily exerting the effect of the conductive adhesive. This is because nickel, aluminum, copper, or tin is likely to cause an increase in the interface resistance value due to corrosion of the metal in the known technique. Examples of the conductive portion of the resin substrate include a tin plating electrode and a Ni plating electrode. The resin substrate is not limited, and examples thereof include an FR-4 substrate and a glass epoxy substrate. Examples of the semiconductor electrode portion include a tin plating electrode, a Ni plating electrode, a gold plating electrode, and a silver plating electrode.

  Another semiconductor device of the present invention includes an LID (lid) which is an electromagnetic wave shielding material for an IC chip, and a resin substrate on which a metal electrode for grounding is formed, and is a cured product of the conductive adhesive. , The LID (lid) and the metal electrode and / or the resin substrate are bonded. The resin substrate is not limited, and examples thereof include an FR-4 substrate and a glass epoxy substrate. The lid is not limited, and examples thereof include a lid having nickel, aluminum, copper, or tin on at least its surface. Such a lid can be formed by coating a metal with high thermal conductivity such as copper. The metal electrode is the same as the conductive part of the resin substrate.

  The semiconductor device of the present invention has a small connection resistance value between the electrode portion of the semiconductor element and the conductive portion of the resin substrate, and is highly reliable.

  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.

[Preparation of sample for evaluation]
Components other than the component (C) were dispersed by a hybrid mixer at the ratios shown in Tables 1 to 3. In Example 19, 0.21 parts by mass of BYK-116 and oleic acid were added.

  Next, component (C) was added to the obtained dispersion, and the mixture was stirred with a rotation and revolution type stirrer. Here, since morpholine is usually in a liquid state, there is no need for roll dispersion. In addition, solid morpholines (for example, 4- (3-hydroxypropyl) morpholine, 4- (4-aminophenyl) morpholine, 1,1-dioxothiomorpholine), and 8-quinolinol are dispersed in a roll mill. I let you. Finally, using Brookfield HBDV-I (SC4-14 spindle), adjust the viscosity with butyl carbitol acetate (BCA) so that the viscosity at 10 rpm is 50 Pa · s. While stirring, the bubbles in the dispersion were completely removed to obtain a conductive adhesive.

  In Comparative Example 1, the component (E) was not used. In Comparative Example 2, BYK-116 without an acid group was used instead of (E) component, in Example 3, oleic acid was used instead of (E) component, and in Comparative Example 4, silane was used instead of (E) component. A coupling agent was used. In Comparative Example 5, an acid anhydride was used instead of the component (B), and the component (C) was not used. In Comparative Example 6, adipic acid was used instead of the component (C). Aminophenethyl alcohol was used in place of the component (C).

〔Evaluation method〕
<Measurement of connection resistance>
A conductive adhesive was printed on a Ni-plated Cu lead frame (thickness: 200 μm) to mount a 3216 size AgPd end face electrode. After being cured in an oven at 150 ° C. for 30 minutes, the resistance value between the lead frame and the electrode was measured by a four-terminal method to obtain a connection resistance value. The connection resistance value is preferably less than 3000 mΩ, and more preferably less than 1000 mΩ. Tables 1 to 3 show the results of connection resistance values.

<Adhesive strength>
A conductive adhesive was printed on a Ni-plated Cu lead frame (thickness: 200 μm), and a 2 mm square silicon chip (no electrode) was mounted. After being held for 30 minutes in an oven at 150 ° C. and cured, the shear strength was measured using a strength tester (model number: Model 1605HTP manufactured by Aiko Engineering Co., Ltd.) to determine the adhesive strength at normal temperature. The adhesive strength with Ni is preferably 10 N / mm ² or more, and the adhesive strength with resin is preferably 6 N / mm ² or more. Tables 1 to 3 show the results of adhesive strength with Ni and adhesive strength with resin.

  As can be seen from Tables 1 to 3, in all of Examples 1 to 22, the connection resistance value was as low as less than 3000 mΩ, and the adhesion strength with Ni and resin was also good. On the other hand, the comparative example 1 which did not use (E) component had low adhesive strength with Ni and resin. In Comparative Example 2 using BYK-116 having no acid group instead of the component (E), the adhesive strength with the resin was low. In Comparative Example 3 in which oleic acid was used instead of the component (E), the adhesive strength with Ni was low. In Comparative Example 4 in which a silane coupling agent was used instead of the component (E), the adhesive strength with the resin was low. In Comparative Example 5 in which an acid anhydride was used instead of the component (B) and the component (C) was not used, the connection resistance value was high, and the adhesive strength between Ni and the resin was low. The comparative example 6 which uses adipic acid instead of (C) component had high connection resistance value, and its adhesive strength with Ni was low. In Comparative Example 7 in which aminophenethyl alcohol was used instead of the component (C), the connection resistance value was high.

  As described above, the conductive adhesive of the present invention can reduce the connection resistance value after curing, and can increase the adhesive strength of both the metal and the resin.

Claims (9)

(A) epoxy resin,
(B) a phenolic curing agent and / or an amine curing agent,
(C) a morpholine reducing agent and / or 8-quinolinol,
A conductive adhesive comprising (D) a conductive filler and (E) an additive containing an acid group and an amino group.   Component (C) is morpholine, 2,6-dimethylmorpholine, 4- (3-hydroxypropyl) morpholine, 4-methylmorpholine, 4- (4-aminophenyl) morpholine, thiomorpholine and 1,1-dioxothio The conductive adhesive according to claim 1, which is at least one selected from the group consisting of morpholine.   (C) The conductive adhesive of Claim 1 or 2 whose component is 0.05-1.00 mass part with respect to a total of 100 mass parts of (A)-(E) component.   (E) The conductive adhesive of any one of Claims 1-3 whose acid value and amine value of a component are 20-200 mgKOH / g, respectively.   (D) The component is a powder containing at least one metal or alloy selected from the group consisting of silver, nickel, copper, tin, aluminum, silver alloy, nickel alloy, copper alloy, tin alloy and aluminum alloy, The conductive adhesive according to any one of claims 1 to 4. Including a resin substrate having a conductive portion and a semiconductor element having an electrode portion;
A semiconductor device, wherein the conductive part of the resin substrate and the electrode part of the semiconductor element are bonded to each other by the cured product of the conductive adhesive according to claim 1.   The semiconductor device according to claim 6, wherein the conductive portion of the resin substrate is nickel, aluminum, copper, or tin. Including a lid that is an electromagnetic wave shielding material for an IC chip, and a resin substrate on which a metal electrode for grounding is formed,
A semiconductor device in which the lid is bonded to the metal electrode and / or the resin substrate with the cured product of the conductive adhesive according to claim 1.   The semiconductor device according to claim 8, wherein the lid has nickel, aluminum, copper, or tin at least on a surface thereof.