JP2005248047A - Conductive resin composition, preparation method therefor, and electrical/electronic component using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a conductive resin composition wherein mechanical bondability, strength, or the like are improved without deteriorating conductivity or electrical connection reliability. <P>SOLUTION: The conductive resin composition contains (A) a resin component, (B) a conductive filler, and (C) an organic solvent as essential components, wherein (A) the resin component has repeating units of formula (1) (wherein R<SB>1</SB>is a bivalent group having an organosiloxane backbone; R<SB>2</SB>is a tetravalent aromatic or aliphatic group; R<SB>3</SB>and R<SB>4</SB>are each hydrogen or a monovalent group having a vinyl or (meth)acrylic group at its end; and (n) and (m) are each a positive number). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a conductive resin composition, a method for producing the same, and an electric / electronic component using the same.

  In the field of electrical and electronic parts, conductive resin compositions in which conductive fillers such as metal powders are blended into resin to provide conductivity are used to form electrodes and connect electrodes to conductors such as external leads. It is used for etc. For example, in a vibrator device, an adhesive made of a conductive resin composition is used for electrical connection and mechanical joining between an electrode of a piezoelectric element and a lead conductor. In the solid electrolytic capacitor, a conductive resin composition is used for forming the cathode layer.

  The vibrator device is manufactured, for example, by connecting a metal electrode of a piezoelectric element to a lead conductor of a cover plate, and covering the cover plate with a cover and sealing. Since it is necessary to mechanically couple the metal electrode of the piezoelectric element and the lead conductor while maintaining conduction, a conductive adhesive made of a conductive resin composition is used for these connections. The solid electrolytic capacitor has a configuration in which a dielectric layer is formed on an anode body made of metal, for example, and a semiconductor layer, a carbon layer, and a cathode layer are formed on the dielectric layer. In such a solid electrolytic capacitor, a cathode layer formed of a conductive resin composition is bonded and fixed to a cathode lead frame. The cathode layer functions as an electrical connection layer and a mechanical bonding layer with the cathode lead frame.

  As the conductive resin composition used as the above-described electrode forming material, conductive adhesive, or the like, for example, an epoxy resin is used as a base resin (binder resin), and silver powder or the like is blended therein. However, the conductive resin composition using the epoxy resin has such problems as large volume shrinkage at the time of curing, high hardness, coating film thickness uniformity (leveling property) and inferior heat resistance. Invite the following problems. For example, when a high-frequency thin piezoelectric element is applied to a vibrator device, the piezoelectric element cracks due to large volume shrinkage when the epoxy resin conductive adhesive is cured, Since the hardness is high, there is a problem that an oscillation failure tends to occur in the drop test of the vibrator device.

  In addition, since the epoxy resin-based conductive resin composition has low leveling properties, there is a problem that the shape of the cathode layer of the solid electrolytic capacitor tends to be non-uniform. Specifically, the surface portion of the cathode layer becomes thick and the corner portion tends to become thin. When the outer peripheral surface of a solid electrolytic capacitor having a cathode layer having such a shape is coated with an exterior resin, the thickness of the exterior resin layer varies, so that the volume of the exterior resin layer changes when a thermal load is applied to the capacitor. It becomes uneven. This becomes a factor which gives stress to each layer inside the capacitor, and the solid electrolytic capacitor is likely to fail. Furthermore, since the thickness of the exterior resin layer is set with reference to the thickest portion of the cathode layer, the non-uniformity of the thickness of the cathode layer hinders the downsizing and thinning of the solid electrolytic capacitor.

In order to improve the leveling property, low heat resistance, volume shrinkage, and the like of the conductive resin composition described above, a polyimide resin, a polyamideimide resin, or the like is applied to the binder resin of the conductive resin composition. However, since electrode layers and adhesive layers using these resins generally become brittle, they are peeled off, for example, between the cathode layer and cathode lead frame of a solid electrolytic capacitor or between the metal electrode and lead conductor of a vibrator device. Etc. are likely to occur. Furthermore, a conductive resin composition using a resin in which a siloxane chain (—Si—O—) is introduced into a polyamide skeleton, a polyamideimide skeleton, or the like as a binder resin (see, for example, Patent Documents 1 and 2) has also been proposed. Sufficient adhesion, low hardness, etc. are not necessarily obtained. In addition, although patent document 3 describes the resin which introduce | transduced the siloxane chain into the polyimide frame | skeleton, the compatibility to the conductive resin composition of such resin is not fully examined.
JP-A-61-116517 JP-A-6-136300 JP 2002-332305 A

  As described above, conventional conductive resin compositions are inferior in coating thickness uniformity, large volume shrinkage during curing, low strength and heat resistance after curing, and adhesion to metal electrodes, lead conductors, etc. Cannot be raised sufficiently. Furthermore, in order to achieve higher performance and smaller and thinner electrical and electronic components such as vibrator devices and solid electrolytic capacitors, conductive resin compositions have improved mechanical bondability. Therefore, there is a demand for improving electrical conductivity and electrical connection reliability.

  The present invention has been made in order to cope with such problems, and has made it possible to improve mechanical bondability, strength, and the like without deteriorating conductivity and electrical connection reliability. It aims at providing the resin composition and its manufacturing method, and also the conductive resin composition which improved the uniformity of coating film thickness, volume shrinkage at the time of hardening, etc., and its manufacturing method. Furthermore, it aims at providing the electrical / electronic component which improved the characteristic, reliability, etc. by using such a conductive resin composition.

で表される繰返し単位を有する樹脂成分と、（Ｂ）導電性充填剤と、（Ｃ）有機溶剤とを必須成分として含有することを特徴としている。 The conductive resin composition of the present invention comprises (A)

It contains the resin component which has a repeating unit represented by (B), an electroconductive filler, and (C) the organic solvent as an essential component.

で表される繰返し単位を有する樹脂成分を作製する工程と、前記樹脂成分を導電性充填剤および有機溶剤と混合して導電性樹脂組成物を作製する工程とを具備することを特徴としている。 The method for producing a conductive resin composition of the present invention comprises an esterification reaction of an aromatic or aliphatic tetracarboxylic acid or a dianhydride thereof with a hydroxy compound having a vinyl group or a (meth) acryl group, A step of subjecting the esterification reaction product, a tetracarboxylic acid or a dianhydride thereof, and a diamine having an organosiloxane skeleton to a polycondensation reaction under the addition of a dehydration condensing agent; and a part of the polycondensation reaction product. A step of imidizing and purifying a polycondensation reaction product obtained by imidizing the part,

And a step of preparing a conductive resin composition by mixing the resin component with a conductive filler and an organic solvent.

  A first electric / electronic component according to the present invention includes a component main body having an electrode, and a conductor bonded to the electrode through the cured product of the conductive resin composition of the present invention described above. Yes. The second electrical / electronic component according to the present invention comprises a component body having an electrode made of a cured product of the conductive resin composition of the present invention described above, and a conductor bonded to the electrode. It is said.

  According to the conductive resin composition of the present invention, based on the characteristics of the resin component that functions as the binder resin of the conductive filler, the electrical conductivity of the connection portion and the electrical connection reliability are improved, and mechanical bonding is performed. It is possible to improve properties and strength. Furthermore, uniformity of the coating thickness, volume shrinkage at the time of curing, and the like can be improved. According to the electrical / electronic component having the electrode and the conductor connected using such a conductive resin composition, and the electrical / electronic component having the electrode formed using the conductive resin composition, characteristics, reliability, etc. Can be improved.

で表される繰返し単位を有するものである。 Hereinafter, modes for carrying out the present invention will be described. The conductive resin composition according to an embodiment of the present invention contains (A) a resin component, (B) a conductive filler, and (C) a solvent as essential components. Among these essential components, the resin component that becomes the binder resin of the component (A)

It has a repeating unit represented by these.

In the component (A) having the repeating unit represented by the above formula (1), the R ₁ group is a divalent group having an organosiloxane structure represented by the following formula (2), for example.

In the above formula (2), the R ₅ group is a divalent organic group, and specific examples include an unsubstituted or substituted alkylene group having 1 to 5 carbon atoms, a phenylene group, and an alkyl-substituted phenylene group. . The R ₆ group is a monovalent organic group, and specific examples include an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, a phenyl group, and an alkyl-substituted phenyl group. It is preferable to apply a group, an alkyl-substituted phenyl group. Such R ₁ groups (silicone resin portion) is one that results in the (A) improvement in the adhesion to various substrates of the components of the binder resin, flexible grant like.

The R ₂ group in the formula (1) is an aromatic or aliphatic tetravalent group. For example, the tetravalent organic group represented by the following formulas (3) to (8) derived from an aromatic acid: And tetravalent organic groups represented by the following formula (9) derived from aliphatic acids.

Among the tetravalent organic groups described above, it is preferable to apply a tetravalent organic group derived from an aromatic acid as the R ₂ group, and further —O— represented by the formulas (5) to (8), A tetravalent organic group containing —CO—, —SO ₂ —, —C (CF ₃ ) ₂ — is more preferably used. These R ₂ groups are introduced based on aromatic tetracarboxylic acids, aliphatic tetracarboxylic acids, or dianhydrides thereof described later.

In the formula (1), the R ₃ group and the R ₄ group are hydrogen or a monovalent group having a vinyl group or a (meth) acrylic group at the end, and an ester component is bonded to the acid component forming the R ₂ skeleton. It is introduced by this. Examples of the R ₃ group and the R ₄ group include a vinyl group, a (meth) acryl group, and an organic group having these groups, and a part thereof may be a hydrogen group.

The binder resin of component (A) described above is a polyamic acid silicone resin part (n amount) having (a) a silicone resin component (R ₁ ) and a polyamic acid component containing a COOR ₃ (R ₄ ) group that is not imidized. Resin part) and (b) a polyimide silicone resin part (m amount of resin part) having a silicone resin component (R ₁ ) and a polyimide resin component. Thus, without imidating a part of the polyamic acid, the reactive group (COOR ₃ (R ₄ ) group or the like) is left as the (a) polyamic acid silicone resin portion, thereby allowing the metal of the conductive resin composition to remain. Adhesiveness to electrodes, lead conductors, etc. can be enhanced.

  Furthermore, the binder resin of component (A) is based on (b) the polyimide silicone resin part, and has properties such as excellent coating thickness uniformity and small volume shrinkage during curing. Furthermore, based on (b) the polyimide silicone resin portion and the cured (a) polyamic acid silicone resin portion, a cured product having excellent coating strength, flexibility, hardness maintenance ability, heat resistance, and the like can be obtained. At the same time, the electrical conductivity and the reliability of electrical connection can be improved. These provide good characteristics when the conductive resin composition is applied to, for example, a conductive adhesive between an electrode and a conductor in various electric / electronic parts, an electrode forming material having adhesiveness, and the like.

  In the ratio of the (a) polyamic acid silicone resin part and the (b) polyimide silicone resin part in the component (A), for example, n and m in the formula (1) satisfy a ratio of n / (n + m) = 0.1 to 0.9. It is preferable to set it as a component ratio. That is, the component (A) preferably contains (a) the polyamic acid silicone resin part in the range of 10 to 90 mol%. (A) When the ratio of the polyamic acid silicone resin part is less than 10 mol%, the adhesiveness of the conductive resin composition cannot be sufficiently increased, and the strength of the cured product is insufficient. On the other hand, when the ratio of the (a) polyamic acid silicone resin part exceeds 90 mol%, the heat resistance and flexibility of the cured product are lowered, and volume shrinkage during curing tends to be large. (A) The ratio of the polyamic acid silicone resin part is more preferably in the range of 30 to 70 mol%.

  As the conductive filler of the component (B) in the conductive resin composition of this embodiment, for example, metallic powder such as silver powder, silver-coated copper powder having a silver layer on the surface, copper powder, nickel powder, etc. A powder is mentioned, These can be used individually or in mixture of 2 or more types. Among the above-mentioned metallic powders, it is desirable to use a conductive filler containing silver such as silver powder or silver-coated copper powder. The shape of the conductive filler is not particularly limited, but it is preferable to use a powder having an average particle size of 20 μm or less. When the average particle diameter of the conductive filler exceeds 20 μm, the dispersibility of the component (A) in the binder resin decreases, and the workability when applying the conductive resin composition decreases. The average particle size of the conductive filler is more preferably in the range of 0.5 to 10 μm.

  The blending amount of the conductive filler of the component (B) described above is, for example, 60 to 99% by mass based on the total amount of the solid content of the binder resin of the component (A) and the conductive filler of the component (B). It is preferable to be in the range. When the blending amount of the conductive filler is less than 60% by mass with respect to the total amount of the component (A) and the component (B), sufficient conductivity may not be imparted to the conductive resin composition. . Thereby, the electrical connection reliability by the electrode formed using the conductive resin composition, or the electrical connection reliability between the metal electrode joined using the conductive resin composition and the conductor is impaired. On the other hand, when the blending amount of the conductive filler exceeds 99% by mass with respect to the total amount of the component (A) and the component (B), the coating property of the conductive resin composition, the uniformity of the coating film, and the like decrease. . The blending amount of the conductive filler is more preferably in the range of 75 to 90% by mass with respect to the total amount of the component (A) and the component (B).

  The organic solvent of component (C) dilutes the conductive resin composition and imparts coating workability and the like. The blending amount of the component (C) is appropriately set according to the desired application work viscosity and the like, and is not particularly limited, but is generally 100 parts by weight of the binder resin of the component (A). It is preferable to set it as the range of 30-300 mass parts with respect to this. Specific examples of the organic solvent used as the diluent include dioxane, hexane, toluene, methyl cellosolve, cyclohexanone, cyclopentanone, butyl cellosolve, butyl cellosolve acetate, butyl carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, n-methyl Examples include pyrrolidone, dimethylformamide, dimethylacetamide and the like, and these are used alone or in admixture of two or more.

  In addition to the essential components (A) to (C) described above, other resin components and additives may be blended in the conductive resin composition of this embodiment as necessary. Examples of other resin components blended in the conductive resin composition include melamine resin, epoxy resin, acrylic resin, polybutadiene resin, and silicone resin. Other additives include inorganic fillers such as silica and alumina, cross-linking agents, curing accelerators (curing catalysts), leveling agents, antifoaming agents, surface treatment agents such as silane coupling agents, and the like. These other resin components and additives can be blended as long as the effects of the present invention are not impaired.

  Next, the manufacturing method of the conductive resin composition of embodiment mentioned above is demonstrated. First, the manufacturing process of the binder resin (A) will be described.

That is, an aromatic or aliphatic tetracarboxylic acid or its dianhydride to form a first R2 skeleton, and a hydroxy compound to introduce the R ₃ and R ₄ groups esterification reaction. Examples of the acid component that is one starting material of the esterification reaction include pyromellitic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. 3,4,3 ′, 4′-benzophenone tetracarboxylic acid, 3,4,3 ′, 4′-diphenyl ether tetracarboxylic acid, 3,4,3 ′, 4′-diphenylsulfone tetracarboxylic acid, bis (1 , 1-trifluoromethyl) diphenylmethane-3,4,3 ', 4'-tetracarboxylic acid and other aromatic tetracarboxylic acids and their dianhydrides, such as cyclohexane-1,2,4,5-tetracarboxylic acid Aliphatic tetracarboxylic acids and their dianhydrides are used.

Among the acid components as described above, in particular, aromatic tetracarboxylic acids represented by the following formulas (10) to (13) and dianhydrides thereof, that is, —O—, —CO—, —SO ₂ —, — It is preferable to use an aromatic tetracarboxylic acid containing C (CF ₃ ) ₂ — and its dianhydride.

  Examples of the hydroxy compound that is the other starting material for the esterification reaction include alcohols having a vinyl group or (meth) acrylic group such as vinyl alcohol, hydroxyethyl (meth) acrylate, hydroxymethyl (meth) acrylate, pentaerythritol triacrylate, etc. Is used. These can be used alone or in admixture of two or more. The esterification reaction is preferably carried out using an aprotic polar solvent such as N-methyl-2-pyrrolidone suitable for the synthesis of the polyimide precursor as a reaction solvent. Furthermore, in order to perform esterification reaction smoothly, it is preferable to make it react at normal temperature in presence of basic catalysts, such as a triethylamine, a pyridine, and a triethanolamine. The basic catalyst is preferably used in a range of 1.5 to 3 moles, more preferably in a range of 2 to 2.5 moles, relative to the acid component.

で表されるジアミノシロキサンが挙げられる。 Next, the above-mentioned esterification reaction product (ester compound), tetracarboxylic acid or a dianhydride thereof, and a diamine having an organosiloxane skeleton are subjected to a polycondensation reaction under the addition of a dehydrating condensing agent. As the diamine having an organosiloxane skeleton used here,

The diaminosiloxane represented by these is mentioned.

Above (14) R ₅ groups and R ₆ groups in the formula is the same as R ₅ groups and R ₆ groups in the aforementioned (2). Specific examples of such diaminosiloxane include TSL-9306 (trade name) manufactured by GE Toshiba Silicone Co., Ltd., KF-8101 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. The addition amount of diaminosiloxane is preferably equimolar to the total amount of the ester compound and tetracarboxylic acid or dianhydride thereof, but it is used in the range of 0.5 to 2 times the molar amount depending on the purpose of use, final viscosity, molecular weight, etc. can do. Moreover, in addition to diaminosiloxane, you may use together aromatic diamine and aliphatic diamine as a diamine component.

  The polycondensation of the esterification reaction product, tetracarboxylic acid or its dianhydride, and a diamine having an organosiloxane skeleton includes (1) an acid chloride method using thionyl chloride or the like, and (2) dicyclohexylcarbodiimide. Direct polycondensation method using carbodiimides as representative dehydration condensation agents, (3) In place of carbodiimides, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate, diphenyl (2,3- And a polycondensation method using at least one selected from dihydro-2-thioxo-3-benzothiazole) phosphonate and derivatives thereof as a dehydrating condensing agent.

  Among these polycondensation methods, (1) the acid chloride method causes the liberated chloro ions to reduce the reliability of electrical and electronic parts, so it is necessary to thoroughly wash with pure water after polycondensation. is there. Moreover, even if it is sufficiently washed with pure water, a slight amount of residual ions may have an adverse effect. (2) Carbodiimides used as a dehydration condensing agent in the direct polycondensation method have drawbacks such as side reactions, gelling of polyimide precursors, and toxicity themselves, and by-products As a result, it is difficult to completely remove urea. Therefore, it must be used by cooling the reaction system, adding the dehydrating condensing agent in several portions, breaking the molar balance of the acid component and the diamine component, or the like.

  Compared to the above (1) acid chloride method and (2) direct polycondensation method, (3) diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate, diphenyl (2,3-dihydro- The polycondensation method using at least one selected from 2-thioxo-3-benzothiazole) phosphonate and derivatives thereof as a dehydrating condensing agent is capable of stably polycondensing an acid component and a diamine component under mild conditions. Furthermore, it has characteristics such as low toxicity of by-products and free of ionic impurities. For this reason, it is preferable to apply the polycondensation method (3) to the production of the binder resin of the conductive resin composition mainly used for electric / electronic parts. The dehydrating condensing agent in the polycondensation method of (3) is preferably used in a range of 1 to 3 moles relative to the total amount of the esterification reaction product and tetracarboxylic acid or its dianhydride, more preferably It is in the range of 2 to 2.5 moles.

  In addition, polycondensation of the esterification reaction product with tetracarboxylic acid or its dianhydride and a diamine having an organosiloxane skeleton includes, for example, N-methylpyrrolidone, N, N′-dimethylacetamide, N, N′-dimethylformamide. It is preferable to use an aprotic polar solvent such as cyclohexanone or cyclopentanone as a polymerization solvent. The above polymerization solvents can be used alone or in admixture of two or more.

Next, a part of the polycondensation reaction product obtained in the above polycondensation step is imidized. The imidization step is performed by applying a general dehydration ring closure reaction of polyamic acid by heating, a dehydration ring closure reaction using an acetic anhydride / pyridine mixed solution, or the like. At this time, by controlling the reaction temperature, reaction time, etc., only a part of the polycondensation reaction product is imidized, and the resin part ((a) polyamic acid silicone having a reactive group such as a COOR ₃ (R ₄ ) group) Resin part) remains. As a result, a binder resin excellent in adhesiveness and the like can be obtained.

  The slurry-like polycondensation reaction product partially imidized in this way is purified by stirring and washing in a poor solvent such as methanol, ethanol, isopropyl alcohol and water. For example, by drying the purified product under reduced pressure, a resin having the repeating unit represented by the above-described formula (1), that is, a binder resin of component (A) is obtained. And the binder resin of (A) component obtained in this way is mixed with the conductive filler of (B) component, and the organic solvent of (C) component, and the target conductive resin composition is produced.

  The conductive resin composition is prepared by thoroughly mixing the above-described essential components (A) to (C) and optional components as necessary, and further kneading with a disperser, a kneader, a three-roll mill, etc. It can be obtained by defoaming. Curing of such a conductive resin composition is usually carried out by heating at 100 to 200 ° C. for about 5 to 45 minutes using a high temperature bath. The conductive resin composition can be easily cured by such heat treatment. Such a conductive resin composition is effectively used as an electrode forming material, a conductive adhesive or the like.

  The electrical / electronic component of the present invention uses the above-described conductive resin composition as an electrode forming material, a conductive adhesive, or the like, and the electrode provided on the component body and the lead conductor are connected to the conductive resin. Examples include electric / electronic components bonded through a cured product of the composition, and electric / electronic components formed by forming the electrode of the component body with a cured product of a conductive resin composition and bonding the electrode to a lead conductor or the like. . Specific examples of such electric / electronic components include, for example, a vibrator device and a solid electrolytic capacitor, but are not limited thereto. For example, electrical connection and mechanical joining are required at the same time. The present invention can be applied to various electric / electronic parts having parts.

  A vibrator device as an embodiment of the electric / electronic component of the present invention includes a piezoelectric element having a metal electrode. The piezoelectric element includes, for example, a crystal of crystal or ceramic formed into a predetermined shape. These sizes and shapes are not particularly limited, but generally those having a thickness of about 80 μm to those having a thickness of about 350 μm are used. The metal electrode of the piezoelectric element is connected to the lead conductor of the cover plate. These metal electrodes and the lead conductor are connected using the conductive resin composition of the above-described embodiment as a conductive adhesive. Furthermore, the vibrator device is configured by covering the lid plate with a cover and sealing. According to such a configuration, since the change in hardness of the conductive adhesive used for bonding the metal electrode and the lead conductor is small and high adhesive strength and flexibility are obtained, the bonding reliability is excellent and the length is long. A vibrator device that can maintain characteristics over a period of time can be provided.

  A solid electrolytic capacitor as an embodiment of the electric / electronic component of the present invention includes an anode body made of a metal such as tantalum, aluminum, niobium, and the like, and a dielectric formed on the anode body. With layers. For example, a semiconductor layer, a carbon layer, and a cathode layer are sequentially formed on the dielectric layer. A cathode layer consists of hardened | cured material of the conductive resin composition of embodiment mentioned above. The cathode layer made of such an adhesive resin layer is bonded and fixed to the cathode lead frame. Furthermore, a solid electrolytic capacitor is formed by covering these outer peripheral surfaces with an exterior resin. According to such a configuration, the conductive resin composition forming the cathode layer is excellent in leveling property, adhesiveness, conductivity, etc., so that it is possible to reduce the size and thickness, and improve the bonding reliability and various characteristics. It is possible to provide a solid electrolytic capacitor that achieves the above.

  Next, specific examples of the present invention and evaluation results thereof will be described. However, the present invention is not limited to these examples.

Example 1
First, 1 liter of N-methyl-2-pyrrolidone was charged into a reaction flask equipped with a nitrogen introduction tube, and 1 mol of benzophenone tetracarboxylic dianhydride and 1.1 mol of hydroxyethyl methacrylate were added and stirred. Subsequently, 1.1 mol of triethylamine was added dropwise over 30 minutes, and the mixture was left in that state for 3 hours. Next, 1 mol of TSL-9306 (trade name, manufactured by GE Toshiba Silicone Co., Ltd.) was added as a diaminosiloxane and stirred for 30 minutes, and then diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate 2.1. Mole was added in 5 portions, and a polycondensation reaction was carried out in that state for 5 hours. The obtained slurry mixture was poured into a large amount of methanol and washed, and the obtained solid resin was dried for 12 hours by a vacuum dryer.

  30 g of the resin component thus obtained (resin component represented by the above formula (1) / n = about 50 mol%) was dissolved in 70 g of cyclohexanone, and the resulting slurry was filtered through a 1 μm mesh. did. To 40 parts by mass (solid content = 50% by mass) of the obtained resin slurry, 68 parts by mass of silver powder having a particle size of 1 to 5 μm, 1 part by mass of a thickener and 1 part by mass of an antifoaming agent are added and mixed thoroughly Further, the intended conductive adhesive was produced by kneading with three rolls.

Comparative Example 1
First, 35 parts by mass of Death Module BL1100 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd.) and 5 parts by mass of Nippon Run 800 (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) were mixed. By adding 227 parts by mass of silver powder having a particle diameter of 1 to 5 μm, 2 parts by mass of a thickener, and 3 parts by mass of an antifoaming agent to this mixture and mixing them well, the mixture is further kneaded with three rolls. A conductive adhesive was prepared.

  The characteristics of each conductive adhesive according to Example 1 and Comparative Example 1 described above were measured and evaluated as follows. First, a conductive adhesive was applied on a slide glass to a width of 5 mm and a thickness of 10 μm, and the volume resistivity after curing of this coating film was measured. Furthermore, the pencil hardness of this coating film was measured according to JIS K5600-5-4. Further, after applying a conductive adhesive to a silver-plated copper frame, a 2 mm square silicon chip was mounted, and the adhesive strength in the shear direction was measured after the coating film was cured. These volume resistivity, pencil hardness, and adhesive strength were measured after the coating film was cured and after applying a heat load at 150 ° C. for 300 hours. These measurement results are shown in Table 1.

  As is apparent from Table 1, since the conductive adhesive of Comparative Example 1 uses rubber urethane as the binder resin, although the hardness at the initial stage of curing is low, the hardness change after applying a heat load is large, and the adhesive is bonded. The strength was also low. Along with these, the characteristic values also changed greatly. Such a change in the adhesive layer is considered to cause stress on the piezoelectric element and lead to failure of the vibrator device. On the other hand, the conductive adhesive of Example 1 is excellent in adhesive strength while having flexibility, and the hardness change after applying a heat load is small. By using such a conductive adhesive for fixing the piezoelectric element of the vibrator device, it is possible to provide a vibrator device that has excellent bonding reliability and can maintain characteristics over a long period of time.

Example 2
In the same manner as in Example 1, the resin component (n = about 50 mol%) represented by the above formula (1) was produced. 30 g of this resin component was dissolved in 70 g of cyclohexanone, and the resulting slurry was filtered through a 1 μm mesh. 100 parts by mass (solid content = 50% by mass) of the obtained resin slurry, 50 parts by mass of melamine resin / Uban (trade name, manufactured by Mitsui Cymek), 600 parts by mass of silver powder having a scale shape of 3 to 10 μm Then, 150 parts by mass of cyclohexanone was added and mixed well, and further kneaded with a disperse to produce the intended conductive paint.

Comparative Example 2
24 parts by mass of epoxy resin / epitaxial coat 1004 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), 6 parts by mass of phenol resin / markalinker M (trade name, manufactured by Maruzen Petrochemical Co., Ltd.), 120 parts by mass of butyl cellosolve acetate Was dissolved and mixed in a heated flask, 170 parts by mass of silver powder was added and mixed well, and further kneaded with a disperse to prepare the intended conductive paint.

Comparative Example 3
By thoroughly mixing 100 parts by mass of polyamideimide resin HR-13NX (trade name, manufactured by Toyobo Co., Ltd.), 150 parts by mass of N-methylpyrrolidone and 180 parts by mass of silver powder, and further kneading with a disperse, The intended conductive paint was prepared.

  The characteristics of each conductive paint according to Example 2 and Comparative Examples 2 to 3 described above were measured and evaluated as follows. First, a conductive paint was dip-coated on a 5 mm square cube. After hardening this coating film, the cross section was observed with an electron microscope, and the film thickness of the surface part and the corner part was measured. Further, after applying a conductive adhesive to a silver-plated copper frame, a 2 mm square silicon chip was mounted, and the adhesive strength in the shear direction was measured after the coating film was cured. In addition, a solid electrolytic capacitor was produced using conductive paint, and the characteristics of the capacitor's capacitance, tan δ, equivalent series resistance, and impedance were measured with an LCR meter (measurement frequency: 1.0 kH, measurement signal level: 1.0 V). It measured using. These measurement results are shown in Table 2.

  As can be seen from Table 2, the conductive paint of Comparative Example 2 uses a phenol curable epoxy resin as the binder resin, and thus it can be seen that there is a large variation in the coating thickness. Moreover, since the conductive paint of Comparative Example 3 uses polyamideimide resin as the binder resin, the adhesive strength is low and the capacitor characteristics are also inferior. In contrast, the conductive paint of Example 2 is excellent in leveling properties and conductivity, and has high capacitor characteristics and coating strength. By forming the cathode layer of the solid electrolytic capacitor using such a conductive paint, it is possible to provide a solid electrolytic capacitor having excellent bonding reliability and characteristics.

Claims (8)

(A)

A conductive resin composition comprising a resin component having a repeating unit represented by formula (B), a conductive filler, and (C) an organic solvent as essential components.   2. The conductive resin composition according to claim 1, wherein n and m in the formula (1) are numbers satisfying a ratio of n / (n + m) in the range of 0.1 to 0.9. _3. The conductive resin according to claim 1, wherein R _{2 in the} formula (1) contains —O—, —CO—, —SO ₂ —, or —C (CF ₃ ) ₂ —. Composition.   The conductive filler of the component (B) is contained in a range of 60 to 99% by mass with respect to the total amount of the solid content of the resin component of the component (A) and the component (B). The conductive resin composition according to any one of claims 1 to 3. An esterification reaction of an aromatic or aliphatic tetracarboxylic acid or a dianhydride thereof with a hydroxy compound having a vinyl group or a (meth) acryl group;
A step of subjecting the esterification reaction product, a tetracarboxylic acid or a dianhydride thereof, and a diamine having an organosiloxane skeleton to a polycondensation reaction under the addition of a dehydrating condensing agent;
Imidating a part of the polycondensation reaction product;
Purifying the polycondensation reaction product imidized partly,

Producing a resin component having a repeating unit represented by:
A process for producing a conductive resin composition by mixing the resin component with a conductive filler and an organic solvent.   The dehydrating condensing agent is selected from diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate, diphenyl (2,3-dihydro-2-thioxo-3-benzothiazole) phosphonate, and derivatives thereof. The method for producing a conductive resin composition according to claim 5, wherein at least one compound is used. A component body having electrodes;
An electrical / electronic component comprising: a conductor bonded to the electrode through a cured product of the conductive resin composition according to any one of claims 1 to 4. A component main body having an electrode made of a cured product of the conductive resin composition according to any one of claims 1 to 4,
An electrical / electronic component comprising: a conductor bonded to the electrode.