KR100616368B1 - Electroconductive resin composition and electronic parts using the same - Google Patents

Abstract

A conductive powder (A1) containing silver plated copper powder (a1) having an aspect ratio of 1 to 20 and a silver powder, a thermoplastic resin (B1) having at least one functional group selected from the group consisting of an amide group, an ester group, an imide group and an ether group; , Conductive resin composition containing organic solvent (C); A conductive resin composition comprising a silver-plated copper powder (a2) having a copper exposed portion on a part of the surface and a conductive powder (A2) containing silver powder, the thermoplastic resin (B1), and an organic solvent (C); A conductive resin composition comprising a thermoplastic resin (B2) selected from the group consisting of the conductive powder (A1), a polyamide silicone resin, a polyamideimide silicone resin and a polyimide silicone resin, and an organic solvent (C); And the conductive powder (A2), the thermoplastic resin (B2), and an organic solvent (C).

Description

Conductive Resin Composition and Electronic Component Using Them {ELECTROCONDUCTIVE RESIN COMPOSITION AND ELECTRONIC PARTS USING THE SAME}

The present invention relates to a conductive resin composition and an electronic component using the same.

BACKGROUND OF THE INVENTION In the field of electronic components, it is generally performed to mix a conductive material including a metal with a resin to form a paste resin composition, which is used for forming an electric circuit or an electrode. Silver is the most representative conductive material among them, but when voltage is applied under high humidity conditions, silver is easily ionized, and migration of silver called migration is frequently observed. When migration occurs, a short circuit occurs between the electrodes, which causes a decrease in moisture resistance and reliability in the electronic component.

The addition of nickel powder, palladium powder, or copper powder instead of silver powder and the addition of various additives have been studied, but in all cases, improvement has been required in view of high resistance as an electrode material.

Japanese Patent Laid-Open No. 2-283010 and Japanese Patent Laid-Open No. 6-151261 disclose a prior art relating to migration prevention in a solid electrolytic capacitor.

According to the 1st aspect of this invention, the electroconductive powder (A1) containing silver plating copper powder (a1) and silver powder whose aspect ratio is 1-20, an amide group, ester group, and imide group And a conductive resin composition containing a thermoplastic resin (B1) having at least one functional group selected from the group consisting of an ether group, and an organic solvent (C) (hereinafter referred to as "composition K").

According to the second aspect of the present invention, there is provided a silver-plated copper powder (a2) having a copper exposed portion on a part of the surface thereof, and a conductive powder (A2) containing silver powder, an amide group, an ester group, an imide group and an ether group. A conductive resin composition (hereinafter referred to as "composition L") containing a thermoplastic resin (B1) having one or more selected functional groups and an organic solvent (C) is provided.

According to the third aspect of the present invention, there is provided a silver-plated copper powder (a1) having an aspect ratio of 1 to 20 and an electrically conductive powder (A1) containing silver powder, and polyamide silicon, polyamideimide silicon, and polyimide silicon. A conductive resin composition (hereinafter referred to as "composition M") containing the selected thermoplastic resin (B2) and the organic solvent (C) is provided.

According to the 4th aspect of this invention, the silver-plated copper powder (a2) which has a copper exposed part in a part of surface, and the electroconductive powder (A2) containing silver powder, polyamide silicone, polyamideimide silicone, and polyimide silicone A conductive resin composition (hereinafter referred to as "composition N") containing a thermoplastic resin (B2) selected from the group and an organic solvent (C) is provided.

According to the fifth aspect of the present invention, there is provided an electronic component having a conductor layer formed using the conductive resin composition (compositions K, L, M, N) according to the present invention.

Embodiment of invention

The conductive resin composition according to the present invention is a paste-like resin composition, which is simply referred to as "composition" or "paste" in the following description.

Composition K is a thermoplastic resin (B1) having at least one functional group selected from the group consisting of silver-plated copper powder (a1) having an aspect ratio of 1 to 20 and conductive powder (A1) containing silver powder, an amide group, an ester group, an imide group and an ether group ) And an organic solvent (C). In the case of using a scale-like conductive powder, the coverability of the edge when applied to a member (polyhedron) having a complicated shape is not sufficient, and an increase in electrical resistance and nonuniformity of interfacial resistance occurs, thereby causing the electrical It is easy to produce a defect in a characteristic, and even when sheathed with resin, it may lead to the fall of dimensional accuracy. In particular, when used for the formation of the cathode of a solid electrolytic capacitor using a valve-action metal as the anode, the leakage current LC of the product tends to increase. On the other hand, the composition K has good applicability, shows good conductivity after drying, and the obtained coating film is excellent in stability (migration resistance) and dimensional accuracy (edge covering property) under high temperature and high humidity. Therefore, by using the composition K, it is possible to provide an electronic component having excellent moisture resistance and dimensional accuracy. For example, the composition K is used for forming a cathode to provide a solid electrolyte capacitor having good moisture resistance and low leakage current. can do.

The composition L is a thermoplastic having a silver-plated copper powder (a2) having a copper exposed portion on a part of the surface and a conductive powder (A2) containing silver powder, at least one functional group selected from the group consisting of amide groups, ester groups, imide groups and ether groups It is a composition containing resin (B1) and the organic solvent (C). Currently, the addition of copper powder as the conductive powder is generally performed. In this case, the resistance value is better than that in the case of using nickel powder or palladium powder, but there is a problem in aging stability such that the paste viscosity increases due to oxidation or aggregation of copper powder. In addition, when soldering to a conductive paste containing silver powder, since thermal decomposition of the binder resin is used as a mechanism for soldering, there is a problem that a part of the coating film is missing and bonding is not performed sufficiently. Moreover, the conventional conductive paste using silver powder and copper powder also points out a problem that soldering cannot be applied because oxygen and copper powder in the air and the binder resin react and an oxide film is formed on the surface thereof. On the contrary, the composition L is excellent in aging stability of the paste viscosity and can form a solderable coating film. Therefore, by using the composition L, the electronic component and the solder composition L having excellent solder heat resistance are used for forming the cathode, thereby providing a solid electrolytic capacitor having excellent solder adhesion to the cathode extracting member and excellent solder heat resistance. can do.

The composition M is a thermoplastic resin (B2) selected from the group consisting of silver-plated copper powder (a1) having an aspect ratio of 1 to 20 and conductive powder (A1) containing silver powder, polyamide silicon, polyamideimide silicon, and polyimide silicon, And an organic solvent (C). Conventionally, pastes using thermosetting resins are also widely used, but the resulting coating film has a problem in that the coating film strength and toughness are inferior, and the impact resistance after circuit formation is inferior. Moreover, when this paste is used for the electrode of a solid electrolytic capacitor, since coating film strength and toughness are inferior, there exists a problem that the overvoltage load characteristic is not enough. On the contrary, the composition M can form a dry coating film excellent in coating film strength and toughness, and can provide an electronic component such as a solid electrolytic capacitor, which is particularly excellent in overvoltage load characteristics.

Composition N is a thermoplastic resin (B2) selected from the group consisting of silver-plated copper powder (a2) having a copper-exposed portion on a part of the surface, and conductive powder (A2) containing silver powder, polyamide silicon, polyamideimide silicon, and polyimide silicon. ), And an organic solvent (C). In the case of a paste using a thermosetting resin as a binder, the resulting coating film is inferior in flexibility, and in the case of forming circuits on the flexible substrate, if the bending rate is large, cracks are generated in the coating film and the circuit is disconnected. There is a problem that this happens. On the other hand, the composition N can form the dry coating film excellent in flexible property, and can use it, and can provide electronic components, such as a solid electrolytic capacitor, which was especially excellent in thermal shock.

In the composition K and the composition M, the silver-plated copper powder (a1) whose aspect ratio is 1-20, and the electroconductive powder (A1) containing silver powder are used. This aspect ratio means the ratio (long diameter / short diameter) of the long diameter and short diameter of the particle | grains of silver plating copper powder. In the present invention, the silver-plated copper powder particles are mixed well in a curable resin having a low viscosity, the particles are allowed to settle, the particles are cured, the resin is cured, the obtained cured product is cut in the vertical direction, and the particles appear on the cut surface. A shape is magnified and observed with a microscope, and the long diameter / short diameter of each particle is calculated | required about at least 100 particle | grains, and it is set as an aspect ratio with these average values. Here, the short diameter is a distance between two parallel lines which are selected to interpose particles with the two parallel lines which are in contact with the outside of the particles with respect to the particles shown on the cut surface, and which are the shortest intervals among those combinations. On the other hand, a long diameter is two parallel lines orthogonal to the parallel line which determines the said short diameter, and is the distance of the two parallel lines which become the longest interval among the combination of two parallel lines which contact | connect the outer side of particle | grains. The rectangle formed by these four lines becomes the size which a particle fills in the center exactly. The specific method performed in the present invention will be described later.

Silver-plated copper powder a1 means the electroconductive powder which coat | covered silver on one part or all part of the surface of copper powder. This is obtained by, for example, coating the atomized copper powder with silver by a method such as substitution plating, electroplating or electroless plating. It is preferable to coat | cover with a substitution plating method from the thing with the high adhesive force of copper powder and silver, and the low running cost.

In the composition K, the coating amount of silver of the silver-plated copper powder (a1) is not particularly limited, but in consideration of conductivity and migration resistance, 0.5 to 50 parts by weight is preferable, and 1.0 to 35 parts by weight based on 100 parts by weight of copper. More preferably, 1.5-25 weight part is further more preferable. As for the aspect ratio of silver plating copper powder a1, 1-20 are chosen from a viewpoint of the applicability | paintability of a paste. If the aspect ratio exceeds 20, the applicability of the paste is deteriorated. In particular, when used for the cathode of the solid electrolytic capacitor, the edge cover property of the device is low, which may lead to an increase in leakage current. In consideration of the conductivity of the coating film, the aspect ratio is preferably from 1.5 to 18, more preferably from 2.5 to 12, and the average particle diameter of the silver-plated copper powder (a1) is the dispersibility of the paste, the leveling property, the edge cover property, and the film. In consideration of conductivity, 0.2 µm to 20 µm are preferable, 1 µm to 12 µm is more preferable, and 1.5 µm to 8 µm are further preferred. If the average particle diameter is less than 0.2 µm, the paste tends to aggregate, and if it exceeds 20 µm, the edge cover property and resistance tend to decrease. This average particle diameter can be measured by a laser scattering flow distribution measuring device.

In composition M, 1-20 are chosen as the aspect ratio of silver plating copper powder (a1). If the aspect ratio exceeds 20, the applicability of the paste, the strength and toughness of the conductive coating film are lowered, and in particular, when used for the cathode of the solid electrolytic capacitor, the overvoltage load characteristics may deteriorate and cause a decrease in the impedance. . Considering the conductivity of the coating film, the aspect ratio is preferably from 1.5 to 18, more preferably from 2.5 to 12, and the coating amount of silver of the silver-plated copper powder (a1) is not particularly limited, but the conductivity and migration resistance In consideration of this, 0.5 to 50 parts by weight is preferable, more preferably 1.0 to 35 parts by weight, and still more preferably 1.5 to 25 parts by weight with respect to 100 parts by weight of copper. If the coating amount of silver is less than 1 part by weight, the conductivity tends to be low, and if it exceeds 30 parts by weight, the overvoltage load characteristic of the capacitor tends to be lowered. The average particle diameter of the silver-plated copper powder (a1) is preferably 0.2 µm to 20 µm, more preferably 1 µm to 12 µm, more preferably 1.5 µm to 8 in view of the dispersibility, viscosity, workability and conductivity of the coating. Μm is further preferred. If the average particle diameter is less than 0.2 µm, the paste tends to aggregate, and if it exceeds 20 µm, the coating property and the resistance tend to decrease. The average particle diameter can be measured by a laser scattering flow distribution measuring device.

The silver powder contained in the electroconductive powder (A1) is not specifically limited, The thing of the shape, such as a scaly piece, a spherical form, and a lump, which are generally used, can be used. In consideration of conductivity, coatability, and edge cover properties, it is preferable that the particle size be 0.2 µm to 12 µm, more preferably 1 µm to 8 µm, as a scale piece shape and spherical shape.

Although the ratio (weight ratio) of the silver powder of silver-plated copper powder (a1) in electroconductive powder (A1) is not specifically limited, The ratio of silver powder with respect to 100 weight part of silver-plated copper powder (a1) is 25 weight from a viewpoint of the electroconductivity of a coating film. It is preferably 400 parts by weight or less, more preferably 42.8 to 233.3 parts by weight, and even more preferably 66.6 to 150 parts by weight from the viewpoint of leakage current or overvoltage load characteristics of the capacitor.

In the composition L and the composition N, the silver-plated copper powder (a2) which has a copper exposed part in a part of surface, and the electroconductive powder (A2) containing silver powder are used. This silver plating copper powder a2 exposes a part of copper alloy powder (ie, silver plating copper powder), and the surface is coat | covered with silver substantially. When using silver coated on the whole surface without exposing a part of copper of silver plating copper powder, solderability deteriorates in composition L, and thermal shock property deteriorates in composition N. FIG. In addition, silver powder is used in order to improve electroconductivity, and the composition which does not contain silver powder is not suitable for use as a conductor layer.

As copper powder of silver plating copper powder a2, what is arbitrary shape, such as spherical shape, scale shape, lump shape, and crushed shape, can be used, Preferably the atomized copper powder is used. In the silver-plated copper powder (a2), the copper exposed area is preferably 10 to 70% in terms of paste viscosity, time stability, solderability, oxidation of exposed parts, conductivity, thermal shock, and the like, and the range of 10 to 50% is more. Preferably, 10 to 30% of range is further more preferable. The copper exposure area can be obtained from the difference between the surface area of copper powder and the coating area of silver.

Silver-plated copper powder (a2) can be obtained by coat | covering silver with atomized copper powder by methods, such as substitution plating, electroplating, and electroless plating. It is preferable to coat with a substitution plating method because the adhesion between copper powder and silver is high and running costs are low.

The coating amount of silver on the surface of the copper powder is preferably in the range of 5 to 25 parts by weight with respect to 100 parts by weight of copper in terms of time stability of the paste viscosity, solder adhesion, cost, and conductivity improvement, and in the range of 10 to 23 parts by weight. More preferred.

The silver powder contained in the electroconductive powder (A2) is not specifically limited, The thing of the shape, such as the scale piece shape, spherical shape, and lump shape which are generally used, can be used. In consideration of conductivity, coatability, and edge cover properties, it is preferable that the particle size be 0.2 µm to 12 µm, more preferably 1 µm to 8 µm, as a scale piece shape and spherical shape.

Although the mixing ratio of silver plating copper powder (a2) and silver powder is not specifically limited, When electroconductivity is considered, it is preferable that the ratio of silver powder is 25 weight part-266 weight part with respect to 100 weight part of silver plating copper powder (a2), 66 As for a weight part-150 weight part, it is more preferable.

When silver-plated copper powder (a2) has few contact points of powders, the resistance of the coating film obtained will become high easily. In order to increase the contact area between the silver-plated copper powders and to obtain high conductivity, it is preferable to apply a shock to the silver-plated copper powder a2 to deform the shape of the particles into a flat shape. Although the average particle diameter of silver plating copper powder (a2) is not specifically limited, 1-20 micrometers is preferable and 1-10 micrometers is more preferable in consideration of paste applicability | paintability, dispersion stability, etc. The average particle diameter can be measured by a laser scattering flow distribution measuring device.

In the composition K and the composition L, a thermoplastic resin having at least one functional group selected from the group consisting of an amide group, an ester group, an imide group, and an ether group from the viewpoints of adhesiveness, filler dispersibility and solubility in an organic solvent, etc. (B1) is used. This thermoplastic resin (B1) can also be used in combination of multiple types.

Although it does not specifically limit as thermoplastic resin (B1), What has an aromatic ring from a viewpoint of heat resistance etc. is preferable. It is preferable to have an ether bond from a viewpoint of the solubility to the organic solvent (C). For example, polyphenylene etheramide having a phenylene ether (phenylene oxide) bond and an amide bond in the main chain, polyphenylene ether imide having a phenylene ether bond and an imide bond in the main chain, and a phenylene ether bond and an amide in the main chain. Polyphenylene etheramideimide having a bond and imide bond, polyphenyleneamide having a phenylene bond and an amide bond in the main chain, polyphenyleneimide having a phenylene bond and an imide bond in the main chain, and phenylene in the main chain Polyphenylene amideimide having a bond, an amide bond, and an imide bond, a polysilylene amide having a xylylene bond and an amide bond in a main chain, and a polysilylene having a xylylene bond and an imide bond in a main chain The polyxylene amideimide which has a xylylene bond, an amide bond, and an imide bond in a mid | membrane, a principal chain, etc. are mentioned, Any one or more of these can be used preferably. Can be. These may further contain an ester bond, a sulfide bond, etc., and the benzene ring may be substituted by arbitrary substituents.

More specifically, the thermoplastic resin (B1) is more preferably a resin having a repeating unit represented by the following general formula (I) or (II). It is also preferable that it is resin which has both a repeating unit of (I) and a repeating unit of (II).

Formula (I):

Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen, a lower alkyl group, a lower alkoxy group or a halogen atom, and X ¹ represents a single bond, -O-, -S-, -CO-, -SO- _2- , -SO-,

Wherein R ⁵ and R ⁶ each independently represent hydrogen, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group, and Y represents

Wherein Ar ¹ represents an aromatic divalent group, Ar ² represents an aromatic trivalent group, and Ar ³ represents an aromatic tetravalent group.)

Formula (II):

(Wherein R ⁷ , R ⁸ and R ⁹ each independently represent a lower alkyl group, a lower alkoxy group or a halogen atom, s, t and u are each independently an integer of 0 to 4 representing the number of substituents, R ⁷ , When two or more R <^8> and R <^9> couple | bonds, respectively, may be same or different in each, X <^2> and X <^3> respectively independently represent -O- or

Wherein R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group, and Y is as defined in the general formula (I).)

In said general formula (I) and (II), it is preferable that a lower alkyl group and a lower alkoxy group are a C1-C4 alkyl group and a C1-C4 alkoxy group. The phenyl group of R ⁵ , R ⁶ , R ¹⁰ and R ¹¹ in the general formulas (I) and (II) may be unsubstituted or substituted with arbitrary substituents such as methyl group, ethyl group and sulfone group.

As represented by the following general formula (III), the repeating unit represented by the said General formula (1), It is preferable that the benzene ring couple | bonded with each other in 1, 4-position.

The repeating unit represented by the general formula (II) is also preferably the same as those represented by the following general formula (IV), in which benzene rings are bonded to each other at the 1,4-position.

The thermoplastic resin (B1) having the above repeating unit is an acid component (S) described below, that is, an aromatic dicarboxylic acid, an aromatic tricarboxylic acid, an aromatic tetracarboxylic acid, or a reactive acid derivative thereof, and a diamine described below. It can be prepared by reacting. You may use an acid component and diamine in combination of multiple types, respectively.

The repeating units represented by the general formulas (I) and (III) are diamines, for example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl -4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4-aminophenoxy Phenyl] butane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dibromo-4- (4- Aminophenoxy) phenyl] butane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 1,1 -Bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclopentane, bis [4- (4-aminophenoxy) phenyl] Sulfone, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-carbonylbis (p-phenyleneoxy) dianiline, It is preferable to form using 1 or more types, such as 4,4'-bis (4-aminophenoxy) biphenyl. Among these, 2,2-bis [4- (4-aminophenoxy) phenyl] propane is particularly preferable.

The repeating units represented by general formulas (II) and (IV) are diamines such as 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-[1,4-phenyl It is preferable to form using one or more types, such as lenbis (1-methylethylidene)] bisaniline and 3,3 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline. Do.

In addition to the diamines exemplified above, as forming repeating units of general formulas (I), (II), (III), and (IV), 4,4'-diaminodiphenylether, 4,4'-diaminodi Phenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylether, 4,4'-diamino-3,3', 5,5'-tetramethyldiphenylmethane , 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylether, 2,2'-[4,4'-diamino-3,3 ', 5,5'-tetra Methyldiphenyl] propane, metaphenylenediamine, paraphenylenediamine, 3,3'-diaminodiphenylsulfone, piperadine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylenediamine, m- One or more of these may be used in combination, such as xylenediamine, o-xylenediamine, 3-methylheptamethylenediamine, 1,3-bis (3-aminopupil) tetramethyldisiloxane, and the like.

Aromatic dicarboxylic acid is a carboxylic acid which two carboxyl groups couple | bonded with the aromatic ring. The aromatic tricarboxylic acid is a carboxylic acid in which three carboxyl groups are bonded to an aromatic ring, and two of the three carboxyl groups are preferably bonded to adjacent carbon atoms. The aromatic tetracarboxylic acid is a carboxylic acid in which four carboxyl groups are bonded to an aromatic ring, and two of the four carboxyl groups are preferably bonded to adjacent carbon atoms. Here, the aromatic ring may be one in which a hetero atom is introduced (aromatic heterocycle), or the aromatic rings may be bonded via an alkylene group, oxygen, a single bond, a carbonyl group, or the like. Furthermore, these aromatic rings may contain substituents that do not participate in condensation reactions such as alkoxy groups, alkyloxy groups, alkylamino groups, and halogens.

As aromatic dicarboxylic acid, For example, terephthalic acid, isophthalic acid, 4,4'- diphenyl ether dicarboxylic acid, 4,4'- diphenyl sulfone dicarboxylic acid, 4,4'- diphenyl dicarboxylic acid, 1, 5- naphthalenedicarboxylic acid Although etc. are mentioned, terephthalic acid and isophthalic acid are preferable because it is easy to obtain and inexpensive. As a reactive derivative of aromatic dicarboxylic acid, the dihydride, dibromide, diester, etc. of said aromatic dicarboxylic acid are meant.

As aromatic tricarboxylic acid, trimellitic acid, 3,3 ', 4- benzophenone tricarboxylic acid, 2,3,4'- diphenyl tricarboxylic acid, 2,3,6-pyridine tricarboxylic acid, 3,4 , 4'-benzanilidetricarboxylic acid, 1,4,5-naphthalintricarboxylic acid, 2'-chloro-3,4,4'-benzanilidetricarboxylic acid, and the like are preferable. As a reactive derivative of aromatic tricarboxylic acid, it means the acid anhydride, halide, ester, amide, ammonium salt, etc. of said aromatic tricarboxylic acid. Specifically, trimellitic anhydride, trimellitic anhydride monochloride, 1,4-dicarboxy-3-N, N-dimethylcarbamoylbenzene, 1,4-dicarbomethoxy-3-carboxybenzene, 1, 4-dicarboxy-3-carbophenoxybenzene, 2,6-dicarboxy-3-carbomethoxypyridine, 1,6-dicarboxy-5-carbamoylnaphthalin, the aromatic tricarbonates and ammonia, Ammonium salt etc. which consist of dimethylamine, trimethylamine, etc. are mentioned as a suitable example. Among these, trimellitic anhydride and trimellitic anhydride monochloride are preferred because they are readily available and inexpensive.

Examples of the aromatic tetracarboxylic acid include pyromellitic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 1,2,5,6 Naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 3,4,9 , 10-perylenetetracarboxylic acid, 4,4'-sulfonyldiphthalic acid, m-terphenyl-3,3 ", 4,4" -tetracarboxylic acid, p-terphenyl-3,3 ", 4,4 "-Tetracarboxylic acid, 4,4'- oxydiphthalic acid, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3-dicarboxyphenyl) propane, 2,2 -Bis (2,3-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2'- Bis [4- (2,3-dicarboxyphenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2'-bis [4- (3,4-dicarboxy Phenoxy) phenyl] propane and the like are preferred. As a reactive derivative of aromatic tetracarboxylic acid, the acid dianhydride, halide, ester, amide, ammonium salt, etc. of said aromatic tetracarboxylic acid are meant.

The acid component (S) composed of aromatic dicarboxylic acid, aromatic tricarboxylic acid, aromatic tetracarboxylic acid, or reactive derivatives thereof is based on the total amount of diamine in terms of molecular weight, mechanical strength, heat resistance, and the like based on 100 mol% of the total amount of diamine. It is preferable to use 80-120 mol%, and it is especially preferable to use 95-105 mol%.

In the composition M and the composition N, as the binder resin, a thermoplastic resin (B2) selected from polyamide silicone resin, polyamideimide silicone resin and polyimide silicone resin is selected from the viewpoints of improving the heat resistance and low elastic modulus of the coating film formed. Used. This thermoplastic resin (B2) can also be used in combination of multiple types.

Although these thermoplastic resins (B2) are not specifically limited, For example, they are obtained by polycondensing acid components, such as aromatic dicarboxylic acid, aromatic tricarboxylic acid, aromatic tetracarboxylic acid, or their reactive derivatives, and diamine which has diamino silicone as an essential component. Can be.

As diamino silicone, the following general formula (V) is mentioned, for example:

(Wherein Y ¹ represents a divalent hydrocarbon group, Y ² represents a monovalent hydrocarbon group, two Y ¹ may be the same or different from each other, a plurality of Y ² may be the same or different from each other, and m is an integer of 1 or more) .)

It is preferable to use what is represented by.

Examples of the divalent hydrocarbon group represented by Y ¹ include an alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted phenylene group, and the like. Examples of the monovalent hydrocarbon group represented by Y ² include a carbon atom having a number of carbon atoms. The alkyl group which is 1-10, a substituted or unsubstituted phenyl group, etc. are mentioned, It is preferable that m is an integer of 1-100. These diamino silicon can be used individually or in combination of 2 or more types.

There is no restriction | limiting in particular as other diamine which can be used with the said diamino silicon, It is preferable to use aromatic diamine from a viewpoint of heat resistance of resin, the solubility to an organic solvent, and a melt viscosity, and also phenylene in a principal chain Preference is given to using polyphenyleneetherdiamine comprising ether.

Specifically, it is more preferable to use aromatic diamine represented by the following general formula (VI).

Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and X ¹ represents a single bond, -O-, -S-, -CO-, -SO _2- , -SO-,

Wherein R ⁵ and R ⁶ each independently represent hydrogen, a lower alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a trichloromethyl group, or a substituted or unsubstituted phenyl group).

As for the polyphenylene ether diamine of the said general formula (VI), Preferably, it is preferable that the benzene ring couple | bonded with each other in 1, 4-position as represented by following General formula (VII).

As aromatic diamine (e1) which has an ether bond represented by the said General formula (VI), For example, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 2, 2-bis [3-methyl- 4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4-aminophenoxy ) Phenyl] butane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dibromo-4- (4-amino Phenoxy) phenyl] butane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 1,1- Bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclopentane, bis [4- (4-aminophenoxy) phenyl] sulfone , Bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-carbonylbis (p-phenyleneoxy) dianiline, 4 , 4'-bis (4-aminophenoxy) biphenyl, and the like, and these may be used alone or in combination. . Among these, 2,2-bis [(4-aminophenoxy) phenyl] propane is preferable.

Examples of the aromatic diamines (e2) other than the above (e1) include 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, and 1,4-bis (4- Aminophenoxy) benzene, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-[1,4-phenylenebis (1-methylethylli Den)] bisaniline, 3,3 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4'- diaminophenyl ether, 4,4'-diaminodiphenyl Methane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylether, 4,4'-diamino-3,3', 5,5'-tetradimethylphenylmethane, 4 , 4'-diamino-3,3 ', 5,5'-tetraethyldiphenylether, 2,2- [4,4'-diamino-3,3', 5,5'-tetramethyldiphenyl ] Propane, metaphenylenediamine, paraphenylenediamine, 3,3'- diaminodiphenyl sulfone, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, etc. are mentioned, These may be used alone or in combination.

As diamines other than said (e1) and (e2), ie, aliphatic or alicyclic diamine (e3), piperadine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, 3-methylheptamethylenediamine, etc. are mentioned, for example. These can be used individually or in combination.

As an acid component which polycondenses with the diamine which makes the said diamino silicone an essential component in order to synthesize | combine a thermoplastic resin (B2), the said acid component (S) used in the synthesis | combination of resin (B1) mentioned above is equally preferable. Can be used. The acid component (S) composed of these aromatic dicarboxylic acids, aromatic tricarboxylic acids, aromatic tetracarboxylic acids or reactive derivatives thereof is based on 100 mol% of the total amount of diamine from the viewpoints of molecular weight, mechanical strength, heat resistance and the like of the obtained polymer. It is preferable to use 80-120 mol% in total amount, and it is especially preferable to use 95-105 mol%.

In composition K, although the mixing ratio of electroconductive powder (A1) and a thermoplastic resin (B1) is not specifically limited, From a viewpoint of the electroconductivity of the coating film formed, etc., it is (B1) component with respect to 100 weight part of (A1) component. It is preferable that it is 2-25 weight part, and 4-14 weight part is more preferable.

In composition L, although the mixing ratio of electroconductive powder (A2) and a thermoplastic resin (B1) is not specifically limited, From a viewpoint of the electroconductivity of the coating film formed, etc., it is (B1) component with respect to 100 weight part of (A2) component. It is preferable that it is 2-25 weight part, and 4-14 weight part is more preferable.

In composition M, although the mixing ratio of electroconductive powder (A1) and a thermoplastic resin (B2) is not specifically limited, From a viewpoint of coating film strength, toughness, electroconductivity, etc., with respect to 100 weight part of (A1) component, it is (B2) It is preferable that a component is 2-25 weight part, and 4-14 weight part is more preferable.

In composition N, although the mixing ratio of electroconductive powder (A2) and a thermoplastic resin (B2) is not specifically limited, From a viewpoint of the flexibility, electroconductivity, etc. of a coating film, about 100 weight part of (A) component, (B) The component is preferably 2 to 25 parts by weight, and more preferably 4 to 14 parts by weight.

As an organic solvent (C) used for composition K, L, M, N, Aromatic solvents, such as benzene, toluene, xylene; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol colldimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene Ester solvents such as glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and γ-butyrolactone; Amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. These solvents are used for melt | dissolution of resin at the time of paste preparation, or viscosity adjustment of a paste, and can be used individually or in combination of 2 or more types.

The amount of the organic solvent (C) added is generally within the range of 75 to 4600 parts by weight based on 100 parts by weight of the thermoplastic resin, from the viewpoints of the solubility of the resin, the viscosity in the case of the paste, the dispersibility of the conductive powder, and the coating film forming ability. It is used, Preferably it is 125-3060 weight part.

Each composition containing the above-mentioned compounding components can be manufactured by kneading and dispersing each component with a kneader, 3-roll, a ball mill, a disper, etc., for example. In order to improve the dispersibility and coating property of an electroconductive powder (filler), you may add a dispersing agent and a coupling agent.

As a dispersing agent, For example, saturated fatty acids, such as palmitic acid and stearic acid of 16-20 carbon atoms; Unsaturated fatty acids such as oleic acid and linolenic acid having 16 to 18 carbon atoms; One or more types of metal salts with sodium, potassium, calcium, zinc, copper and the like of these saturated / unsaturated paper dispersants can be preferably used. It is preferable that it is 0.2-240 weight part with respect to 100 weight part of resin from a viewpoint of the dispersibility of electroconductive powder, the electroconductivity of a coating film, and the adhesiveness of a coating film and a base material, and, as for the compounding quantity of a dispersing agent, the range of 2-120 weight part is more preferable. .

Examples of the coupling agent include vinylmethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ- Silane coupling agents such as aminopropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane, titanate coupling agents, aluminate coupling agents, zircoaluminate coupling agents and the like can be used. It is preferable to add in the addition amount of 30 weight part or less with respect to 100 weight part of thermoplastic resins.

The composition according to the present invention can be suitably used as a conductor layer of various electronic components, such as a conductive circuit or an electrode material.

The electronic component which concerns on this invention has a conductor layer formed using the composition which concerns on this invention. As various electronic components, aluminum electrolytic capacitor, tantalum solid electrolytic capacitor, ceramic capacitor, etc. which used this composition as an electrode material; Various substrates on which a conductive circuit made of the composition of the present invention is formed by screen printing; An IC card etc. in which the electrically conductive circuit which consists of compositions of this invention were formed as a circuit for antennas are mentioned. Especially, the composition of this invention can be used suitably as a negative electrode material of the solid electrolytic capacitor which used the valve action metal for the positive electrode.

Therefore, the electronic component of the present invention is preferably a solid on which a cathode layer including a dielectric oxide film, a solid electrolyte layer, and a conductor layer formed using the composition of the present invention is formed on an anode gas made of a valve action metal. It is an electrolytic capacitor.

As an example is shown in FIG. 1, the solid electrolytic capacitor 10 includes a positive electrode substrate 2 in which an anode line 1 is embedded, and a dielectric oxide film (anode oxidation) sequentially formed on the positive electrode substrate 2. Film) 3, a solid electrolyte layer (semiconductor layer) 4, and a capacitor element including a cathode layer 5 composed of a carbon layer 51 and a conductor layer 52. It is preferable to use a valve action metal such as tantalum, aluminum, titanium, niobium or the like for the positive electrode body 2. The shape of the positive electrode body 2 is preferably a box, a plate or a rod. The positive electrode body 2 is formed by embedding a positive electrode wire 1 such as tantalum and the like by compression molding the valve-action metal powder and heating it for 10 minutes at a temperature of about 2000 ° C. in a vacuum to form a sintered body. .

Next, the obtained sintered body (positive electrode body 2) is formed by applying a voltage in a chemical solution such as nitric acid or phosphoric acid, and a dielectric oxide film such as Ta ₂ O ₅ is formed on the surface of the positive electrode body 2. (3) is formed. The oxide film 3 is preferably a layer made of an oxide of the anode gas metal itself, but may be a layer of another dielectric oxide as the anode gas. After the dielectric oxide film 3 is formed, the sintered body is immersed in a semiconductor mother liquor such as a manganese nitrate solution, and the liquid is impregnated, and then calcined at a temperature of 200 ° C to 350 ° C. The solid electrolyte layer 4 mainly formed etc. is formed. After pyrolysis, chemical conversion is performed to repair the dielectric oxide film 3 damaged by sintering. The above immersion, firing, and recyclability steps are repeated 5 to 10 times as necessary to form the solid electrolyte layer 4 having a desired thickness. This solid electrolyte layer can also be formed using a TCNQ (7,7,8,8-tetracyanoquinomethane) complex, which is referred to as an organic semiconductor, or polypyrrole, polythiophene, polyaniline, or the like, which is a conductive polymer.

After the solid electrolyte layer 4 is formed, carbon paste is applied and dried to form a carbon layer 51 as part of the cathode layer 5, and thereon a conductor layer (silver layer or silver as another part of the cathode layer) thereon. Paste layer) 52 is formed using the composition of the present invention. The lead frame 7 for negative electrode extraction is connected to the obtained conductor layer 52 using solder, a conductive adhesive 6, or the like, while the cathode wire 1 from the sintered body 2 is connected to the lead frame 7. Weld on the back. Finally, the whole is encapsulated by the external resin 8 by the resin dip method, the resin molding method, or the like. The solid electrolytic capacitor obtained in this way is generally a magnitude | size of about 2-7 mm in length, 1.25-4.3 mm in width, and about 1.2-2.8 mm in height.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically an example of the solid electrolytic capacitor which is one Embodiment of the electronic component which concerns on this invention.

Next, an Example demonstrates this invention further in detail. In the following example, the measurement and evaluation method of various characteristics are as follows.

[Aspect Ratio]                 

8 g of the main material (No. 10-8130) of the low-viscosity epoxy resin (manufactured by Burr Corporation) and 2 g of the curing agent (No. 10-8132) are mixed, and 2 g of the powder to be measured are mixed and dispersed well. After vacuum degassing at 30 degreeC as it is, it left still at 30 degreeC for 10 hours to precipitate a particle | grain and harden resin. Then, the obtained hardened | cured material was cut | disconnected to the vertical direction, the cut surface was enlarged 1000 times with the electron microscope, the long diameter / short diameter was calculated | required about 150 particle | grains which showed on the cut surface, and it was set as the aspect ratio with those average values.

[Average particle diameter]

The average particle diameter of the powder was measured using the master sizer (made by Malvern).

[Exposure area]

Five particles of silver-plated copper powder were randomly taken out, and quantitative analysis of precious metals (silver) and non-noble metals (copper) was carried out from the Auger phase observed with a scanning-type Auger Electron Spectroscopy apparatus to calculate the kinematic share ratio. The average value of 5 particles was made into copper exposure area (%).

[Paste viscosity]

The temperature in a constant temperature layer was set to 25 degreeC using the 3 degree cone of the E-type viscosity meter made from a copper boundary, and the value 10 minutes after the measurement start was made into the viscosity of a paste.

[Time Change of Paste Viscosity]

After the paste was produced, it was left to stand in a thermostat bath at 30 DEG C for 6 months, and then viscosity measurement was performed.

[Volume resistivity]

The volume resistivity of the dry coating film obtained using the paste was measured by the double bridge type resistance side device (TYPE2769 by a transverse electric company).

[Migration characteristics]

Using a dry coating film used for measuring the volume resistivity, an electrode having a spacing of 2 mm was formed at the center of the dry coating film, pure water was added dropwise so as to cover the entire electrode, and a voltage of 7 V was applied to both ends, and silver was transferred to the electrodes. The migration characteristics were evaluated by measuring the time until short circuit.

[Edge covering property]

A cubic tantalum sintered body of 1 mm x 1 mm x 1.5 mm was immersed in the paste to be measured and dried. The obtained device was sheathed with a transparent epoxy resin and allowed to stand at room temperature for 10 hours to cure. Then, the long side center part of the cube was cut | disconnected with the diamond cutter, and it grind | polished using sandpaper and abrasive grains, and it was set as the element for evaluation. In the device for evaluation, the covering state of the four corners of the paste was observed with an electron microscope. Evaluation A: Good, B: The coating film thickness of the edge part is 1 micrometer or less, C: The edge part has a defect part.

 [Film Strength]

Using an applicator on a Teflon plate, the silver film was produced so that the film thickness after drying at 180 degreeC for 1 hour may be set to 50 micrometers. The film was peeled off from the Teflon plate, and a single test piece of 5 mm x 40 mm in width was produced.

Thereafter, the coating film strength was measured using a tensile strength tester (manufactured by Money Maker: Tensile Compression Tester SL-2001).

[Flexibility of coating]                 

The paste was applied on a PET film having a thickness of 125 μm, a width of 1 cm, and a length of 10 cm in 2 millimeter widths, and after drying at 180 ° C. for 1 hour, the ends of the film were brought into contact with each other, and then the back surfaces were brought into contact with each other. The operation was repeated to determine how many times a crack formed in the coating film.

[Capacitor Characteristics]

According to JIS C 5102-1994 (Testing method of fixed capacitor for electronic equipment), the characteristic of the tantalum capacitor was measured. Equivalent series resistance (ESR) was measured using an LCR meter. Regarding the leakage current LC, a tantalum capacitor was produced using a digital microammeter (advanced test; R8340A) and a paste to be measured in the conductor layer, and left for 1000 hours and 2000 hours in an 85 ° C 85% RH atmosphere. The value at time was measured. tan δ and inductance were measured using a Hewlett-Packard Co. LCR meter (4284A). Cap (capacitance) was measured using an LCR meter (4284A manufactured by Hewlett-Packard).

[Overvoltage Load Characteristics of Capacitors]

An overvoltage was applied to the rated voltage of the tantalum capacitor, the subsequent capacitor characteristics were measured, and the breakdown number of the capacitor was confirmed.

[Solder Adhesiveness]

An aluminum plate having a width of 1 cm, a length of 2 cm, and a thickness of 0.5 mm was immersed in 1 cm in the paste to be measured, and dried at 180 ° C. for 1 hour in an oven dryer to prepare a sample for evaluation. After the sample for evaluation was immersed in the flux, it was immersed in the solder bath of each preset temperature, and the adhesion state of the solder was observed. The coating area of the solder was evaluated as A, 50% or more, less than 80%, B, 30% or more, and less than 50%, C, less than 30%, and D.

[Solder Heat Resistance of Capacitor]

The rate of change in capacity after the tantalum capacitor was immersed in the solder bath for 10 seconds was measured. Solder bath temperature: 230 ℃, 260 ℃, 290 ℃

[Heat resistance of capacitor]

The tantalum capacitor was put into a thermal shock tester, and it was taken out every 1000 cycles, and the capacitor characteristic was measured. Thermal shock conditions were performed at -50 degreeC-80 degreeC. That is, after leaving for 30 minutes in a bath at -50 ° C, it is transferred to an 80 ° C bath within 3 minutes, and left for 30 minutes, and then transferred to a bath at -50 ° C within 3 minutes. This was 1 cycle.

<Synthesis example 1 of the thermoplastic resin (B1)>

100 g (0.24 mole) of BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) was used as the diamine, and this was a 4-liter, one-liter four-hole equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. In the flask, it was dissolved in 400 g of N-methyl-2-pyrrolidone under a nitrogen gas atmosphere. The resulting solution was cooled to −10 ° C. and 49.5 g (0.24 mol) of isophthalic acid dichloride was added so that the temperature of the solution did not exceed −5 ° C., then 56.6 g of propylene oxide was added, followed by 3 hours at room temperature. Stirred. The reaction solution was poured into pure water to isolate the polymer, dried, and then dissolved in N-methyl-2-pyrrolidone. The resulting solution was poured into pure water to purify the polyamide polymer.

<Synthesis example 2 of thermoplastic resin (B1)>

205 g (500 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was used as the diamine, which was used in a 3-liter four-necked flask equipped with a thermometer, agitator, nitrogen introduction tube and cooling tube. It was dissolved in 11177 g of diethylene glycol dimethyl ether under a nitrogen gas atmosphere. The obtained solution was cooled to -10 ° C, and 105.3 g of trimellitic anhydride monochloride was added so that the temperature of the solution did not exceed -5 ° C. After that, 87 g of propylene oxide was added, and the mixture was stirred at room temperature for 3 hours. When the viscosity of the reaction solution was increased and the liquid became transparent, 841 g of diethylene glycol dimethyl ether was added, followed by further stirring for 1 hour. Then, 128 g of acetic anhydride and 64 g of pyridine were added, and the liquid stirring was continued overnight at 60 degreeC. The obtained reaction solution was poured into 250 g of methanol to isolate the polyamideimide polymer. After drying, it was dissolved in N, N-dimethylformamide again, and poured into methanol to obtain a product of a polyamideimide polymer.

<Synthesis example 1 of the thermoplastic resin (B2)>

65.6 g (160 mmol) 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine in a nitrogen gas atmosphere in a four-necked flask equipped with a thermometer, agitator, nitrogen introduction tube and cooling tube, and Diamino siloxane represented by said general formula (V) (made by Shinwol Chemical Co., Ltd., X-22-161B; In general formula (V), m = 38, Y < ¹ > -C <_3> H <_6> -, Y ² = -CH ₃ ) 64 g (40 mmol) (80 mol% / 20 mol% in molar ratio) was added and dissolved in 335 g of diethylene glycol dimethyl ether.

The obtained solution was cooled to -10 占 폚, and 40.6 g (200 mmol) of isophthalic acid dichloride was added so that the temperature of the solution did not exceed -5 占 폚. Then, 23.2 g of propylene oxide was added, 96 g of diethylene glycol dimethyl ether was added, and it stirred at room temperature for 3 hours. The reaction solution was poured into methanol to isolate the polymer, dried and dissolved in dimethylformamide, which was then poured into methanol to purify the polyamide silicone copolymer.

<Synthesis example 2 of thermoplastic resin (B2)>

174.3 g (425 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube under a nitrogen gas atmosphere, And 18.6 g of diaminopropyltetramethyldisiloxane (manufactured by Shinwol Chemical Co., Ltd., LP7100 (75 mmol) (85 mol% / 15 mol% in molar ratio) were added and dissolved in 1177 g of diethylene glycol dimethyl ether.

The obtained solution was cooled to -10 占 폚, and 105.3 g (500 mmol) of trimellitic anhydride monochloride was added so that the temperature of the solution did not exceed -5 占 폚. Thereafter, 87 g of propylene oxide was added, and the mixture was stirred at room temperature for 3 hours to increase the viscosity of the reaction solution, and when the liquid became transparent, 841 g of diethylene glycol dimethyl ether was added, followed by further stirring for 1 hour. Then, 128 g of acetic anhydride and 64 g of pyridine were added, and the solution was stirred overnight at 60 ° C. The obtained reaction solution was poured into a large amount of mixed solvent of n-hexane / methanol = 1/1 (weight ratio), the polymer was isolated, dried, dissolved in N, N-dimethylformamide, and poured into methanol to obtain poly The amideimide silicone copolymer was purified and dried under reduced pressure.

<Production example of silver plated copper powder (a1)>

Spheroidal copper powder (SFR-Cu, manufactured by Nippon Atomizing Processing Co., Ltd., trade name SFR-Cu) having an average particle diameter of 5.1 µm prepared by the atomizing method was washed with dilute hydrochloric acid and pure water, and then a plating solution containing 80 g of AgCN and 75 g of NaCN per liter of water. In the above, spherical copper powder was subjected to substitution plating so that the amount of silver was 15% by weight, washed with water and dried to obtain silver-plated copper powder.

In a 2 liter ball mill container, 750 g of the obtained silver-plated copper powder and 3 kg of a zirconia ball having a diameter of 5 mm were charged and rotated for 40 minutes to obtain a silver-plated copper powder having an average aspect ratio of 1.3 and a long diameter of 5.5 µm.

<Production example of silver plated copper powder (a2)>

Spheroidal copper powder (SFR-Cu, manufactured by Nippon Atomizing Processing Co., Ltd., trade name SFR-Cu) having an average particle diameter of 5.1 µm prepared by the atomizing method was washed with dilute hydrochloric acid and pure water, and then a plating solution containing 80 g of AgCN and 75 g of NaCN per liter of water. Substituted plating was carried out so that the amount of silver was 20% by weight with respect to the spherical copper powder, washed with water and dried to obtain a silver-plated copper powder.

750 g of silver-plated copper powder and 3 kg of zirconia ball having a diameter of 5 mm were charged in a 2 liter ball mill container, and then rotated for 40 minutes to obtain a silver-plated copper powder having an average particle diameter of 8.1 µm.

Example K1

Silver-plated copper powder and silver powder (deguza) obtained in the preparation examples of the silver-plated copper powder (a1) were added to 22.2 parts by weight of diethylene glycol dimethyl ether in 22.2 parts by weight of the polyamide polymer obtained in Synthesis Example 1 of the thermoplastic resin (B1). SF # 7 scale piece average particle diameter 6.8 micrometers made from Corporation were mix | blended in the ratio shown in Table 1, and it disperse | distributed for 20 minutes with the disper, and the composition (paste) K was obtained. After degassing the obtained paste, a predetermined amount was applied on the slide glass by screen printing (coating area: 1 cm × 7.5 cm, coating pressure: 40 ± 10 μm), and then dried in a batch drying furnace at 180 ° C. for 1 hour and dried. A coating film was obtained. The volume resistivity and the migration characteristics of the obtained dried coating film were measured. Using this paste, tantalum capacitors were prepared, and the equivalent series resistance and leakage current were measured to evaluate edge covering properties.

Example K2

The average particle diameter of the spherical copper powder produced by the atomization method was 5.9 micrometers, it carried out similarly to Example K1 except having an aspect ratio of silver-plated copper powder 1.5 and an average particle diameter of 6.7 micrometer.

Example K3

The average particle diameter of the spherical copper powder produced by the atomization method was 5.9 micrometers, the rotation time of the ball mill was 60 minutes, and it carried out similarly to Example K1 except having an aspect ratio of silver-plated copper powder of 2.5 and an average particle diameter of 8.0 micrometers.

Example K4

The average particle diameter of the spherical copper powder produced by the atomization method was 4.2 micrometers, the rotation time of the ball mill was 120 minutes, and it carried out similarly to Example K1 except having an aspect ratio 12 and an average particle diameter of 7.2 micrometers of silver-plated copper powder.

Example K5

The average particle diameter of the spherical copper powder produced by the atomization method was 3.5 micrometers, the rotation time of the ball mill was 180 minutes, and it carried out similarly to Example K1 except having an aspect ratio of silver-plated copper powder and an average particle diameter of 6.2 micrometers.

Example K6

The average particle diameter of the spherical copper powder produced by the atomization method was 0.1 micrometer, it carried out similarly to Example K1 except having an aspect ratio of silver-plated copper powder 3.2 and an average particle diameter of 0.2 micrometer.

Example K7

The average particle diameter of the spherical copper powder produced by the atomization method was 0.6 micrometers, and it carried out similarly to Example K1 except having an aspect ratio 3 and an average particle diameter 1.0 micrometer of silver-plated copper powder.

Example K8

It carried out similarly to Example K1 except having the average particle diameter of the spheroidal copper powder produced by the atomizing method being 1.0 micrometer, the aspect ratio of silver-plated copper powder 3.1, and the average particle diameter 1.5 micrometer.

Example K9

It carried out similarly to Example K1 except having the average particle diameter of the spheroidal copper powder produced by the atomization method being 5.5 micrometers, the aspect ratio of silver-plated copper powder 3.1, and the average particle diameter 8.0 micrometers.

Example K10

It carried out similarly to Example K1 except having the average particle diameter of the spheroidal copper powder produced by the atomization method being 8.2 micrometers, the aspect ratio of silver-plated copper powder 3.2, and the average particle diameter 12 micrometers.                 

Example K11

It carried out similarly to Example K1 except having the average particle diameter of the spheroidal copper powder produced by the atomizing method being 13.6 micrometers, the aspect ratio 3.0 of silver-plated copper powder, and an average particle diameter of 20 micrometers.

Example K12

The average particle diameter of the spheroidal copper powder produced by the atomization method was the same as Example K1 except that the substitution plating amount of silver was 0.5 weight%, the aspect ratio of silver plating copper powder 3.5, and the average particle diameter 6.7 micrometers with respect to spherical copper powder.

Example K13

The average particle diameter of the spheroidal copper powder produced by the atomizing method was the same as Example K1 except that the substitution plating amount of silver was 1.0 weight%, the aspect ratio of silver-plated copper powder 3.1, and the average particle diameter of 5.3 micrometers with respect to spherical copper powder.

Example K14

The average particle diameter of the spherical copper powder produced by the atomizing method was 3.6 µm, and the substitution plating amount of silver was 1.5% by weight, the aspect ratio of the silver-plated copper powder was 3.5, and the average particle diameter was 5.2 µm, except for the spherical copper powder.

Example K15

The average particle diameter of the spherical copper powder produced by the atomization method was 4.3 µm, and the same as in Example K1 except that the substitution plating amount of silver was 25% by weight, the aspect ratio 3.4 of the silver-plated copper powder, and the average particle diameter of 6.2 µm.

Example K16

The average particle diameter of the spheroidal copper powder produced by the atomization method was 5.0 µm, and the same as in Example K1 except that the substitution plating amount of silver was 35% by weight, the aspect ratio of the silver-plated copper powder, and the average particle diameter of 7.5 µm.

Example K17

The average particle diameter of the spheroidal copper powder produced by the atomizing method was 4.7 µm, and the same as in Example K1 except that the substitution plating amount of silver was 50% by weight, the aspect ratio 4.0 of the silver-plated copper powder, and the average particle diameter of 7.1 µm.

Example K18

The average particle diameter of the spherical copper powder produced by the atomization method was 5.9 µm, and the substitution plating amount of silver was 20% by weight with respect to the spherical copper powder, the aspect ratio of the silver-plated copper powder was 2.5, and the average particle diameter was 8.0 µm. The shape was the same as that of Example K1 except that the shape was spherical and the average particle diameter was 2.0 m.

Example K19

The average particle diameter of the spheroidal copper powder produced by the atomization method was the same as Example K1 except that the substitution plating amount of silver was 20 weight%, the aspect ratio 2.5 and the average particle diameter 8.0 micrometer of silver plating copper powder with respect to spherical copper powder.

Example K20

The average particle diameter of the spheroidal copper powder produced by the atomization method was the same as Example K1 except that the substitution plating amount of silver was 20 weight%, the aspect ratio 2.5 and the average particle diameter 8.0 micrometer of silver plating copper powder with respect to spherical copper powder.                 

Example K21

The average particle diameter of the spheroidal copper powder produced by the atomization method was the same as Example K1 except that the substitution plating amount of silver was 20 weight%, the aspect ratio 2.5 and the average particle diameter 8.0 micrometer of silver plating copper powder with respect to spherical copper powder.

Example K22

The average particle diameter of the spheroidal copper powder produced by the atomization method was the same as Example K1 except that the substitution plating amount of silver was 20 weight%, the aspect ratio 2.5 and the average particle diameter 8.0 micrometer of silver plating copper powder with respect to spherical copper powder.

Example K23

The average particle diameter of the spheroidal copper powder produced by the atomization method was the same as Example K1 except that the substitution plating amount of silver was 20 weight%, the aspect ratio 2.5 and the average particle diameter 8.0 micrometer of silver plating copper powder with respect to spherical copper powder.

Example K24

The average particle diameter of the spheroidal copper powder produced by the atomization method was the same as Example K1 except that the substitution plating amount of silver was 20 weight%, the aspect ratio 2.5 and the average particle diameter 8.0 micrometer of silver plating copper powder with respect to spherical copper powder.

Example K25

The average particle diameter of the spheroidal copper powder produced by the atomization method using the polyamideimide polymer obtained in Synthesis Example 2 of the thermoplastic resin (B1) was 5.9 µm, and the substitution plating amount of silver was 15 wt%, It carried out similarly to Example K1 except having an aspect ratio of 2.5 and an average particle diameter of 8.0 µm.

Example K26

The average particle diameter of the spheroidal copper powder produced by the atomization method using the polyamideimide polymer obtained in Synthesis Example 2 of the thermoplastic resin (B1) was 4.4 µm, and the substitution plating amount of silver was 15 wt%, It carried out similarly to Example K1 except having an aspect ratio of 3.2 and an average particle diameter of 6.5 mu m.

Comparative Example K1

The spheroidal copper powder produced by the atomization method had an average particle diameter of 13.8 µm, and the silver-plated copper powder having a substitution plating amount of silver of 15% by weight and a ball mill rotation time of 240 minutes, an aspect ratio of 25 and an average particle diameter of 26 µm was used for the spherical copper powder. Except that, it carried out similarly to Example K1.

Comparative Example K2

Using the polyamide-imide polymer obtained in Synthesis Example 2 of the thermoplastic resin (B1), the average particle diameter of the spherical copper powder produced by the atomization method was 13.8 µm, and the substitution plating amount of silver was 15% by weight with respect to the spherical copper powder, and the ball mill was used. It carried out similarly to Example K1 except having used the silver plating copper powder whose rotation time is 240 minutes, aspect ratio 25, and an average particle diameter of 26 micrometers.

Comparative Example K3

It carried out similarly to Example K1 except having used spherical copper powder (Samjung Metal Mine MFP1110 average particle diameter 1.1 micrometer) instead of silver plating copper powder.

Comparative Example K4

It carried out similarly to Example K1 except not containing silver powder.

Comparative Example K5

It carried out similarly to Example K1 except not containing silver plating copper powder.

The results obtained are shown in Tables K1 and K2.

Example L1

Silver-plated copper powder (copper exposure area 20%) obtained in the silver-plated copper powder (a2) preparation example to the varnish which added 222.2 weight part of diethylene glycol dimethyl ether to 22.2 weight part of polyamide polymers obtained by the synthesis example 1 of the said thermoplastic resin (B1), and melt | dissolved. 118.8 parts by weight and 79.2 parts by weight of silver powder (SF # 7 scale piece average particle diameter of Deguza Co., Ltd. 6.8 mu m) were combined and dispersed in a 20-minute disper to obtain a composition (paste) L having a viscosity of 2000 mPa · s. After degassing the obtained paste, it was applied on a certain amount of slide glass by screen printing (coating area: 1 cm × 7.5 cm coating pressure: 40 ± 10 μm), and dried in a batch drying furnace for 1 hour to obtain a dry coating film. . The volume resistivity of the obtained dry coating film was measured. In addition, in order to measure the time-dependent change in paste viscosity, a part of the paste was transferred to a 50 ml polycontainer, left in a high temperature bath at 30 ° C., and after six months, the viscosity was measured, and the change rate was calculated. Moreover, the solder adhesiveness of the obtained paste was evaluated. Furthermore, this paste was used for the cathode to produce a tantalum capacitor, and the solder heat resistance was tested.

Example L2

It carried out similarly to Example L1 except having the copper-exposed area of the silver-plated copper powder obtained in 60 minutes for the ball mill rotation time at the time of silver-plated copper powder production.                 

Example L3

The substitution plating amount of silver at the time of preparation of silver plating copper powder was 15 weight%, and it carried out similarly to Example L1 except having the copper exposure area of the obtained silver plating copper powder being 40%.

Example L4

The ball mill rotation time in the production of silver-plated copper powder was 80 minutes, and the same as in Example L3 except that the copper exposure area of the obtained silver-plated copper powder was 60%.

Example L5

It carried out similarly to Example L2 except having used the polyamide-imide polymer obtained by the synthesis example 2 of the said thermoplastic resin (B1).

Comparative Example L1

The silver substitution plating amount in production of silver-plated copper powder was 30 parts by weight, the rotation time of the ball mill was 20 minutes, and the same as in Example L1 except that the copper exposure area of the obtained silver-plated copper powder was 0%.

Comparative Example L2

It carried out similarly to Example L1 except having used silver plating copper powder and 198 weight part of silver powders.

Comparative Example L3

It carried out similarly to Example L1 except having used spherical copper powder produced by the atomization method instead of silver plating copper powder.

The result thus obtained is shown in Table L1.                 

Example M1

118.8 parts by weight of silver-plated copper powder obtained in the preparation example of silver-plated copper powder (a1) and silver powder were added to 22.2 parts by weight of diethylene glycol dimethyl ether in 22.2 parts by weight of the polyamide silicone copolymer obtained in Synthesis Example 1 of the thermoplastic resin (B2). (SF # 7 scale piece average particle diameter of 6.8 micrometers made by Deguza Co., Ltd.) 79.2 weight part was mix | blended, and it disperse | distributed with 20 minutes of dispers, and obtained the composition (paste) M of viscosity 2000mPa * s. After degassing the obtained paste, it was applied on a certain amount of slide glass by screen printing (coating area: 1 cm × 7.5 cm coating pressure: 40 ± 10 μm), and dried in a batch drying furnace for 1 hour to obtain a dry coating film. . The volume resistivity of the obtained dry coating film was measured. Moreover, using the obtained paste, the sample for coating-film strength measurement was produced and the coating-film strength was measured. Further, this paste was used as a cathode to produce a tantalum capacitor (nominal voltage 4V), and the capacitor characteristics after the inlash test were measured to confirm the destruction of the capacitor.

Example M2

The ball mill rotation time at the time of preparation of silver-plated copper powder was 80 minutes, and it carried out similarly to Example M1 except having an aspect ratio of obtained silver-plated copper powder.

Example M3

The ball mill rotation time at the time of preparation of silver-plated copper powder was 120 minutes, and it carried out similarly to Example M1 except having an aspect ratio of the obtained silver-plated copper powder.

Example M4

The ball mill rotation time at the time of preparation of silver-plated copper powder was 150 minutes, and it carried out similarly to Example M1 except having an aspect ratio of the obtained silver-plated copper powder 19.3.

Example M5

It carried out similarly to Example M2 except having used the polyamide-imide silicone copolymer obtained by the synthesis example 2 of the said thermoplastic resin (B2).

Comparative Example M1

The ball mill rotation time at the time of preparation of silver-plated copper powder was 180 minutes, and it carried out similarly to Example M1 except the aspect ratio of the obtained silver-plated copper powder is 23.0.

Comparative Example M2

Instead of the polyamide silicone copolymer, it carried out similarly to Example M2 except having used the polyamide polymer obtained by the synthesis example 1 of the said thermoplastic resin (B1).

Comparative Example M3

It carried out similarly to Example M1 except having used the silver powder of aspect ratio 3.5 instead of silver plating copper powder.

Comparative Example M4

It carried out similarly to Example M1 except having used the copper powder of aspect ratio 1 instead of silver plating copper powder.

Comparative Example M5

60 parts by weight of an epoxy resin (Samsung Chemical Co., Ltd., brand name 140C) instead of a polyamide silicone copolymer, 40 parts by weight of aliphatic diglycidyl ether (manufactured by Wookku Kogyo Co., Ltd., trade name ED-503), 2P4MHZ ( The same procedure as in Example M2 was carried out except that 3 parts by weight of tetrachambering agent, cured sol, and 3 parts by weight of dicyandiamide (Hwagwang Pure Chemical Co., Ltd.) were added.

The results obtained are shown in Table M1.

Example N1

Silver-plated copper powder (copper exposure area 30%) obtained in the silver-plated copper powder (a2) preparation example to the varnish which added 222.2 parts by weight of diethylene glycol dimethyl ether to 22.2 parts by weight of the polyamide silicone copolymer obtained in Synthesis Example 1 of the thermoplastic resin (B1). ) 118.8 parts by weight and silver powder (SF # 7 scale piece average particle diameter of 6.8 μm manufactured by Deguza Co., Ltd.) were blended and dispersed in a 20-minute disper to obtain a composition (paste) N having a viscosity of 2000 mPa · s. After degassing the obtained paste, it was applied on a slide glass by a screen printing method (coating area: 1 cm × 7.5 cm coating thickness: 40 ± 10 μm) and dried in a batch drying furnace for 1 hour to obtain a dry coating film. . The volume resistivity of the obtained dry coating film was measured. In addition, the flexibility of the obtained paste was measured. Furthermore, the tantalum capacitor was produced using this paste composition for the negative electrode, the thermal shock test was done, and the leakage current (LC) of the capacitor was measured.

Example N2

It carried out similarly to Example N1 except having used the polyamide-imide silicone copolymer obtained by the synthesis example 2 of the thermoplastic resin (B2).

Example N3

Using the polyamideimide silicone copolymer obtained in Synthesis Example 2 of the thermoplastic resin (B2), the substitution plating amount of silver at the time of preparation of silver-plated copper powder was 15% by weight, the ball mill rotation time was 80 minutes, and the copper-exposed area of the obtained silver-plated copper powder was Except for 50%, it carried out similarly to Example N1.

Comparative Example N1

The silver substitution plating amount at the time of preparation of silver plating copper powder was 30 weight part, the rotation time of the ball mill was 20 minutes, and it carried out similarly to Example N1 except having the copper exposure area of the obtained silver plating copper powder being 0%.

Comparative Example N2

60 parts by weight of an epoxy resin (Samsung Chemical Co., Ltd., brand name 140C) instead of a polyamide silicone copolymer, 40 parts by weight of aliphatic diglycidyl ether (manufactured by Wookku Kogyo Co., Ltd., trade name ED-503), 2P4MHZ ( The same procedure as in Example N1 was carried out except that 3 parts by weight of tetrachambering agent, cured sol, and 3 parts by weight of dicyandiamide (Hwagwang Pure Chemical Co., Ltd.) were added.

The results obtained are shown in Table N1.

The present disclosure discloses Japanese Patent Application No. 2001-322320, filed October 19, 2001, Japanese Patent Application No. 2001-322321, filed October 19, 2001, and Japanese Patent Application, Oct. 31, 2001. It is associated with the subject matter of Japanese Patent Application No. 2001-333649, and Japanese Patent Application No. 2001-333650, filed October 31, 2001, the disclosures of all of which are incorporated herein by reference.

 It should be noted that, in addition to those already described, various modifications or changes may be made to the above embodiments without departing from the novel and advantageous features of the present invention. Accordingly, all such modifications and changes are intended to be included in the appended claims.

Table K1 Formulation Table

TABLE K2

TABLE L1

TABLE M1

TABLE N1

Claims (9)

A conductive powder (A1) containing silver plated copper powder (a1) having an aspect ratio of 1 to 20 and a silver powder, a thermoplastic resin (B1) having at least one functional group selected from the group consisting of an amide group, an ester group, an imide group and an ether group; , Conductive resin composition containing organic solvent (C). A silver-plated copper powder (a2) having a copper exposed portion on a part of its surface and a conductive powder (A2) containing silver powder, and a thermoplastic resin (B1) having at least one functional group selected from the group consisting of amide groups, ester groups, imide groups and ether groups ) And an organic solvent (C). The said thermoplastic resin (B1) is a polyphenylene etheramide, polyphenylene etherimide, polyphenylene etheramideimide, polyphenylene amide, polyphenylene imide, and polyphenyl of Claim 1 or 2 A conductive resin composition selected from the group consisting of renamideimide, polyxylyleneamide, polyxylyleneimide, and polyxyleneyleneimide. The said thermoplastic resin (B1) is a following general formula (I):

Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen, a lower alkyl group, a lower alkoxy group or a halogen atom, and X ¹ represents a single bond, -O-, -S-, -CO-, -SO _2- , -SO-,

Wherein R ⁵ and R ⁶ each independently represent hydrogen, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group, and Y represents

Wherein Ar ¹ represents an aromatic divalent group, Ar ² represents an aromatic trivalent group, and Ar ³ represents an aromatic tetravalent group.) A repeating unit represented by the following general formula (II): (Wherein R ⁷ , R ⁸ and R ⁹ each independently represent a lower alkyl group, a lower alkoxy group or a halogen atom, s, t and u are each independently an integer of 0 to 4 representing the number of substituents, R ⁷ , When two or more R <^8> and R <^9> couple | bonds, respectively, may be same or different in each, X <^2> and X <^3> respectively independently represent -O- or

Wherein R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group, or a phenyl group, and Y is as defined in the general formula (I).) A conductive resin composition which is a resin having at least one of the repeating units represented by. A conductive powder (A1) containing silver plated copper powder (a1) having an aspect ratio of 1 to 20 and silver powder, a thermoplastic resin (B2) selected from the group consisting of polyamide silicone resin, polyamideimide silicone resin and polyimide silicone resin; , Conductive resin composition comprising an organic solvent (C). Silver-plated copper powder (a2) having a copper exposed portion on a part of its surface and conductive powder (A2) containing silver powder, and a thermoplastic resin (B2) selected from the group consisting of polyamide silicone resin, polyamideimide silicone resin and polyimide silicone resin ) And an organic solvent (C). The conductive resin composition according to claim 2 or 6, wherein an exposed area of copper in the silver plated copper powder (a2) is 10 to 70%. An electronic component having a conductor layer formed using the conductive resin composition according to any one of claims 1, 2, 5, and 6. A dielectric oxide film, a solid electrolyte layer, and the electroconductor according to any one of claims 1, 2, 5 and 6, on an anode base made of a valve action metal. An electronic component comprising a solid electrolytic capacitor having a negative electrode layer including a conductor layer formed using a resin composition.

Images