CN100467539C - Conductive resin composition and electronic component using same - Google Patents

Abstract

The present invention discloses a conductive powder (A) comprising silver-plated copper powder (a1) and silver powder with an aspect ratio of 1 to 20, and a conductive powder (A) consisting of amide group, ester group, imide group and ether group A conductive resin composition consisting of a thermoplastic resin (B1) with more than one functional group selected from among them and an organic solvent (C); including: a conductive resin containing silver-plated copper powder (a2) and silver powder with a part of the surface having copper exposure. conductive powder (A2), and the aforementioned thermoplastic resin (B1), and a conductive resin composition of an organic solvent (C); containing the aforementioned conductive powder (A1), and polyamide polysiloxane resin, polyamideimide A conductive resin composition comprising a thermoplastic resin (B2) selected from the group of silicone resins and polyimide silicone resins, and an organic solvent (C); containing the aforementioned conductive powder (A2), and a thermoplastic resin ( B2), and the conductive resin composition of the organic solvent (C).

Description

Conductive resin composition and electronic component using same

This application is a divisional application of the application number 02819480.2, the application date is October 18, 2002, and the invention title is a conductive resin composition and an electronic component using the same.

technical field

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

Background technique

In the field of electronic components, a conductive substance represented by metal is generally kneaded with a resin to form a paste-like resin composition, which is then used to form circuits or electrodes. Among them, silver is the most representative conductive substance. However, when a voltage is applied under high humidity conditions, it is very easy to ionize, and a silver migration phenomenon called migration is often observed. In addition, when migration occurs, a short circuit between electrodes is caused, which causes a decrease in the moisture resistance reliability of electronic components.

It has been considered to add nickel powder, palladium powder, or copper powder instead of silver powder, or to add various additives. However, in any case, improvements are expected in terms of increasing the resistance value of the electrode material.

JP-A-2-283010 and JP-A-6-151261 disclose prior art for preventing migration of solid electrolytic capacitors.

Contents of the invention

The first aspect of the present invention is to provide a conductive resin composition (hereinafter referred to as "composition K"), which comprises: conductive powder (a1) containing silver-plated copper powder (a1) and silver powder ( A1); and a thermoplastic resin (B1) having at least one functional group selected from an amide group, an ester group, an imide group, and an ether group; and an organic solvent (C).

The second aspect of the present invention is to provide a conductive tree composition (hereinafter referred to as "composition L"), which comprises: silver-plated copper powder ( a2) and a conductive powder (A2) that is 25 to 266 parts by weight of silver powder relative to 100 parts by weight of the silver-plated copper powder (a2); and has an amino group, an ester group, an imide group and an ether A thermoplastic resin (B1) having at least one functional group selected from the group; and an organic solvent (C).

The third aspect of the present invention is to provide a conductive resin composition (hereinafter referred to as "composition M"), which comprises: conductive powder containing silver-plated copper powder (a1) and silver powder ( A1); and a thermoplastic resin (B2) selected from the group consisting of polyamide silicone, polyamideimide silicone and polyimide silicone; and an organic solvent (C).

The fourth aspect of the present invention provides a conductive resin composition (hereinafter referred to as "composition N"), which includes: silver-plated copper powder ( a2) and a conductive powder (A2) of 25 parts by weight to 266 parts by weight of silver powder relative to 100 parts by weight of the silver-plated copper powder (a2); and polyamide silicone, polyamideimide silicone and a thermoplastic resin (B2) selected from the polyimide silicone group; and an organic solvent (C).

The fifth aspect of the present invention provides an electronic component having a conductor layer formed using the above-mentioned conductive resin composition (composition K, L, M, N) of the present invention.

Description of drawings

FIG. 1 is a schematic cross-sectional view showing an example of a solid electrolytic capacitor according to an embodiment of the electronic component of the present invention.

In the figure: 1 anode wire, 2 anode substrate, 3 dielectric oxide film, 4 solid electrolyte layer, 5 cathode layer, 6 conductive adhesive, 7 lead frame, 8 exterior resin, 10 solid electrolytic capacitor, 51 carbon layer, 52 conductive body layer.

Detailed ways

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

Composition K is a conductive powder (A1) comprising: silver-plated copper powder (a1) and silver powder with an aspect ratio of 1 to 20; A thermoplastic resin (B1) having at least one functional group; and a composition of an organic solvent (C). When using flaky conductive powder, when it is coated on complex-shaped parts (polyhedrons), the edge coatability will be insufficient, which will cause increased resistance or deviation of inter-plane resistance, so it is easy to cause defects in electrical characteristics of electronic components. And it reduces the dimensional accuracy of the resin exterior. In particular, when it is used to form a cathode of a solid electrolytic capacitor using a valve metal as an anode, it has been found that it tends to increase the leakage current (LC) of the product. On the contrary, Composition K has good coatability and good electrical conductivity after drying. In addition, the obtained coating film has excellent stability (migration resistance) and dimensional accuracy (edge wrapping property) under high temperature and high humidity. Therefore, the use of composition K can provide electronic components with excellent moisture resistance reliability and dimensional accuracy. For example, when the composition K is used to form a cathode, it can provide a solid electrolytic capacitor with good moisture resistance reliability and low leakage.

Composition L is a conductive powder (A2) comprising: silver-plated copper powder (a2) and silver powder with copper exposed on part of the surface; A thermoplastic resin (B1) having at least one functional group; and a composition of an organic solvent (C). At present, the general conductive powder is copper powder. In this case, although the resistance value is better than that of nickel powder or palladium powder, there is a problem of stability over time, such as oxidation of copper powder or increase in viscosity of the paste due to aggregation. In addition, when soldering a conductive paste using silver powder, thermal decomposition of the binder resin is used as a soldering mechanism, so there is a problem that the coating film is partially chipped and cannot be bonded sufficiently. In addition, conventional conductive pastes using silver powder and copper powder cannot be used for soldering because the copper powder reacts with the oxygen contained in the air and the binder resin to form an oxide film on the surface. On the contrary, the paste viscosity of the composition L has excellent stability over time, so a solderable coating film can be formed. Therefore, the use of the composition L can provide electronic components excellent in soldering heat resistance. For example, when the composition is used for forming a cathode, it can provide a solid electrolytic capacitor having excellent solderability with the extracted cathode member and excellent soldering heat resistance.

Composition M is comprising: a conductive powder (A1) containing silver-plated copper powder (a1) and silver powder with an aspect ratio of 1 to 20; and polyamide silicone, polyamideimide silicone and polyimide A thermoplastic resin (B2) selected from the silicone group; and a composition of an organic solvent (C). At present, thermosetting resins are widely used as adhesive pastes, but the obtained coating film has poor film strength and toughness, and has poor impact resistance after forming a circuit. In addition, when this paste is used as an electrode of a solid electrolytic capacitor, the strength and toughness of the coating film are poor, resulting in insufficient overvoltage load characteristics. On the contrary, the composition M can form a dried coating film having excellent coating film strength and toughness, and its use can provide electronic parts such as solid electrolytic capacitors which are excellent in particularly overvoltage load characteristics.

Composition N is a conductive powder (A2) comprising: silver-plated copper powder (a2) and silver powder with copper exposed on part of the surface; and polyamide silicone, polyamideimide silicone and polyimide A thermoplastic resin (B2) selected from the silicone group; and a composition of an organic solvent (C). When a thermosetting resin is used as an adhesive paste, the resulting coating film has poor flexibility. Therefore, when it is used to form a circuit on a flexible substrate, the coating film will crack due to a large bending rate, causing a short circuit problem. On the other hand, since composition N forms a dry coating film excellent in flexibility, its use can provide electronic components such as solid electrolytic capacitors, especially excellent in thermal shock resistance.

In Composition K and Composition M, conductive powder (A1) containing silver-plated copper powder (a1) and silver powder with an aspect ratio of 1 to 20 is used. The aspect ratio refers to the ratio of the particle major diameter to the minor diameter (major diameter/short diameter) of the silver-plated copper powder. In the present invention, silver-plated copper powder particles are uniformly mixed in a low-viscosity curable resin, and the resin is cured at the same time as the particles are allowed to settle, and then the obtained cured product is cut in a vertical direction, and the cross-section is magnified and observed with a microscope. For the shape of the particles that appear, the average value obtained by calculating the long axis/short axis of at least 100 particles one by one is the aspect ratio. Here, the short diameter refers to the distance between two parallel lines at the shortest interval when two parallel lines pinch the outside of the particles appearing in the cross section. In addition, the long diameter refers to the distance between two parallel lines perpendicular to the short diameter when the outer side of the particle is sandwiched between two parallel lines perpendicular to the short diameter. The size of the rectangle formed by the four lines is just enough to accommodate particles. The specific method used in the present invention will be described later.

The silver-plated copper powder (a1) refers to a conductive powder in which a part or all of the surface of the copper powder is coated with silver. For example, it can be obtained by coating silver powder on atomized copper powder by methods such as displacement plating, electroplating, and electroless plating. Among them, the coating method of the displacement plating method, which has high adhesion between copper powder and silver and has low operating costs, is ideal.

In the composition K, the amount of silver coated on the silver-plated copper powder (a1) is not particularly limited, but it is preferably 0.5 to 50 parts by weight relative to 100 parts by weight of copper, more preferably 1.0 to 35 parts by weight, ideally 1.5 to 25 parts by weight. The silver-plated copper powder (a1) may have an aspect ratio of 1 to 20 from the viewpoint of paste coatability and the like. When the aspect ratio exceeds 20, the spreadability of the paste will be deteriorated, especially when used in the cathode of a solid electrolytic capacitor, the edge wrapping property of the element will be reduced, and leakage current may increase. The aspect ratio is preferably 1.5 to 18, more preferably 2.5 to 12 in consideration of the conductivity of the coating film and the like. In terms of paste dispersion, leveling, edge wrapping and film conductivity, the average particle size of the silver-plated copper powder (a1) is preferably 0.2 μm to 20 μm, more preferably 1 μm to 12 μm, and most preferably 1.5 μm to 1.5 μm. 8 μm. When the average particle size is less than 0.2 μm, the paste tends to coagulate, and when it exceeds 20 μm, edge wrapping properties and electrical resistance decrease. The average particle diameter can be measured with a laser scattering type flow distribution measuring device.

In composition M, the silver-plated copper powder (a1) may have an aspect ratio of 1 to 20. When the aspect ratio exceeds 20, the applicability of the paste, the strength and toughness of the conductive coating film will be reduced, especially when used as a cathode of a solid electrolytic capacitor, the overvoltage load characteristic will be deteriorated, and it will become the main reason for the decrease in impedance. reason. The aspect ratio is preferably 1.5 to 18, more preferably 2.5 to 12 in consideration of the electrical conductivity of the coating film and the like. The amount of silver coated on the silver-plated copper powder (a1) is not particularly limited, but it is preferably 0.5 to 50 parts by weight, more preferably 1.0 to 35 parts by weight, and more preferably 100 parts by weight of copper, in consideration of electrical conductivity and migration resistance. 1.5 to 25 parts by weight. When the coating amount of silver is less than 1 part by weight, the electrical conductivity will be lowered, and when it exceeds 30 parts by weight, the overvoltage load characteristics of the capacitor will be lowered. Considering the dispersibility, viscosity, workability and film conductivity of the paste, the average particle size of the silver-plated copper powder (a1) is preferably 0.2 μm to 20 μm, more preferably 1 μm to 12 μm, and more preferably 1.5 μm to 8 μm. When the average particle size is less than 0.2 μm, the paste tends to coagulate, and when it exceeds 20 μm, the spreadability and electrical resistance decrease. The average particle diameter can be measured with a laser scattering type flow distribution measuring device.

The silver powder contained in the conductive powder (A1) is not particularly limited, and generally used shapes such as scales, spheres, and lumps can be used. In consideration of electrical conductivity, coatability and edge wrapping properties, it is more ideal to be a scaly and spherical powder with a particle size of 0.2 μm to 12 μm, and it is particularly ideal to be a powder with a particle size of 1 μm to 8 μm.

The ratio (weight ratio) of the silver-plated copper powder (a1) to the silver powder in the conductive powder (A1) is not particularly limited, and the silver powder ratio of 100 parts by weight of the silver-plated copper powder (a1) is relatively low in terms of the conductivity of the coating film. It is preferably 25 parts by weight or more, more preferably 400 parts by weight or less, more preferably 42.8 to 233.3 parts by weight, and most preferably 66.6 to 150 parts by weight from the viewpoint of leakage current or overvoltage load characteristics of the capacitor.

In composition L and composition N, the electroconductive powder (A2) containing the silver-plated copper powder (a2) and silver powder which partly had a copper exposure part on the surface was used. The silver-plated copper powder (a2) is a silver-plated copper powder in which a part of the copper alloy powder (that is, the silver-plated copper powder) is exposed and the surface is almost coated with silver. When the silver-plated copper powder is used in which part of the copper powder is exposed and the entire surface is covered with silver, the solderability of the composition L deteriorates, and the thermal shock property of the composition N deteriorates. In addition, silver powder is used to improve conductivity, and a composition not containing silver powder is not suitable for use in a conductive layer.

The copper powder of the silver-plated copper powder (a2) can be in any shape such as spherical shape, scale shape, massive shape, broken shape, etc., and the copper powder in mist shape is more ideal. In terms of paste viscosity stability over time, solderability, oxidation of exposed parts, electrical conductivity, thermal shock resistance, etc., the copper exposed area of the silver-plated copper powder (a2) is preferably 10% to 70%, more preferably 10%. to 50%, ideally 10% to 30%. The exposed area of copper can be obtained from the difference between the surface area of the copper powder and the surface area of the copper powder after measuring the silver coating area.

The silver-plated copper powder (a2) can be obtained by coating silver on the atomized copper powder by methods such as displacement plating, electroplating, and electroless plating. Among them, the displacement plating method coating that can improve the adhesion of copper powder and silver and lower operating costs is ideal.

The amount of silver coating on the surface of the copper powder is preferably 5 to 25% by weight, particularly preferably 10 to 23% by weight, based on 100 parts by weight of copper powder, from the viewpoint of improving the stability over time of paste viscosity, weldability, cost, and electrical conductivity. %.

The silver powder contained in the conductive powder (A2) is not particularly limited, and generally used shapes such as scales, spheres, and lumps can be used. In consideration of electrical conductivity, coatability, and edge wrapping properties, the scale-shaped and spherical particles with a particle size of 0.2 μm to 12 μm are ideal, and the most ideal size is 1 μm to 8 μm.

The mixing ratio of silver-plated copper powder (a2) and silver powder is not particularly limited. Considering the conductivity, the ratio of silver powder to 100 parts by weight of silver-plated copper powder (a2) is preferably 25 parts by weight to 266 parts by weight, more preferably 66 parts by weight to 150 parts by weight.

When the contact between the powders of the silver-plated copper powder (a2) is reduced, the resistance of the resulting coating film tends to increase. In addition, in order to increase the contact area between the silver-plated copper powders to improve electrical conductivity, it is desirable to give impact to the silver-plated copper powder (a2) to deform the particle shape into a flat shape. The average particle size of the silver-plated copper powder (a2) is not particularly limited, and is preferably 1 to 20 μm, more preferably 1 to 10 μm, considering the spreadability and dispersion stability of the paste. The average particle diameter can be measured with a laser scattering type flow distribution measuring device.

In Composition K and Composition L, as the binder resin, from the viewpoints of adhesion, filler dispersibility, and solubility in organic solvents, a compound having an amide group, an ester group, an imide group, and an ether group is used. A thermoplastic resin (B1) having at least one functional group selected from the group. This thermoplastic resin (B1) can be used in various combinations.

The thermoplastic resin (B1) is not particularly limited, but preferably has an aromatic ring from the viewpoint of heat resistance and the like. From the viewpoint of solubility in the organic solvent (C), it is also desirable to have an ether bond. For example, polyphenylene ether amide 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 , polyphenylene ether amide imide with phenylene ether bond, amide bond and imide bond in the main chain, polyphenylene amide with phenylene bond and amide bond in the main chain, phenylene ether bond in the main chain Polyphenylene imide with radical bond and imide bond, polyphenylene amide imide with phenylene bond, amide bond and imide bond in the main chain, xylylene bond in the main chain and Polyxylylene amide having an amide bond, polyxylylene imide having a xylylene bond and an imide bond in the main chain, and a polyxylylene imide having a xylylene bond, an amide bond, and an imide bond in the main chain Polyxylylene amidoimide and the like are preferably used at least one of them. In addition, an ester bond, a sulfide bond, etc. may be included, or a benzene ring may be substituted with an arbitrary substituent.

Specifically, the thermoplastic resin (B1) is preferably a resin having a repeating unit represented by the following general formula (I) or (II). In addition, a resin having both (I) and (II) repeating units is more desirable.

General formula (I):

或；R⁵及R⁶各自独立为氢、低级烷基、三氟甲基、三氯甲基或苯基；Y为

或

；Ar¹表示芳香族的2价基；Ar²表示芳香族的3价基；Ar³表示芳香族的4价基)(In the formula: R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, lower alkyl, lower alkoxy or halogen atom; X ¹ is a single bond, -O-, -S-, -CO-, -SO ₂ -, -SO-,

or ; R ⁵ and R ⁶ are each independently hydrogen, lower alkyl, trifluoromethyl, trichloromethyl or phenyl; Y is

or

; Ar ¹ represents an aromatic 2-valent group; Ar ² represents an aromatic 3-valent group; Ar ³ represents an aromatic 4-valent group)

General formula (II):

；R¹⁰及R¹¹各自独立为氢原子、低级烷基、三氟甲基、三氯甲基或苯基；Y同上述通式(I))(In the formula: R ⁷ , R ⁸ and R ⁹ are each independently a lower alkyl group, a lower alkoxy group or a halogen atom; s, t and u are each independently an integer from 0 to 4 in the number of substituents; R ⁷ , R ⁸ and When each of ^R9 is a plurality of bonds, each of them may be the same or different; each ^{of X2} and ^X3 is independently -O- or

; R ¹⁰ and R ¹¹ are each independently hydrogen atom, lower alkyl, trifluoromethyl, trichloromethyl or phenyl; Y is the same as above-mentioned general formula (I))

In the general formulas (I) and (II), lower alkyl, lower alkoxy, alkyl having 1 to 4 carbons, and alkoxy having 1 to 4 carbons are preferable. The phenyl groups of R ⁵ , R ⁶ , R ¹⁰ , and R ¹¹ in the general formulas (I) and (II) may be unsubstituted or substituted by random substituents such as methyl, ethyl, and sulfo.

The repeating unit represented by the above general formula (I) is preferably a compound in which the benzene ring is bonded to each other at the 1,4-position as represented by the following general formula (III).

Likewise, the repeating unit represented by the above general formula (II) is preferably a compound that is connected to a benzene ring at the 1,4-position as shown in the following general formula (IV).

The thermoplastic resin (B1) having the above-mentioned repeating unit can be composed of the acid component (S) described below, that is, aromatic dicarboxylic acid, aromatic tricarboxylic acid, aromatic tetracarboxylic acid or their reactive acid derivatives and the following Obtained by the reaction of the indicated diamine. In addition, acid components and diamines can be used in combination of various types.

Among the repeating units represented by the above-mentioned general formulas (I) and (III), diamine is more desirable, 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)diphenylamine, 4,4′-bis(4-aminophenoxy) Formed from one or more types of biphenyl and the like. Among them, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is particularly preferable.

Among the repeating units represented by the above-mentioned general formulas (II) and (IV), it is preferable to use 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene as the diamine, for example, Oxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-[1,3-phenylenebis(1-methylethylene)]bisaniline, 4,4 '-[1,4-phenylenebis(1-methylethylene)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethylene)]bisaniline Wait for more than one kind to form.

When forming the repeating unit of the general formula (I), (II), (III), (IV), in addition to the above-mentioned diamines, 4,4'-diaminodiphenylether, 4,4'-diamine can be used in combination. Aminodiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyldiphenyl ether, 4,4'-diamino-3,3',5,5'- Tetramethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraethyldiphenyl ether, 2,2'-[4,4'-diamino-3, 3',5,5'-tetramethyldiphenyl]propane, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylsulfone, piperazine, hexamethylenediamine, seven Methylenediamine, tetramethylenediamine, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 3-methylheptamethylenediamine, 1,3-bis One or more kinds of (3-aminopropyl)tetramethyldisiloxane and the like.

The aromatic dicarboxylic acid is a carboxylic acid in which two carboxyl groups are bonded to an aromatic ring. The aromatic tricarboxylic acid is a carboxylic acid in which three carboxyl groups are bonded to an aromatic ring, and preferably two of the three carboxyl groups are 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 preferably two of the four carboxyl groups are bonded to adjacent carbon atoms. The aromatic ring may be a ring into which a heteroatom is introduced (aromatic heterocyclic ring), or an aromatic ring bonded via an alkylene group, oxygen, a single bond, a carbonyl group, or the like. In addition, the aromatic ring may contain a substituent not involved in the condensation reaction of an alkoxy group, an allyloxy group, an alkylamino group, a halogen, or the like.

Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'- Diphenyldicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and the like, but terephthalic acid and isophthalic acid, which are easily available and inexpensive, are preferred. The reactive derivatives of aromatic dicarboxylic acids refer to dihydrogenates, dibromides, diesters, and the like of the aforementioned aromatic dicarboxylic acids.

Aromatic tricarboxylic acids such as trimellitic acid, 3,3',4-benzophenonetricarboxylic acid, 2,3,4'-diphenyltricarboxylic acid, 2,3,6- Pyridinetricarboxylic acid, 3,3,4'-benzoanilinetricarboxylic acid, 1,4,5-naphthalenetricarboxylic acid, 2'-chloro-3,4,4'-benzoanilinetricarboxylic acid and the like. The reactive derivatives of aromatic tricarboxylic acids refer to acid anhydrides, halides, esters, amides, ammonium salts, and the like of the aforementioned aromatic tricarboxylic acids. Preferable examples of specific examples include trimellitic anhydride, trimellitic anhydride monochloride, 1,4-dicarboxy-3-N,N-dimethylcarbamoylbenzene, 1,4-dimethylcarboxylate-3-carboxybenzene , 1,4-dicarboxy-3-phenoxycarbonylbenzene, 2,6-dicarboxy-3-methoxypyridine, 1,6-dicarboxy-5-carbamoylnaphthalene, the aforementioned aromatic tricarboxylates Ammonium salts formed with ammonia, dimethylamine, trimethylamine, etc. Among them, trimellitic anhydride and trimellitic anhydride monochloride, which are easily available and inexpensive, are ideal.

Aromatic tetracarboxylic acids are ideal, such as pyromellitic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 1, 2,5,6-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 2,3,5,6-pyridine tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 3,4,9,10-perillene tetracarboxylic acid, 4,4′-sulfonyl diphthalic acid, m-terphenyl-3,3”, 4,4”-tetracarboxylic acid, p-linked Triphenyl-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, etc. The reactive derivatives of aromatic tetracarboxylic acids refer to the aforementioned Dianhydrides, halides, esters, amides, ammonium salts, etc. of aromatic tetracarboxylic acids.

The usage amount of the acid component (S) formed from aromatic dicarboxylic acid, aromatic tricarboxylic acid, aromatic tetracarboxylic acid or their reactive derivatives depends on the molecular weight, mechanical strength, heat resistance, etc. of the obtained polymer. , with respect to 100 mol% of the total amount of diamines, it is more desirable to be 80 to 120 mol% in total, and particularly ideal to be 95 to 105 mol%.

When composition M and composition N are used as the binder resin, the thermoplastic resin (B2) used is selected from polyamide silicone resin, poly Selected from amidoimide resin and polyimide silicone resin. This thermoplastic resin (B2) can be used in various combinations.

The thermoplastic resin (B2) is not particularly limited. For example, an acid component such as an aromatic dicarboxylic acid, an aromatic tricarboxylic acid, an aromatic tetracarboxylic acid or a reactive derivative thereof may be mixed with diaminosilicone as an essential component. obtained by polycondensation of diamines.

The diaminosilicone used is ideal as follows general formula (V):

(wherein: Y ¹ is a divalent hydrocarbon group, Y ² is a monovalent hydrocarbon group, in addition, two Y ¹ can be the same or different, a plurality of Y ² can be the same or different, and m is an integer greater than 1) thing.

The divalent hydrocarbon group represented by Y ¹ is, for example, an alkylene group with 1 to 10 carbons, substituted or unsubstituted phenylene, etc., and the monovalent hydrocarbon group represented by Y ² is, for example, an alkyl group with 1 to 10 carbons, substituted or For an unsubstituted phenyl group, etc., m is preferably an integer of 1 to 100. These diaminosilicones can be used alone or in combination of two or more.

Other diamines that can be used together with the above-mentioned diaminosilicone are not particularly limited, but from the viewpoints of resin resistance, solubility in organic solvents, and solution viscosity, it is ideal to use aromatic diamines, and more preferably to use Polyphenylene ether diamine containing phenylene ether in its main chain.

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

；R⁵及R⁶各自独立为氢、碳数1至4的低级烷基、三氟甲基、三氯甲基、取代或无取代的苯基)。(wherein: R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, or a halogen atom; X ¹ is a single bond, -O -, -S-, -CO-, -SO ₂ -, -SO-, or

; R ⁵ and R ⁶ are each independently hydrogen, lower alkyl with 1 to 4 carbons, trifluoromethyl, trichloromethyl, substituted or unsubstituted phenyl).

The polyphenylene ether diamine of the general formula (VI) is preferably a compound represented by the following general formula (VII), which is linked to a benzene ring at the 1,4-position.

Aromatic diamines (e1) having ether bonds represented by the above general formula (VII) such as 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-hexafluoro-2,2-bis[3-methyl- 4-(4-aminophenoxy)phenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-amino Phenoxy)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)diphenylamine, 4,4'-bis(4-aminophenoxy)biphenyl, etc., in addition , can be used alone or in combination. Among them, 2,2-bis[(4-aminophenoxy)phenyl]propane is more preferable.

Aromatic diamines (e2) other than the above (e1) 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-methylethylene)]bisaniline, 4,4'-[1,4-phenylene Bis(1-methylethylene)]bisaniline, 3,3′-[1,3-phenylenebis(1-methylethylene)]bisaniline, 4,4′-diaminobenzene Base ether, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyldiphenyl ether, 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′-tetramethyldiphenyl]propane, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenylsulfone, o- Xylylenediamine, m-xylylenediamine, p-xylylenediamine, etc. can also be used singly or in combination.

Diamines other than (e1) and (e2) above, i.e. aliphatic or alicyclic diamines (e3) such as piperazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine , 3-methylheptamethylenediamine, and the like can be used singly or in combination.

When synthesizing the thermoplastic resin (B2), the acid component that reacts with the diamine containing the above-mentioned diaminosilicone as an essential component may be the above-mentioned acid component (S) for the above-mentioned synthetic resin (B1). The amount of the acid component (S) formed from these aromatic dicarboxylic acids, aromatic tricarboxylic acids, aromatic tetracarboxylic acids or their reactive derivatives depends on the molecular weight, mechanical strength, heat resistance, etc. of the obtained polymer. From the point of view, the total amount of diamines is preferably 80 to 120 mol%, particularly preferably 95 to 105 mol%, based on 100 mol% of the total amount of diamines.

In the composition K, the mixing ratio of the conductive powder (A1) and the thermoplastic resin (B1) is not limited, but from the viewpoint of the conductivity of the formed coating film, etc., to 100 parts by weight of the component (A1) (B1) The ingredients are preferably 2 to 25 parts by weight, more preferably 4 to 14 parts by weight.

In the composition (L), the mixing ratio of the conductive powder (A2) and the thermoplastic resin (B1) is not limited, but from the viewpoint of the conductivity of the formed coating film, for 100 parts by weight of the (A2) component ( The component B1) is preferably 2 to 25 parts by weight, more preferably 4 to 14 parts by weight.

In the composition (M), the mixing ratio of the conductive powder (A1) and the thermoplastic resin (B2) is not limited, but from the viewpoints of coating film strength, toughness, and conductivity, for 100 parts by weight of the (A1) component ( The component B2) is preferably 2 to 25 parts by weight, particularly ideally 4 to 14 parts by weight.

In the composition N, the mixing ratio of the conductive powder (A2) and the thermoplastic resin (B2) is not limited, but from the viewpoint of the flexibility and conductivity of the coating film, the ratio of the (B2) component to 100 parts by weight of the (A2) component More preferably, it is 2 to 25 parts by weight, and more preferably, it is 4 to 14 parts by weight.

Examples of organic solvents (C) used in compositions K, L, M, and N include aromatic solvents such as benzene, toluene, and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Ketone and other ketone solvents; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol Ether solvents such as alcohol diethyl ether; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone and other ester solvents; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and other amide solvents. This solvent is used to dissolve the resin or adjust the viscosity of the paste when making the paste, and it can be used singly or in combination of two or more.

The amount of the organic solvent (C) to be added is generally 75 to 4600 parts by weight relative to 100 parts by weight of the thermoplastic resin, and is preferably 125 to 3060 parts by weight.

Examples of each composition containing the above-mentioned added components can be obtained by kneading and dispersing each component using a Lycra machine, a three-seat roller machine, a ball mill, a disperser, and the like. In addition, in order to improve the dispersibility and coatability of the conductive powder (filler), a dispersant or a coupling agent may be added.

The dispersant used is ideal, such as saturated fatty acids such as palmitic acid and stearic acid with 16 to 20 carbons; unsaturated fatty acids such as oleic acid and linoleic acid with 16 to 18 carbons; sodium of the saturated/unsaturated fatty acids , Potassium, calcium, zinc, copper and other metal salts at least one. The amount of dispersant to be added is preferably 0.2 to 240 parts by weight, more preferably 2 to 120 parts by weight, based on 100 parts by weight of the resin, from the viewpoint of the dispersibility of the conductive powder, the conductivity of the coating film, and the adhesion between the coating film and the substrate. parts by weight.

Coupling agents such as vinylmethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, β-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropyl Silane coupling agents such as methyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, or The titanate-based coupling agent, aluminate-based coupling agent, zircoaluminate-based coupling agent, and the like are preferably added in an amount of 30 parts by weight or less to 100 parts by weight of the above-mentioned thermoplastic resin.

The composition of the present invention is suitable for conductor layers of various electronic parts, such as conductive circuits or electrode materials.

The electronic component of the present invention is an electronic component having a conductor layer formed using the composition of the present invention. Various electronic components, such as aluminum electrolytic capacitors, tantalum solid electrolytic capacitors, ceramic capacitors, etc., using the composition as electrode materials; various substrates that form conductive circuits from the composition of the present invention by screen printing; formed by the composition of the present invention The conductive circuit of the IC card as an antenna circuit. The composition of the present invention is also suitable as a cathode material for solid electrolytic capacitors using a valve metal in the anode.

The electronic component of the present invention is preferably a solid electrolytic capacitor in which a dielectric oxide film, a solid electrolyte layer, and a cathode layer including a conductor layer formed using the composition of the present invention are formed on an anode base formed of a valve metal.

The solid electrolytic capacitor 10 illustrated in FIG. 1 includes an anode base 2 in which an anode wire 1 is embedded, a dielectric oxygen film (anodized film) 3 and a solid electrolyte layer (semiconductor layer) 4 sequentially formed on the anode base 2, And the capacitor element of the cathode 5 constituted by the carbon layer 51 and the conductor layer 52 . The valve metal used for the anode base 2 is preferably tantalum, aluminum, titanium, niobium, or the like. The shape of the anode base 2 is preferably foil, plate or rod. The anode base 2 is formed by compressing and molding valve action metal powder in the form of anode wire 1 embedded with a tantalum lead wire, and then heating at 2000° C. for several 10 minutes in a vacuum to form a sintered body.

Next, a voltage is applied to the obtained sintered body (anode base 2 ) in a chemical conversion solution such as nitric acid or phosphoric acid, and a dielectric oxide film 3 such as Ta ₂ O ₃ is formed on the surface of the anode base 2 after chemical conversion. The oxide film 3 is preferably a layer formed of the oxide of the anode base metal itself, but may also be a dielectric oxide layer different from the anode base. After the dielectric oxide film 3 is formed, the sintered body is immersed in a semiconductor mother liquid such as manganese nitrate solution, and after being immersed in the liquid, it is fired and thermally decomposed at 200 to 350°C, and a manganese dioxide layer is formed inside the sintered body (on the surface of the sintered body). The main solid electrolyte layer 4 . Thermal decomposition and then chemical formation to repair the dielectric oxide film 3 damaged during sintering. If necessary, repeat the impregnation, sintering and re-forming steps more than 5 to 10 times to form the solid electrolyte layer 4 with a desired thickness. In addition, as the solid electrolyte layer, TCNQ (7,7,8,8-tetracyanodimethylbenzoquinone) complexes called organic semiconductors or conductive polymers such as polypyrrole, polythiophene, and polyaniline can be used. And so formed.

After the solid electrolyte layer 4 is formed, the carbon paste is coated and dried to form the carbon layer 51 of a part of the cathode layer 5, and then the conductor layer (silver layer or silver paste layer) of the other part of the cathode layer is formed on it using the composition of the present invention 52. The lead frame 7 for taking out the cathode is connected to the obtained conductor layer 52 by welding or the conductive adhesive 6, and the anode wire 1 drawn from the sintered body 2 is welded to the lead frame 7 or the like. Finally, the exterior resin 8 is sealed as a whole by resin impregnation or resin molding. The size of the obtained solid electrolytic capacitor is generally 2 to 7 mm in length, 1.25 to 4.3 mm in width, and 1.2 to 2.8 mm in height.

Hereinafter, the present invention will be described in more detail with examples. In addition, the measurement methods and evaluation methods of various characteristics in the examples are as follows.

[aspect ratio]

After mixing 8g of main agent (No.10-8130) and 2g of curing agent (No.10-8132) of low-viscosity epoxy resin (manufactured by Murat), add 2g of powder for measurement, fully disperse and vacuum at 30°C After defoaming, let stand at 30°C for 10 hours to precipitate the particles and solidify the resin. Thereafter, the obtained cured product was cut in a vertical direction, and then the section was observed with a microscope at 1000 times, and the major diameter/short diameter of 150 particles appearing in the cross section were calculated, and the average value was used as the aspect ratio.

[The average particle size]

The average particle size of the powder was measured with a Masda classifier (manufactured by Maruman).

[copper exposure area]

Take out 5 silver-plated copper powder particles that make at will, utilize scanning type Auger electron spectroscopic analysis device to observe, and carry out the quantitative analysis of noble metal (silver) and non-noble metal (copper) by Auger image, after calculating the copper occupancy rate, The average value of five samples for measurement was used as the copper exposed area (%).

[paste viscosity]

The temperature inside the constant temperature layer was set at 25°C, and measured with a 3° cone E-type viscometer manufactured by Tokyo Keiki, and the value of the paste viscosity was 10 minutes after the start of the measurement.

[Time-dependent changes in paste viscosity]

The resulting paste was placed in a 30°C constant temperature bath for 6 months, and its viscosity was measured.

[Volume resistivity]

The volume resistivity of the dry coating film obtained using the paste was measured with the double bridge type resistance measuring device (TYPE2769 by Yokogawa Electric Co., Ltd.).

[Migration Features]

Use a dry coating film for volume resistivity measurement, form electrodes at a distance of 2mm in the center of the dry coating film, drop pure water to cover all electrodes, and apply a voltage of 7V to both ends to move the measured silver until the electrodes are short-circuited time to assess migration properties.

[Edge wrapping]

A 1 mm x 1 mm x 1.5 mm cube-shaped tantalum sintered body was immersed in the measurement paste, dried, and the obtained element was covered with a transparent epoxy resin, and left at room temperature for 10 hours to cure. Afterwards, the central part of the long side of the cube was cut off with a diamond cutting machine, ground with sandpaper and abrasive particles, and used as an evaluation element. The paste-coated state of the four corners of the element for evaluation was observed with an electron microscope. Evaluation A: Good, B: The coating film thickness of the edge portion is 1 μm or less, C: There is a chipped portion in the edge portion.

[Film strength]

After drying at 180° C. for 1 hour with a coater, a silver film with a film thickness of 50 μm was formed on a Teflon plate. The film was peeled off from the Teflon plate, and a rectangular test piece with a width of 5 mm×40 mm was produced.

Thereafter, the strength of the coating film was measured using a tensile strength tester (manufactured by Imada Seisakusho: tensile compression tester SL-2001).

[Flexibility of Coating Film]

Apply the paste on a PET film with a thickness of 125 μm, a width of 1 cm, and a length of 10 cm in a width of 2 mm, and dry it at 180° C. for 1 hour. Repeat the contact between the end of the film and the surface of the end, and then contact the back surface. Cracks appeared in the coating film after several times of measurement.

[Capacitor Characteristics]

According to JIS C 5102-1994 (Test methods for fixed capacitors for electronic equipment), the characteristics of tantalum capacitors are measured. In addition, the equivalent series resistance (ESR) was measured with an LCR meter. For the leakage current (LC), after making a tantalum capacitor using the paste for measurement as the conductor layer, measure the value of 1000h and 2000h at 85°C and 85%RH environment with a data micro ammeter (Aardman test; R8340A). The tan δ and the impedance were measured with an LCR meter (4284A) manufactured by Theraton Corporation. Cap (capacitance) was measured by LCR (4284A manufactured by Hullaton).

[Overvoltage load characteristics of capacitors]

After an overvoltage is applied to the rated voltage of a tantalum capacitor, the characteristics of the capacitor are measured to confirm the number of breakdowns of the capacitor.

[Solder Adhesiveness]

An aluminum plate with a width of 1 cm, a length of 2 cm, and a thickness of 0.5 mm was dipped in the measurement paste for 1 cm, taken out, and dried at 180° C. for 1 hour with a baking dryer to be used as a sample for evaluation. After immersing the samples for evaluation in the flux, they were then immersed in soldering baths at various set temperatures to observe the bonding state of the soldering. Evaluation A: solder coating area 80% or more, B: 50% or more and less than 80%, C: 30% or more and less than 50%, D: less than 30%.

[Solder Adhesion Test Conditions]

[Solder heat resistance of capacitors]

The rate of change in capacitance of a tantalum capacitor after being immersed in a solder bath for 10 seconds was measured. Soldering bath temperature: 230°C, 260°C, 290°C.

[Thermal shock resistance of capacitors]

Put the tantalum capacitor into the thermal shock tester, and take it out after 1000 cycles to measure the characteristics of the capacitor. Thermal shock conditions are performed at -50°C to 80°C. That is, after standing in a tank at -50°C for 30 minutes, transfer it to a tank at 80°C within 3 minutes for 30 minutes, and then transfer it to a tank at -50°C within 3 minutes, which is considered as one cycle.

<Synthesis Example 1 of Thermoplastic Resin (B1)>

Under nitrogen, 100 g (0.24 moles) of BAPP (2,2-bis[4-(4-aminophenoxy)phenyl]propane) as a diamine was dissolved in the 400 g of N-methyl-2-pyrrolidone in a 1-liter four-neck flask. After cooling the obtained solution to -10°C, 49.5 g (0.24 moles) of isophthalic acid dichloride and 56.6 g of propylene oxide were added at a temperature not higher than -5°C. After stirring at room temperature for 3 hours, the reaction solution was put into pure water to isolate the polymer, and after drying, it was dissolved in N-methyl-2-pyrrolidone, and then the resulting solution was put into pure water to refine the polyamide polymer. .

<Synthesis Example 2 of Thermoplastic Resin (B1)>

Under nitrogen, 205 g (500 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane) as diamine was dissolved in a container equipped with a thermometer, a stirrer, a nitrogen introduction pipe, and a cooling pipe. 11177g of diethylene glycol dimethyl ether in a 3-liter four-necked flask. After cooling the obtained solution to -10°C, 105.3 g of trimellitic anhydride monochloride and 87 g of propylene oxide were added so that the solution temperature did not exceed -5°C. After stirring at room temperature for 3 hours, the viscosity of the reaction liquid was increased to form a transparent liquid, and then 841 g of diethylene glycol dimethyl ether was added, followed by further stirring for 1 hour. Thereafter, 128 g of acetic anhydride and 64 g of pyridine were added, and stirring was continued at 60° C. for a whole day and night. The resulting reaction solution was put into 250 g of methanol to isolate the polyamideimide, and after drying, it was dissolved in N,N-dimethylformamide, and then put into methanol to obtain a polyamideimide polymer product .

<Synthesis Example 1 of Thermoplastic Resin (B2)>

Under nitrogen, 2,2-bis[4-(4-aminophenoxy)phenyl] propane 65.6g (160 mmoles) and diaminosiloxane ( Shin-Etsu Chemical Co., Ltd., X-22-161B; in general formula (V), m=38, Y ¹ =-C ₃ H ₆ -, Y ² =-CH ₃ ) 64g (40 mmol) (molar ratio 80 mol%/20 mol%) was dissolved in 335 g of diethylene glycol dimethyl ether in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube.

After cooling the resulting solution to -10°C, add 40.6g (200 mmol) of isophthalic acid dichloride, and then add 23.2g of propylene oxide, and then add diethylene dichloride at a temperature not exceeding -5°C. Alcohol dimethyl ether 96g, after stirring at room temperature for 3 hours, put the reaction solution into methanol to isolate the polymer, then dissolve it in dimethylformamide after drying, and then put it into methanol to refine polyamide silicone copolymerization thing.

<Synthesis Example 2 of Thermoplastic Resin (B2)>

Under nitrogen, 174.3 g (425 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 18.6 g of diaminopropyltetramethyldisiloxane ( Shin-Etsu Chemical Co., Ltd., LP7100) (75 mmol) (molar ratio: 85 mol %/15 mol %) dissolved in diethylene diethylene glycol in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Alcohol dimethyl ether 1177g.

After the resulting solution was cooled to -10°C, 105.3 g (500 mmol) of trimellitic anhydride monochloride was added at a temperature not higher than -5°C, and 87 g of propylene oxide was added. After stirring at room temperature for 3 hours to increase the viscosity of the reaction liquid to become a transparent liquid, 841 g of diethylene glycol dimethyl ether was further added. After stirring for 1 hour, 128 g of acetic anhydride and 64 g of pyridine were added, followed by stirring at 60° C. for a whole day and night. The resulting reaction solution was put 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 then put into In methanol, the polyamide-imide-silicone copolymer was refined, and then dried under reduced pressure.

<Preparation example of silver-plated copper powder (a1)>

Spherical copper powder with an average particle size of 5.1 μm (manufactured by Nippon Spray Processing Co., Ltd., trade name SFR-Cu) obtained by spraying method was washed with dilute hydrochloric acid and pure water, and the powder containing 80 g of AgCN and 75 g of NaCN per 1 liter of water was washed. In the silver plating solution, the spherical copper powder is replaced with 15% by weight of silver, then washed with water and dried to obtain the silver-plated copper powder.

750 g of the obtained silver-plated copper powder and 3 kg of zirconia balls with a diameter of 5 mm were put into a 2-liter ball mill container, and after rotating for 40 minutes, the silver-plated copper powder with an average aspect ratio of 1.3 and an average long-diameter particle diameter of 5.5 μm was obtained.

<Preparation example of silver-plated copper powder (a2)>

Spherical copper powder with an average particle size of 5.1 μm (manufactured by Nippon Spray Processing Co., Ltd., trade name SFR-Cu) obtained by spraying was washed with dilute hydrochloric acid and pure water, and then mixed with 80 g of AgCN and 75 g of NaCN per 1 liter of water. In the silver plating solution, the spherical copper powder is replaced by 20% by weight of silver, washed with water, and dried to obtain silver-plated copper powder.

750 g of the obtained silver-plated copper powder and 3 kg of zirconia balls with a diameter of 5 mm were put into a 2-liter ball mill container, and after rotating for 40 minutes, silver-plated copper powder with an average particle diameter of 8.1 μm was obtained.

Implementation

Example K1

According to the ratio shown in Table 1, add the silver-plated copper powder and silver powder (SF#7 scale-like average particle size manufactured by Dekusa Co., Ltd., 6.8 μm) obtained in the production example of the above-mentioned silver-plated copper powder (a1) to the above-mentioned thermoplastic resin (B1 ) in the synthesis example obtained by adding 22.2 parts by weight of the polyamide polymer obtained by adding 222.2 parts by weight of diethylene glycol dimethyl ether to the varnish obtained by dissolving, and dispersing for 20 minutes by a disperser to obtain a composition (paste) K. After defoaming the obtained paste, apply a certain amount on a glass slide by screen printing method (coating area: 1cm×7.5cm, coating thickness: 40±10μm), and then use a batch drying oven to dry at 180°C 1 hour to dry the coating film. The volume resistivity and migration characteristics of the resulting dried coating film were measured. Tantalum capacitors were fabricated using the obtained paste, and the equivalent in-line resistance and leakage current were measured, and edge wrapping properties were evaluated.

Example K2

Except that the average particle size of the spherical copper powder obtained by the spraying method is 5.9 μm, the aspect ratio of the silver-plated copper powder is 1.5 and the average particle size is 6.7 μm, the others are the same as in the embodiment K1.

Example K3

Except that the average particle size of the spherical copper powder produced by the spray method is 5.9 μm, the rotation time of the ball mill is 60 minutes, the aspect ratio of the silver-plated copper powder is 2.5 and the average particle size is 8.0 μm, other is the same as embodiment K1 .

Example K4

Except that the average particle size of the spherical copper powder produced by the spray method is 4.2 μm, the rotation time of the ball mill is 120 minutes, the aspect ratio of the silver-plated copper powder is 12 and the average particle size is 7.2 μm, other is the same as embodiment K1 .

Example K5

Except that the average particle size of the spherical copper powder produced by the spray method is 3.5 μm, the rotation time of the ball mill is 180 minutes, the aspect ratio of the silver-plated copper powder is 20 and the average particle size is 6.2 μm, other is the same as embodiment K1 .

Example K6

Except that the average particle size of the spherical copper powder obtained by the spraying method is 0.1 μm, the aspect ratio of the silver-plated copper powder is 3.2 and the average particle size is 0.2 μm, the others are the same as in the embodiment K1.

Example K7

Except that the average particle size of the spherical copper powder obtained by the spraying method is 0.6 μm, the aspect ratio of the silver-plated copper powder is 3 and the average particle size is 1.0 μm, the others are the same as in the embodiment K1.

Example K8

Except that the average particle size of the spherical copper powder obtained by the spraying method is 1.0 μm, the aspect ratio of the silver-plated copper powder is 3.1 and the average particle size is 1.5 μm, the others are the same as in the embodiment K1.

Example K9

Except that the average particle size of the spherical copper powder obtained by the spraying method is 5.5 μm, the aspect ratio of the silver-plated copper powder is 3.1 and the average particle size is 8.0 μm, the others are the same as in the embodiment K1.

Example K10

Except that the average particle size of the spherical copper powder obtained by the spraying method is 8.2 μm, the aspect ratio of the silver-plated copper powder is 3.2 and the average particle size is 12 μm, the others are the same as in the embodiment K1.

Example K11

Except that the average particle size of the spherical copper powder obtained by the spraying method is 13.6 μm, the aspect ratio of the silver-plated copper powder is 3.0 and the average particle size is 20 μm, the others are the same as in the embodiment K1.

Example K12

Except that the average particle size of the spherical copper powder produced by the spray method is 4.6 μm, the silver replacement amount to the spherical copper powder is 0.5% by weight, the aspect ratio of the silver-plated copper powder is 3.5 and the average particle size is 6.7 μm, Others are the same as embodiment K1.

Example K13

Except that the average particle size of the spherical copper powder produced by the spray method is 3.8 μm, the silver substitution amount to the spherical copper powder is 1.0% by weight, the aspect ratio of the silver-plated copper powder is 3.1 and the average particle size is 5.3 μm, Others are the same as embodiment K1.

Example K14

Except that the average particle size of the spherical copper powder produced by the spray method is 3.6 μm, the silver substitution amount to the spherical copper powder is 1.5% by weight, the aspect ratio of the silver-plated copper powder is 3.5 and the average particle size is 5.2 μm, Others are the same as embodiment K1.

Example K15

Except that the average particle size of the spherical copper powder produced by the spray method is 4.3 μm, the silver substitution amount to the spherical copper powder is 25% by weight, the aspect ratio of the silver-plated copper powder is 3.4 and the average particle size is 6.2 μm, Others are the same as embodiment K1.

Example K16

Except that the average particle size of the spherical copper powder produced by the spray method is 5.0 μm, the silver substitution amount to the spherical copper powder is 35% by weight, the aspect ratio of the silver-plated copper powder is 3.8 and the average particle size is 7.5 μm, Others are the same as embodiment K1.

Example K17

Except that the average particle size of the spherical copper powder produced by the spray method is 4.7 μm, the silver replacement amount to the spherical copper powder is 50% by weight, the aspect ratio of the silver-plated copper powder is 4.0 and the average particle size is 7.1 μm, Others are the same as embodiment K1.

Example K18

Except that the average particle size of the spherical copper powder produced by the spray method is 5.9 μm, the silver replacement amount of the spherical copper powder is 20% by weight, the aspect ratio of the silver-plated copper powder is 2.5 and the average particle size is 8.0 μm, the silver powder (Deli Chemical TCG-1) is the same as Example K1 except that the shape is spherical and the average particle diameter is 2.0 μm.

Example K19

Except that the average particle size of the spherical copper powder produced by the spray method is 5.9 μm, the silver replacement amount to the spherical copper powder is 20% by weight, the aspect ratio of the silver-plated copper powder is 2.5 and the average particle size is 8.0 μm, Others are the same as embodiment K1.

Example K20

Except that the average particle size of the spherical copper powder produced by the spray method is 5.9 μm, the silver replacement amount to the spherical copper powder is 20% by weight, the aspect ratio of the silver-plated copper powder is 2.5 and the average particle size is 8.0 μm, Others are the same as embodiment K1.

Example K21

Except that the average particle size of the spherical copper powder produced by the spray method is 5.9 μm, the silver replacement amount to the spherical copper powder is 20% by weight, the aspect ratio of the silver-plated copper powder is 2.5 and the average particle size is 8.0 μm, Others are the same as embodiment K1.

Example K22

Except that the average particle size of the spherical copper powder produced by the spray method is 5.9 μm, the silver replacement amount to the spherical copper powder is 20% by weight, the aspect ratio of the silver-plated copper powder is 2.5 and the average particle size is 8.0 μm, Others are the same as embodiment K1.

Example K23

Except that the average particle size of the spherical copper powder produced by the spray method is 5.9 μm, the silver replacement amount to the spherical copper powder is 20% by weight, the aspect ratio of the silver-plated copper powder is 2.5 and the average particle size is 8.0 μm, Others are the same as embodiment K1.

Example K24

Except that the average particle size of the spherical copper powder produced by the spray method is 5.9 μm, the silver replacement amount to the spherical copper powder is 20% by weight, the aspect ratio of the silver-plated copper powder is 2.5 and the average particle size is 8.0 μm, Others are the same as embodiment K1.

Example K25

In addition to using the polyamide-imide polymer obtained in Synthesis Example 2 of the above-mentioned thermoplastic resin (B1), the average particle size of the spherical copper powder obtained by the spray method was 5.9 μm, and the silver substitution amount for the spherical copper powder was 15 wt. %, the aspect ratio of the silver-plated copper powder is 2.5 and the average particle diameter is 8.0 μm, other is the same as embodiment K1.

Example K26

In addition to using the polyamide-imide polymer obtained in Synthesis Example 2 of the above-mentioned thermoplastic resin (B1), the average particle diameter of the spherical copper powder obtained by the spray method was 4.4 μm, and the silver substitution amount for the spherical copper powder was 15 wt. %, the aspect ratio of the silver-plated copper powder is 3.2 and the average particle diameter is 6.5 μm, other is the same as embodiment K1.

Comparative example K1

Except that the average particle size of the spherical copper powder produced by the spraying method is 13.8 μm, the silver replacement amount to the spherical copper powder is 15% by weight, the rotation time of the ball mill is 240 minutes, and the aspect ratio of the silver-plated copper powder is 25 and Except that the average particle diameter is 26 μm, the others are the same as in Example K1.

Comparative example K2

In addition to using the polyamide-imide polymer obtained in Synthesis Example 2 of the above-mentioned thermoplastic resin (B1), the average particle size of the spherical copper powder obtained by the spray method was 13.8 μm, and the silver substitution amount for the spherical copper powder was 15 wt. %, the rotation time of the ball mill is 240 minutes, the aspect ratio of the silver-plated copper powder is 25 and the average particle diameter is 26 μm, other is the same as embodiment K1.

Comparative example K3

Except that the silver-plated copper powder is replaced by spherical copper powder (Mitsui Metal Mine MFP1110 average particle diameter 1.1 μm), other is the same as embodiment K1.

Comparative example K4

Except not containing silver powder, other is the same as embodiment K1.

Comparative example K5

Except not containing silver-plated copper powder, other is the same as embodiment K1.

The obtained results are shown in Table K1 and Table K2.

Example L1

Add 118.8 parts by weight of silver-plated copper powder (copper exposed area 20%) and 79.2 parts by weight of silver powder (SF#7 scale-like average particle diameter of 6.8 μm manufactured by Dekusa Co., Ltd.) obtained in the production example of silver-plated copper powder (a2) to the above-mentioned Add 22.2 parts by weight of polyamide polymer obtained in Synthesis Example 1 of thermoplastic resin (B1) into the varnish obtained by dissolving 222.2 parts by weight of diethylene glycol dimethyl ether, and disperse with a disperser for 20 minutes to obtain a viscosity of 2000 mPa. Composition (cream) L of s. After defoaming the obtained paste, apply a certain amount on a glass slide by screen printing method (coating area: 1cm×7.5cm, coating thickness: 40±10μm), and then use a batch drying oven to dry at 180°C 1 hour to dry the coating film. The volume resistivity of the resulting dried coating film was measured. In order to measure the change of paste viscosity over time, part of the paste was transferred into a 50ml poly container, and then placed in a high-temperature tank at 30°C, and the viscosity was measured again after 6 months to calculate the rate of change. In addition, the solder adhesiveness of the obtained paste was evaluated. In addition, this paste was used for a cathode to produce a tantalum capacitor, and soldering heat resistance was tested.

Example L2

Except that the ball mill rotation time when making silver-plated copper powder is 60 minutes, and the copper exposed area of the obtained silver-plated copper powder is 30%, other is the same as embodiment L1.

Example L3

Except that the silver replacement amount when making the silver-plated copper powder was 15% by weight, and the copper exposed area of the obtained silver-plated copper powder was 40%, the others were the same as in Example L1.

Example L4

Except that the ball mill rotation time when making the silver-plated copper powder is 80 minutes, and the copper exposed area of the gained silver-plated copper powder is 60%, other is the same as embodiment L3.

Example L5

Except for using the polyamide-imide polymer obtained in Synthesis Example 2 of the above-mentioned thermoplastic resin (B1), the others were the same as in Example L2.

Comparative example L1

Except that the amount of silver replacement when making the silver-plated copper powder is 30 parts by weight, the rotation time of the ball mill is 20 minutes, and the copper exposed area of the obtained silver-plated copper powder is 0%, other is the same as embodiment L1.

Comparative example L2

Except that no silver-plated copper powder is used, and the amount of silver powder is 198 parts by weight, the others are the same as in Example L1.

Comparative example L3

Except that the silver-plated copper powder is replaced by the spherical copper powder prepared by the spraying method, the others are the same as in the embodiment L1.

The above obtained results are shown in Table L1.

Example M1

Add 118.8 parts by weight of silver-plated copper powder obtained in the production example of silver-plated copper powder (a1) and 79.2 parts by weight of silver powder (SF#7 scale-like average particle diameter of 6.8 μm manufactured by Tekusa Co., Ltd.) to the thermoplastic resin (B2) Add 22.2 parts by weight of the polyamide-silicone copolymer obtained in Synthesis Example 1 to the varnish obtained by dissolving 222.2 parts by weight of diethylene glycol dimethyl ether, and disperse it with a disperser for 20 minutes to obtain a combination with a viscosity of 2000 mPa·s. Thing (paste) M. After defoaming the obtained paste, apply a certain amount on a glass slide by screen printing method (coating area: 1cm×7.5cm, coating thickness: 40±10μm), and then use a batch drying oven to dry at 180°C 1 hour to dry the coating film. The volume resistivity of the resulting dried coating film was measured. In addition, a sample for measuring coating film strength was produced using the obtained paste, and then the coating film strength was measured. In addition, this paste was used in the cathode to produce a tantalum capacitor (rated voltage 4V), and the capacitor characteristics after the activation test were measured, and the destruction of the capacitor was confirmed.

Example M2

Except that the rotation time of the ball mill when making the silver-plated copper powder was 80 minutes, and the aspect ratio of the obtained silver-plated copper powder was 6.8, the others were the same as in the embodiment M1.

Example M3

Except that the rotation time of the ball mill when making the silver-plated copper powder is 120 minutes, and the aspect ratio of the obtained silver-plated copper powder is 12, the others are the same as the embodiment M1.

Example M4

Except that the rotation time of the ball mill when making the silver-plated copper powder was 150 minutes, and the aspect ratio of the obtained silver-plated copper powder was 19.3, the others were the same as in the embodiment M1.

Example M5

Except for using the polyamide-imide-silicone copolymer obtained in Synthesis Example 2 of the above-mentioned thermoplastic resin (B2), the others were the same as in Example M2.

Comparative example M1

Except that the rotation time of the ball mill when making the silver-plated copper powder was 180 minutes, and the aspect ratio of the obtained silver-plated copper powder was 23.0, the others were the same as in the embodiment M1.

Comparative example M2

Except that the polyamide polymer obtained in Synthesis Example 1 of the thermoplastic resin (B1) was used instead of the polyamide-silicone copolymer, the others were the same as in Example M2.

Comparative example M3

Except that the silver powder with an aspect ratio of 3.5 is used to replace the silver-plated copper powder, the others are the same as in the embodiment M1.

Comparative example M4

Except that the silver-plated copper powder and the silver powder are replaced by copper powder with an aspect ratio of 1, the others are the same as in the embodiment M1.

Comparative example M5

In addition to 60 parts by weight of epoxy resin (manufactured by Mitsui Chemicals Co., Ltd., trade name 140C), 40 parts by weight of aliphatic diglycidyl ether (manufactured by Asahi Denka Industry Co., Ltd., trade name ED-503), 2P4MHZ (Shikoku Chemical Industry Co., Ltd. (Co., Ltd., Thiazole) 3 parts by weight and dicyandiamide (Wako Pure Chemical Industry Co., Ltd.) 3 parts by weight to replace the polyamide-silicone copolymer, the others are the same as in Example M2.

The obtained results are shown in Table M1.

Example N1

118.8 parts by weight of silver-plated copper powder (copper exposed area 30%) and 79.2 parts by weight of silver powder (SF#7 scale-like average particle diameter of 6.8 μm manufactured by Dekusa Co., Ltd.) obtained in the production example of silver-plated copper powder (a2) were added. The varnish obtained by adding 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 above-mentioned thermoplastic resin (B2) was dispersed in a disperser for 20 minutes to obtain Composition (paste) N with a viscosity of 2000 mPa·s. After defoaming the obtained paste, apply a certain amount on a glass slide by screen printing method (coating area: 1cm×7.5cm, coating thickness: 40±10μm), and then use a batch drying oven to dry at 180°C 1 hour to dry the coating film. The volume resistivity of the resulting dried coating film was measured. In addition, the flexibility of the resulting paste was measured. In addition, this paste composition was used in a cathode to produce a tantalum capacitor, and a thermal shock test was performed to measure the leakage current (LC) of the capacitor.

Example N2

Except for using the polyamide-imide-silicone copolymer obtained in Synthesis Example 2 of the thermoplastic resin (B2), the others were the same as in Example N1.

Example N3

In addition to using the polyamide-imide-silicone copolymer obtained in Synthesis Example 2 of the thermoplastic resin (B2), the amount of silver substitution when producing silver-plated copper powder was 15% by weight, and the rotation time of the ball mill was 80 minutes. The obtained silver-plated copper Except that the copper exposed area of the powder is 50%, the others are the same as in the embodiment N1.

Comparative example N1

Except that the silver replacement amount when making the silver-plated copper powder is 30% by weight, the rotation time of the ball mill is 20 minutes, and the copper exposed area of the gained silver-plated copper powder is 0%, other is the same as embodiment N1.

Comparative example N2

In addition to 60 parts by weight of epoxy resin (manufactured by Mitsui Chemicals Co., Ltd., trade name 140C), 40 parts by weight of aliphatic diglycidyl ether (manufactured by Asahi Denka Industry Co., Ltd., trade name ED-503), 2P4MHZ (Shikoku Chemical Industry Co., Ltd. (Co., Ltd., thiazole) 3 parts by weight and dicyandiamide (Wako Pure Chemical Industry Co., Ltd.) 3 parts by weight to replace the polyamide-silicone copolymer, the others are the same as in Example N1.

The results obtained are shown in Table N1.

The disclosure of this specification is related to Japanese Patent Application No. 2001-322320 filed on October 19, 2001, Japanese Patent Application No. 2001-322321 filed on October 19, 2001, and Japanese Patent Application No. 2001 filed on October 31, 2001. -333649 and the subject matter described in Japanese Patent Application No. 2001-333650 filed on October 31, 2001 are related, and the disclosure thereof is cited.

In addition to the above, the above-described embodiments may be modified or varied without departing from the novel and advantageous features of the invention. Accordingly, the scope of application includes all amendments and changes.

Claims (6)

1. conductive resin composition comprises: contain part surface and have copper exposed portions serve and this to expose area be 10 to 70% silver-plated copper powder (a2) and be the electroconductive powder (A2) of the silver powder of 25 weight part to 266 weight parts with respect to described silver-plated copper powder (a2) 100 weight parts; And has a thermoplastic resin (B1) of from amide group, ester group, imide and ether group, selecting the functional group more than a kind; And organic solvent (C).

2. conductive resin composition as claimed in claim 1, wherein, thermoplastic resin (B1) is the resin that is selected from the material group that is made of polyphenylene ether acid amides, polyphenylene ether imide, polyphenylene ether amide imide, polyphenylene acid amides, polyphenylene imide, polyphenylene amide imide, poly-xylylene acid amides, poly-xylylene imide and poly-xylylene amide imide.

3. conductive resin composition as claimed in claim 1 or 2, wherein, thermoplastic resin (B1) is to have to remember repeating unit shown in the general formula (I) and/or the following resin of remembering the repeating unit shown in the general formula (II) down,

In the formula: R ¹, R ², R ³And R ⁴Independent separately is the low alkyl group of hydrogen, carbon number 1～4, the lower alkoxy or the halogen atom of carbon number 1～4; X ¹For singly-bound ,-O-,-S-,-CO-,-SO ₂-,-SO-,

Or

R herein ⁵And R ⁶Independent separately is low alkyl group, trifluoromethyl, trichloromethyl or the phenyl of hydrogen, carbon number 1～4; Y represents

Or

Ar ¹Represent aromatic divalent base; Ar ²Be aromatic 3 valency bases; Ar ³Be aromatic 4 valency bases,

In the formula: R ⁷, R ⁸And R ⁹Independent separately is the low alkyl group of carbon number 1～4, the lower alkoxy or the halogen atom of carbon number 1～4; S, t and u are separately independently for replacing 0 to 4 integer of radix; R ⁷, R ⁸And R ⁹When respectively doing for oneself a plurality of bonding, each is identical or different; X ²And X ³Independently separately be-O-or

R herein ¹⁰And R ¹¹Independent separately is low alkyl group, trifluoromethyl, trichloromethyl or the phenyl of hydrogen atom, carbon number 1～4; Y is identical with the definition in the above-mentioned general formula (I).

4. conductive resin composition comprises: contain part surface and have copper exposed portions serve and this to expose area be 10 to 70% silver-plated copper powder (a2) and be the electroconductive powder (A2) of the silver powder of 25 weight part to 266 weight parts with respect to described silver-plated copper powder (a2) 100 weight parts; And the thermoplastic resin of from polymeric amide silicone resin, polyamidoimide silicone resin and polyimide silicone resin group, selecting (B2); And organic solvent (C).

5. an electronic unit has and uses the conductor layer that forms as each described conductive resin composition in the claim 1,2,4.

6. as electronic unit as described in the claim 5, it is a kind of solid electrolytic capacitor, it is formed with dielectric oxide film, solid electrolyte layer and contains the cathode layer that uses the conductor layer that forms as each described conductive resin composition in the claim 1,2,4 on the anode substrate that is made of valve metals.

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