JPWO2016009754A1 - Manufacturing method of conductive resin, conductive resin, conductive paste, and electronic member - Google Patents

Abstract

The method for producing a conductive resin of the present invention includes a dissolution step of dissolving a metal compound and a polymerizable monomer in a solvent, and a polymerization step of polymerizing the polymerizable monomer in the presence of a solvent that dissolves the metal compound. ing. Thereby, even when exposed to high load conditions such as high temperature and high humidity, a conductive resin having excellent conductivity, a conductive paste and an electronic member, and a method for producing a conductive resin can be provided. .

Description

  The present invention relates to a method for producing a conductive resin, a conductive resin, a conductive paste, and an electronic member.

  Up to now, through holes have been provided in land parts of printed circuit boards such as paper-based phenolic resin substrates or glass cloth-based epoxy resin substrates, and conductive silver paste is embedded in them by screen printing, followed by heat curing and printed wiring. Recently, methods for producing plates have been actively used. However, in recent years, migration problems have frequently occurred in pattern circuits that have become finer pitches, and higher conductivity is required. Therefore, attention has been paid to conductive paste using copper.

  For example, Patent Document 1 describes that a copper paste can be obtained by kneading dendritic copper powder into a thermosetting resin. The method for producing a copper paste described in Patent Document 1 finds that the cause of the decrease in conductivity is in a kneading apparatus having a strong dispersion force, and employs a method of kneading with a weak dispersion force.

Japanese Patent Laid-Open No. 08-199109

  The method for producing a copper paste described in Patent Document 1 employs a step of kneading copper powder into a thermosetting resin. However, as a result of studies by the present inventors, it has been found that the kneading method described in the above literature has room for improvement in conductivity when exposed to high load conditions such as high temperature and high humidity.

The present invention includes the following configurations.
[1]
A dissolution step of dissolving the metal compound and the polymerizable monomer in a solvent;
A polymerization step of polymerizing the polymerizable monomer in the presence of the solvent that dissolves the metal compound,
A method for producing a conductive resin.
[2]
The method for producing a conductive resin according to [1], wherein the polymerizable monomer has one or more selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a carboxyl group, a thiol group, and an isocyanate group.
[3]
The method for producing a conductive resin according to [1] or [2], wherein the solvent contains one or more selected from the group consisting of water, alcohols, ketones, and glycols.
[4]
The method for producing a conductive resin according to [3], wherein when the solvent contains water, the metal compound and the polymerizable monomer are dissolved in the water.
[5]
The metal compound includes one or more metal salts selected from the group consisting of chloride, fluoride, sulfate, nitrate, acetate, perchlorate,
The metal of the metal salt is made of aluminum, titanium, chromium, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium, gold, platinum, iron, zinc, manganese, magnesium, calcium, silver, vanadium, tin. The method for producing a conductive resin according to any one of [1] to [4], which is selected from the group.
[6]
Conductivity according to [2], wherein the polymerizable monomer contains one or more selected from the group consisting of phenols, epoxy compounds, amine compounds, carboxylic acid compounds, carboxylic anhydride compounds, thiol compounds, and isocyanate compounds. For producing a functional resin.
[7]
The method for producing a conductive resin according to any one of [1] to [6], wherein the polymerizable monomer has a flux activity.
[8]
When the polymerizable monomer contains phenols, the solvent further contains aldehydes,
The method for producing a conductive resin according to [6], wherein the polymerization step includes a step of condensation polymerization of the phenols and the aldehydes.
[9]
The method for producing a conductive resin according to any one of [1] to [8], wherein the solvent further contains a polymerization catalyst.
[10]
A conductive resin obtained from the method for producing a conductive resin according to any one of [1] to [9],
A conductive resin containing fine metal particles derived from the metal compound.
[11]
The conductive resin according to [10], wherein the content of the metal fine particles is 0.01% by mass to 25% by mass with respect to 100% by mass of the entire conductive resin.
[12]
The conductive resin according to [10] or [11], wherein the median diameter of the metal fine particles is 10 nm or more and 20 μm or less.
[13]
[10] A conductive paste comprising the conductive resin according to any one of [12] and conductive fine particles.
[14]
The conductive paste according to [13], wherein the content of the conductive fine particles is 0.1% by mass or more and 95% by mass or less with respect to 100% by mass of the entire conductive paste.
[15]
The conductive paste according to [13] or [14], wherein the median diameter of the conductive fine particles is 0.1 μm or more and 100 μm or less.
[16]
The conductive fine particles are made of aluminum, titanium, chromium, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium, osmium, gold, platinum, iron, zinc, manganese, magnesium, calcium, silver, vanadium, tin. The conductive paste according to any one of [13] to [15], comprising one or more selected from the group.
[17]
The conductive paste according to any one of [13] to [16], which is used for an electronic member.
[18]
An electronic member comprising the conductive paste according to [17] as a constituent member.

  According to the present invention, it is possible to provide a conductive resin, a conductive paste and an electronic member, and a method for producing a conductive resin that can maintain excellent conductivity even under high load conditions such as high temperature and high humidity. it can.

  The method for producing a conductive resin according to the present embodiment includes a dissolution step of dissolving a metal compound and a polymerizable monomer in a solvent, and a polymerization step of polymerizing the polymerizable monomer in the presence of the solvent that dissolves the metal compound. ,have.

  As a result of investigation by the inventor, a metal derived from the metal compound is contained in a resin formed by polymerizing the polymerizable monomer by polymerizing the polymerizable monomer in the presence of a solvent that dissolves the metal compound. Turned out to be very well dispersed. Although the detailed mechanism is not clear, since the polymerizable monomer is polymerized while maintaining the coordinate bond with the metal derived from the metal compound, the metal is coordinated in the resin, and the metal is a conductive resin. It is thought that it will disperse very well inside. Thereby, the electroconductive resin excellent in the dispersibility of a metal particle can be obtained.

  According to the present embodiment, the conductive resin obtained by the above-described method for producing a conductive resin is capable of maintaining excellent conductivity even under high load conditions such as high temperature and high humidity. It becomes possible to compose a paste.

(Method for producing conductive resin)
The manufacturing method of the conductive resin of this embodiment is demonstrated.

The manufacturing method of the conductive resin which concerns on this embodiment has a melt | dissolution process and a superposition | polymerization process. In the dissolution step, the metal compound and the polymerizable monomer are dissolved in a solvent (hereinafter also referred to as “solvent used in the dissolution step”). In the polymerization step, the polymerizable monomer is polymerized in the presence of a solvent that dissolves the metal compound.
The inventor presumes that in such a polymerization step, a conductive resin in which a metal derived from a metal compound is coordinated in a resin in which a polymerizable monomer is polymerized can be obtained.

  In this embodiment, a conductive resin composition shall contain the said conductive resin and a solvent (it is set as a concept different from the solvent used for a melt | dissolution process on the definition of this specification). The conductive resin composition may contain other components of the conductive resin and the solvent. Depending on the purpose of use, an appropriate solvent type and content can be selected.

  Hereinafter, a solvent, a polymerizable monomer, and a metal compound are mainly demonstrated as a component used for the manufacturing method of the conductive resin of this embodiment.

  The solvent used in the dissolution step of the present embodiment is not particularly limited. For example, water; alcohols such as methanol and ethanol; ketones such as acetone and cyclohexanone; glycols such as ethylene glycol and diethylene glycol; Etc. These can be used alone or in combination of two or more. Among these, it is preferable to use water because it is easy to dissolve the metal compound, and it can be handled with good handling with little environmental load.

In the present embodiment, the solvent-soluble metal compound means a metal compound having a property of being dissolved in a solvent used in the dissolution step. The solvent-soluble monomer means a polymerizable monomer having a property of being dissolved in the solvent used in the dissolution step.
For example, in this embodiment, when water is used as the solvent used in the dissolution step, a water-soluble metal compound and a water-soluble monomer can be used as the metal compound and the polymerizable monomer, respectively.

Although it does not specifically limit as a metal compound of this embodiment, For example, using 1 type, or 2 or more types selected from the metal salt which consists of a chloride, fluoride, a sulfate, nitrate, acetate, and a perchlorate is used. Can do.
The metal constituting the metal salt is not particularly limited. For example, aluminum, titanium, chromium, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium, osmium, gold, platinum, iron, zinc, manganese, magnesium One or two or more metals selected from the metal group consisting of calcium, silver, vanadium, and tin can be used. These can be used alone or in combination of two or more. Among these, copper chloride, copper sulfate, copper nitrate, and copper acetate are more preferable from the viewpoint of cost and migration suppression.

Although the polymerizable monomer of this embodiment is not specifically limited, For example, it can select suitably from polymerization types, such as condensation polymerization or addition polymerization. One or two or more of these polymerizable monomers may be used.
Although it does not specifically limit as said polymerizable monomer, For example, phenols, an epoxy compound, an amine compound, a carboxylic acid compound, a carboxylic anhydride compound, a thiol compound, an isocyanate compound etc. are mentioned. These can be used alone or in combination of two or more.

  In addition, the polymerizable monomer of the present embodiment is not particularly limited. For example, the polymerizable monomer may have a polar group (polar functional group) such as a hydroxyl group, an epoxy group, an amino group, a carboxyl group, a thiol group, and an isocyanate group. Good. Thereby, it is guessed that the said polymerizable monomer can form a coordinate bond with a metal atom in a solution.

  The polymerizable monomer of this embodiment may have flux activity. For example, flux activity can be exhibited by introducing an electron-donating functional group into the polymerizable monomer. Although it does not specifically limit as a functional group with an electron-donating property, For example, a hydroxyl group, an epoxy group, a carboxyl group etc. are used. Among these, from the viewpoint of electron donating property, a polymerizable monomer having a hydroxyl group is preferable, and specifically, phenols are more preferable. Thus, although the detailed mechanism is not clear, in the manufacturing process of the present embodiment, the metal compound can be reduced, so that the metal particles derived from the metal compound highly dispersed in the resin are maintained in the reduced state. Therefore, it is considered that high conductivity can be exhibited.

  In the present embodiment, the phenols are not particularly limited. For example, phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol Xylenol such as 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenol such as o-ethylphenol, m-ethylphenol, p-ethylphenol; isopropylphenol, Butylphenol such as butylphenol and p-tert-butylphenol; alkylphenol such as p-tert-amylphenol, p-octylphenol, p-nonylphenol and p-cumylphenol; fluorophenol, chlorophenol, bromophenol, iodine Monovalent phenols such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol and trinitrophenol; and monovalent phenols such as 1-naphthol and 2-naphthol. Examples include phenols and polyhydric phenols such as resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol S, and dihydroxynaphthalene. These can be used alone or in combination of two or more.

  In the present embodiment, when the phenols are used, for example, aldehydes can be further used as the polymerizable monomer. That is, the dissolution step of this embodiment may include a step of dissolving phenols and aldehydes in a solvent used in the dissolution step. Thereby, the low molecular weight condensation polymer (phenol resin) of phenols and aldehydes is easily compoundable. These phenols and aldehydes show water solubility.

  The aldehydes are not particularly limited. For example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, capro Examples include aldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like. These can be used alone or in combination of two or more. Among these, it is preferable to use formaldehyde and paraformaldehyde from the viewpoints of reactivity and curability.

  Further, the epoxy compound is not particularly limited. For example, bisphenol type epoxy such as bisphenol A type epoxy, bisphenol F type epoxy, brominated bisphenol type epoxy; biphenyl type epoxy; biphenyl aralkyl type epoxy; stilbene Type epoxy; naphthalene type epoxy; dicyclopentadiene type epoxy; dihydroxybenzene type epoxy; glycidyl ester; glycidyl amine and the like. One or more of these can be used in combination.

In this embodiment, a catalyst can be further used. The catalyst is a polymerization catalyst that can promote the polymerization of the polymerizable monomer of the present embodiment. Such a catalyst may be used by adding to the solvent used in the dissolution step. Thereby, the low molecular weight polymer which consists of a raw material component containing a solvent-soluble monomer is easily compoundable.
The catalyst of the present embodiment is not particularly limited. For example, when phenols and aldehydes are used, an acidic catalyst such as oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfonic acid, or lithium hydroxide, water Basic catalysts such as sodium oxide, magnesium hydroxide, barium hydroxide, calcium hydroxide, potassium hydroxide, ammonia and triethylamine can be used.

  In the present embodiment, for example, a raw material component containing phenols and aldehydes is reacted with aldehydes (F) with phenols (P) in the presence of an acidic catalyst such as oxalic acid, hydrochloric acid, sulfuric acid, and toluenesulfonic acid. Although the molar ratio (F / P) is not particularly limited, for example, a B-stage novolac-type phenol resin can be synthesized by setting the molar ratio to 0.5 or more and 0.9 or less. On the other hand, in the presence of a basic catalyst such as lithium hydroxide, sodium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydroxide, potassium hydroxide, ammonia, triethylamine, etc., the raw material components containing phenols and aldehydes The reaction molar ratio (F / P) of the aldehydes (F) to the phenols (P) is not particularly limited. For example, by setting the reaction molar ratio to 1.0 or more and 3.0 or less, a B-stage resol type phenol Resins can be synthesized.

(Conductive resin)
The conductive resin according to this embodiment will be described.
The conductive resin of the present embodiment has metal particles derived from a metal compound (hereinafter may be referred to as metal fine particles). The metal atoms constituting the metal fine particles can be present in a dispersed state inside and / or on the surface of the conductive resin. This is because it is presumed that the functional group (polar functional group) of the conductive resin and the metal atom form a coordinate bond.

  Moreover, the conductive resin composition according to the present embodiment includes the conductive resin and a solvent. Although it does not specifically limit as a solvent of the conductive resin composition of this embodiment, For example, you may select from the same kind as the solvent used for a conductive paste. Such a solvent may be the same or different from the solvent, but by using the same type, the conductive resin composition can be suitably used for the conductive paste.

  In the present embodiment, the following method can be used to examine the presence or absence of a coordinate bond between a polar functional group of a conductive resin and a metal atom. For example, when the conductive resin is analyzed by X-ray photoelectron spectroscopy (ESCA (Electron Spectroscopic for Chemical Analysis)), a bond between a polar functional group of the conductive resin and a metal atom is observed.

As an example using such an analysis method, a case where a resin synthesized by polymerization of a polymerizable monomer is, for example, a phenol resin will be described.
In this case, metal atoms constituting the metal fine particles are coordinated to oxygen atoms in the phenol resin. The oxygen atom forming the coordination bond is not limited to the phenolic hydroxyl group possessed by the phenol resin, and may be an oxygen atom derived from a functional group other than this. In this way, oxygen atoms and metal atoms derived from various functional groups can interact.

  In the present embodiment, the lower limit of the content of the metal fine particles is not particularly limited with respect to 100% by mass of the entire conductive resin, but is preferably 0.01% by mass or more, and 0.05% by mass. The above is more preferable. Although the upper limit of content of metal fine particles is not specifically limited, For example, 25 mass% or less is preferable and 15 mass% or less is more preferable. In the present embodiment, the fine metal particles in the above content range can be included in the conductive resin. By setting it to the above lower limit or more, it is possible to obtain an effect of improving the reliability of moisture resistance. Moreover, by setting it as the above upper limit value or less, metal fine particles having an appropriate size can be obtained without sintering (aggregation) of the solvent-soluble metal compound and / or the reduced metal.

  In the present embodiment, the median diameter of the metal fine particles is not particularly limited, but is preferably 10 nm or more and 20 μm or less, and more preferably 20 nm or more and 5 μm or less. By setting it within the above range, an effect of further increasing the conductivity in the conductive paste can be obtained by a synergistic effect with the conductive fine particles in the conductive paste described later.

  In the present embodiment, the particle size of the metal particles can be determined by observing with a transmission electron microscope (TEM), for example. More specifically, the surface of the resin is observed with a transmission electron microscope (TEM), the particle size is measured for 100 arbitrarily selected metal particles, and this average value is used as the average particle size of the metal particles. be able to.

Here, the inventor's inference will be described with respect to a mechanism in which the metal atom of the metal fine particle exhibits very excellent dispersibility in the conductive resin of the present embodiment.
First, it is presumed that the solvent-soluble metal compound when uniformly dissolved in the solvent is dispersed in the solvent at the molecular level. Next, when the solvent-soluble monomer and the solvent-soluble metal compound dissolved in the solvent are mixed, the solvent-soluble monomer and the solvent-soluble metal compound are considered to form a coordination bond, and are dispersed at the molecular level by being uniformly dissolved. It is estimated that The solvent-soluble monomer can have a polar group (functional group) capable of forming a coordination bond. Each of these polar groups has a pair of electrons, and it is presumed that chelation is formed between the pair of electrons and the metal.
At this time, when a monomer having flux activity is used as the solvent-soluble monomer, it is presumed that the solvent-soluble metal compound is in a reduced state.
Thereafter, in the course of the synthesis reaction using the solvent-soluble monomer as a starting material component, the solvent-soluble metal compound and / or the reduced metal can maintain a coordinate bond with the solvent-soluble monomer. For this reason, it is estimated that the progress of the sintering (aggregation) of the solvent-soluble metal compound and / or the reduced metal can be suppressed. Therefore, it is presumed that the fine metal particles present in the obtained conductive resin are fine and the degree of dispersion in the conductive resin is very high. Thus, it is thought that the metal microparticle which exists in a conductive resin exists in the state disperse | distributed to the inside and / or surface of a conductive resin. Therefore, in this embodiment, it is considered that the effect of improving the reliability of moisture resistance is obtained.

(Conductive paste)
The conductive paste according to this embodiment will be described in detail.
The conductive paste of this embodiment can contain the conductive resin and conductive fine particles. Such a conductive paste may further contain a solvent.

  The conductive fine particles used in the conductive paste of the present embodiment are not particularly limited. For example, aluminum, titanium, chromium, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium, osmium, One or more metal atoms selected from the group consisting of gold, platinum, iron, zinc, manganese, magnesium, calcium, silver, vanadium, and tin can be included. Such conductive fine particles may be a metal composed of the metal atom or a metal compound containing the metal atom. Even if these metal or the compound containing those metals are the electroconductive fine particles which consist of a single metal atom of these, or a compound containing those single metal atoms, 2 or more types of these Conductive fine particles made of an alloy using metal atoms or a compound containing two or more metal atoms thereof may be used. In addition, as the conductive fine particles used in the conductive paste of the present embodiment, conductive fine particles obtained by coating these conductive fine particles with other kinds of metals, fine particles made of other kinds of compounds, these metals or those Conductive fine particles coated with a compound containing any of these metals can also be used. Among these, metals or alloys are preferable from the viewpoint of conductivity. Moreover, from the viewpoints of conductivity, handleability, cost, etc., electrolytic copper powder is a particularly preferable example. Further, the metal atoms constituting the conductive fine particles may be the same or different from the metal atoms constituting the metal fine particles.

  The shape of the conductive fine particles is not particularly limited, but conventionally used ones such as dendrites, spheres, flakes, flakes, and foils can be used.

  In the present embodiment, the particle diameter of the conductive fine particles is not particularly limited, but the median diameter is preferably 0.1 μm or more and 100 μm or less, and preferably 0.5 μm or more and 10 μm or less. More preferred. By setting it within the above range, an effect of further increasing the conductivity in the conductive paste can be obtained due to a synergistic effect with the metal fine particles in the resin composition.

  In the present embodiment, the lower limit of the content of the conductive fine particles is not particularly limited, but is preferably 0.1% by mass or more and 20% by mass or more with respect to 100% by mass of the entire conductive paste. More preferred is 30% by mass or more. Although the upper limit of content of electroconductive fine particles is not specifically limited, For example, 95 mass% or less is preferable, 80 mass% or less is more preferable, and it is further more preferable that it is 65 mass% or less. In the present embodiment, conductive fine particles in the above-mentioned content range can be included in the conductive paste. When the content of the conductive fine particles is within this range, good conductivity can be obtained. By setting it to the upper limit value or less, it is possible to suppress the binding force from becoming insufficient, the conductive fine particles from being sufficiently pressed against each other, and good conductivity not being expressed. Moreover, it can suppress that contact between microparticles | fine-particles decreases and favorable electroconductivity is not expressed by setting it as a lower limit or more.

  A solvent can be used for the conductive paste of this embodiment as needed. In the case of using the solvent, it is preferable to select a solvent that can suppress the drying of the screen printing plate and is easy to dry after printing. Such a solvent is not particularly limited, but glycol ethers are preferable, and can be appropriately selected and used from the glycol ethers exemplified below in accordance with facility capacity and use conditions. it can. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, ethylene glycol mono Isopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol monoisobutyl ether Diethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di Butyl ether, triethylene glycol dimethyl ether, and the like, and esterifications thereof are used, but those having an appropriate boiling point and vapor pressure can be selected depending on the solubility and drying conditions of the binder resin to be used. It is also possible to use a mixed system of

  The method for producing the conductive paste of the present embodiment is not particularly limited, and various methods can be applied. Generally, the components are mixed and then kneaded with a three-roll. is there. In the present embodiment, the conductive fine particles can be well dispersed in and / or on the surface of the conductive paste by appropriately selecting a kneading method or a solvent. In this embodiment, the order in which the constituent components are mixed is not particularly limited. For example, the conductive resin and the conductive fine particles may be mixed in a solvent, but the conductive resin composition and the conductive fine particles may be mixed in the solvent. You may mix. In addition, various antioxidants, dispersants, fine fused silica, coupling agents, antifoaming agents, leveling agents and the like can be added to the composition as necessary.

The electronic member according to this embodiment will be described.
The electronic member of this embodiment is characterized by using the conductive paste. The electronic member is not particularly limited, and examples thereof include a printed circuit board using the conductive paste for embedding a substrate through hole, and an electromagnetic wave shield substrate using the conductive paste as a conductor.

  As an example of this embodiment, a printed circuit board manufacturing method using the conductive paste for embedding a substrate through hole will be described. For example, first, a through hole is formed in a land portion of a printed circuit board such as a paper base phenolic resin substrate or a glass cloth base epoxy resin substrate, and the conductive paste is embedded in the land by screen printing or the like, and then cured by heating. Thus, a printed wiring board can be manufactured.

  Moreover, as a metal atom contained in metal fine particles or conductive fine particles, for example, by using copper, it can be suitably used for parts of various electronic devices in which electrodes and wirings are formed. Thereby, the electronic device can be used even under a high load condition such as high temperature and high humidity.

Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto.

Example 1
1. Production of resin composition (resin composition A)
100 parts by weight of phenol, 100 parts by weight of water, 27 parts by weight of 10% aqueous copper chloride solution, 129 parts by weight of 37% formalin, and 5 parts by weight of triethylamine were added and reacted for 2 hours under reflux conditions, followed by dehydration. Thereby, a conductive resin was obtained. Thereafter, 90 parts by mass of ethylene glycol monomethyl ether was added to the conductive resin to obtain 200 parts by mass of a resin composition A having a copper fine particle content of 0.5% by mass. The median diameter of the copper fine particles in the resin composition A was 0.1 μm.

2. Production of Conductive Paste 100 parts by mass of FCC-TB (electrolytic copper powder having a median diameter of 6.6 μm and an apparent density of 1.87 g / cm ³ ) manufactured by Fukuda Metal Foil Powder Co., Ltd. as a conductive fine particle 15 parts by mass of the resin composition A prepared above, 30 parts by mass of a 1: 1: 2 mixed solvent of ethylene glycol monobutyl ether, propylene glycol monobutyl ether and propylene glycol monopropyl ether as a solvent, and 5 hydroquinone as a reducing agent Using 3 parts by mass of an aminosilane coupling agent (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) as an additive and 3 parts by mass, the mixture was kneaded with three rolls at room temperature for 10 minutes to obtain a conductive paste.

3. Evaluation of conductive paste (Preparation of test piece for evaluation)
The obtained conductive paste was filled by screen printing into a 0.5 mmφ through hole provided on a paper base phenolic resin substrate PLC-2147RH (plate thickness 1.6 mm) manufactured by Sumitomo Bakelite Co., Ltd. A test piece for evaluation was produced by curing in a dryer at 150 ° C. for 30 minutes.

  Initial conduction resistance value: The conduction resistance value per through-hole of the obtained test specimen for evaluation was measured by a four-terminal method using 580MICRO-OHM METER manufactured by KEITHLEY, and used as an initial conduction resistance value.

  Moisture absorption test: Thereafter, a moisture absorption treatment was performed for 1000 hours under moisture absorption conditions of a temperature of 40 ° C. and a humidity of 90% RH. After the moisture absorption treatment, the inside of the through hole of the test piece for evaluation was observed in cross section, and it was visually confirmed whether or not cracks or peeling occurred on the cured body of the conductive paste. Further, after the moisture absorption treatment, the conduction resistance value per through hole of the test piece for evaluation was measured again using 580MICRO-OHM METER manufactured by KEITHLEY, and was defined as the conduction resistance value after moisture absorption.

(Comparative Example 1)
1. Production of resin composition (resin composition B)
After adding 100 parts by weight of phenol, 129 parts by weight of 37% formalin, and 5 parts by weight of triethylamine, the mixture was reacted under reflux conditions for 2 hours, and then subjected to a dehydration reaction. Thereafter, 40 parts by mass of ethylene glycol monomethyl ether was added to obtain 200 parts by mass of a resin composition B.
2. Production and Evaluation of Conductive Paste After obtaining a conductive paste in the same manner as in Example 1 except that the produced resin composition B was used, a test piece for evaluation was prepared in the same manner as in Example 1. Example 1 Evaluation was performed in the same manner as above. The above results are shown in Table 1.

表１から明らかなとおり、本発明の導電性樹脂の製造方法により合成され、溶媒可溶性金属化合物由来の金属微粒子を含む樹脂組成物Ａを用いた実施例１では、初期段階での優れた導電性を示すだけでなく、高温高湿度などの高負荷条件下に晒された場合においても、良好な導電性を維持できることが分かった。一方、溶媒可溶性金属化合物を用いておらず、樹脂組成物中に金属微粒子を含まない樹脂組成物Ｂを用いた比較例１では、初期段階での導電性が劣るだけでなく、高温高湿度などの高負荷条件下に晒された場合において、クラックや剥離等が発生していないにもかかわらず、導電性が大幅に低下すること分かった。

As is clear from Table 1, in Example 1 using the resin composition A synthesized by the method for producing a conductive resin of the present invention and containing metal fine particles derived from a solvent-soluble metal compound, excellent conductivity at the initial stage was obtained. It was also found that good conductivity can be maintained even when exposed to high load conditions such as high temperature and high humidity. On the other hand, in Comparative Example 1 using the resin composition B that does not use a solvent-soluble metal compound and does not contain metal fine particles in the resin composition, not only the conductivity at the initial stage is inferior, but also high temperature and high humidity. It has been found that when exposed to high load conditions, the conductivity is greatly reduced despite the absence of cracks or peeling.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
Hereinafter, examples of the reference form will be added.
[1] A method for producing a resin composition, comprising melting and mixing raw material components including a solvent, a solvent-soluble metal compound, and a solvent-soluble monomer.
[2] The method for producing a resin composition according to [1], wherein the solvent is water, the solvent-soluble metal compound is a water-soluble metal compound, and the solvent-soluble monomer is a water-soluble monomer.
[3] The solvent-soluble metal compound is aluminum, titanium, chromium, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium, osmium, gold, platinum, iron, zinc, manganese, magnesium, calcium, silver, vanadium, Production of a resin composition according to [1] or [2], which is at least one selected from the group consisting of chlorides, fluorides, sulfates, nitrates, acetates and perchlorates of metals selected from tin. Method.
[4] The solvent-soluble monomer is at least one selected from the group consisting of phenols, epoxy compounds, amine compounds, carboxylic acid compounds, carboxylic anhydride compounds, thiol compounds, and isocyanate compounds [1] to [3] The manufacturing method of the resin composition as described in any one of these.
[5] The method for producing a resin composition according to any one of [1] to [4], wherein the solvent-soluble monomer is a monomer having flux activity.
[6] The method for producing a resin composition according to any one of [1] to [5], wherein the solvent-soluble monomer is a phenol.
[7] The method for producing a resin composition according to [6], further including an aldehyde as the raw material component.
[8] The method for producing a resin composition according to any one of [1] to [7], further including a catalyst as the raw material component.
[9] A resin composition characterized by being synthesized by the method for producing a resin composition according to any one of [1] to [8].
[10] The resin composition according to [9], wherein the metal fine particles derived from the solvent-soluble metal compound are present in a dispersed state in and / or on the surface of the resin composition.
[11] The resin composition according to [10], wherein the content of the metal fine particles is 0.01% by mass or more and 25% by mass or less of the entire resin composition.
[12] The resin composition according to [10] or [11], wherein the median diameter of the metal fine particles is 10 nm or more and 20 μm or less.
[13] A conductive paste comprising the resin composition according to any one of [9] to [12] and conductive fine particles.
[14] The conductive paste according to [13], wherein the conductive fine particles are present in a dispersed state in and / or on the surface of the conductive paste.
[15] The conductive paste according to [13] or [14], wherein the content of the conductive fine particles is 0.1% by mass or more and 95% by mass or less of the entire conductive paste.
[16] The conductive paste according to any one of [13] to [15], wherein a median diameter of the conductive fine particles is 0.1 μm or more and 100 μm or less.
[17] The conductive fine particles are aluminum, titanium, chromium, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium, osmium, gold, platinum, iron, zinc, manganese, magnesium, calcium, silver, vanadium, tin. The conductive paste according to any one of [13] to [16], which is at least one selected from the group consisting of metals selected from:
[18] The conductive paste according to any one of [13] to [17], which is used for an electronic member.
[19] An electronic member comprising the conductive paste according to [18].
Moreover, the manufacturing method of the resin composition of this embodiment may synthesize | combine by melt-mixing the raw material component containing a solvent, a solvent soluble metal compound, and a solvent soluble monomer. Thereby, the resin composition in which the metal fine particles derived from the solvent-soluble metal compound are present in a state of being dispersed inside and / or on the surface of the resin can be easily obtained. Moreover, the resin composition of this embodiment is compoundable with the manufacturing method of the above-mentioned resin composition. The resin composition obtained by this can be used suitably for the electroconductive paste excellent in electroconductive moisture-resistant reliability. Moreover, the conductive paste of the present embodiment may include the above-described resin composition and conductive fine particles. Since the conductive paste is excellent in conductive moisture resistance reliability, it can be suitably used for an electronic member such as a through-hole portion in a printed circuit board exposed to a high load condition such as high temperature and high humidity.

  The invention according to the present embodiment provides a conductive paste with excellent moisture resistance reliability that can maintain good conductivity even when exposed to high load conditions such as high temperature and high humidity. Therefore, it can be suitably used for an electronic member that requires moisture resistance reliability, such as a through-hole portion in a printed circuit board or a conductor portion of an electromagnetic wave shield substrate.

  This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2014-144003 for which it applied on July 14, 2014, and takes in those the indications of all here.

Claims (18)

A dissolution step of dissolving the metal compound and the polymerizable monomer in a solvent;
A polymerization step of polymerizing the polymerizable monomer in the presence of the solvent that dissolves the metal compound,
A method for producing a conductive resin.   The manufacturing method of the conductive resin of Claim 1 in which the said polymerizable monomer has 1 type, or 2 or more types selected from the group which consists of a hydroxyl group, an epoxy group, an amino group, a carboxyl group, a thiol group, and an isocyanate group.   The manufacturing method of the conductive resin of Claim 1 or 2 with which the said solvent contains the 1 type (s) or 2 or more types selected from the group which consists of water, alcohol, ketones, glycols.   The method for producing a conductive resin according to claim 3, wherein when the solvent contains water, the metal compound and the polymerizable monomer are dissolved in the water. The metal compound includes one or more metal salts selected from the group consisting of chloride, fluoride, sulfate, nitrate, acetate, perchlorate,
The metal of the metal salt is made of aluminum, titanium, chromium, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium, gold, platinum, iron, zinc, manganese, magnesium, calcium, silver, vanadium, tin. The method for producing a conductive resin according to claim 1, which is selected from the group.   The conductive material according to claim 2, wherein the polymerizable monomer contains one or more selected from the group consisting of phenols, epoxy compounds, amine compounds, carboxylic acid compounds, carboxylic anhydride compounds, thiol compounds, and isocyanate compounds. For producing a functional resin.   The method for producing a conductive resin according to claim 1, wherein the polymerizable monomer has a flux activity. When the polymerizable monomer contains phenols, the solvent further contains aldehydes,
The method for producing a conductive resin according to claim 6, wherein the polymerization step includes a step of condensation polymerization of the phenols and the aldehydes.   The method for producing a conductive resin according to claim 1, wherein the solvent further contains a polymerization catalyst. A conductive resin obtained from the method for producing a conductive resin according to any one of claims 1 to 9,
A conductive resin containing fine metal particles derived from the metal compound.   11. The conductive resin according to claim 10, wherein the content of the metal fine particles is 0.01% by mass or more and 25% by mass or less with respect to 100% by mass of the entire conductive resin.   The conductive resin according to claim 10 or 11, wherein a median diameter of the metal fine particles is 10 nm or more and 20 µm or less.   A conductive paste comprising the conductive resin according to any one of claims 10 to 12 and conductive fine particles.   The conductive paste according to claim 13, wherein a content of the conductive fine particles is 0.1% by mass or more and 95% by mass or less with respect to 100% by mass of the entire conductive paste.   The electrically conductive paste of Claim 13 or 14 whose median diameter of the said electroconductive fine particles is 0.1 micrometer or more and 100 micrometers or less.   The conductive fine particles are made of aluminum, titanium, chromium, cobalt, nickel, copper, ruthenium, rhodium, palladium, rhenium, osmium, gold, platinum, iron, zinc, manganese, magnesium, calcium, silver, vanadium, tin. The electrically conductive paste of any one of Claims 13-15 containing 1 type, or 2 or more types selected from a group.   The conductive paste according to any one of claims 13 to 16, which is used for an electronic member.   An electronic member comprising the conductive paste according to claim 17 as a constituent member.