JP2019057586A - Conductor, forming method therefor, structure and manufacturing method thereof - Google Patents

Abstract

To provide a forming method for a conductor which improves conductivity and adhesiveness with an adherend.SOLUTION: The present invention relates to a forming method for a conductor for forming the conductor on an adherend. The forming method for the conductor includes the steps of: providing a porous conductor layer on the adherend, the conductor layer including a first outer surface in contact with the adherend, a second outer surface being different from the first outer surface, and a communication hole communicating the first outer surface and the second outer surface; and filling the communication hole with a resin and a coupling agent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductor and a method for forming the conductor, and a structure and a method for manufacturing the structure.

  As a method for forming a metal pattern, a step of applying a conductive material such as ink or paste containing metal particles such as copper onto a substrate by ink jet printing, screen printing, etc., and heating the conductive material to fuse the metal particles In addition, a so-called printed electronics method is known which includes a conductor-forming step for developing conductivity.

  In the printed electronics method, there is a method in which a conductor is formed using a conductive material including metal particles having an organic substance attached as a coating material on the surface in order to suppress the oxidation of the metal and improve the storage stability. In Patent Document 1, an ink containing predetermined copper particles coated with an organic substance that can be fused at a low temperature and exhibits good conductivity is heated to 300 ° C. at a rate of 60 ° C./min in an argon atmosphere. And the method of forming a conductor by hold | maintaining for 30 minutes is disclosed. Patent Document 2 discloses a method of forming a conductor (thin film) by heating ink containing predetermined copper particles at 200 ° C.

  The printed electronics method also includes a method of forming a conductor using a conductive material containing metal particles and a resin. Patent Document 3 includes a step of applying a conductive silver paste containing silver powder, an epoxy resin, and a curing agent on a substrate, and a step of heat-curing the coating film obtained in the step. A forming method is disclosed.

JP 2012-72418 A JP 2014-148732 A JP 2012-248370 A

  In recent years, with the background of improvement in production efficiency, etc., a technology that achieves both fusion of metal particles (conductivity) at a lower temperature (eg, 180 ° C. or less) and adhesion to an adherend such as a substrate. Development is required. Although the electroconductive substance (conductor) formed by the method described in Patent Document 1 and Patent Document 2 exhibits a certain conductivity, it does not consider the adhesiveness to an adherend such as a substrate. Moreover, although the conductor formed by the formation method of the conductor using the electrically conductive paste described in patent document 3 shows adhesiveness with a to-be-adhered body, it is used for wiring because of the compounded resin and the hardening | curing agent. Does not have sufficient electrical conductivity. Even for a coupling agent that is commonly used to improve the adhesion to the base material, if the blending amount with respect to the conductive paste is excessively increased, the electrical conductivity is lowered. Thus, in the conductive paste field, coexistence of conductivity and adhesiveness is a problem.

  An object of this invention is to provide the conductor excellent in electroconductivity and adhesiveness with a to-be-adhered body, its formation method, a structure provided with this conductor, and its manufacturing method in view of the said situation.

Means for solving the above problems are as follows.
<1> A conductor forming method for forming a conductor on an adherend, wherein the conductor is a porous conductor layer on the adherend, the first outer surface being in contact with the adherend, the first A step of providing a second outer surface different from the outer surface, and a conductor layer having a communication hole for communicating the first outer surface with the second outer surface, and filling the communication hole with resin and a coupling agent A method for forming a conductor.
<2> The method for forming a conductor according to <1>, wherein a filling amount of the coupling agent is 0.1 to 80 parts by mass with respect to 100 parts by mass of the resin.
<3> The method for forming a conductor according to <1> or <2>, wherein the conductor layer has a porosity of 10 to 70%.
<4> A method of manufacturing a structure including an adherend and a conductor provided on the adherend, the porous conductor layer on the adherend, and being in contact with the adherend Providing a conductor layer having a first outer surface, a second outer surface different from the first outer surface, and a communication hole for communicating the first outer surface and the second outer surface; a resin; And a step of filling the communicating hole with a coupling agent.
The manufacturing method of the structure as described in <4> whose filling amount of <5> coupling agent is 0.1-80 mass parts with respect to 100 mass parts of resin.
<6> The method for producing a structure according to <4> or <5>, wherein the conductor layer has a porosity of 10 to 70%.
<7> Porous conductor layer, the first outer surface, the second outer surface different from the first outer surface, and the communication for communicating the first outer surface and the second outer surface A conductor comprising: a conductor layer having holes; and a resin portion filled in the communication holes and containing a resin or a cured product thereof and a coupling agent or a reaction product thereof.
<8> A structure comprising an adherend and a conductor provided on the adherend, wherein the conductor is a porous conductor layer and is a first outer surface in contact with the adherend. A second outer surface different from the first outer surface, a conductor layer having a communication hole for communicating the first outer surface and the second outer surface, and a resin filled in the communication hole or its curing And a resin part containing a coupling agent or a reaction product thereof.

  ADVANTAGE OF THE INVENTION According to this invention, the conductor excellent in electroconductivity and adhesiveness with a to-be-adhered body, its formation method, a structure provided with this conductor, and its manufacturing method can be provided.

It is a SEM image for demonstrating the formation method of a conductor. (A) is the SEM image of the cross section of the conductor layer before filling resin and a coupling agent. (B) is the SEM image of the cross section of the conductor obtained by filling resin and a coupling agent.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless explicitly specified, unless otherwise clearly considered essential in principle. The same applies to numerical values and ranges thereof, and the present invention is not limited thereto.

  In this specification, the term “process” is not limited to an independent process, and is included in this term if the purpose of the process is achieved even when it cannot be clearly distinguished from other processes. In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity. In the present specification, the particle diameter of each component in the composition is a mixture of the plurality of types of particles present in the composition unless there is a specific indication when there are a plurality of types of particles corresponding to each component in the composition. Means the value of. In this specification, the term “film” includes not only a configuration of a shape formed on the entire surface but also a configuration of a shape formed on a part when observed as a plan view.

  In the present specification, “conducting” means that metal-containing particles are fused to be changed into a conductor. The “conductor” refers to an object having conductivity, and more specifically, an object having a volume resistivity of 300 μΩ · cm or less. “Percent” means a percentage (percentage) based on the number.

<Conductor formation method>
In the method for forming a conductor according to this embodiment, first, a conductor layer is provided on an adherend (conductor layer installation step).

  The adherend may be a substrate, for example. The material of the base material is not particularly limited, and may or may not have conductivity. Specific examples of the base material include metals such as Cu, Au, Pt, Pd, Ag, Zn, Ni, Co, Fe, Al, and Sn, alloys of these metals, and semiconductors such as ITO, ZnO, SnO, and Si. , Glass, graphite, carbon materials such as graphite, resin, paper, and combinations thereof. In the case of using a metal component that can be made into a conductor at a low temperature as will be described later, in particular, a base material made of a material having relatively low heat resistance can be suitably used. A thermoplastic resin is mentioned as a material with comparatively low heat resistance. Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, and polymethylpentene, and polycarbonate resins. The shape of the substrate is not particularly limited, and may be a plate shape, a rod shape, a roll shape, a film shape, or the like.

  The adherend may have other layers other than the base material. Examples of other layers include a primer layer. The primer layer is formed of, for example, a layer containing a silane coupling agent.

  For example, the conductor layer is formed by forming a conductor-forming composition layer made of a conductor-forming composition containing a metal component and a dispersion medium on an adherend, and heating the conductor-forming composition layer. (Conductor layer forming step). The conductor forming composition layer is formed, for example, by printing and applying the conductor forming composition on the adherend. When copper-containing particles described later are used as the metal component, in the conductor layer forming step, the organic substances on the surface of the copper-containing particles contained in the conductor-forming composition are thermally decomposed and the copper-containing particles are fused. Thus, a conductor layer is obtained.

  The heating temperature in the conductor layer forming step is, for example, 250 ° C. or lower, 230 ° C. or lower, or 210 ° C. or lower, and is 100 ° C. or higher, 110 ° C. or higher, or 120 ° C. or higher. When the conductor-forming composition contains copper-containing particles, which will be described later, as a metal component, it can be made into a conductor at a low temperature, and therefore the heating temperature in the conductor layer forming step is, for example, 200 ° C. or less, preferably 150. It is below ℃.

  The atmosphere in which the conductor layer forming step is performed is not particularly limited, and can be selected from an atmosphere such as nitrogen or argon used in a normal conductor manufacturing process. The conductor layer forming step may be performed in a reducing gas atmosphere in which a reducing substance such as hydrogen or formic acid is saturated with nitrogen or the like. In one embodiment, the conductor layer forming step is performed in a reducing gas atmosphere and at a heating temperature of 100 to 250 ° C. The pressure at the time of heating is not particularly limited, but may be reduced because it tends to promote the formation of a conductor at a low temperature.

  The rate of temperature increase in the conductor layer forming step may be constant or may be changed irregularly. The time for the conductor layer forming step is not particularly limited, and can be selected in consideration of the heating temperature, the heating atmosphere, the amount of the metal component, and the like. The heating method is not particularly limited, and examples thereof include heating with a hot plate, heating with an infrared heater, and heating with a pulse laser.

  The kind of metal component is not particularly limited. Examples of metal components include silver, nickel, beryllium, platinum, cobalt, antimony, germanium, thallium, iridium, zinc, niobium, gold, palladium, cadmium, ruthenium, copper, titanium, indium, tungsten, molybdenum, aluminum, lead , Bismuth, rhodium, chromium, tin, iron, vanadium, manganese, and other metal components having conductivity, or alloys containing these metal components. The metal component is preferably at least one selected from the group consisting of gold, silver, copper or alloys containing these metals from the viewpoint of conductivity, and preferably gold, silver or these from the viewpoint of oxidation resistance. From the viewpoint of cost, it is preferably at least one selected from the group consisting of copper and alloys containing copper. The metal component contained in the composition for forming a conductor may be only one type or two or more types.

  The shape of the metal component contained in the conductor forming composition is not particularly limited. Specific examples of the shape of the metal component include a spherical shape, a long granular shape, a flat shape, and a fibrous shape. The shape of the metal component can be selected according to the use of the metal component. When the conductor-forming composition is applied to a printing method, the shape of the metal component is preferably spherical or long granular. The shape of the metal component contained in the conductor-forming composition may be only one type or two or more types.

  The metal component is preferably copper-containing particles. The copper-containing particles are, for example, copper-containing particles having core particles containing copper and organic substances present on at least a part of the surface of the core particles.

  Since the copper-containing particles of the present embodiment have the above-described configuration, they have excellent fusion properties (conductivity) at low temperatures (for example, 150 ° C.). That is, in the copper-containing particles, an organic substance present on at least a part of the surface of the core particles containing copper serves as a protective material and suppresses oxidation of the core particles. For this reason, good fusion properties at low temperatures are maintained even after long-term storage in the atmosphere. In addition, this organic substance is thermally decomposed by heating when the conductor is produced by fusing the copper-containing particles and disappears.

  The organic substance present on at least a part of the surface of the core particle containing copper preferably contains alkylamine, a substance derived from alkylamine, and the like. Presence of an organic substance such as alkylamine is confirmed by heating the copper-containing particles at a temperature equal to or higher than the temperature at which the organic substance is thermally decomposed in a nitrogen atmosphere, and comparing the mass before and after the heating. As an alkylamine, the alkylamine used for the manufacturing method of the copper containing particle | grains mentioned later is mentioned, for example.

  The organic substance present on at least a part of the surface of the core particle is preferably 0.1% by mass to 20% by mass, more preferably 0.3% by mass to 10% by mass with respect to the total of the core particle and the organic substance. %, More preferably 0.5% by mass to 5% by mass. When the proportion of the organic substance is 0.1% by mass or more, sufficient oxidation resistance tends to be obtained. When the ratio of the organic substance is 20% by mass or less, the fusion property at a low temperature tends to be good.

  The core particles include at least copper (metallic copper), and may include other substances as necessary. Examples of substances other than copper include metals such as gold, silver, platinum, tin, and nickel, or compounds containing these metal elements, fatty acid copper described later, organic compounds derived from reducing compounds or alkylamines, copper oxide, copper chloride, etc. Can be mentioned. From the viewpoint of forming a conductor having excellent conductivity, the content of copper (metal copper) in the core particles is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. .

  Since the organic substance is present on at least a part of the surface of the core particle, the copper-containing particles suppress copper oxidation even when stored in the air, and the oxide content is small. For example, in one embodiment, the content rate of the oxide in a copper containing particle is 5 mass% or less. The oxide content in the copper-containing particles is measured by, for example, XRD (X-ray diffraction, X-ray diffraction).

<Method for producing copper-containing particles>
The method for producing the copper-containing particles is not particularly limited. For example, the copper-containing particles are produced by a method having a step of heating a composition containing a metal salt of a fatty acid and copper, a reducing compound, and an alkylamine. The method may have steps such as a centrifugal separation step and a washing step after the step of heating the composition as necessary.

  The said method uses the metal salt of a fatty acid and copper as a copper precursor. This makes it possible to use an alkylamine having a lower boiling point (that is, having a lower molecular weight) as a reaction medium than the method described in Patent Document 1 using silver oxalate or the like as a copper precursor. It is done. As a result, in the obtained copper-containing particles, organic substances present on the surface of the core particles are more likely to be thermally decomposed or volatilized, and it is considered easier to conduct the conductor at a low temperature.

(fatty acid)
The fatty acid is a monovalent carboxylic acid represented by RCOOH (R is a chained hydrocarbon group, which may be linear or branched). The fatty acid may be either a saturated fatty acid or an unsaturated fatty acid. From the viewpoint of efficiently covering the core particles and suppressing oxidation, the fatty acid is preferably a linear saturated fatty acid. Only one type or two or more types of fatty acids may be used.

  The carbon number of the fatty acid is preferably 9 or less. Examples of saturated fatty acids having 9 or less carbon atoms include acetic acid (2 carbon atoms), propionic acid (3 carbon atoms), butyric acid and isobutyric acid (4 carbon atoms), valeric acid and isovaleric acid (5 carbon atoms), capron Examples include acids (carbon number 6), enanthic acid and isoenanthic acid (carbon number 7), caprylic acid, isocaprilic acid and isocaproic acid (carbon number 8), nonanoic acid and isononanoic acid (carbon number 9). Examples of the unsaturated fatty acid having 9 or less carbon atoms include those having one or more double bonds in the hydrocarbon group of the saturated fatty acid.

  The type of fatty acid can affect properties such as dispersibility of the copper-containing particles in the dispersion medium and fusing properties. For this reason, it is preferable to select the kind of fatty acid according to the use of copper-containing particles. From the viewpoint of homogenizing the particle shape, it is preferable to use a fatty acid having 5 to 9 carbon atoms and a fatty acid having 4 or less carbon atoms in combination. For example, nonanoic acid having 9 carbon atoms and acetic acid having 2 carbon atoms are preferably used in combination. The ratio in the case of using together the fatty acid having 5 to 9 carbon atoms and the fatty acid having 4 or less carbon atoms is not particularly limited.

  The method for obtaining a salt compound of fatty acid and copper (fatty acid copper) is not particularly limited. For example, it may be obtained by mixing copper hydroxide and a fatty acid in a solvent, or commercially available fatty acid copper may be used. Alternatively, by mixing copper hydroxide, a fatty acid and a reducing compound in a solvent, the formation of fatty acid copper and the formation of a complex formed between the fatty acid copper and the reducing compound are performed in the same process. Also good.

(Reducing compounds)
The reducing compound is considered to form a complex compound such as a complex between both compounds when mixed with fatty acid copper. As a result, the reducing compound becomes an electron donor to the copper ion in the fatty acid copper, the reduction of the copper ion is more likely to occur, and the liberation of copper atoms by spontaneous pyrolysis than the fatty acid copper in a state where no complex is formed. Is likely to occur. A reducing compound may be used individually by 1 type, or may be used together 2 or more types.

  Specific examples of the reducing compound include hydrazine compounds such as hydrazine, hydrazine derivatives, hydrazine hydrochloride, hydrazine sulfate and hydrazine hydrate, hydroxylamine compounds such as hydroxylamine and hydroxylamine derivatives, sodium borohydride, sodium sulfite, and sulfite. Examples thereof include sodium compounds such as sodium hydrogen, sodium thiosulfate, and sodium hypophosphite.

  The reducing compound is preferably a reduction having an amino group, from the viewpoint of easily forming a coordination bond to the copper atom in the fatty acid copper, and easily forming a complex while maintaining the structure of the fatty acid copper. It is a sex compound. Examples of the reducing compound having an amino group include hydrazine and derivatives thereof, hydroxylamine and derivatives thereof, and the like.

  From the viewpoint of lowering the heating temperature (for example, 150 ° C. or less) in the step of heating the composition containing fatty acid copper, the reducing compound and the alkylamine (hereinafter also referred to as “heating step”), the reducing compound is preferably Is a reducing compound capable of forming a complex that causes reduction and liberation of copper atoms in a temperature range that does not cause evaporation or decomposition of the alkylamine. Examples of such reducing compounds include hydrazine and its derivatives, hydroxylamine and its derivatives, and the like. These reducing compounds can form a complex by forming a coordinate bond between a nitrogen atom constituting the skeleton and a copper atom. In addition, since these reducing compounds generally have a stronger reducing power than alkylamines, the resulting complexes tend to spontaneously decompose under relatively mild conditions, and tend to reduce and release copper atoms.

  By selecting a suitable one of these derivatives instead of hydrazine or hydroxylamine, the reactivity with the fatty acid copper can be adjusted, and a complex that generates spontaneous decomposition under a desired condition can be generated. Examples of hydrazine derivatives include methyl hydrazine, ethyl hydrazine, n-propyl hydrazine, isopropyl hydrazine, n-butyl hydrazine, isobutyl hydrazine, sec-butyl hydrazine, t-butyl hydrazine, n-pentyl hydrazine, isopentyl hydrazine, and neo-pentyl hydrazine. , T-pentylhydrazine, n-hexylhydrazine, isohexylhydrazine, n-heptylhydrazine, n-octylhydrazine, n-nonylhydrazine, n-decylhydrazine, n-undecylhydrazine, n-dodecylhydrazine, cyclohexylhydrazine, phenyl Examples include hydrazine, 4-methylphenylhydrazine, benzylhydrazine, 2-phenylethylhydrazine, 2-hydrazinoethanol, and acetohydrazine. Rukoto can. Examples of hydroxylamine derivatives include N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) hydroxylamine and the like. Can do.

  The ratio of the copper and the reducing compound contained in the fatty acid copper is not particularly limited as long as a desired complex is formed. For example, the ratio (copper: reducing compound) is in the range of 1: 1 to 1: 4, preferably in the range of 1: 1 to 1: 3, more preferably 1: 1 to 1: 1, in molar ratio. 2 range.

(Alkylamine)
Alkylamine is considered to function as a reaction medium for a decomposition reaction of a complex formed from fatty acid copper and a reducing compound. Furthermore, it is considered that protons generated by the reducing action of the reducing compound are captured, and the reaction solution is inclined to be acidic and suppress the oxidation of copper atoms.

The alkylamine is a primary amine represented by RNH ₂ (R is a hydrocarbon group and may be cyclic, linear or branched), R ¹ R ² NH (R ¹ and R ² are hydrocarbons) R ¹ and R ² may be cyclic or branched), and two amino groups are substituted on the hydrocarbon chain. Means an alkylene diamine or the like. The alkylamine may have one or more double bonds, and may have atoms such as oxygen, silicon, nitrogen, sulfur, and phosphorus. The alkylamine may be only one type or two or more types.

  The carbon number of the hydrocarbon group of the alkylamine is preferably 7 or less, more preferably 6 or less, and even more preferably 3 or more. When the carbon number of the hydrocarbon group of the alkylamine is 7 or less, the alkylamine tends to be thermally decomposed during heating for fusing the copper-containing particles to form a conductor, and a good conductor can be achieved. It is in.

  Specific examples of the primary amine include ethylamine, 2-ethoxyethylamine, propylamine, butylamine, isobutylamine, pentylamine, isopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, Examples include hexadecylamine, oleylamine, 3-methoxypropylamine, and 3-ethoxypropylamine.

  Specific examples of the secondary amine include diethylamine, dipropylamine, dibutylamine, ethylpropylamine, ethylpentylamine, dibutylamine, dipentylamine, and dihexylamine.

  Specific examples of alkylenediamine include ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine, 2,2 -Dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamino-2-methylpentane, 1,6-diaminohexane, N, N′-dimethyl-1,6-diaminohexane, 1,7-diaminoheptane, 1, Examples thereof include 8-diaminooctane, 1,9-diaminononane, 1,12-diaminododecane and the like.

  The alkylamine preferably contains at least one alkylamine whose hydrocarbon group has 7 or less carbon atoms. Thereby, the copper containing particle | grains which are excellent by the melt | fusion property in low temperature can be manufactured. Alkylamines may be used alone or in combination of two or more. The alkylamine may include an alkylamine having a hydrocarbon group having 7 or less carbon atoms and an alkylamine having a hydrocarbon group having 8 or more carbon atoms. When an alkylamine having a hydrocarbon group having 7 or less carbon atoms and an alkylamine having 8 or more carbon atoms in a hydrocarbon group are used in combination, the alkylamine having a hydrocarbon group having 7 or less carbon atoms in the entire alkylamine The ratio is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more.

  The ratio of copper and alkylamine contained in fatty acid copper is not particularly limited as long as desired copper-containing particles are obtained. For example, the ratio (copper: alkylamine) is in the range of 1: 1 to 1: 8, preferably in the range of 1: 1 to 1: 6, more preferably 1: 1 to 1: 4 in molar ratio. Range.

(Heating process)
The method for carrying out the step of heating the composition containing fatty acid copper, reducing compound and alkylamine is not particularly limited. For example, a method in which fatty acid copper and a reducing compound are mixed in a solvent and then heated by adding an alkylamine, a method in which fatty acid copper and an alkylamine are mixed in a solvent and then further heated by adding a reducing compound, a fatty acid A method of heating copper hydroxide, a fatty acid, a reducing compound, and an alkylamine, which are copper starting materials, in a solvent, a method of heating, a method of mixing a fatty acid copper and an alkylamine in a solvent, and then adding a reducing compound and heating Etc.

  The heating step can be performed at a relatively low temperature by using fatty acid copper having 9 or less carbon atoms as a copper precursor. The implementation temperature of a heating process is 150 degrees C or less, for example, Preferably it is 130 degrees C or less, More preferably, it is 100 degrees C or less.

The composition containing fatty acid copper, a reducing compound and an alkylamine may further contain a solvent. The composition preferably contains a polar solvent from the viewpoint of promoting the formation of a complex of fatty acid copper and a reducing compound. Here, the polar solvent means a solvent that dissolves in water at 25 ° C.
The polar solvent is preferably an alcohol. Use of alcohol tends to promote complex formation. Although the reason is not clear, it is considered that contact with a water-soluble reducing compound is promoted while dissolving fatty acid copper which is a solid. A solvent may be used individually by 1 type, or may use 2 or more types together.

  As alcohol which melt | dissolves in water at 25 degreeC, C1-C8 can be mentioned and the alcohol which has one hydroxyl group in a molecule | numerator can be mentioned. Examples of such alcohols include linear alkyl alcohols, phenols, and those obtained by replacing hydrogen atoms of hydrocarbons having an ether bond in the molecule with hydroxyl groups. The alcohol that dissolves in water at 25 ° C. is preferably an alcohol containing two or more hydroxyl groups in the molecule from the viewpoint of developing stronger polarity. Moreover, you may use alcohol containing a sulfur atom, a phosphorus atom, a silicon atom, etc. according to the use of the copper containing particle | grains manufactured.

  Specific examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol, allyl alcohol, benzyl alcohol, pinacol, propylene glycol, menthol, catechol, hydroquinone, and salicyl. Examples thereof include alcohol, glycerin, pentaerythritol, sucrose, glucose, xylitol, methoxyethanol, triethylene glycol monomethyl ether, ethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol.

  The alcohol is preferably methanol, ethanol, 1-propanol and 2-propanol having a very high solubility in water, more preferably 1-propanol and 2-propanol, and still more preferably 1-propanol.

  In the copper-containing particles, the ratio of copper-containing particles having a major axis length of 50 nm or less is preferably 55% or less. In this specification, the major axis of the copper-containing particles means a distance between two planes selected so that the distance between the two planes circumscribing the copper-containing particles and parallel to each other is maximized. In this specification, the ratio of the copper-containing particles having a major axis length of 50 nm or less is a ratio of the 200 copper-containing particles selected at random. For example, when 110 copper-containing particles having a major axis length of 50 nm or less are present in 200, the ratio of copper-containing particles having a major axis length of 50 nm or less is 55%.

  When the ratio of copper-containing particles having a major axis length of 50 nm or less (hereinafter also referred to as “small-diameter particles”) is 55% or less, the copper-containing particles are fused at a low temperature as the entire copper-containing particles. Excellent wearability.

  Reason why the ratio of the small-diameter particles in the copper-containing particles is 55% or less (that is, the ratio of the copper-containing particles having a major axis length of more than 50 nm exceeds 45%) and excellent fusion properties at low temperatures. Although it is not clear, the present inventors consider as follows. The copper-containing particles originally tend to melt as the size decreases. On the other hand, in the case of copper-containing particles whose major axis exceeds 50 nm, particles on the surface of the particles are difficult to desorb and are not easily affected by oxidation. For some reason, such as the specific surface area of which is not increased and is not easily affected by oxidation, there are cases where the long axis is longer than the small-diameter particles and thus is easily melted. As a result, when the ratio of the copper-containing particles having a major axis length of more than 50 nm exceeds 45%, the copper-containing particles tend to have excellent fusion properties at low temperatures.

  Patent Document 1 and Patent Document 2 describe that the average particle diameter of copper particles is 50 nm or less, and further the average particle diameter is 20 nm. Patent Document 2 describes that copper particles having a particle diameter of 10 nm or less and copper particles having a particle diameter of 100 to 200 nm were mixed in the copper particles obtained in the examples. However, there is no specific description regarding the proportion of small-diameter particles in the entire copper particles in any of the patent documents, and there is no description suggesting that if the proportion of small-diameter particles is small, the fusion property is improved.

  From the viewpoint of fusion at low temperature, the proportion of copper-containing particles having a major axis length of 50 nm or less is preferably 50% or less, more preferably 35% or less, and even more preferably 20% or less. It is.

  From the viewpoint of fusion at low temperatures, the proportion of copper-containing particles having a major axis length of 70 nm or more is preferably 30% or more, more preferably 50% or more, and even more preferably 60% or more. It is. In this specification, the ratio of the copper-containing particles having a major axis length of 70 nm or more is a ratio of the 200 copper-containing particles selected at random.

  From the viewpoint of fusion at low temperatures, the average value of the major axis length of the copper-containing particles is preferably 55 nm or more, more preferably 70 nm or more, and further preferably 90 nm or more. From the viewpoint of fusion at low temperatures, the average value of the major axis length of the copper-containing particles is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less. In this specification, the average value of the length of the major axis is an arithmetic average value of the length of the major axis measured for 200 copper-containing particles selected at random. In addition, the length of the major axis of the copper-containing particles, the presence or absence of surface irregularities described later, and the aspect ratio are measured by a known method such as observation with an electron microscope. Although the magnification in the case of observing with an electron microscope is not specifically limited, For example, it is 20 to 50000 times. In addition, the copper containing particle | grains whose particle diameter is less than 3.0 nm are excluded from the object of a measurement.

  From the viewpoint of fusion at low temperature, the length of the long axis of the copper-containing particles having the longest long axis length (hereinafter also referred to as “maximum diameter particle”) is preferably 350 nm or less, more preferably It is 300 nm or less, more preferably 250 nm or less. In the present specification, the length of the long axis of the largest-diameter particle is the length of the long axis of the copper-containing particle having the longest long axis length among 200 randomly selected copper-containing particles.

  From the viewpoint of fusion property at low temperature, the length of the major axis of the copper-containing particles having the shortest major axis length (hereinafter also referred to as “minimum diameter particle”) is preferably 5 nm or more, more preferably It is 8 nm or more, more preferably 10 nm or more. In the present specification, the length of the long axis of the smallest diameter particle is the length of the long axis of the copper-containing particle having the shortest long axis length among the 200 copper-containing particles randomly selected.

  Adjustment of the length of the major axis of the copper-containing particles is, for example, the conditions of the raw material in the method for producing copper-containing particles described later, the temperature when mixing the raw materials, the reaction time, the reaction temperature, the washing step, the washing solvent, etc. Is done by adjusting.

From the viewpoint of promoting fusion at a low temperature, the copper-containing particles of the present embodiment preferably include copper-containing particles having irregularities on the surface. The copper-containing particles having irregularities on the surface are preferably copper-containing particles having a circularity of 0.70 to 0.99. In this specification, the circularity is a value represented by 4π × S / (perimeter length) ² , S is the surface area of the measurement target particle, and the perimeter length is the perimeter length of the measurement target particle. . The circularity can be obtained by analyzing an electron microscope image using image processing software. Although the magnification in the case of observing with an electron microscope is not specifically limited, For example, it is 20 to 50000 times. In addition, the copper containing particle | grains whose particle diameter is less than 3.0 nm are excluded from the object of a measurement.

  The reason why the copper-containing particles include copper-containing particles having irregularities on the surface to promote fusion at low temperatures is not clear, but the presence of irregularities on the surface of the copper-containing particles causes a so-called nanosize effect. It is presumed that the melting point is lowered and the fusion property at a low temperature is promoted.

  The shape of the copper-containing particles is not particularly limited and may be selected depending on the application. For example, the aspect ratio that is the ratio of the major axis to the minor axis (major axis / minor axis) of the copper-containing particles may be selected from the range of 1.0 to 10.0. When a mixture of copper-containing particles and a dispersion medium is applied to a substrate by a printing method, the average value of the aspect ratio, which is the ratio of the major axis to the minor axis (major axis / minor axis) of the copper-containing particles, is a mixture. From the viewpoint of easy adjustment of the viscosity, it is preferably 1.5 to 8.0. The minor axis of the copper-containing particles means a distance between two planes selected so that a distance between two planes circumscribing the copper-containing particles and parallel to each other is minimized.

  The average aspect ratio of the copper-containing particles is preferably 1.0 to 8.0, more preferably 1.1 to 6.0, and still more preferably 1.2 to 3.0. In the present specification, the average value of the aspect ratio is obtained by respectively obtaining the arithmetic average value of the long axis and the arithmetic average value of the short axis of the 200 copper-containing particles selected at random, and the arithmetic average of the obtained long axis. It is a value obtained by dividing the value by the arithmetic average value of the minor axis.

  The adjustment of the aspect ratio of the copper-containing particles is performed, for example, by adjusting conditions such as the number of carbon atoms of fatty acids used in the method for producing copper-containing particles described later.

  The kind in particular of the dispersion medium contained in the composition for conductor formation is not restrict | limited, It can select from the organic solvent generally used according to the use of the composition for conductor formation. A dispersion medium may be used individually by 1 type, or may use 2 or more types together. When applying the conductor-forming composition to the printing method, from the viewpoint of controlling the viscosity of the conductor-forming composition, the dispersion medium is preferably terpineol, isobornylcyclohexanol, dihydroterpineol and dihydroterpineol acetate. At least one selected from the group consisting of:

  The viscosity of the conductor-forming composition is not particularly limited, and can be selected according to the method of using the conductor-forming composition. For example, when the conductor-forming composition is applied to the screen printing method, the viscosity is preferably 0.1 Pa · s to 30 Pa · s, more preferably 1 Pa · s to 30 Pa · s. When the composition for forming a conductor is applied to the ink jet printing method, the viscosity is preferably 0.1 mPa · s to 30 mPa · s, more preferably 5 mPa · s to 20 mPa, although it depends on the standard of the ink jet head to be used. -S. In the present invention, the “viscosity of the composition for forming a conductor” refers to an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: VISCOMETER-TV22, applicable cone plate type rotor: 3 ° × R17.65). Used, means the value measured at 25 ° C.

  Examples of the conductor forming composition include conductive paints, conductive pastes, and conductive inks.

  The composition for forming an electric conductor may contain a component other than the metal component and the dispersion medium as necessary. Examples of such components include silane coupling agents, polymer compounds, radical initiators, reducing agents, and the like.

  As described above, the conductor layer is obtained on the adherend by the conductor layer forming step. FIG. 1A is an SEM image of a cross section of the conductor layer. The conductor layer 1 is formed of a conductor 1a containing a metal component. The conductor layer 1 includes a first outer surface in contact with the adherend, a second outer surface different from the first outer surface, and a communication hole 1b that communicates the first outer surface with the second outer surface. Have The conductor layer 1 may be a porous conductor layer (porous body layer) formed of, for example, a conductor 1a containing a metal component. The thickness of the conductor layer 1 is, for example, 0.4 to 100 μm.

  The conductor layer 1 preferably has a porosity of 10% or more, more preferably a porosity of 13% or more, and further preferably a porosity of 15% or more, from the viewpoint of excellent adhesion to an adherend. The conductor layer 1 preferably has a porosity of 70% or less, more preferably a porosity of 55% or less, and further preferably a porosity of 40% or less from the viewpoint of excellent conductivity. The conductor layer 1 is 10 to 70%, 10 to 55%, 10 to 40%, 13 to 70%, 13 to 55%, and 13 to 40% from the viewpoint of excellent conductivity and adhesion to an adherend. It may have a porosity of 15-70%, 15-55% or 15-40%. In this specification, “porosity” means a cross section of a conductor layer obtained by analyzing a cross-sectional image of a conductor layer observed with a scanning electron microscope, a scanning ion microscope, or the like, using image analysis software. The ratio of the area of the non-conductor portion to the total area of

  In the method for forming a conductor according to the present embodiment, the resin and coupling agent are filled in the communication holes after the conductor layer installation step (filling step). The resin and the coupling agent are filled in the communication hole by, for example, being applied to the conductor layer. Examples of the coating method include inkjet, dispensing, screen printing, spin coating, die coating, spray coating, dip coating, and the like. In the filling step, the resin and the coupling agent may be filled simultaneously (as a composition containing the resin and the coupling agent), or the resin and the coupling agent may be filled separately. When the resin and the coupling agent are filled separately, the order of filling in the filling step is arbitrary. Preferably, the coupling agent is filled in the communication holes first, and then the resin is filled in the communication holes.

  Examples of the resin include a thermosetting resin, a photocurable resin, and a moisture curable resin.

  Examples of the thermosetting resin include epoxy resin, phenol resin, unsaturated polyester resin, saturated polyester resin, polyamide resin, polyimide resin, polyamideimide resin, and acrylic resin.

  The epoxy resin is preferably a polyfunctional epoxy resin. Examples of the polyfunctional epoxy resin include a bisphenol A type epoxy resin having an aliphatic skeleton.

  When the resin is a thermosetting resin, in addition to the resin and the coupling agent, the curing agent may be further filled in the communication hole. Examples of the curing agent include amines and imidazoles. Examples of amines include modified polyamines.

  Examples of the photocurable resin include compounds having at least one ethylenically unsaturated group in the molecule. Specifically, compounds having at least one ethylenically unsaturated group in the molecule include n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, and n-pentyl (meth) acrylate. , N-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, And alkyl (meth) acrylates such as lauryl (meth) acrylate and tridecyl (meth) acrylate. These are used alone or in combination of two or more.

  When the resin is a photocurable resin, in addition to the resin and the coupling agent, a photopolymerization initiator may be further filled in the communication hole. As the photopolymerization initiator, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Aromatic ketones such as 1-propanone; quinone compounds such as alkylanthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoins; benzyl derivatives such as benzyldimethyl ketal; 2- (2-chlorophenyl)- 4,5-diphenylimidazole dimer (for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole), 2- (2-fluorophenyl) -4 2,4,5-triaryl, such as 2,5-diphenylimidazole dimer Imidazole dimer; 9-phenyl acridine, 1,7 (9,9'-acridinyl) acridine derivatives such as heptane, and the like. These are used alone or in combination of two or more.

  Examples of the moisture curable resin include a binder resin. The binder resin is, for example, a modified silicone or an epoxy resin. The binder resin may be one of these alone or a mixture thereof.

  When the resin is a moisture curable resin, in addition to the resin and the coupling agent, a binder resin curing agent may be further filled in the communication hole. Examples of the binder resin curing agent include a curing agent capable of moisture curing at room temperature. When the binder resin includes an epoxy resin, specifically, the curing agent capable of moisture curing at room temperature is ketimine, oxazolidine, or the like.

  Other components (components other than the resin and the coupling agent) such as the above curing agent, photopolymerization initiator, and binder resin curing agent may be filled in the communication holes simultaneously with the resin and the coupling agent, The communication holes may be filled separately from each of the resin and the coupling agent. When the resin and the coupling agent are filled in the communication holes at the same time, the other components are preferably filled at the same time as the resin and the coupling agent (as a composition containing the resin, the coupling agent and other components). When the resin and the coupling agent are separately filled in the communication holes, the other components are preferably filled at the same time as the resin (as a composition containing the resin and other components).

  The type of the coupling agent is not particularly limited, and is selected according to the type of adherend, conductor layer and resin, or required characteristics. The coupling agent may be, for example, a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, a zirconate coupling agent, or the like. These coupling agents are used alone or in combination of two or more.

  The coupling agent preferably has at least one of an amino group and a mercapto group. When the coupling agent has these groups, when the conductor layer contains copper, the affinity with copper is improved and the adhesion can be further improved, and the resin is an epoxy resin. When it contains, it becomes possible to form a chemical bond by reacting with an epoxy resin.

  The silane coupling agent preferably has at least one of an amino group and a mercapto group. Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl)- Examples include 2-aminoethyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, and the like. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.

  The silane coupling agent may be another silane coupling agent having no amino group and mercapto group. Other silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltrimethoxysilane. Ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, hexamethyldisilazane, vinyltri Methoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyl dimeth Sisilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, tris- (trimethoxy Silylpropyl) isocyanurate, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxy) Rirupuropiru) tetrasulfide, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, and the like. These are used alone or in combination of two or more.

  The filling amount of the coupling agent is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 60 parts by mass with respect to 100 parts by mass of the resin, from the viewpoint of further excellent adhesion to the adherend. Hereinafter, it is particularly preferably 50 parts by mass or less, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, still more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. The filling amount of the coupling agent is preferably 0.1 to 80 parts by mass, 0.1 to 70 parts by mass, 0.1% to 100 parts by mass with respect to 100 parts by mass of the resin from the viewpoint of further excellent adhesion to the adherend. 1-60 parts by weight, 0.1-50 parts by weight, 1-80 parts by weight, 1-70 parts by weight, 1-60 parts by weight, 1-50 parts by weight, 3-80 parts by weight, 3-70 parts by weight, 3-60 mass parts, 3-50 mass parts, 5-80 mass parts, 5-70 mass parts, 5-60 mass parts, or 5-50 mass parts may be sufficient. When the coupling agent is a silane coupling agent having a mercapto group, the filling amount of the coupling agent is more preferably 30 with respect to 100 parts by mass of the resin from the viewpoint of further excellent adhesion to the adherend. Or less, more preferably 10 parts by mass or more, and even more preferably 10 to 30 parts by mass.

  After the filling step, the resin may be cured (curing step). When a thermosetting resin is used as the resin, it can be cured by heating the thermosetting resin (and a curing agent used as necessary). Moreover, when using a photocurable resin as resin, it can be hardened by irradiating light to a photocurable resin (and photoinitiator used as needed).

  When using a solvent with resin and a coupling agent, you may volatilize a solvent after a filling process (volatilization process). Examples of the solvent volatilization method include a method using a hot plate (heat treatment method), a method using an infrared heater (heat treatment method), and a method using reduced pressure.

  The conductor formation method may further include other steps as necessary. Other steps include a step of removing at least a part of volatile components in the composition for forming a conductor by volatilization or the like before the conductor layer forming step, and heating in a reducing atmosphere after the step of forming the conductor layer. Applying a load to the conductor obtained after the step of reducing the generated metal oxide (copper oxide, etc.), the step of removing the remaining components by performing light baking after the step of forming the conductor layer, and the step of forming the conductor layer A process etc. can be mentioned.

  As described above, the resin and the coupling agent are filled in the communication holes of the conductor layer by the filling step.

  FIG. 1B is an SEM image of a cross section of a conductor obtained by filling a resin and a coupling agent. The conductor 2 is a porous conductor layer, and communicates the first outer surface, the second outer surface different from the first outer surface, and the first outer surface and the second outer surface. A conductor layer having a communication hole, and a resin portion 3 filled in the communication hole and containing a resin or a cured product thereof, and a coupling agent or a reaction product thereof. The conductor layer is formed of the conductor 1a. In addition, the resin part 3 in the conductor 2 may contain a solvent, and may not contain a solvent. The reaction product of the coupling agent contained in the resin part 3 is generated, for example, by reacting the coupling agent with at least one of the adherend, the conductor layer, and the resin, and reacting with each other. The reaction product produced by reacting the reaction product and the coupling agent with moisture contained in the adherend and the resin may be used.

  The volume resistivity of the conductor is preferably 300 μΩ · cm or less, more preferably 100 μΩ · cm or less, still more preferably 30 μΩ · cm or less, and particularly preferably 20 μΩ · cm or less.

  The shape of the conductor is not particularly limited, and may be a thin film shape, a pattern shape, or the like. The conductor of the present embodiment can be used for forming wirings, coatings and the like for various electronic components. In particular, when copper-containing particles are used as the metal component, the conductor of the present embodiment can be manufactured at low temperature, so it is suitable for use in forming a metal foil, a wiring pattern, etc. on a substrate having low heat resistance such as a resin. Used. The conductor is also preferably used for applications such as decoration and printing that are not intended to be energized.

<Structure and manufacturing method thereof>
The structure according to the present embodiment includes an adherend and a conductor provided on the adherend. The conductor is a porous conductor layer, and includes a first outer surface in contact with the adherend, a second outer surface different from the first outer surface, and the first outer surface and the second outer surface. A conductor layer having a communication hole that communicates with the surface, and a resin part filled in the communication hole and containing a resin or a cured product thereof and a coupling agent or a reaction product thereof. Preferred embodiments of the adherend and the conductor are the same as those of the adherend and the conductor in the above-described conductor forming method.

  The structure manufacturing method according to the present embodiment includes a porous conductor layer on an adherend, and a second outer surface that is in contact with the adherend and is different from the first outer surface. A step of providing a conductor layer having a communication hole for communicating the outer surface and the first outer surface and the second outer surface (conductor layer installation step), and a step of filling the communication hole with a resin and a coupling agent (Filling step). The details of the conductor layer installation step and the filling step are the same as the conductor layer installation step and the filling step in the above-described conductor forming method.

  The structure manufacturing method may further include other steps as necessary. The details of the other steps are the same as the other steps in the above-described conductor forming method.

  The conductor and structure of this embodiment can be used for various devices. Specifically, the conductor and the structure are used for electronic components such as an electromagnetic wave shield, a laminated plate, a solar cell panel, a display, a transistor, a semiconductor package, and a laminated ceramic capacitor, and are particularly included in the apparatus of this embodiment. Since the conductor can be formed on a substrate such as a resin, it is suitable for manufacturing a flexible laminated plate, a solar cell panel, a display and the like. In addition, electronic devices, home appliances, industrial machines, transport machines, and the like that incorporate the electronic components are also included in the apparatus of this embodiment.

  The conductor and structure of this embodiment can also be suitably used as a plating seed layer. The conductor and the structure can be applied to any type of metal, electrolytic and electroless plating methods. Moreover, the conductor and structure which gave plating can be used for the above-mentioned various uses.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples at all.

  In Examples and Comparative Examples, conductors were formed using the metal components and resin compositions shown below. Copper-containing particles were synthesized as metal components as follows.

[Synthesis of copper nonanoate]
First, 150 mL of 1-propanol (Kanto Chemical Co., Ltd., special grade) is added to 91.5 g (0.94 mol) of copper hydroxide (Kanto Chemical Co., Ltd., special grade) and stirred. 370.9 g (2.34 mol) (manufactured by company, 90% or more) was added. The obtained mixture was heated and stirred at 90 ° C. for 30 minutes in a separable flask. The obtained solution was filtered while heated to remove undissolved substances. Thereafter, the mixture was allowed to cool, and the produced copper nonanoate was suction filtered and washed with hexane until the washing liquid became transparent. The obtained powder was heated in an explosion-proof oven at 50 ° C. for 3 hours to obtain copper (II) nonanoate. The yield was 340 g (yield 96 mass%).

[Synthesis of copper-containing particles]
Put 15.01 g (0.040 mol) of nonanoate copper (II) obtained above and 7.21 g (0.040 mol) of copper acetate (II) anhydride (manufactured by Kanto Chemical Co., Ltd.) into a separable flask. Then, 22 mL of 1-propanol and 32.1 g (0.32 mol) of hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd., purity 99%) were added and dissolved by heating and stirring at 80 ° C. in an oil bath. After moving to an ice bath and cooling to an internal temperature of 5 ° C., 7.72 mL (0.16 mol) of hydrazine monohydrate (manufactured by Kanto Chemical Co., Ltd., special grade) was stirred in the ice bath. The molar ratio of copper: hexylamine is 1: 4. Subsequently, the mixture was heated and stirred at 90 ° C. for 20 minutes in an oil bath. At that time, the reduction reaction accompanied with foaming progressed, the inner wall of the separable flask exhibited a copper luster, and the solution turned dark red. Centrifugation was performed at 1000 rpm (rotation / min) for 20 seconds to obtain a solid material. The process of further washing the solid with 15 mL of hexane was repeated three times to remove the acid residue, thereby obtaining a copper cake containing powder of copper-containing particles having copper luster.

<Example 1-1>
[Preparation of resin composition]
The materials shown in Table 1 below were mixed by a kneading deaerator to prepare a resin composition. Table 1 shows the contents (parts by mass) of the curing agent and the solvent with respect to 100 parts by mass of the resin, and Table 2 shows the contents (parts by mass) of the coupling agent with respect to 100 parts by mass of the resin.

<Formation of conductor layer>
Copper metal (60 parts by mass), terpineol (20 parts by mass), and isobornylcyclohexanol (trade name: Tersolve MTPH, manufactured by Nippon Terpene Chemical Co., Ltd.) (20 parts by mass) are mixed as metal components to obtain a conductive material. Prepared. The obtained conductive material is applied onto a polyethylene naphthalate (PEN) film, heated to bak the copper-containing particles, and the conductor layer (the first outer surface in contact with the PEN film, which is different from the first outer surface) The second outer surface and a copper layer having a communication hole for communicating the first outer surface and the second outer surface) were formed. Heating was performed by heating to 180 ° C. in a 5% formic acid atmosphere at a heating rate of 40 ° C./min and holding for 60 minutes.

<Filling treatment of resin composition>
The obtained conductor layer was spin-coated with a resin composition (rotation speed: 2000 rpm, 30 seconds) and heated at 140 ° C. for 30 minutes to obtain a conductor.

<Examples 1-2 to 1-10>
A conductor was obtained in the same manner as in Example 1-1 except that the content of the coupling agent (KBM903) was changed to the content in Table 2.
<Comparative Example 1-1>
A conductor was obtained in the same manner as in Example 1-1 except that the resin composition was not filled.
<Comparative Example 1-2>
A conductor was obtained in the same manner as in Example 1-1 except that the resin composition did not contain a coupling agent.

<Examples 2-1 to 2-7>
A conductor was obtained in the same manner as in Example 1-1 except that KBM803 was used instead of KBM903 as the coupling agent, and the content of the coupling agent was changed to the content shown in Table 2.

<Comparative Examples 2-1 and 2-2>
Similar to Example 1-1, except that 30 parts by mass of the resin composition was preliminarily blended with 100 parts by mass of the metal component when the conductive material was prepared, and the resin composition was not filled after the formation of the conductor layer. A conductor was obtained.

<Comparative Example 3-1>
At the time of preparing the conductive material, 5 parts by mass of KBM903 was previously blended with respect to 100 parts by mass of the metal component, and the resin composition was not filled after the formation of the conductor layer. A conductor was obtained.

(Measurement of porosity)
Examples 1-1 to 1-10, 2-1 to 2-7 and Comparative Examples 1-1 and 1-2 use a focused ion beam processing observation apparatus (manufactured by Hitachi High-Tech Science Co., Ltd., FB-2000A). The cross section of the conductor layer was exposed by the focused ion beam, and the cross section was observed. The obtained conductor layer cross-sectional image was binarized using image analysis software (Adobe Photoshop (registered trademark) Elements) so that the conductor portion and the non-conductor portion were separated. From the area ratio of the conductor portion and the non-conductor portion, the ratio of the area of the non-conductor portion to the total area of the conductor layer cross section was obtained, and this ratio was defined as the porosity of the conductor layer. The results are shown in Table 2.

  In Comparative Examples 2-1, 2-2 and 3-1, Examples 1-1 to 1-10 and 2-1 to 2-7 except that the cross section of the conductor was observed instead of the cross section of the conductor layer. And the ratio of the area of the nonconductor part with respect to the total area of a conductor cross section was calculated | required similarly to Comparative Examples 1-1 and 1-2. This ratio was defined as the ratio of the non-conductive portion of the conductive layer. In Comparative Examples 2-1, 2-2, and 3-1, the ratio was 30% (* in Table 2).

(Evaluation of conductivity)
Film thickness obtained by measuring the volume resistivity of the obtained conductor with a surface resistance value measured with a four-end needle surface resistance measuring instrument and a non-contact surface / layer cross-sectional shape measurement system (VertScan, manufactured by Mitsubishi Chemical System Co., Ltd.) And calculated from “A” when the volume resistivity is less than 10 μΩ · cm, “B” when the volume resistivity is less than 10 to 30 μΩ · cm, “C” when the volume resistivity is less than 30 to 100 μΩ · cm, and “D” when the volume resistivity is 100 μΩ · cm or more. " The results are shown in Table 2. In addition, if volume resistivity is less than 100 microhm * cm, it can be said that it is excellent in electroconductivity.

(Adhesive evaluation)
A cross-cut test of the obtained conductor was performed according to JIS K5600 (width 1 mm). Evaluation is that there is no peeling of the conductor after tape peeling, and the adhesive strength is “A” when the number of remaining squares is 100/100, and the number of squares remaining after tape peeling is 90 to “B” when 99/100, and “C” when the number of cells remaining after the tape peeling is 80 to 89/100, “C”, the number of cells remaining after the tape peeling. Was 79 or less / 100, it was performed as “D”. The results are shown in Table 2. In addition, it can be said that it is excellent in adhesiveness if the number of squares remaining after tape peeling is 80 or more / 100.

  By comparing Examples 1-1 to 1-10 and 2-1 to 2-7 with Comparative Examples 1-1 and 1-2, the resin and coupling agent are filled into the communication holes. It can be seen that both adhesion and conductivity are compatible. In Examples 1-1 to 1-10 and 2-1 to 2-7, by adding a coupling agent to the resin, the affinity between the resin, the conductor layer, and the base material is improved and the adhesiveness is improved. It is estimated that From the results of Examples 1-1 to 1-10 and 2-1 to 2-7, the silane coupling agent KBM903 having an amino group had better adhesion than the silane coupling agent KBM803 having a mercapto group. It was. This is presumably because the amino group of KBM903 and the epoxy group of the resin reacted to form a bond.

  Further, from the results of Comparative Examples 2-1 and 2-2, even when a resin and a coupling agent are blended in a conductive material and then fired (a resin and a coupling agent are blended in advance with a metal component to form a conductor). Even so, it can be seen that adhesion and conductivity are not compatible. From the result of Comparative Example 3-1, the adhesiveness and the electrical conductivity were not compatible in the case where only the coupling agent was added to the conductive material and then fired. This is presumed to be because the copper particles were coated and the sintering was inhibited even with a small amount of the coupling agent. On the other hand, since Examples 1-1 to 1-10 and 2-1 to 2-7 are filled with the coupling agent after sintering, both conductivity and adhesiveness can be achieved. As described above, according to the present invention, it is possible to provide a conductor excellent in conductivity and adhesion, a method for forming the conductor, a structure provided with the conductor, and a method for manufacturing the structure.

  DESCRIPTION OF SYMBOLS 1 ... Conductor layer, 1a ... Conductor, 1b ... Communication hole, 2 ... Conductor, 3 ... Resin part.

Claims (8)

A conductor forming method for forming a conductor on an adherend,
A porous conductor layer on the adherend, the first outer surface being in contact with the adherend, a second outer surface different from the first outer surface, and the first outer surface Providing a conductor layer having a communication hole for communicating the surface and the second outer surface;
Filling the communication hole with a resin and a coupling agent;
A method of forming a conductor.   The method for forming a conductor according to claim 1, wherein a filling amount of the coupling agent is 0.1 to 80 parts by mass with respect to 100 parts by mass of the resin.   The method for forming a conductor according to claim 1, wherein the conductor layer has a porosity of 10 to 70%. A manufacturing method of a structure including an adherend and a conductor provided on the adherend,
A porous conductor layer on the adherend, the first outer surface being in contact with the adherend, a second outer surface different from the first outer surface, and the first outer surface Providing a conductor layer having a communication hole for communicating the surface and the second outer surface;
Filling the communication hole with a resin and a coupling agent;
A structure manufacturing method comprising:   The manufacturing method of the structure of Claim 4 whose filling amount of the said coupling agent is 0.1-80 mass parts with respect to 100 mass parts of said resin.   The method for manufacturing a structure according to claim 4 or 5, wherein the conductor layer has a porosity of 10 to 70%. A porous conductor layer comprising a first outer surface, a second outer surface different from the first outer surface, and a communication for communicating the first outer surface with the second outer surface A conductor layer having holes;
A resin part filled with resin or a cured product thereof, and a coupling agent or a reaction product filled in the communication hole;
Comprising a conductor. A structure comprising an adherend and a conductor provided on the adherend,
The conductor is
A porous conductor layer, a first outer surface in contact with the adherend, a second outer surface different from the first outer surface, and the first outer surface and the second outer surface A conductor layer having a communication hole communicating with the surface;
And a resin part containing a resin or a cured product thereof and a coupling agent or a reaction product filled in the communication hole.