Stacked body, method for manufacturing stacked body

Abstract

The present application provides a laminate with excellent adhesion after plating solution immersion and a method for manufacturing the laminate. The laminate of the present application comprises: a substrate; a metal oxide layer comprising a first metal atom selected from the group consisting of a titanium atom, a zirconium atom, and an aluminum atom; and a metal layer X disposed adjacent to the metal oxide layer and comprising a second metal atom different from the first metal atom, wherein the thickness of the metal oxide layer is 50 to 2000 nm.

Description

Technical Field

[0001] This invention relates to a laminate and a method for manufacturing a laminate. Background Technology

[0002] A method for forming a conductive layer by applying a conductive ink containing a metallic component to a substrate using an inkjet recording method is widely known. As a laminate formed using a conductive ink used in this inkjet recording method, Patent Document 1 discloses a substrate that has undergone surface treatment with a specified coupling agent. Previous technical documents Patent documents

[0003] Patent Document 1: International Publication No. 2010 / 029934 Summary of the Invention The technical problem to be solved by the invention

[0004] Based on their research on the laminate as described in Patent Document 1, the inventors discovered that when the laminate is immersed in a plating solution, the metal layer is easily peeled off from the laminate. The following is also referred to as "excellent adhesion after immersion in plating solution" when the metal layer is not easily peeled off from the laminate.

[0005] Therefore, the objective of this invention is to provide a laminate with excellent adhesion after being immersed in a plating solution and a method for manufacturing the laminate. means for solving technical problems

[0006] As a result of in-depth research conducted by the inventors to solve the above-mentioned problems, they discovered that the above-mentioned problems can be solved by the following structure.

[0007] [1] A stack comprising: Substrate; The metal oxide layer comprises a first metal atom selected from the group consisting of titanium atoms, zirconium atoms, and aluminum atoms; and Metal layer X, disposed adjacent to the aforementioned metal oxide layer and containing a second metal atom of a different type than the first metal atom, in the aforementioned laminate... The thickness of the aforementioned metal oxide layer is 50–2000 nm. [2] According to the laminated body described in [1], wherein, The aforementioned metal layer X contains silicon atoms. [3] According to the laminated body described in [1] or [2], wherein, The aforementioned metal layer X contains silicon atoms. In the aforementioned metal layer X, the number of silicon atoms is 0.1 to 10.0 atoms relative to the total number of atoms in the aforementioned metal layer X. [4] The laminate according to any one of [1] to [3], wherein, The aforementioned metal layer X comprises silicon atoms, oxygen atoms, and carbon atoms. In the aforementioned metal layer X, the ratio of the number of silicon atoms to the total number of oxygen atoms and carbon atoms is 0.25 or more. [5] The laminate according to any one of [1] to [4], wherein, The thickness of the aforementioned metal layer X is 0.1–3.0 μm. [6] The laminate according to any one of [1] to [5] has a metal layer Y on the metal layer X, wherein the metal layer Y contains a third metal atom of a different kind from either the first metal atom or the second metal atom. [7] A method for manufacturing a laminate, comprising: Step 1: Coating a composition of coupling agents selected from the group consisting of titanium coupling agents, zirconium coupling agents, and aluminum coupling agents onto a substrate to form a metal oxide layer containing a first metal atom selected from the group consisting of titanium atoms, zirconium atoms, and aluminum atoms; and Step 2 involves coating the aforementioned metal oxide layer with an ink containing a metal compound selected from the group consisting of metal salts and metal complexes to form a metal layer X containing a second type of metal atoms different from the first metal atoms. The thickness of the aforementioned metal oxide layer is 50–2000 nm. [8] According to the manufacturing method of the laminate described in [7], wherein, The inks mentioned above contain silane coupling agents. [9] The method for manufacturing a laminate according to [7] or [8] further includes, after step 2 above: Step 3 involves plating the metal layer X to form a metal layer Y on the metal layer X. The metal layer Y contains a third metal atom of a different type from either the first metal atom or the second metal atom. Invention Effects

[0008] According to the present invention, a laminate with excellent adhesion after being immersed in a plating solution and a method for manufacturing the laminate are provided. Detailed Implementation

[0009] The present invention will now be described in detail. The following description of the constituent elements is based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. Furthermore, in this specification, the numerical range indicated by "~" refers to the range encompassed by the values ​​recorded before and after "~" as the lower and upper limits. Within the numerical ranges described in stages in this specification, the upper or lower limit recorded for a certain numerical range can be replaced with the upper or lower limit of other numerical ranges described in stages. Moreover, within the numerical ranges described in this specification, the upper or lower limit recorded within a certain numerical range can be replaced with the values ​​shown in the embodiments. In this specification, each component may use a single substance corresponding to that component, or two or more substances. When two or more substances are used for each component, unless otherwise stated, the content of that component refers to the total content of the two or more substances. In this specification, a combination of two or more preferred methods is a more preferred method. In this specification, the term "process" includes not only independent processes, but also processes that, even if they cannot be clearly distinguished from other processes, are included in this term as long as the desired purpose of the process is achieved.

[0010] [Layered Body] A stack comprising: Substrate; The metal oxide layer comprises a first metal atom selected from the group consisting of titanium atoms, zirconium atoms, and aluminum atoms; and Metal layer X, disposed adjacent to the metal oxide layer and containing a second metal atom of a different type than the first metal atom, in the above-described laminate... The thickness of the metal oxide layer is 50–2000 nm.

[0011] The reason for the excellent adhesion after immersion in the plating solution is unclear, but it is speculated to be as follows. For example, when a metal layer is formed by plating a laminate containing a metal layer to create a thick film of a metal layer different from the aforementioned metal layer, the metal layer may peel off from the laminate during the plating process. It is speculated that, in contrast, the laminate of the present invention has a metal oxide layer containing a first metal atom arranged adjacent to the metal layer X, and the thickness of the metal oxide layer is within a specific range, therefore the metal layer X is less likely to peel off from the laminate.

[0012] The following is a detailed description of the components that a laminate may contain.

[0013] <Substrate> The laminate includes a substrate. Materials used as substrates include, for example, polyimide, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin (acrylonitrile-butadiene-styrene resin), ABS resin (acrylonitrile-butadiene-styrene copolymer), triacetyl cellulose, polyamide, polyacetal, polyphenylene sulfide, polysulfone, epoxy resin, glass epoxy resin, melamine resin, phenolic resin, urea resin, alkyd resin, fluororesin, polylactic acid, and other synthetic resins; inorganic materials such as copper, steel, aluminum, silicon, sodium glass, alkali-free glass, and indium tin oxide (ITO); and paper types such as base paper, coated paper, coated paper, cast-coated paper, resin-coated paper, and synthetic paper. The substrate can be one layer or two or more layers. When there are two or more substrates, two or more substrates with different materials can also be laminated.

[0014] The substrate is preferably in sheet or film form. The thickness of the substrate is preferably 20–2000 μm.

[0015] The substrate can be surface treated. As a surface treatment, known methods include ozone treatment, plasma treatment, corona treatment, primer treatment, and roughening treatment.

[0016] <Metal oxide layer> The laminate contains a metal oxide layer. The thickness of the metal oxide layer is 50–2000 nm, preferably 60–1000 nm, and more preferably 100–500 nm.

[0017] The metal oxide layer contains the first metal atom selected from the group consisting of titanium atoms, zirconium atoms, and aluminum atoms. From the perspective of better adhesion after immersion in the plating solution, it is preferable that the metal oxide layer contains titanium atoms. Furthermore, the metal oxide layer preferably comprises an oxide of a first metal atom selected from the group consisting of titanium oxide, zirconium oxide, and aluminum oxide, and more preferably comprises titanium oxide. A metal oxide layer may contain other metal atoms as long as it contains a first metal atom, or it may contain two or more first metal atoms or other atoms.

[0018] In the metal oxide layer, the number of the first metal atom is preferably 80 to 100 atoms relative to the total number of metal atoms contained in the metal oxide layer, more preferably 90 to 100 atoms, and even more preferably 99 to 100 atoms. Furthermore, the content of the oxide of the first metal atom relative to the total mass of the metal oxide layer is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 99 to 100% by mass. The number of first metal atoms and the content of oxides of the first metal atoms can be determined, for example, using X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence (XRF).

[0019] <Metal Layer X> The laminate contains a metal layer X. Metal layer X is disposed adjacent to metal oxide layer and contains a second metal atom of a different kind than the first metal atom. The adjacent configuration of metal layer X and metal oxide layer means that metal layer X is configured in a manner that is in contact with metal oxide layer, and that there are no other layers between metal layer X and metal oxide layer. The second metal atom is of a different type than the first metal atom. The second metal atom simply needs to be of a different type than the first metal atom selected from the group consisting of titanium, zirconium, and aluminum atoms. For example, if the first metal atom is titanium, the second metal atom can be any metal atom other than titanium, such as zirconium or aluminum. Furthermore, it is preferable that the second metal atom is of a type different from any of the metal atoms contained in the metal oxide layer. For example, when the metal oxide layer contains titanium and zirconium atoms as the first metal atoms and indium and tin atoms as other metal atoms, it is preferable that the second metal atom is of a type different from any of the titanium, zirconium, indium, and tin atoms.

[0020] Examples of the second metal atom include silver, copper, gold, aluminum, magnesium, tungsten, molybdenum, zinc, nickel, palladium, iron, platinum, tin, and lead. From an electrical conductivity perspective, it is preferable that the second metal atom comprises at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper atoms; more preferably, it comprises at least one selected from silver and copper atoms; and even more preferably, it comprises silver atoms.

[0021] Metal layer X preferably contains silicon atoms. By including silicon atoms in metal layer X, the interaction with the metal oxide layer becomes stronger, resulting in superior adhesion after immersion in the plating solution. In this specification, boron, silicon, and germanium atoms, among other half-metal atoms, are not considered metal atoms.

[0022] Metal layer X preferably comprises a second metal atom, silicon atoms, carbon atoms, and oxygen atoms. When metal layer X comprises silicon atoms, carbon atoms, and oxygen atoms, the silicon atoms, carbon atoms, and oxygen atoms are preferably derived from the coupling agent used in step 1 described later. In other words, metal layer X preferably comprises a hydrolysate or hydrolysis condensate of the second metal atom and the coupling agent. The coupling agent is the coupling agent used in step 1 described later, and is selected from the group consisting of titanium coupling agents, zirconium coupling agents, and aluminum coupling agents. Hydrolysates of coupling agents refer to compounds obtained by hydrolyzing the hydrolyzable groups in the coupling agent. Furthermore, the aforementioned hydrolysates can be those where all hydrolyzable groups are hydrolyzed (complete hydrolysates) or those where only a portion of the hydrolyzable groups are hydrolyzed (partial hydrolysates). That is, the aforementioned hydrolysates can be complete hydrolysates, partial hydrolysates, or mixtures thereof. Furthermore, the hydrolysis condensate of the coupling agent refers to a compound obtained by hydrolyzing the hydrolyzable groups in the coupling agent and condensing the resulting hydrolysates. Additionally, the aforementioned hydrolysis condensate can be obtained by the complete hydrolysis of all hydrolyzable groups and the complete condensation of the hydrolysates (a fully hydrolyzed condensate), or by the partial hydrolysis of some hydrolyzable groups and the partial condensation of the hydrolysates (a partially hydrolyzed condensate). That is, the aforementioned hydrolysis condensate can be a fully hydrolyzed condensate, a partially hydrolyzed condensate, or a mixture thereof.

[0023] The number of the second metal atom is preferably 80 to 100 atoms, more preferably 90 to 100 atoms, and even more preferably 99 to 100 atoms, relative to the total number of metal atoms contained in the metal layer X. The number of the second metal atom relative to the total number of atoms in metal layer X is preferably 30 to 99 atoms, more preferably 50 to 95 atoms, and even more preferably 60 to 95 atoms. The number of the second metal atom can be determined, for example, by the method described above for determining the first metal atom.

[0024] The number of silicon atoms relative to the total number of atoms in metal layer X is preferably 0.1 to 20.0 atoms, more preferably 0.1 to 10.0 atoms, and even more preferably 0.1 to 7.0 atoms. The number of carbon atoms relative to the total number of atoms in metal layer X is preferably 0 to 30.0 atomic%, more preferably 0.1 to 20.0 atomic%, and even more preferably 0.1 to 10.0 atomic%. The number of oxygen atoms relative to the total number of atoms in metal layer X is preferably 0 to 30.0 atomic%, more preferably 0.1 to 20.0 atomic%, and even more preferably 0.1 to 10.0 atomic%. The number of silicon atoms, carbon atoms, and oxygen atoms can be determined, for example, by the method described above for determining the first metal atom.

[0025] When the metal layer X comprises silicon atoms, oxygen atoms, and carbon atoms, the ratio of the number of silicon atoms to the total number of oxygen and carbon atoms in the metal layer X (number of silicon atoms / total number of oxygen and carbon atoms) is preferably 0.10 or more, and more preferably 0.25 or more from the perspective of excellent conductivity and migration suppression. The upper limit is preferably 0.90 or less, and more preferably 0.70 or less.

[0026] The thickness of the metal layer X is preferably 0.1 to 5.0 μm, and more preferably 0.1 to 3.0 μm from the perspective of better adhesion after immersion in the plating solution.

[0027] <Metal Layer Y> The laminate may contain a metal layer Y. Metal layer Y is disposed on metal layer X and contains a third metal atom of a type different from either the first metal atom or the second metal atom. Metal layer Y is preferably formed in step 3 described later.

[0028] The third metal atom is of a different type than the first and second metal atoms. The third metal atom only needs to be of a different type than the first and second metal atoms. For example, if the first metal atom is titanium and the second metal atom is silver, it is preferable that the third metal atom is a metal atom of a type different from either titanium or silver; that is, the third metal atom is a metal atom other than titanium or silver. The third metal atom preferably comprises at least one selected from the group consisting of gold, silver, copper, platinum, palladium, nickel, cobalt, tin, and iron atoms. From the perspectives of conductivity, adhesion, and cost, the third metal atom is preferably a nickel, iron, or copper atom.

[0029] Metal layer Y can contain other atoms as long as it contains a third metal atom. Other atoms, for example, include atoms of various components that may be contained in the plating solution, as described later.

[0030] The number of the third metal atom relative to the total number of atoms in the metal layer Y is preferably 80 to 100 atoms, more preferably 90 to 100 atoms, and even more preferably 99 to 100 atoms.

[0031] The thickness of the metal layer Y is preferably 1 to 50 μm, more preferably 1 to 30 μm.

[0032] [Manufacturing method of laminated bodies] There are no particular restrictions on the method of manufacturing the laminate, as long as it is a method capable of manufacturing the aforementioned laminate. The preferred method for manufacturing the laminated body includes: Step 1: Coating a composition containing a coupling agent selected from the group consisting of titanium coupling agents, zirconium coupling agents, and aluminum coupling agents (hereinafter also referred to as "specific coupling agent") onto a substrate to form a metal oxide layer containing a first metal atom selected from the group consisting of titanium atoms, zirconium atoms, and aluminum atoms; and Step 2: Applying an ink containing a metal compound selected from the group consisting of metal salts and metal complexes onto the metal oxide layer to form a metal layer X containing a second metal atom of a different type than the first metal atom. The thickness of the metal oxide layer is 50–2000 nm. When the metal layer X is formed from an ink containing a metal compound selected from the group consisting of metal salts and metal complexes (especially an ink containing the aforementioned metal compound but not metal particles), the resulting metal layer X exhibits superior adhesion after immersion in a plating solution.

[0033] The manufacturing method of the laminate is also preferably further comprising, after step 2: step 3, performing a plating treatment on the metal layer X to form a metal layer Y on the metal layer X, the metal layer Y containing a third metal atom of a type different from either the first metal atom or the second metal atom.

[0034] <Process 1> Step 1 is a process of coating a substrate with a composition containing a specific coupling agent to form a metal oxide layer containing a first metal atom selected from the group consisting of titanium atoms, zirconium atoms and aluminum atoms. A metal oxide layer can be formed on the substrate through process 1. Furthermore, the first metal atom contained in the metal oxide layer is preferably a metal atom constituting a specific coupling agent contained in the composition. In other words, the first metal atom and the metal atom constituting the specific coupling agent are preferably at least partly or all of the same type of metal atom.

[0035] (Substrate) The substrate is the same as that contained in the laminate, and the preferred method is also the same.

[0036] (Composition) The composition contains a specific coupling agent. By using a specific coupling agent, it is possible to suppress the peeling of metal layer X from the laminate in the obtained laminate. The specific coupling agent preferably includes a titanium coupling agent.

[0037] Examples of titanium coupling agents include titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraoctyl alcohol, titanium tetra-2-ethylhexanol, titanium dioctyloxybis(octyl glycol), tetramethyl titanate, titanium acetylacetone, titanium diisopropoxybis(acetylacetone), titanium tetraacetylacetone, titanium diisopropoxybis(acetoacetate), titanium diisopropoxybis(acetoacetate), titanium ethyl acetoacetate, titanium octanediolate, titanium diisopropoxybis(triethanolamine), titanium triethanolamine, titanium ammonium lactate, titanium lactate, titanium polyhydroxystearate, and oligomers thereof. Among them, titanium coupling agents with tetravalent titanium are preferred, and titanium coupling agents with alkoxy ligands having 3 to 10 carbon atoms and tetravalent titanium are more preferred. Commercially available titanium coupling agents include, for example, KR38S, KR44, KR46B, KR55, KR9SA, KRTTS, KR41B, KR138S, KR238S and KR338X (manufactured by Ajinomoto Fine-Techno Co., Inc.), ATRON (NSi-500) manufactured by Nippon SodaCo., Ltd., and ORGATIX TC-130, ORGATIX PC-200, ORGATIX PC-250, ORGATIX PC-601 and ORGATIX PC-620 manufactured by Matsumoto Fine Chemical Co., Ltd.

[0038] Examples of zirconium oxide coupling agents include, for example, zirconium tetrapropoxide, zirconium tetrabutoxide, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis(ethyl acetoacetate), zirconium dibutoxyacetylacetonate, zirconium tetraacetylacetonate, zirconium tributoxymonostearate, zirconium chloride compounds aminocarboxylic acid, zirconium monoacetylacetonate, zirconium diacetylacetonate, zirconium monoacetoacetate, zirconium diacetylacetonate ethyl acetylacetonate, zirconium acetate, zirconium monostearate and oligomers thereof. Among them, the preferred zirconium oxide coupling agent is one with octyl zirconium oxide.

[0039] Examples of aluminum coupling agents include aluminum isopropoxide, aluminum mono-sec-butoxydiisopropoxide, aluminum sec-butoxide, aluminum ethoxide, aluminum diisopropoxide of ethyl acetoacetate, aluminum tri(ethyl acetoacetate), aluminum diisopropoxide of alkyl acetoacetate, aluminum monoacetylacetonate bis(acetoacetate), aluminum tri(ethyl acetoacetate), aluminum diacetylacetonate / aluminum monoacetylacetonate, and oligomers thereof.

[0040] A specific coupling agent can be used alone or in combination with two or more. The content of the specific coupling agent relative to the total solid content of the composition is preferably 1 to 50% by mass, more preferably 2 to 40% by mass. In this specification, "solid component" of a composition refers to the component that forms the film formed using the composition. Typically, when the composition contains a solvent (e.g., organic solvents and water), it refers to all components other than the solvent. Furthermore, liquid components are also considered solid components as long as they form the film.

[0041] The composition may contain a solvent. Examples of solvents include hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, carbamates, alkenes, amides, ethers, esters, alcohols, thiols, thioethers, phosphine, and water.

[0042] The hydrocarbon is preferably a straight-chain or branched hydrocarbon with 6 to 20 carbon atoms. Specific examples of hydrocarbons include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, hexadecane, octadecane, nonadecane, and eicosane.

[0043] Cyclic hydrocarbons are preferably cyclic hydrocarbons with 6 to 20 carbon atoms. Specific examples of cyclic hydrocarbons include cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and decahydronaphthalene.

[0044] Specific examples of aromatic hydrocarbons include benzene, toluene, xylene, trimethylbenzene, and tetrahydronaphthalene.

[0045] Ethers can be any of the following: straight-chain ethers, branched-chain ethers, and cyclic ethers. Specific examples of ethers include diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, tetrahydropyran, dihydropyran, and 1,4-dioxane.

[0046] Alcohols can be any of the primary, secondary, and tertiary alcohols. Specific examples of alcohols include ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-octanol, 2-octanol, 3-octanol, tetrahydrofurfuryl alcohol, cyclopentanol, terpineol, decanol, isodecanol, lauryl alcohol, isolaryl alcohol, myristol, isomyristol, cetyl alcohol, isocetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, isoleyl alcohol, linoleyl alcohol, palmitol, isopaltol, eicosanol, and isoeicosanol.

[0047] Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0048] Specific examples of esters include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, and 3-methoxybutyl acetate.

[0049] (order) Examples of coating methods for the composition include printing, spraying, roller coating, bar coating, curtain coating, spin coating, and slot coating. The coating film formed by the coating composition can be dried as needed. Examples of drying methods include natural drying and heat drying. Furthermore, atmospheric pressure and reduced pressure drying are also possible.

[0050] The thickness of the metal oxide layer is 50–2000 nm, preferably 60–1000 nm, and more preferably 100–500 nm.

[0051] <Process 2> Step 2 is a process of coating an ink containing a metal compound selected from the group consisting of metal salts and metal complexes onto a metal oxide layer to form a metal layer X containing a second metal atom of a different kind than the first metal atom.

[0052] The ink contains at least one of a metal complex and a metal salt. Considering the excellent adhesion after immersion in the plating solution, inks that do not contain metal particles are preferred. The following sections will describe inks containing metal complexes (hereinafter also referred to as "metal complex inks") and inks containing metal salts (hereinafter also referred to as "metal salt inks"). Furthermore, the ink preferably contains a second metal atom, and more preferably contains a metal compound containing a second metal atom. In other words, the ink is more preferably an ink containing a metal compound selected from the group consisting of metal salts and metal complexes and containing a second metal atom. Additionally, the second metal atom is a metal atom of a different type than the first metal atom contained in the metal oxide layer formed in step 1. As a preferred embodiment of the second metal atom, the second metal atom contained in the aforementioned metal layer X can be cited as an example.

[0053] (Metal complex ink) Metal complex inks are, for example, inks in which metal complexes are dissolved in a solvent.

[0054] -Metal complex- Examples of metals constituting the metal complex include silver, copper, gold, aluminum, magnesium, tungsten, molybdenum, zinc, nickel, palladium, iron, platinum, tin, copper, and lead. From an electrical conductivity perspective, it is preferable that the metal constituting the metal complex includes at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper; more preferably, it includes at least one selected from silver and copper; and even more preferably, it includes silver.

[0055] Metal complexes can be obtained, for example, by reacting a metal salt with a complexing agent. One method for manufacturing metal complexes is to add a metal salt and a complexing agent to an organic solvent and stir for a specified time. The stirring method is not particularly limited and can be appropriately selected from known methods such as stirring with a stirrer, stirring blades, or a mixer, or applying ultrasound.

[0056] Examples of metal salts include metal oxides, thiocyanates, sulfides, chlorides, cyanides, cyanates, carbonates, acetates, nitrates, nitrites, sulfates, phosphates, perchlorates, tetrafluoroborates, acetylacetone complexes, and carboxylates.

[0057] Examples of complexing agents include amines, ammonium carbamate compounds, ammonium carbonate compounds, ammonium bicarbonate compounds, and carboxylic acids. From the perspective of conductivity and the stability of the metal complex, it is preferable that the complexing agent comprises at least one selected from the group consisting of ammonium carbamate compounds, ammonium carbonate compounds, amines, and carboxylic acids having 8 to 20 carbon atoms.

[0058] The metal complex is preferably a metal complex having a structure derived from a complexing agent and having a structure derived from at least one of the groups consisting of ammonium carbamate compounds, ammonium carbonate compounds, amines and carboxylic acids having 8 to 20 carbon atoms.

[0059] Amines that act as complexing agents include, for example, ammonia, primary amines, secondary amines, tertiary amines, and polyamines.

[0060] Specific examples of primary amines having straight-chain alkyl groups include methylamine, ethylamine, 1-propylamine, n-butylamine, n-pentylamine, n-hexylamine, heptylamine, octylamine, nonylamine, n-decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanylamine, and octadecylamine.

[0061] Specific examples of primary amines having branched alkyl groups include isopropylamine, sec-butylamine, tert-butylamine, isopentylamine, 2-ethylhexylamine, and tert-octylamine.

[0062] Specific examples of primary amines with an alicyclic structure include cyclohexylamine and dicyclohexylamine.

[0063] Specific examples of primary amines having a hydroxyalkyl group include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, propanolamine, isopropanolamine, dipropanolamine, diisopropanolamine, tripropanolamine, and triisopropanolamine.

[0064] Specific examples of primary amines having an aromatic ring include benzylamine, N,N-dimethylbenzylamine, aniline, diphenylamine, triphenylamine, aniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, 4-aminopyridine, and 4-dimethylaminopyridine.

[0065] Specific examples of secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diphenylamine, dicyclopentylamine, and methylbutylamine.

[0066] Specific examples of tertiary amines include trimethylamine, triethylamine, tripropylamine, and triphenylamine.

[0067] Specific examples of polyamines include ethylenediamine, 1,3-diaminopropane, diethylenetriamine, triethylenetetramine, tetramethylenepentamine, hexamethylenediamine, tetraethylenepentamine, and combinations thereof.

[0068] The amine is preferably an alkylamine, more preferably an alkylamine with 3 to 10 carbon atoms, and even more preferably a primary alkylamine with 4 to 10 carbon atoms.

[0069] When reacting a metal salt with an amine, the ratio of the mass of the amine to the mass of the metal salt is preferably 1 to 15 times, more preferably 1.5 to 6 times. If the ratio is within the above range, the complex formation reaction is terminated, and a transparent solution is obtained.

[0070] Specific examples of ammonium carbamate compounds that serve as complexing agents include ammonium carbamate, methyl carbamate ammonium, ethyl carbamate ammonium, 1-propyl carbamate ammonium, isopropyl carbamate ammonium, butyl carbamate ammonium, isobutyl carbamate ammonium, pentyl carbamate ammonium, hexyl carbamate ammonium, heptyl carbamate ammonium, octyl carbamate ammonium, 2-ethylhexyl carbamate ammonium, nonyl carbamate ammonium, and decyl carbamate ammonium.

[0071] Specific examples of ammonium carbonate compounds that serve as complexing agents include ammonium carbonate, methyl ammonium carbonate, ethyl ammonium carbonate, 1-propyl ammonium carbonate, isopropyl ammonium carbonate, butyl ammonium carbonate, isobutyl ammonium carbonate, pentyl ammonium carbonate, hexyl ammonium carbonate, heptyl ammonium carbonate, octyl ammonium carbonate, 2-ethylhexyl ammonium carbonate, nonyl ammonium carbonate, and decyl ammonium carbonate.

[0072] Specific examples of ammonium bicarbonate compounds that act as complexing agents include ammonium bicarbonate, methyl ammonium bicarbonate, ethyl ammonium bicarbonate, 1-propyl ammonium bicarbonate, isopropyl ammonium bicarbonate, butyl ammonium bicarbonate, isobutyl ammonium bicarbonate, pentyl ammonium bicarbonate, hexyl ammonium bicarbonate, heptyl ammonium bicarbonate, octyl ammonium bicarbonate, 2-ethylhexyl ammonium bicarbonate, nonyl ammonium bicarbonate, and decyl ammonium bicarbonate.

[0073] When a metal salt is reacted with an ammonium carbamate compound, an ammonium carbonate compound, or an ammonium bicarbonate compound, the ratio of the mass of the ammonium carbamate compound, the ammonium carbonate compound, or the ammonium bicarbonate compound to the mass of the metal salt is preferably 0.01 to 1 times, more preferably 0.05 to 0.6 times.

[0074] Specific examples of carboxylic acids used as complexing agents include hexanoic acid, octanoic acid, nonanoic acid, 2-ethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, and linolenic acid. Preferably, the carboxylic acids mentioned above are carboxylic acids with 8 to 20 carbon atoms, and more preferably are carboxylic acids with 10 to 16 carbon atoms.

[0075] In the metal complex ink, the metal content relative to the total mass of the metal complex ink, calculated in terms of metal atoms, is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 20% by mass.

[0076] In metal complex inks, the content of the metal complex is preferably 10 to 90% by mass relative to the total mass of the ink, more preferably 10 to 40% by mass. If the content of the metal complex is 10% by mass or more, the surface resistivity further decreases. If the content of the metal complex is 90% by mass or less, the ejection stability of the metal complex ink is further improved.

[0077] -Silane coupling agent- Considering the excellent adhesion after immersion in the plating solution, it is preferable that the metal complex ink contains a silane coupling agent. Silane coupling agents are, for example, compounds having hydrolyzable groups that are directly bonded to silicon atoms. Examples of hydrolyzable groups include alkoxy groups (preferably with 1 to 10 carbon atoms) and halogen atoms such as chlorine atoms. From a stability perspective, alkoxy groups are preferred. The silane coupling agent preferably has one or more hydrolyzable groups directly bonded to silicon atoms, more preferably two or more, and even more preferably three or more. There is no upper limit to the above number; for example, it can be 10,000 or less.

[0078] Silane coupling agents are also preferably those with reactive groups. Specific examples of the aforementioned reactive groups include epoxy, oxetyl, vinyl, (meth)acryloyl, styryl, amino, isocyanate, mercapto, and anhydride groups. The silane coupling agent preferably has one or more reactive groups, more preferably two or more, and even more preferably three or more. There is no upper limit to the above number; for example, it can be 10,000 or less. The boiling point (standard boiling point) of the silane coupling agent is preferably above 100°C, and more preferably above 180°C.

[0079] Examples of silane coupling agents include 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3 -Methacryloxypropyltriethoxysilane, 3-Acryloyloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, hexamethyldisilazane, 3-(2-aminoethylaminopropyl)dimethoxymethylsilane, 3-(2-aminoethylaminopropyl)trimethoxysilane, 2-(2-amino... 2-(2-aminoethylthioethyl)triethoxysilane, 3-[2-(2-aminoethylaminoethylamino)propyl]trimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, 3- Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, imidazolylalkyl-trialkoxysilane, diphenyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyltriethoxysilane, phenyltriethoxysilane, tri[3-(trimethoxysilyl)propyl]isocyanate, and 3-trimethoxysilylpropylsuccinic anhydride.

[0080] In the metal complex ink, the content of silane coupling agent is preferably 0.1 to 5.0% by mass relative to the total mass of the metal complex ink, more preferably 0.2 to 4.0% by mass, and even more preferably 0.5 to 3.0% by mass from the perspective of better conductivity and migration inhibition.

[0081] -solvent- Metal complex inks preferably contain solvents. There are no particular limitations on the solvent, as long as it can dissolve the components contained in metal complex inks, such as metal complexes. From the perspective of ease of manufacture, the preferred solvent has a boiling point of 30 to 300°C, more preferably 50 to 200°C, and even more preferably 80 to 180°C.

[0082] The solvent is preferably contained in the metal complex ink at a concentration of 0.01 to 3.6 mmol / g relative to the metal ion concentration of the metal complex (the amount of metal present as free ions relative to 1 g of the metal complex), and more preferably at a concentration of 0.05 to 2 mmol / g. When the concentration of metal ions is within the above range, the metal complex ink exhibits excellent flowability and excellent conductivity.

[0083] Examples of solvents include water, hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, terpenes, carbamates, alkenes, amides, ethers, esters, alcohols, thiols, thioethers, phosphine, and water.

[0084] The hydrocarbon is preferably a straight-chain or branched hydrocarbon with 6 to 20 carbon atoms. Specific examples of hydrocarbons include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, hexadecane, octadecane, nonadecane, and eicosane.

[0085] Cyclic hydrocarbons are preferably cyclic hydrocarbons with 6 to 20 carbon atoms. Specific examples of cyclic hydrocarbons include cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and decahydronaphthalene.

[0086] Specific examples of aromatic hydrocarbons include benzene, toluene, xylene, trimethylbenzene, and tetrahydronaphthalene.

[0087] Specific examples of terpenes include α-bisabolol, borneol, camphor, camphor, δ-3-carene, β-caryophyllene, caryophyllene oxide, α-cedrene, β-eudesmol, and fenchyl. alcohol), geraniol, guaiol, humulene, isoborneol, limonene, linalool, menthol, myrcene, nerol, cis-ocimene, trans-ocimene, α-phellandrene, α-pinene, β-pinene, sabinene, α-terpinene, α-terpineol, terpinolene, α-guaiene, elemene, farnesene, germacrene B B), Guaiac-1(10),11-diene, trans-2-pinanol, celery-3,7(11)-diene and eudesm-7(11)-en-4-ol.

[0088] Ethers can be any of the following: straight-chain ethers, branched-chain ethers, and cyclic ethers. Specific examples of ethers include diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, tetrahydropyran, dihydropyran, and 1,4-dioxane.

[0089] Alcohols can be any of the primary, secondary, and tertiary alcohols. Specific examples of alcohols include ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-octanol, 2-octanol, 3-octanol, tetrahydrofurfuryl alcohol, cyclopentanol, terpineol, decanol, isodecanol, lauryl alcohol, isolaryl alcohol, myristol, isomyristol, cetyl alcohol, isocetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, isoleyl alcohol, linoleyl alcohol, palmitol, isopaltol, eicosanol, and isoeicosanol.

[0090] Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0091] Specific examples of esters include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, and 3-methoxybutyl acetate.

[0092] -reducing agent- Metal complex inks may contain reducing agents. If a reducing agent is included in a metal complex ink, it promotes the reduction from the metal complex to the metal.

[0093] Specific examples of reducing agents include metal borohydride salts, aluminum hydride salts, amines, alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione, and oxime compounds.

[0094] The reducing agent can be any oxime compound described in Japanese Patent Application Publication No. 2014-516463. Specific examples of oxime compounds include acetone oxime, cyclohexanone oxime, 2-butanone oxime, 2,3-butanedione monooxime, dimethylglyoxime, methyl acetoacetate monooxime, methyl pyruvate monooxime, benzaldehyde oxime, 1-indanone oxime, 2-adamantaneone oxime, 2-methylbenzamide oxime, 3-methylbenzamide oxime, 4-methylbenzamide oxime, 3-aminobenzamide oxime, 4-aminobenzamide oxime, acetophenone oxime, benzamide oxime, and pinacolone oxime.

[0095] In the metal complex ink, the content of the reducing agent is preferably 0.1 to 20% by mass relative to the total mass of the metal complex ink, more preferably 0.3 to 10% by mass, and even more preferably 1 to 5% by mass.

[0096] -Resin- Metal complex inks may contain resins. When metal complex inks contain resin, their adhesion to the substrate is improved.

[0097] Examples of resins include polyester, polyethylene, polypropylene, polyacetal, polyolefin, polycarbonate, polyamide, fluoropolymer, silicone resin, ethyl cellulose, hydroxyethyl cellulose, rosin, acrylic resin, polyvinyl chloride, polysulfone, polyvinylpyrrolidone, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polysulfide, polyamide-imide, polyether, polyarylate, polyetheretherketone, polyurethane, epoxy resin, vinyl ester resin, phenolic resin, melamine resin, and urea resin.

[0098] -additive- Metal complex inks may contain additives such as inorganic salts, organic salts, inorganic oxides such as silica, surface conditioners, wetting agents, crosslinking agents, antioxidants, rust inhibitors, heat stabilizers, surfactants, plasticizers, curing agents, and thickeners. In metal complex inks, the preferred additive content is 20% by mass or less relative to the total mass of the metal complex ink. The lower limit can be 0% by mass or more.

[0099] -Physical properties- The viscosity of the metal complex ink is preferably 1 to 100 mPa·s, more preferably 2 to 50 mPa·s, and even more preferably 3 to 30 mPa·s. The viscosity of the metal complex ink is the value measured using a viscometer at 25°C. For example, the viscosity is measured using a VISCOMETER TV-22 viscometer (manufactured by TOKI SANGYO CO.,LTD.).

[0100] The surface tension of the metal complex ink is not particularly limited, but is preferably 20 to 45 mN / m, and more preferably 25 to 35 mN / m. Surface tension is the value measured using a surface tension meter at 25°C. Surface tension is measured, for example, using a DY-700 (manufactured by Kyowa Interface Science Co., Ltd.).

[0101] (Metal salt ink) Metal salt inks are, for example, conductive inks in which metal salts are dissolved in a solvent.

[0102] -Metal Salts- The metal constituting the metal salt is the same as the metal constituting the aforementioned metal complex, and the preferred manner is also the same.

[0103] Examples of metal salts include benzoates, halides, carbonates, citrates, iodates, nitrites, nitrates, acetates, phosphates, sulfates, sulfides, trifluoroacetates, and carboxylates of metals. Furthermore, salts can be composed of two or more elements.

[0104] Considering conductivity and storage stability, metal carboxylates are preferred metal salts. The carboxylic acid that forms the metal carboxylate is preferably at least one selected from the group consisting of formic acid and carboxylic acids having 1 to 30 carbon atoms, more preferably a carboxylic acid having 8 to 20 carbon atoms, and even more preferably a fatty acid having 8 to 20 carbon atoms. The fatty acid can be linear or branched and can have substituents.

[0105] Specific examples of straight-chain fatty acids include acetic acid, propionic acid, butyric acid, valeric acid, pentanoic acid, hexanoic acid, heptanoic acid, behenic acid, oleic acid, octanoic acid, nonanoic acid, decanoic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, and undecanoic acid.

[0106] Specific examples of branched-chain fatty acids include isobutyric acid, isovaleric acid, ethylhexanoic acid, neodecanoic acid, neopentanoic acid, 2-methylvaleric acid, 3-methylvaleric acid, 4-methylvaleric acid, 2,2-dimethylbutyric acid, 2,3-dimethylbutyric acid, 3,3-dimethylbutyric acid, and 2-ethylbutyric acid.

[0107] Specific examples of carboxylic acids with substituents include hexafluoroacetylacetonate, hydroangelic acid, 3-hydroxybutyric acid, 2-methyl-3-hydroxybutyric acid, 3-methoxybutyric acid, acetone dicarboxylic acid, 3-hydroxyglutaric acid, 2-methyl-3-hydroxyglutaric acid, and 2,2,4,4-tetrahydroxyglutaric acid.

[0108] Metal salts can be commercially available products or manufactured using known methods. Silver salts are manufactured, for example, by the following methods.

[0109] First, a silver compound (e.g., silver acetate) serving as a silver source and formic acid or a fatty acid with 1 to 30 carbon atoms, in an amount equal to the molar equivalent of the silver compound, are added to an organic solvent such as ethanol. The mixture is stirred for a specified time using an ultrasonic stirrer, and the resulting precipitate is washed with ethanol and decanted. All these steps can be performed at room temperature (25°C). The molar ratio of the silver compound to formic acid or the fatty acid with 1 to 30 carbon atoms is preferably 1:2 to 2:1, more preferably 1:1.

[0110] In the metal salt ink, the metal content relative to the total mass of the metal salt ink, calculated by metal element conversion, is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 20% by mass.

[0111] In metal salt inks, the content of metal salts relative to the total mass of the metal salt ink is preferably 10 to 90% by mass, more preferably 10 to 60% by mass. If the content of metal salts is 10% by mass or more, the surface resistivity further decreases. If the content of metal salts is 90% by mass or less, the ejection stability is further improved when the metal salt ink is ejected from the nozzle.

[0112] -solvent- Metal salt inks may contain solvents. Examples of solvents include hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, terpenes, carbamates, alkenes, amides, ethers, esters, alcohols, thiols, thioethers, phosphine, and water.

[0113] The hydrocarbon is preferably a straight-chain or branched hydrocarbon with 6 to 20 carbon atoms. Specific examples of hydrocarbons include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, hexadecane, octadecane, nonadecane, and eicosane.

[0114] Cyclic hydrocarbons are preferably cyclic hydrocarbons with 6 to 20 carbon atoms. Specific examples of cyclic hydrocarbons include cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and decahydronaphthalene.

[0115] Specific examples of aromatic hydrocarbons include benzene, toluene, xylene, trimethylbenzene, and tetrahydronaphthalene.

[0116] Specific examples of terpenes include α-bisabolol, borneol, camphor, camphor, δ-3-carene, β-caryophyllene, caryophyllene oxide, α-cedrene, β-eudesmol, and fenchyl. alcohol), geraniol, guaiol, humulene, isoborneol, limonene, linalool, menthol, myrcene, nerol, cis-ocimene, trans-ocimene, α-phellandrene, α-pinene, β-pinene, sabinene, α-terpinene, α-terpineol, terpinolene, α-guaiene, elemene, farnesene, germacrene B B), Guaiac-1(10),11-diene, trans-2-pinanol, celery-3,7(11)-diene and eudesm-7(11)-en-4-ol.

[0117] Ethers can be any of the following: straight-chain ethers, branched-chain ethers, and cyclic ethers. Specific examples of ethers include diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, tetrahydropyran, dihydropyran, and 1,4-dioxane.

[0118] Alcohols can be any of the primary, secondary, and tertiary alcohols. Specific examples of alcohols include ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-octanol, 2-octanol, 3-octanol, tetrahydrofurfuryl alcohol, cyclopentanol, terpineol, decanol, isodecanol, lauryl alcohol, isolaryl alcohol, myristol, isomyristol, cetyl alcohol, isocetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, isoleyl alcohol, linoleyl alcohol, palmitol, isopaltol, eicosanol, and isoeicosanol.

[0119] Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0120] Specific examples of esters include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, and 3-methoxybutyl acetate.

[0121] -Silane coupling agent- Metal salt inks preferably contain silane coupling agents. The silane coupling agent is the same as the silane coupling agent in the aforementioned metal complex ink, and the preferred method is also the same.

[0122] -Other ingredients- Metal salt inks may contain reducing agents, resins, and additives. The reducing agent, resin, and additives are the same as the various components in the aforementioned metal complex ink, and the preferred methods are also the same.

[0123] -Physical properties- The viscosity and surface tension of the metal salt ink are the same as those of the aforementioned metal complex ink, and the preferred method is also the same.

[0124] As an ink coating method, the coating method of the above-described composition can be cited as an example. The coating film formed by applying ink can be dried as needed. Examples of drying methods include natural drying and heat drying. Furthermore, atmospheric pressure and reduced pressure drying are also possible.

[0125] The ink can be applied using inkjet recording. Inkjet recording methods can be any of the following: charge control method that uses electrostatic induction to eject ink; on-demand inkjet method (pressure pulse method) that uses the vibration pressure of piezoelectric elements; acoustic inkjet method that converts electrical signals into sound beams to irradiate ink and ejects ink using radiation pressure; and thermal inkjet method (Bubble Jet (registered trademark)) that forms bubbles by heating ink and uses the resulting pressure.

[0126] As an inkjet recording method, the method described in Japanese Patent Application Publication No. 54-059936 is preferred, and an inkjet recording method in which the ink undergoes a rapid volume change due to heat and is ejected from the nozzle by a force based on this change in state is even more preferred. Furthermore, as an inkjet recording method, the method described in paragraphs 0093 to 0105 of Japanese Patent Application Publication No. 2003-306623 can be cited as an example.

[0127] Examples of inkjet heads used in inkjet recording methods include a reciprocating method that uses a short serial head to scan and record along the width of the substrate, and a linear method that uses a line head to arrange recording elements over an entire area corresponding to at least one side of the substrate.

[0128] In the above linear method, by scanning the substrate in a direction that intersects with the arrangement direction of the recording elements, a pattern can be formed on the entire surface of the substrate, thus eliminating the need for a transport system such as a carrier for scanning short-sized heads. Furthermore, it eliminates the need for carrier movement and complex scanning control of the substrate, moving only the substrate, thus enabling higher forming speeds compared to reciprocating methods.

[0129] As an inkjet recording device that uses inkjet recording to impart insulating ink, an example is the DMP-2850 (manufactured by FUJIFILM DIMATIX).

[0130] Regarding the amount of ink droplets ejected from the nozzle of the inkjet head, it is preferably 1 to 100 pL (picoli), more preferably 2 to 80 pL, and even more preferably 2 to 20 pL per droplet.

[0131] The temperature of the substrate when applying ink is preferably 20–120°C, more preferably 40–100°C. When the substrate temperature is 20–100°C, deformation of the substrate caused by heat is suppressed and ink drying is promoted.

[0132] (Hardening treatment) The method for manufacturing the laminate may further include a curing treatment in which the ink (film) coated on the metal oxide layer is subjected to at least one of heating and light irradiation to harden the coated ink. Thus, the ink hardens to form a metal layer X on the metal oxide layer. Heating and light irradiation can be performed individually or in combination.

[0133] The firing temperature during heating is preferably 80°C or higher, more preferably 100°C or higher. From the perspective of minimizing damage to the substrate, the firing temperature is preferably 250°C or lower, more preferably 200°C or lower. The heating time (firing time) is preferably 1 minute or more. From the viewpoint of reducing damage to the substrate, etc., the firing temperature is preferably 120 minutes or less, and more preferably 60 minutes or less.

[0134] The substrate can be preheated before the ink is applied. In this invention, such heating is also considered a form of heating as described above. The temperature of the substrate when applying the ink is preferably 20 to 180°C, more preferably 40 to 150°C.

[0135] Specific examples of light when it is illuminated include ultraviolet and infrared rays. The peak wavelength of the ultraviolet light is preferably 200–405 nm, more preferably 250–400 nm, and even more preferably 260–400 nm. The preferred exposure amount during light irradiation is 0.1–10000 J / cm. 2 More preferably 1–500 J / cm 2 .

[0136] In this invention, the time from the moment the ink falls onto the substrate to the start of heating or light irradiation is preferably within 1 second, more preferably within 0.8 seconds, and even more preferably within 0.6 seconds. This promotes the reduction of the metal complexes and metal salts contained in the ink falling onto the substrate to the metal (i.e., it suppresses the inhibition of reduction by oxygen in the air), thus enabling the formation of a metal layer X with superior conductivity.

[0137] Step 2 can be repeated. This allows for adjustment of the thickness of metal layer X. The thickness of the metal layer X is preferably 0.1 to 5.0 μm, more preferably 0.1 to 3.0 μm. The thickness of metal layer X can be determined by obtaining a cross-sectional image of metal layer X using a scanning electron microscope, measuring the length at 10 points corresponding to the thickness of metal layer X at different locations, and using the arithmetic mean of the lengths at these 10 points. From the perspective of improving the conductivity of metal layer X, the volume resistivity of metal layer X is preferably 6 μΩ·cm or less, more preferably 5 μΩ·cm or less, and even more preferably 4 μΩ·cm or less. The lower limit is preferably 2 μΩ·cm or more. From the perspective of improving the conductivity of the metal layer X, the porosity of the metal layer X is preferably 24% or less, more preferably 23% or less, and even more preferably 22% or less. There is no specific lower limit for porosity, for example, it can be 0%.

[0138] <Process 3> Step 3 is a process of plating metal layer X after step 2 to form metal layer Y on metal layer X. Metal layer Y contains a third metal atom of a different type from either the first metal atom or the second metal atom. The metal layer Y is the same as the metal layer Y that may be included in the above-mentioned laminate, and the preferred embodiment is also the same. Plating methods may include electroless plating and electrolytic plating, or other known plating methods.

[0139] Electroless plating methods, for example, can form an electroless plating layer (film) composed of a metal film by contacting the electroless plating solution with at least a portion or all of the surfaces of the substrate, the metal oxide layer and the metal layer X, thereby causing the metal such as copper contained in the electroless plating solution to precipitate. As an electroless plating solution, a liquid containing the third metal atom contained in the aforementioned metal layer Y, a reducing agent, and a solvent is preferred. Examples of reducing agents include dimethylamine borane, hypophosphite, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, and phenol. Examples of solvents that may be contained in the above-described composition include, for instance.

[0140] Electroless plating solutions may contain complexing agents. Examples of complexing agents include organic acids and their salts (e.g., sodium, potassium, and ammonium salts), amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetramine. Examples of organic acids and their salts include monocarboxylic acids such as acetic acid and formic acid; dicarboxylic acid compounds such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid; hydroxycarboxylic acid compounds such as malic acid, lactic acid, glycolic acid, gluconic acid, and citric acid; amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, and glutamic acid; and aminopolycarboxylic acid compounds such as iminodiacetic acid, hypozinotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid.

[0141] Electroplating is a method in which, for example, an electric current is applied while the electroplating solution is in contact with the surface of an electroless plating layer (film) formed by electroless plating treatment. This causes metals such as copper contained in the electroplating solution to be deposited onto the surface of the electroless plating layer (film) formed by electroless treatment and placed on the cathode, thereby forming an electroplating layer (film).

[0142] The electroplating solution preferably contains the third metal atom contained in the metal layer Y, acids such as sulfuric acid and carboxylic acid, and a solvent. Examples of solvents that may be contained in the above composition include, for instance. Example

[0143] The present invention will now be described in further detail with reference to embodiments. The materials, quantities, proportions, processing contents, and processing order shown in the following embodiments can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited by the embodiments shown below.

[0144] [Ink Preparation] <Ink 1> Silver neodecanoate was added to a 2000 mL three-necked flask. Next, a solution of limonene dissolved in a ratio of 3% by mass of 2,2,6,6-tetramethyl-3,5-heptadecyl dione and 1.5% by mass of 3-epoxypropoxypropyltrimethoxysilane was added and stirred to obtain a solution containing silver salt. This solution was filtered using a 0.45 μm PTFE (polytetrafluoroethylene) membrane filter to obtain ink 1. In addition, the content of silver neodecanoate is 45% by mass relative to the total mass of the silver salt solution, and the content of limonene solution is 55% by mass relative to the total mass of the silver salt solution.

[0145] <Ink 2-5> The content of 3-epoxypropoxypropyltrimethoxysilane in each ink was changed to the values ​​in the table below. Otherwise, inks 2 to 5 were prepared in the same order as ink 1.

[0146] [Example 1] <Process 1> A solution containing ethyl acetate / butanol at a volume ratio of 1:1 was used to obtain a 16% by mass dilution of titanium coupling agent (PC200, manufactured by Matsumoto Fine Chemical Co., Ltd.). The dilution was then applied to a glass slide (S9111, manufactured by Matsunami Glass Ind., Ltd.) using a #4 bar coater, and dried at 120°C for 30 seconds to form a metal oxide layer on the substrate, resulting in a substrate with an attached metal oxide layer. The thickness of the metal oxide layer was 200 nm.

[0147] <Process 2> Ink 5 was filled into an inkjet recording device (product name "Samba G3L", manufactured by FUJIFILM DIMATIX). Regarding image recording conditions, the resolution was set to 1200 dpi (dots per inch), and the droplet ejection rate was set to 5 pL per dot. A 3 mm × 50 mm, 40 μm (Wet) image was printed at 23°C onto a substrate with an attached metal oxide layer prepared in step 1. Subsequently, using a hot plate, it was sintered at 180°C for 60 minutes to form a metal layer X on the metal oxide layer, obtaining the laminate of Example 1.

[0148] [Examples 2-12 and Comparative Examples 1-3] Except for the conditions shown in the table below, each laminate was obtained in the same order as in Example 1.

[0149] [Determination of the number of atoms contained in metal layer X] For each stack, Ag3d, C1s, O1s, Si2s, Ti2p, Zr3d, and Al2p were analyzed in 300 μm squares using an X-ray photoelectron spectroscopy (XPS) system (UlvacPHI). Ar sputtering was used for depth-direction analysis.

[0150] [Adhesion after plating solution immersion] A 5cm square solid image sample was fabricated from the various layers. The obtained sample was immersed in the following plating solution heated to 60°C for 30 minutes. Afterward, the sample was removed from the plating solution and dried at 60°C for 30 minutes.

[0151] ---------------- ... plating solution ---------------- ... NiSO4·6H2O 0.95mol / L ·NiCl2·6H2O 0.17mol / L ·H3BO3 0.49mol / L ·FeSO4·7H2O 0.35mol / L ·C7H4NNaO3S·2H2O 0.008mol / L ·Malondiic acid 0.1 mol / L ---------------- ...

[0152] The adhesion of the sample after immersion in the plating solution was evaluated by performing a cross-cut test on the sample treated with the plating solution using the following method. Six cuts were made on the surface of metal layer X in mutually orthogonal directions. After attaching a piece of transparent adhesive tape ("Cellotape (registered trademark) CT-18", manufactured by NICHIBAN Co., Ltd.) to the metal layer X with the cuts, the tape was peeled off from metal layer X. The amount of metal layer X peeled off (exposing the underlying layer) and the amount of metal layer X adhering to the peeled tape were visually observed. Based on the observation results, the adhesion after plating solution immersion was evaluated according to the following evaluation criteria.

[0153] <Evaluation Criteria for Adhesion After Plating Solution Immersion> “5”: No peeling was observed on the surface of the metal layer X and no black or silver residue was observed on the tape. “4”: Only a slight peeling of metal layer X is observed at the intersection of the cuts on the surface of metal layer X, and / or a slight black or silver residue is observed on the tape. “3”: Only a slight peeling of metal layer X is observed at the intersection of the cuts on the surface of metal layer X, and black or silver residue is observed on the tape in an area of ​​less than 10% of the area of ​​the part cut into the cross-cut. "2": Delamination of metal layer X is observed on the surface of metal layer X in an area of ​​less than 10% relative to the area of ​​the cross-cutting cut, and / or black or silver residue is observed on the tape in an area of ​​more than 10% but less than 50% relative to the area of ​​the cross-cutting cut. "1": Delamination of metal layer X is observed on the surface of metal layer X, covering an area of ​​more than 10% of the area of ​​the portion cut in a cross pattern, and / or black or silver residue is observed on the tape covering an area of ​​more than 50% of the area of ​​the portion cut in a cross pattern.

[0154] [Conductivity (volume resistivity)] The resistance of each metal layer X was measured at room temperature (23°C) using a ohmmeter (product name "DT4222", manufactured by HIOKI EE CORPORATION). Furthermore, the cross-sectional area of ​​each laminate was measured at room temperature (23°C) using a scanning electron microscope (product name "S-4700", manufactured by HITACHI). The volume resistivity (μΩ·cm) was calculated from the measured resistance and cross-sectional area, and the obtained volume resistivity was evaluated according to the following criteria. A lower volume resistivity indicates better conductivity of the laminate.

[0155] <Evaluation Criteria for Conductivity> "5": Less than 10 μΩ·cm "4": ≥10μΩ·cm and <15μΩ·cm "3": ≥15μΩ·cm and <17.5μΩ·cm "2": ≥17.5 μΩ·cm and <20 μΩ·cm "1": Above 20 μΩ·cm

[0156] [Migration occurred] Using photolithography, the metal layers of each laminate were X-etched into a comb shape with a linewidth / spacing (L / S) of 50 / 50 μm, forming comb-shaped silver wiring. FOTEC H-7025 (manufactured by Hitachi Chemical Co., Ltd.) was used as the dry film resist, and AGRIP 940 (manufactured by Meltex Inc.) was used as the silver etching solution. Cytop (registered trademark) CTL107MK (manufactured by AGC Inc., an amorphous fluoropolymer) was spin-coated onto the obtained silver wiring until the dried film thickness reached 1 μm. Afterward, the wiring substrate for migration evaluation was fabricated by drying at 140°C for 20 minutes to form a sealing layer. The obtained wiring board was subjected to a life test under the conditions of 85% relative humidity, 85°C temperature, 1.0 atm pressure, and 60V voltage (applied by EHS-221MD, manufactured by ESPEC CORP). Specifically, under the above conditions, the voltage was continuously applied to the silver wiring between adjacent comb teeth of the comb shape (silver wiring distance 100μm). Then, the short circuit occurrence time from the start of the application to the short circuit between the silver wiring caused by migration was measured.

[0157] <Evaluation Criteria for Migration Occurrence> "3": The short circuit occurred more than 400 minutes ago. "2": The short circuit occurred more than 300 minutes but less than 400 minutes ago. "1": The short circuit occurred less than 300 minutes ago.

[0158] In the table, “SR” indicates E-Green Solder Resistance (SR) plate (FR-4, 1.6t), manufactured by Showa Industrial Co., Ltd. When the "First Metal Atom" column is "Ti", a titanium coupling agent (PC200, manufactured by Matsumoto Fine Chemical Co., Ltd.) is used, and each metal oxide layer is formed in the order of Example 1. When the "First Metal Atom" column is "Zr", a zirconium coupling agent (Zr-540, manufactured by Matsumoto Fine Chemical Co., Ltd.) is used instead of a titanium coupling agent, and each metal oxide layer is formed in the order of Example 1. When the "First Metal Atom" column is "Al", an aluminum coupling agent (aluminum ethyl acetoacetate diisopropoxide, manufactured by FUJIFILM Wako Pure Chemical Corporation) is used instead of a titanium coupling agent, and each metal oxide layer is formed in the order of Example 1. "GSC content" indicates the content of 3-epoxypropoxypropyltrimethoxysilane (silane coupling agent) relative to the total mass of the ink. "Si / (O+C)" represents the ratio of the number of silicon atoms to the total number of oxygen and carbon atoms (number of silicon atoms / total number of oxygen and carbon atoms). "Si content", "O content", and "C content" represent the content of each atom relative to the total number of atoms in metal layer X.

[0159] [Table 1]

[0160] The evaluation results shown in the table confirm that as long as it is a laminate of the present invention or a laminate manufactured by the manufacturing method of the present invention, the adhesion after immersion in the plating solution is excellent (Examples 1-12). It was confirmed that the adhesion after immersion in the plating solution was better when the metal layer X contained silicon atoms (comparison of Example 1 and Examples 2-12, etc.). It was confirmed that when the number of silicon atoms in metal layer X is 0.1 to 10.0 atomic% relative to the total number of atoms in metal layer X, the conductivity is superior, and migration can be further suppressed (Examples 1-9, 11-12). Furthermore, it was confirmed from the same comparison that when metal layer X contains oxygen and carbon atoms and the ratio of the number of silicon atoms in metal layer X to the total number of oxygen and carbon atoms is 0.25 or higher, the conductivity is superior, and migration can be further suppressed. It was confirmed that the adhesion after immersion in the plating solution was better when the first metal atom contained titanium atoms (comparison of Examples 2-9 and Examples 11-12, etc.). It was confirmed that the adhesion after immersion in the plating solution was better when the thickness of the metal layer X was 0.1 to 3.0 μm (comparison of Examples 2 to 9, etc.).

Claims

1. A laminate comprising: Substrate; The metal oxide layer comprises a first metal atom selected from the group consisting of titanium atoms, zirconium atoms, and aluminum atoms; and Metal layer X is disposed adjacent to the metal oxide layer and contains a second metal atom of a different type than the first metal atom. In the laminated body, The thickness of the metal oxide layer is 50–2000 nm.

2. The laminated body according to claim 1, wherein, The metal layer X contains silicon atoms.

3. The laminate according to claim 1 or 2, wherein, The metal layer X contains silicon atoms. In the metal layer X, the number of silicon atoms is 0.1 to 10.0 atoms relative to the total number of atoms in the metal layer X.

4. The laminate according to claim 1 or 2, wherein, The metal layer X comprises silicon atoms, oxygen atoms, and carbon atoms. In the metal layer X, the ratio of the number of silicon atoms to the total number of oxygen atoms and carbon atoms is 0.25 or more.

5. The laminate according to claim 1 or 2, wherein, The thickness of the metal layer X is 0.1 to 3.0 μm.

6. The laminate according to claim 1 or 2, wherein, A metal layer Y is provided on the metal layer X, and the metal layer Y contains a third metal atom of a different type from either the first metal atom or the second metal atom.

7. A method for manufacturing a laminate, comprising: Step 1: Coating a composition of coupling agents selected from the group consisting of titanium coupling agents, zirconium coupling agents, and aluminum coupling agents onto a substrate to form a metal oxide layer containing a first metal atom selected from the group consisting of titanium atoms, zirconium atoms, and aluminum atoms; and Step 2 involves coating the metal oxide layer with an ink containing a metal compound selected from the group consisting of metal salts and metal complexes to form a metal layer X containing a second type of metal atoms different from the first metal atoms. The thickness of the metal oxide layer is 50–2000 nm.

8. The method for manufacturing a laminate according to claim 7, wherein, The ink contains a silane coupling agent.

9. The method for manufacturing a laminate according to claim 7 or 8, wherein The process further includes the following steps after step 2: Step 3 involves plating the metal layer X to form a metal layer Y on the metal layer X, wherein the metal layer Y contains a third metal atom of a different type from either the first metal atom or the second metal atom.

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