Composition for forming a metal-containing member, metal-containing member, method for manufacturing a metal-containing member, laminate, and device

Abstract

To provide a metal-containing member forming composition that can give a metal-containing member having high strength, a metal-containing member containing the metal-containing member forming composition that has been converted into metal, a method for producing a metal-containing member by using the metal-containing member forming composition, and a laminate and a device including the metal-containing member.SOLUTION: A metal-containing member forming composition contains a metal precursor, a granular filler and a solvent. There are also provided: a metal-containing member containing the metal-containing member forming composition that has been converted into metal; a method for producing a metal-containing member by using the metal-containing member forming composition; and a laminate and a device each including the metal-containing member.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composition for forming a metal-containing member, a metal-containing member, a method for producing a metal-containing member, a laminate, and a device. [Background technology]

[0002] BACKGROUND ART In recent years, metal-containing members have been used in electronic devices as, for example, heat-conducting members, heat-dissipating members, reflecting members, decorative members, conductive members, and the like. It is expected that demands for higher performance in electronic devices such as portable information terminals will continue to increase in the future, and in order to meet this demand, further improvements in various physical properties of metal-containing components will be required.

[0003] For example, Patent Document 1 describes a method for producing a thin film-forming composition, which comprises contacting a solution of alkylamine diluted with an organic solvent such as an aromatic hydrocarbon or other hydrocarbon with an aqueous solution of a metal salt of a group III-V, VIII, VIa, VIIa, Ib, or IIb metal, the pH of which has been adjusted in advance, to extract the metal salt into the organic solvent layer, and then separating and removing the aqueous layer to obtain an organic solvent solution containing a metal alkylamine complex; or further comprising evaporating and distilling off the organic solvent used during extraction, and adding to the resulting solution a substituting organic solvent such as hydrocarbons, alcohols, esters, β-diketoesters, ethers, β-diketones, or glycols, or a mixture thereof. Patent Document 2 describes a method for producing a film mirror having a reflective layer provided on a film substrate, the method comprising the steps of: adding a reducing agent to at least one of an underlayer on which the reflective layer is formed and a coating liquid containing a silver complex compound; applying the coating liquid to the underlayer to form a coating film; and heating and baking the coating film to form the reflective layer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-269656 [Patent Document 2] Special Publication No. 2012-181301 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention aims to provide a composition for forming a metal-containing member that can give a metal-containing member with excellent strength, a metal-containing member obtained by converting the composition for forming a metal-containing member into a metal, a method for manufacturing a metal-containing member using the composition for forming a metal-containing member, and a laminate and a device that include the metal-containing member. [Means for solving the problem]

[0006] Examples of typical embodiments of the present invention are given below. <1> A composition for forming a metal-containing member, comprising a metal precursor, a particulate filler, and a solvent. <2> The particulate filler comprises an inorganic compound. <1> The composition for forming a metal-containing member according to claim 1. <3> The solvent comprises water. <1> or <2> The composition for forming a metal-containing member according to claim 1. <4> the metal precursor comprises a silver precursor; <1> ~ <3> 10. The composition for forming a metal-containing member according to claim 9, wherein the metal-containing member is a fluororesin. <5> Used in film formation, <1> ~ <4> 10. The composition for forming a metal-containing member according to claim 9, wherein the metal-containing member is a fluororesin. <6> containing a reducing agent, <1> ~ <5> 10. The composition for forming a metal-containing member according to claim 9, wherein the metal-containing member is a fluororesin. <7> The arithmetic mean diameter of the granular filler is 0.2 to 1 μm when calculated according to the method described in JIS Z 8901:2006. <1> ~ <6> 10. The composition for forming a metal-containing member according to claim 9, wherein the metal-containing member is a fluororesin. <8> The granular filler contains multiple types of particles in which the ratio of arithmetic mean diameters of the granular filler is 0.1:1 to 0.8:1 when calculated according to the method described in JIS Z 8901:2006. <1> ~ <7> 10. The composition for forming a metal-containing member according to claim 9, wherein the metal-containing member is a fluororesin. <9> Used to form heat-conducting members, heat-dissipating members, reflecting members, decorative members, or conductive members, <1> ~ <8> 10. The composition for forming a metal-containing member according to claim 9, wherein the metal-containing member is a fluororesin. <10> <1> ~ <9> 1. A metal-containing member obtained by converting a metal precursor in the composition for forming a metal-containing member according to any one of 1 to 10 into a metal. <11> <1> ~ <9> an application step of applying the composition for forming a metal-containing member according to any one of the above to a substrate to form a metal precursor-containing layer; a conversion step of converting the metal precursor contained in the metal precursor-containing layer into a metal, A method for manufacturing a metal-containing member. <12> the converting step is a step including heating the metal precursor-containing layer at 80°C to 150°C; <11> The method for producing a metal-containing member according to claim 1. <13> The thickness of the obtained metal-containing member is 1 to 500 μm. <11> or <12> The method for producing a metal-containing member according to claim 1. <14> a substrate and a substrate disposed on the substrate; <10> and the metal-containing member according to claim 1. <15> <10> or <14> A device comprising the laminate described in claim 1. [Effects of the Invention]

[0007] According to the present invention, there are provided a composition for forming a metal-containing member that can give a metal-containing member having excellent strength, a metal-containing member obtained by converting the composition for forming a metal-containing member into a metal, a method for manufacturing a metal-containing member using the composition for forming a metal-containing member, and a laminate and a device that include the metal-containing member. [Brief explanation of the drawings]

[0008] [Figure 1]1 is a schematic cross-sectional view showing an example of a heat-conducting member and a laminate of the present invention. [Figure 2] FIG. 2 is a schematic cross-sectional view showing a part of the configuration of a device having a heat dissipation member produced in an example. DETAILED DESCRIPTION OF THE INVENTION

[0009] A typical embodiment of the present invention will be described below. For convenience, each component will be described based on this typical embodiment, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, respectively. In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, so long as the intended effect of the step can be achieved. In the present specification, when a group (atomic group) is represented without specifying whether it is substituted or unsubstituted, it means that it includes both a group having no substituent and a group having a substituent. For example, when simply referring to an "alkyl group," it means that it includes both an alkyl group having no substituent (an unsubstituted alkyl group) and an alkyl group having a substituent (a substituted alkyl group). Furthermore, when simply referring to an "alkyl group," it means that it may be chain-like or cyclic, and if it is chain-like, it may be linear or branched. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, the solid content in a composition means other components excluding the solvent, and the content (concentration) of the solid content in a composition is expressed as the mass percentage of other components excluding the solvent relative to the total mass of the composition, unless otherwise specified. In this specification, unless otherwise specified, the temperature is 23° C. and the pressure is 101325 Pa (1 atmosphere). As used herein, combinations of preferred embodiments are more preferred embodiments.

[0010] <Composition for forming metal-containing parts> The composition for forming a metal-containing member of the present invention contains a metal precursor, a particulate filler, and a solvent. According to the composition for forming a metal-containing member of the present invention, a metal-containing member containing a particulate filler and a metal obtained by converting a metal precursor is formed. The metal-containing member-forming composition of the present invention is preferably used for forming a film, and the film preferably contains a metal obtained by converting a metal precursor and a particulate filler. The method for forming a metal-containing member (for example, the above-mentioned film) using the composition for forming a metal-containing member of the present invention will be described in detail below. Furthermore, the composition for forming a metal-containing member is not particularly limited, but is preferably used to form a heat-conducting member, a heat-dissipating member, a reflecting member, a decorative member, or a conductive member. That is, the metal-containing member formed from the composition for forming a metal-containing member is not particularly limited, but is preferably a heat-conducting member, a heat-dissipating member, a reflecting member, a decorative member, or a conductive member.

[0011] Here, as described in Patent Documents 1 and 2, for example, it is known to form a metal-containing member using a composition containing a metal precursor and a solvent. The present inventors have found that when a metal-containing component is formed using a conventional composition containing a metal precursor and a solvent, the resulting component is weak against stress, and is prone to bending when the component is thin, and warping due to shrinkage occurs when the component is thick. Therefore, the present inventors conducted extensive research and found that a metal-containing member having high strength can be obtained by using a composition containing a metal precursor, a particulate filler, and a solvent. Although the details of the mechanism by which the above-mentioned effects are achieved are unknown, it is thought that the inclusion of a granular filler in the component increases the stress resistance of the metal-containing component itself, making it less likely to bend even in a thin configuration, and also reduces the effect of volume change when converting the metal precursor into metal, thereby suppressing warping due to shrinkage. Furthermore, it has been known for some time that a hybrid material can be formed by combining a metal-containing component with another component in order to improve the strength of the component. However, the use of the composition of the present invention has the advantage of being able to suppress damage to the adherend due to heat or the like. Here, neither Patent Document 1 nor Patent Document 2 describes or suggests the use of a granular filler. Hereinafter, each component contained in the composition for forming a metal-containing member of the present invention will be described in detail.

[0012] [Metal precursor] The metal precursor is not particularly limited as long as it is a compound that can be converted into a metal by a chemical or physical treatment, but is preferably a compound that can be converted into a metal by heating, and examples thereof include metal salts having a ligand. The conjugate acid of the ligand preferably has a boiling point at 1 atmospheric pressure of 150°C or lower, more preferably 120°C or lower. Examples of the ligand include organic acids such as acetic acid, formic acid, oxalic acid, trifluoroacetic acid, and acetylacetic acid; inorganic acids such as carbonic acid, nitric acid, nitrous acid, phosphoric acid, and sulfuric acid; halogen atoms such as fluorine, chlorine, bromine, and iodine; and oxygen atoms.

[0013] The metal contained in the metal precursor is not particularly limited, but examples thereof include silver, copper, gold, platinum, cobalt, palladium, nickel, zinc, aluminum, tin, and iron. The type of metal may be selected depending on the application of the metal-containing member, but silver, for example, is preferred. That is, the metal precursor is preferably a silver precursor.

[0014] Examples of metal precursors include organic acid salts of metals such as acetates, formates, oxalates, lactates, trifluoroacetates, and acetylacetates; inorganic acid salts of metals such as carbonates, phosphates, nitrates, nitrites, cyanates, thiocyanates, and perchlorates; metal halides such as fluorides, chlorides, bromides, and iodides; metal oxides; and metal cyanides. Preferred silver precursors include silver acetate, silver formate, silver carbonate, silver fluoride, silver oxalate, silver lactate, silver nitrate, silver nitrite, silver thiocyanate, silver cyanide, silver cyanate, silver perchlorate, silver chloride, silver bromide, silver iodide, silver phosphate, silver trifluoroacetate, silver acetylacetate, silver sulfate, silver oxide, and the like. Of these, silver carbonate, silver acetate, or silver oxide is preferred.

[0015] The content of the metal precursor relative to the total solid content of the composition for forming a metal-containing member is preferably 1 to 50 mass %, more preferably 3 to 40 mass %, and even more preferably 5 to 30 mass %. The composition for forming a metal-containing member may contain two or more types of metal precursors, and when two or more types are contained, the total amount thereof is preferably within the above range.

[0016] [Granular filler] The composition for forming a metal-containing member of the present invention contains a particulate filler. The shape of the granular filler is not particularly limited, and may be any shape such as fiber, plate, scale, rod, sphere, tube, curved plate, needle, or other shape. The particulate filler may be hollow or solid, or may have a multi-layer structure such as a core-shell structure, or a porous structure.

[0017] The particulate filler may be an inorganic compound, an organic compound, or a hybrid particle of an inorganic compound and an organic compound, but is preferably an inorganic compound. Examples of granular fillers that are inorganic compounds include silicon compounds such as silica, silicates, and silicates; metal oxides such as alumina, zinc oxide, magnesium oxide, antimony oxide, titanium oxide, beryllium oxide, zirconium oxide, copper oxide, and cuprous oxide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal nitrides such as boron nitride and titanium nitride; metal carbonates such as calcium carbonate; carbon compounds such as carbon black and acetylene black; and other ceramics. Alternatively, semiconductor or conductive thermally conductive particles may be coated or surface-treated with an electrically insulating material such as silica. This configuration facilitates individual control of thermal conductivity and electrical insulation, making it easier to adjust the thermal conductivity and electrical insulation. For example, methods for forming a silica film on the surface include the water glass method and the sol-gel method. Among these, metal-free compounds are preferred as particulate fillers, silicon compounds are more preferred, and silica particles are more preferred. Examples of granular fillers that are organic compounds include particles containing polystyrene, polystyrene / divinylbenzene copolymer, polymethyl (meth)acrylate, crosslinked polymethyl (meth)acrylate, styrene / acrylic copolymer, melamine / formaldehyde condensate, benzoguanamine / formaldehyde condensate, and benzoguanamine / melamine / formaldehyde condensate. Examples of hybrid particles of inorganic compounds and organic compounds include particles in which an organic polymer layer (e.g., a layer containing a resin exemplified as an organic compound above) is formed on the surface of a particle made of an inorganic compound such as a silica particle or a metal particle (such as the metal oxides mentioned above).

[0018] The granular filler may be surface-treated by silane coupling treatment, titanate coupling treatment, epoxy treatment, urethane treatment, oxidation treatment, etc. Examples of surface treatment agents used for the surface treatment include polyol, aluminum oxide, aluminum hydroxide, silica (silicon oxide), hydrated silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, silane coupling agents, titanate coupling agents, etc.

[0019] The granular filler may be a commercially available product, and examples of commercially available products include SEAHOSTAR (registered trademark) KE-E10, KE-E30, KE-E150, KE-W10, KE-W30, KE-W50, KE-P10, KE-P30, KE-P50, KE-P100, KE-P150, KE-P250, KE-S10, KE-S30, KE-S50, KE-S100, KE-S150, KE-S250, ZIRCOSTAR (registered trademark) ZP-153, HR-101, EPOSTASTER (registered trademark) MX020W, MX030W, MX050W, MX100W, MX200W, MX300W, MS, M05, L15, M30, SS, S, FS, S6, and S12 (all manufactured by Nippon Shokubai Co., Ltd.).

[0020] From the viewpoint of improving the strength of the resulting metal-containing member, the arithmetic mean diameter of the granular filler, calculated according to the method described in JIS (Japanese Industrial Standards) Z 8901:2006, is preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm, and even more preferably 0.2 to 1 μm. When the composition for forming a metal-containing member of the present invention contains two or more types of particulate fillers, it is sufficient that one of them is within the above range, and it is also one preferred embodiment of the present invention that all of them are within the above range.

[0021] Furthermore, from the viewpoint of improving the strength of the resulting metal-containing component, when the composition for forming a metal-containing component of the present invention contains two or more types of granular filler, it is preferable that the granular filler contains multiple types of particles in which the ratio of the arithmetic mean diameters of the granular fillers is 0.1:1 to 0.8:1. The above ratio is preferably 0.3:1 to 0.8:1, and more preferably 0.5:1 to 0.8:1. This structure is believed to improve strength by filling the gaps between larger particles with smaller particles, and also to improve the thermal conductivity of the metal-containing component, since the spacing between the granular fillers is reduced and the number of contact points increases compared to when only granular fillers of a single diameter are included. Furthermore, when the composition for forming a metal-containing member of the present invention contains three or more types of particulate filler, it is sufficient that there is at least one combination in which the ratio of the arithmetic mean values ​​of the diameters of the particulate fillers falls within the above range.

[0022] The Vickers hardness of the particulate filler material is preferably 0.1 to 100 GPa, more preferably 1 to 50 GPa, and even more preferably 5 to 30 GPa.

[0023] For example, when the metal-containing member is used as a heat-conducting member, a heat-dissipating member, or the like, the granular filler is preferably thermally conductive. The thermal diffusivity of the granular filler is, for example, 1.0 × 10 -6 m 2 s -1 That is 2.0 x 10 -6 m 2 s -1 It is preferable that the value is 3.0×10 or more. -6 m 2 s -1 The upper limit of the thermal diffusivity of the particulate filler is not particularly limited, but in practice it is 1.0 × 10 -4 m 2 s -1 The following is the result.

[0024] The density (true specific gravity) of the granular filler is, for example, 10.0 g / cm 3is less than or equal to 5.0 g / cm 3 The lower limit of the density of the granular filler is not particularly limited, but is, for example, 1.0 g / cm 3 In addition, when the granular filler is a porous or hollow particle having voids or cavities, the density of the granular filler in this specification means the density of the solid content of the components constituting the granular filler.

[0025] The content of the particulate filler relative to the total solid content of the composition for forming a metal-containing member of the present invention is preferably 0.5 to 50 mass %, more preferably 1.0 to 40 mass %, and even more preferably 3.0 to 30 mass %. The composition for forming a metal-containing member may contain two or more types of particulate filler, and when two or more types are contained, the total amount thereof is preferably within the above range. Furthermore, the content of the granular filler in the metal-containing component, which is obtained by converting the metal precursor in the composition for forming a metal-containing component into metal, is preferably 10 to 90 volume %, more preferably 20 to 80 volume %, and even more preferably 30 to 70 volume %.

[0026] 〔solvent〕 The composition for forming a metal-containing member of the present invention contains a solvent. Examples of solvents include water, alcohols (e.g., methanol, ethanol, isopropanol, 1-methoxypropanol, butanol, ethylhexyl alcohol, terpineol, etc.), glycols (ethylene glycol, diethylene glycol, triethylene glycol, glycerin, etc.), acetates (ethyl acetate, butyl acetate, methoxypropyl acetate, carbitol acetate, ethyl carbitol acetate), ethers (methyl cellosolve, butyl cellosolve, diethyl ether, tetrahydrofuran, dioxane), ketones (methyl ethyl ketone, acetone, dimethylformamide, 1-methyl-2-pyrrolidine, etc.), and the like. Examples of suitable solvents include hexane, heptane, methyl isobutyl ketone, alkoxyalkanols (methoxyethanol, methoxypropanol, ethoxyethanol, etc.), ketone alcohols (acetol, diacetone alcohol, etc.), hydrocarbons (hexane, heptane, dodecane, paraffin oil, mineral spirits, benzene, toluene, xylene, etc.), halogen-substituted solvents (chloroform, methylene chloride, carbon tetrachloride, etc.), alkyl oximes (acetone oxime, dimethylglyoxime, 2-butanone oxime, 2,3-butadione monooxime, etc.), acetonitrile, dimethyl sulfoxide, and mixtures thereof. Among these, the composition for forming a metal-containing member of the present invention preferably contains water as a solvent.

[0027] The content of the solvent in the composition for forming a metal-containing component is preferably an amount that makes the ratio of the total solid content to the total mass of the composition for forming a metal-containing component 5 to 70 mass%, more preferably an amount that makes the ratio 10 to 60 mass%, and even more preferably an amount that makes the ratio 20 to 50 mass%. The composition for forming a metal-containing member may contain two or more solvents, and when two or more solvents are contained, the total amount thereof is preferably within the above range. The water content relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Another preferred embodiment of the present invention is one in which the water content relative to the total mass of the solvent is 90% by mass or more (even 95% by mass or more). The upper limit of the water content relative to the total mass of the solvent is not particularly limited, and may be 100% by mass.

[0028] [Reducing Agent] The composition for forming a metal-containing member of the present invention preferably further contains a reducing agent. The inclusion of a reducing agent may facilitate the conversion of the metal precursor to the metal. The reducing agent may be an inorganic compound such as a metal salt, such as sodium, potassium borohydride, ferrous chloride, or ferrous sulfate, hydrogen iodide, or carbon monoxide, or an organic compound, but is preferably an organic compound. Examples of reducing agents that are organic compounds include amine compounds such as hydrazine, acetic hydrazide, trisodium citrate, methyldiethanolamine, and dimethylamine borane; aldehyde compounds such as formaldehyde and acetaldehyde; organic compounds such as glucose, ascorbic acid, salicylic acid, tannic acid, pyrogallol, and hydroquinone; metal salts such as sodium, potassium boron hydroxide, ferrous chloride, and ferrous sulfate; and inorganic compounds such as hydrogen iodide and carbon monoxide.

[0029] It is also preferable to use a compound represented by the following formula (R-1) as the reducing agent. [ka] In formula (R-1), R 1 represents a hydrogen atom or a monovalent organic group having one or more aldehyde groups. R 1Examples of the alkyl group include a hydrogen atom, an aldehyde group, an alkyl group having 1 to 20 carbon atoms and having one or more aldehyde groups, an aryl group having 5 to 20 carbon atoms and having one or more aldehyde groups, an amino group having one or more aldehyde groups, and a heterocyclic group having 5 to 20 carbon atoms and having one or more aldehyde groups. Preferred are a hydrogen atom, an aldehyde group, a methyl group having one or more aldehyde groups, an ethyl group having one or more aldehyde groups, and a benzene ring having one or more aldehyde groups, and more preferred is a hydrogen atom. Examples of the compound represented by formula (R-1) include formic acid, 2-methyl-3-oxopropanoic acid, 3-oxopropanoic acid, phthalaldehyde acid, isophthalaldehyde acid, and terephthalaldehyde acid.

[0030] The content of the reducing agent relative to the total solid content of the composition for forming a metal-containing member is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.5 to 3 mass %. The composition for forming a metal-containing member may contain two or more reducing agents, and when two or more reducing agents are contained, the total amount thereof is preferably within the above range.

[0031] [Amine Compounds] The composition for forming a metal-containing member of the present invention preferably contains an amine compound. At least a portion of the amine compound may form a complex with the metal precursor in the composition for forming a metal-containing member. By including an amine compound, the solubility of the metal precursor is improved, and the content of the metal precursor in the composition for forming a metal-containing member can be increased, or the storage stability of the composition for forming a metal-containing member can be improved in some cases.

[0032] The amine compound is preferably an organic amine, more preferably an alkylamine.

[0033] Alkylamine refers to an amino group having at least one alkyl group. Here, the alkyl group may be linear, cyclic, branched, or a combination thereof. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 2 to 10 carbon atoms, for example. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, an isopentyl group, a cyclohexyl group, and a cyclopentyl group. The alkylamine may be any of a primary, secondary, or tertiary amine, but is preferably a primary or secondary amine, and more preferably a primary amine. The alkylamine preferably has 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 3 to 8 carbon atoms.

[0034] The boiling point of the organic amine at 1 atmospheric pressure is preferably 150°C or lower, more preferably 140°C or lower, and even more preferably 120°C or lower. The boiling point of the organic amine at 1 atmosphere is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher.

[0035] Examples of the amine compound include, but are not limited to, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n-heptylamine, n-octylamine, isooctylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, arylamine, hydroxyamine, ammonium hydroxide, methoxyamine, 2-ethanolamine, propanolamine, butanolamine, hexanolamine, dimethylethanolamine, methoxyethylamine, ethoxyethylamine, 2-hydroxypropylamine, 2-hydroxy-2-methylpropylamine, methoxypropylamine, cyanoethylamine, ethoxyamine, n-butoxyamine, 2- Examples of the amine include hexyloxyamine, methoxyethoxyethylamine, methoxyethoxyethoxyethylamine, dimethylamine, diethylamine, dipropylamine, diethanolamine, hexamethyleneimine, morpholine, piperidine, N-methylpiperidine, piperazine, N,N'-dimethylpiperazine, 1-amino-4-methylpiperazine, pyrrolidine, N-methylpyrrolidineethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, 2,2-(ethylenedioxy)bisethylamine, triethylamine, triethanolamine, pyrrole, imidazole, pyridine, aminoacetaldehyde dimethyl acetal, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aniline, anisidine, aminobenzonitrile, benzylamine and derivatives thereof, and polymer compounds and derivatives thereof such as polyarylamine and polyethyleneimine.

[0036] Among these, the amine compound is preferably a primary amine compound branched at the β-position and represented by the following formula (A-1). R 11 -CHR 12 -CH2-NH2 (A-1) In formula (A-1), R 11and R 12 each independently represents a hydrocarbon group having 1 to 12 carbon atoms.

[0037] R 11 and R 12 The hydrocarbon group having 1 to 12 carbon atoms represented by the formula (I) may be either an unsubstituted alkyl group or a substituted alkyl group. The unsubstituted alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the substituent of the substituted alkyl group include an aryl group (e.g., a phenyl group, a naphthyl group), an alkoxy group (e.g., a methoxy group, an ethoxy group, etc., preferably having 1 to 4 carbon atoms), a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), a cyano group, an amino group, and a heterocyclic group (e.g., a cyclic group such as a nitrogen-containing heterocyclic group such as a pyrrolidine ring, a pyrrole ring, an imidazole ring, etc., or an oxygen-containing heterocyclic group such as a furan ring, a tetrahydrofuran ring, etc.). Suitable examples of the substituted alkyl group include an arylalkyl group (alkyl moiety having 1 to 4 carbon atoms), a cyanoalkyl group (alkyl moiety having 1 to 4 carbon atoms), a halogenated alkyl group (alkyl moiety having 1 to 4 carbon atoms), and a cycloolefin-bonded alkyl group. Of the above, R 11 and R 12 At least one of the groups is preferably an ethyl group. The reason for this is not entirely clear and is merely speculation, but it is thought that the two carbon atoms of the ethyl group and the nitrogen and hydrogen atoms of the amino group form a six-membered ring, which extends the HOMO from the nitrogen atom to the ethyl group, thereby stabilizing the formation of the complex. Furthermore, R 11 is a butyl group, and R 12 It is more preferred that is an ethyl group.

[0038] Examples of the compound represented by general formula (A-1) include the following compounds. Of these, isobutylamine, 2-ethylbutylamine, and 2-ethylhexylamine are preferred, and 2-ethylbutylamine and 2-ethylhexylamine are more preferred.

[0039] [ka]

[0040] The molecular weight of the primary amine compound represented by general formula (A-1) is preferably in the range of 70 to 400, more preferably in the range of 80 to 300, and particularly preferably in the range of 90 to 200. A molecular weight of 70 or more is advantageous in terms of wettability during application, and a molecular weight of 400 or less is advantageous in terms of solubility in polar solvents.

[0041] The content of the amine compound relative to the total solid content of the composition for forming a metal-containing component may be determined appropriately taking into consideration the solubility of the metal precursor, etc., but is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 80 mass %. The composition for forming a metal-containing member may contain two or more types of amine compounds, and when two or more types are contained, the total amount thereof is preferably within the above range.

[0042] [Other complexing agents] The composition for forming a metal-containing member of the present invention may further contain other complexing agents in addition to or instead of the above-mentioned amine compounds. At least a portion of the other complexing agent may form a complex with the metal precursor in the composition for forming a metal-containing member. Other complexing agents include ammonium carbamate compounds, ammonium carbonate compounds, and the like. The ammonium carbamate compound or ammonium carbonate compound is preferably a compound represented by any one of the following formulas (C-1) to (C-3). [ka] In formulas (C-1) to (C-3), R 1 ~R 6each independently represents a substituent selected from a hydrogen atom, an aliphatic alkyl group having 1 to 30 carbon atoms, an alicyclic alkyl group, an aryl group or an aralkyl group, an alkyl group substituted with a functional group, an aryl group substituted with a functional group, a heterocyclic compound group, and a polymer compound or a derivative thereof.

[0043] Specific examples of the compounds represented by formulas (C-1) to (C-3) include ammonium carbamate, ammonium carbonate, and ammonium bicarbonate. bicarbonate), ethylammonium ethyl carbamate, isopropylammonium isopropyl carbamate, n-butylammonium n-butyl carbamate, isobutylammonium isobutyl carbamate, t-butylammonium t-butyl carbamate, 2-ethylhexylammonium 2-ethylhexyl carbamate, 2-ethylhexylammonium 2-ethyl carbamate, octadecylammonium octadecyl carbamate, 2-methoxyethylammonium 2-methoxyethyl carbamate, 2-cyanoethylammonium 2-cyanoethyl carbamate, dibutylammonium dibutyl carbamate, dioctadecylammonium dioctadecyl carbamate, methyldecylammonium methyldecyl carbamate, hexamethyleneimineammonium hexamethyleneimine carbamate, morpholinium morpholine carbamate, pyridium ethylhexyl carbamate, triethylenediamine isopropyl Bicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethyl carbonate, isopropylammonium isopropyl carbonate, isopropylammonium bicarbonate, n-butylammonium n-butyl carbonate, isobutylammonium isobutyl carbonate, t-butylammonium t-butyl carbonate, t-butylammonium bicarbonate, 2-ethylhexylammonium 2-ethylhexyl carbonate, 2-ethylhexylammonium bicarbonate, 2-methoxyethylammonium 2-methoxyethyl carbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium 2-cyanoethyl carbonate, 2-cyanoethylammonium bicarbonate, octadecylammonium octadecyl carbonate, dibutylammonium dibutyl carbonate,Examples of the dioctadecylammonium carbonate include dioctadecylammonium dioctadecyl carbonate, dioctadecylammonium bicarbonate, methyldecylammonium methyldecyl carbonate, hexamethyleneimineammonium hexamethyleneimine carbonate, morpholineammonium morpholine carbonate, benzylammonium benzyl carbonate, triethoxysilylpropylammonium triethoxysilylpropyl carbonate, pyridium bicarbonate, triethylenediaminium isopropyl carbonate, triethylenediaminium bicarbonate, and derivatives thereof. These may be used singly or as a mixture of two or more kinds. The present invention is not limited to the above specific examples.

[0044] Furthermore, the type and method of preparation of ammonium carbamate compounds or ammonium carbonate compounds are not particularly limited. For example, U.S. Patent No. 4,542,214 describes the preparation of ammonium carbamate compounds from a primary amine, a secondary amine, a tertiary amine, or a mixture of at least one of these with carbon dioxide. Adding 0.5 moles of water per mole of amine yields ammonium carbonate compounds, while adding 1 mole or more of water yields ammonium bicarbonate compounds. In this case, the compounds can be prepared directly under normal or elevated pressure without using a special solvent, or using a solvent. When a solvent is used, examples thereof include water, alcohols such as methanol, ethanol, isopropanol, and butanol, glycols such as ethylene glycol and glycerin, acetates such as ethyl acetate, butyl acetate, and carbitol acetate, ethers such as diethyl ether, tetrahydrofuran, and dioxane, ketones such as methyl ethyl ketone and acetone, hydrocarbons such as hexane and heptane, aromatic solvents such as benzene and toluene, halogen-substituted solvents such as chloroform, methylene chloride, and carbon tetrachloride, and mixtures of these solvents. Carbon dioxide can be bubbled in the gas phase or solid-phase dry ice can be used, and can also contribute to the reaction in a supercritical state. The production of ammonium carbamate derivatives or ammonium carbonate derivatives involves the above In addition to the above methods, any known method may be used as long as the structure of the final substance is the same. In other words, there is no need to particularly limit the solvent, reaction temperature, concentration, catalyst, etc. for production, and the production yield is not affected.

[0045] [Other additives] The composition for forming a metal-containing member of the present invention may further contain other additives. Other additives include stabilizers, leveling agents, thin film aids, thermal decomposition reaction accelerators, surfactants, and the like.

[0046] Stabilizers include, for example, phosphorus compounds such as phosphines, phosphites, and phosphates, sulfur compounds such as thiols and sulfides, and mixtures thereof. Examples of phosphorus compounds include those represented by the general formula R3P, (RO)3P, or (RO)3PO, where R represents an alkyl group or aryl group having 1 to 20 carbon atoms, and specific examples include tributylphosphine, triphenylphosphine, triethylphosphite, triphenylphosphite, dibenzylphosphate, and triethylphosphate. Specific examples of sulfur compounds include butanethiol, n-hexanethiol, diethyl sulfide, tetrahydrothiophene, aryl disulfide, 2-mercaptobenzoazole, tetrahydrothiophene, and octylthioglycolate. The content of the stabilizer is not particularly limited, but is preferably 0.1 to 90% by molar amount relative to the molar amount of the metal precursor. The composition for forming a metal-containing member may contain two or more stabilizers, and when two or more stabilizers are contained, the total amount thereof is preferably within the above range.

[0047] Film forming aids include organic acids, organic acid derivatives, or mixtures thereof. Specific examples of organic acids include acetic acid, butyric acid, valeric acid, pivalic acid, hexanoic acid, octanoic acid, 2-ethyl-hexanoic acid, neodecanoic acid, lauric acid, stearic acid, and naphthalic acid. Specific examples of the organic acid derivatives include organic acid ammonium salts such as ammonium acetate, ammonium citrate, ammonium laurate, ammonium lactate, ammonium maleate, ammonium oxalate, and ammonium molybdate; and organic acid metal salts containing metals such as Au, Cu, Zn, Ni, Co, Pd, Pt, Ti, V, Mn, Fe, Cr, Zr, Nb, Mo, W, Ru, Cd, Ta, Re, Os, Ir, Al, Ga, Ge, In, Sn, Sb, Pb, Bi, Sm, Eu, Ac, and Th, such as manganese oxalate, gold acetate, palladium oxalate, silver 2-ethylhexanoate, silver octanoate, silver neodecanoate, cobalt stearate, nickel naphthalate, and cobalt naphthalate. The content of the thin film auxiliary agent is not particularly limited, but is preferably 0.1 to 25% by molar amount relative to the molar amount of the metal precursor. The metal-containing member-forming composition may contain two or more thin film auxiliary agents, and when two or more thin film auxiliary agents are contained, the total amount thereof is preferably within the above range.

[0048] Specific examples of the thermal decomposition reaction accelerator include polyhydric phenol compounds, phenol resins, alkyd resins, pyrroles, and oxidation polymerizable resins such as ethylenedioxythiophene (EDOT). The content of the thermal decomposition reaction accelerator relative to the total solid content of the composition for forming a metal-containing member is preferably 0.01 to 20 mass %, more preferably 0.1 to 10 mass %, and even more preferably 0.2 to 5 mass %. The composition for forming a metal-containing member may contain two or more types of thermal decomposition reaction accelerators, and when two or more types are contained, the total amount thereof is preferably within the above range.

[0049] As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and silicone surfactants can be used.

[0050] By incorporating a surfactant into the metal-containing layer-forming composition of the present invention, the uniformity and liquid saving of the formed metal precursor-containing layer can be further improved. That is, when a metal-containing layer-forming composition containing a surfactant is applied to a substrate to form a metal precursor-containing layer, the interfacial tension between the coated surface and the composition is reduced, improving the wettability of the coated surface and the coatability of the coated surface. Therefore, it is possible to more suitably form a film of uniform thickness with little thickness unevenness.

[0051] The content of the surfactant is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on the total solid content of the composition. The surfactant may be one type only, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

[0052] [Method of preparing the composition] The above-described compositions can be prepared by mixing the aforementioned ingredients. When preparing the composition, the components may be mixed together or may be dissolved or dispersed in a solvent and then mixed sequentially. There are no particular restrictions on the order of addition or working conditions when mixing. For example, a metal precursor may be reacted with an amine compound or other complexing agent in a solvent to form a metal complex, and then other components such as a particulate filler and a reducing agent may be further added.

[0053] A step of dispersing a granular filler may also be performed. Examples of the step of dispersing a granular filler include those using mechanical forces such as compression, squeezing, impact, shear, and cavitation to disperse the granular filler. Specific examples of these processes include bead mills, sand mills, roll mills, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. Furthermore, the processes and dispersers described in "Dispersion Technology Encyclopedia," published by Johokki Co., Ltd., July 15, 2005, and "Dispersion Technology and Industrial Applications Focused on Suspensions (Solid / Liquid Dispersion Systems): Comprehensive Data Collection," published by the Management Development Center Publishing Department, October 10, 1978, can be suitably used.

[0054] The composition can be stirred using, for example, a stirrer (stirring bar) or a stirring blade. The rotation speed is preferably, for example, 10 to 2000 rpm. The lower limit is preferably 100 rpm or more, more preferably 300 rpm or more. The upper limit is preferably 1500 rpm or less, more preferably 1000 rpm or less. Stirring can also be performed by methods such as bubbling or ultrasonic waves.

[0055] A conventionally known container can be used as a container for storing the composition of the present invention. Furthermore, in order to prevent impurities from being mixed into the raw materials or the composition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six-layer resin, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0056] When preparing the composition, filtration may be performed using a filter to remove foreign matter, reduce defects, etc. Filters that have been conventionally used for filtration purposes can be used without any particular limitation. Examples include filters made of fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), and polyolefin resins (including high-density and ultra-high-molecular-weight resins) such as polyethylene and polypropylene (PP). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0057] The pore size of the filter is suitably about 0.01 to 100 μm, preferably about 0.1 to 50 μm, and more preferably about 1 to 30 μm. By setting the pore size within this range, it becomes possible to reliably remove fine foreign matter that would hinder the preparation of a uniform composition in a subsequent process. It is also preferable to use a fibrous filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, and glass fiber. Examples of the fibrous filter medium that can be used include filter cartridges from the SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by ROKI TECHNO CORPORATION.

[0058] When using filters, different filters may be combined. In this case, filtering with a first filter may be performed only once or may be performed two or more times. For example, filtering with a first filter may be performed on only the dispersion containing the particulate filler, and after mixing with other components, filtering with a second filter may be performed.

[0059] Furthermore, first filters with different pore sizes within the above-mentioned range may be combined. The pore sizes here refer to the nominal values ​​of the filter manufacturers. Commercially available filters can be selected from various filters provided by, for example, Nippon Pall Corporation (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), or Kitz Microfilter Co., Ltd.

[0060] The second filter may be made of the same material as the first filter described above.

[0061] (Metal-containing member and its manufacturing method) The metal-containing member of the present invention is a metal-containing member obtained by converting the metal precursor in the composition for forming a metal-containing member of the present invention into a metal. The method for converting the metal precursor into the metal is not particularly limited, but may include heating. The metal-containing member of the present invention is not particularly limited, but is preferably a heat-conducting member, a heat-dissipating member, a reflecting member, a decorative member, or a conductive member.

[0062] <Heat conductive materials, heat dissipation materials> Hereinafter, the case where the metal-containing member of the present invention is a heat-conducting member will be described. FIG. 1 is a schematic cross-sectional view showing an example of the heat-conducting member and laminate of the present invention. For example, as shown in Fig. 1, a heat-conducting member 4 of the present invention has a structure in which a granular filler 3 is dispersed inside a metal-containing member 2 formed on a substrate 1. The heat-conducting member 4 contains the granular filler 3, and therefore has excellent strength. Here, for example, if there is a heat source on the substrate 1 side, the thermal energy E transferred to the heat-conducting member 4 is transmitted through the metal-containing member 2 and released to the side of the metal-containing member 2 opposite to the side where the substrate 1 exists.

[0063] The thermal diffusivity of the heat-conducting material is 3.0 x 10 -7 m 2 s -1 It is preferable that the value is equal to or greater than 1.0×10 -6m 2 s -1 The upper limit of the thermal diffusivity of the heat-conducting member is not particularly limited, but is, for example, 1.0×10 -4 m 2 s -1 The following is the result. Such a heat-conducting member has excellent thermal conductivity and can therefore be suitably used as a heat-conducting member for devices such as LSI devices. 1 can also be used as the heat dissipation member. In this case, the preferred configuration and preferred thermal diffusivity of the heat dissipation member are the same as those of the heat conductive member. When the metal-containing member of the present invention is a heat dissipation member, it is not particularly limited, but can be used as, for example, the conductive heat dissipation member disclosed in JP-A-2012-231169.

[0064] The method for producing the metal-containing member will be described below. The method for producing a metal-containing member of the present invention includes an application step of applying the composition for forming a metal-containing member of the present invention to a substrate to form a metal precursor-containing layer, and a conversion step of converting the metal precursor contained in the metal precursor-containing layer into a metal. Each step will be described in detail below.

[0065] <Applicable process> In the application step, the composition for forming a metal-containing member of the present invention is applied to a substrate to form a metal precursor-containing layer. Examples of the method for applying the composition for forming a metal-containing member in the application step include spin coating, bar coating, spray coating, slit coating, spiral coating, screen printing, inkjet printing, casting coating, roll coating, and dropping (drop casting). Among these, spin coating, bar coating, spray coating, and slit coating are preferred, and spin coating is more preferred.

[0066] The thickness of the metal precursor-containing layer (e.g., coating thickness) is preferably 0.2 to 50 μm. The lower limit of this range is more preferably 0.5 μm or more, and even more preferably 1.0 μm or more. The upper limit of this range is more preferably 35 μm or less, and even more preferably 20 μm or less. The thickness of the metal precursor-containing layer can be adjusted, for example, by selecting an application method or by applying the layer multiple times.

[0067] [Base material] The substrate is not particularly limited and can be selected appropriately depending on the application. Examples of substrates that can be used include transparent substrates used in liquid crystal display devices, light-emitting devices, solid-state imaging devices, semiconductor memories, thermally conductive sheets, metal substrates, substrates with metal wiring, metal substrates, and semiconductor substrates used in ceramic substrates. Transparent substrates include, for example, quartz glass, alkali-free glass, soda glass, borosilicate glass, aluminosilicate glass, and resin. These transparent substrates may have other structures formed thereon, such as a transparent conductive film, a reflective film, and a protective film. Semiconductor substrates include, for example, silicon, sapphire, silicon carbide, gallium nitride, aluminum, amorphous aluminum oxide, polycrystalline aluminum oxide, silicon nitride, silicon oxynitride, GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP, and ZnO. These semiconductor substrates may have other structures formed thereon, such as a PN junction layer, a light-emitting layer, a photoelectric conversion layer, a complementary metal-oxide semiconductor (CMOS) layer, and an electrode layer. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface. The undercoat layer may contain the above-mentioned reducing agent, amine compound, etc. to promote conversion of the metal precursor to the metal.

[0068] The substrate may have any shape such as a flat surface, a diffusing surface, a concave surface, or a convex surface. The substrate may be subjected to a surface treatment in advance. Examples of surface treatments include treatments that decompose and activate the surface, such as UV irradiation, ozone treatment, plasma treatment, corona treatment, and flame treatment; treatments with alkaline solutions such as hydrazine, N-methylpyrrolidone, sodium hydroxide solution, and potassium hydroxide solution; and treatments with acidic solutions such as sulfuric acid, hydrochloric acid, and nitric acid. Examples of treatments that remove dirt from the substrate surface and clean it include treatments with organic solvents such as methanol, ethanol, toluene, ethyl acetate, and acetone, and washing with water to remove adhering dust. These surface treatments may be performed in combination.

[0069] The metal precursor-containing layer may also be dried during the application step. The drying method is not particularly limited, but examples include drying by heating, reduced pressure, and the like. The drying means is not particularly limited, and known heating devices, pressure reducing devices, etc. can be used. Furthermore, when the conversion step described below is carried out by heating, drying may not be carried out in the application step, and drying of the metal precursor-containing layer and conversion of the metal precursor to metal may be carried out simultaneously in the conversion step.

[0070] <Conversion process> In the conversion step, the metal precursor contained in the metal precursor-containing layer is converted into a metal. The conversion method is not particularly limited, but conversion by heating (firing) is preferred. That is, the conversion step is preferably a step including heating the metal precursor-containing layer. Heating, for example, reduces a metal precursor (eg, a metal salt) and converts it to the metal. The heating temperature is not particularly limited and may be determined in consideration of the types of components such as the metal precursor and reducing agent, but is preferably 70 to 800°C, more preferably 80 to 300°C, and even more preferably 80 to 150°C. The heating time may be determined in consideration of the types of components such as the metal precursor and reducing agent, and is not particularly limited, but is preferably 10 seconds to 30 minutes, more preferably 30 seconds to 5 minutes. The heating means is not particularly limited, but examples thereof include a hot plate, an electric furnace, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven, and the like.

[0071] Heating may be carried out stepwise. Furthermore, cooling may be carried out after heating, and in this case, the cooling rate is preferably 1 to 5°C / min.

[0072] <Other processes> The method for producing a metal-containing member of the present invention may further include other steps. Other steps include, for example, a topcoat layer forming step of forming a topcoat layer on the metal precursor-containing layer. The topcoat layer forming step may be carried out after the converting step, but may also be carried out before the converting step or after the applying step. Examples of the overcoat layer include a layer containing the above-mentioned reducing agent, amine compound, other complexing agent, etc., for promoting the conversion of the metal precursor to the metal. Furthermore, a layer having functions such as insulation, conductivity, refractive index adjustment, and heat conduction may be formed as an overcoat layer.

[0073] In addition, the method for producing a metal-containing member of the present invention may further include a step known in the art, such as a step of surface treating the metal-containing member.

[0074] The thickness of the metal-containing member formed is preferably 1 to 500 μm. The lower limit of this numerical range is more preferably 1.5 μm or more, and even more preferably 2 μm or more. The upper limit of this numerical range is more preferably 300 μm or less, and even more preferably 100 μm or less.

[0075] (Laminates and Devices) The laminate of the present invention comprises a substrate and the metal-containing member of the present invention formed on the substrate. Another layer such as an undercoat layer may be present between the substrate and the metal-containing member. The metal-containing member may have other layers, such as a topcoat layer, on the side opposite to the substrate. The laminate may also include multiple layers of metal-containing members. When the metal-containing member is a heat-conducting member, the laminate of the present invention may further include a heat-absorbing part in contact with the heat-conducting member. The heat-absorbing part is a cooling module, such as a heat dissipation fin, a heat pipe, a Peltier module, or a cooling plate.

[0076] The device of the present invention is a device having the metal-containing member of the present invention or the laminate of the present invention.

[0077] The present invention is applicable to logic integrated circuits such as ASICs (Application Specific Integrated Circuits), FPGAs (Field Programmable Gate Arrays), and ASSPs (Application Specific Standard Products). It is also applicable to microprocessors such as CPUs (Central Processing Units) and GPUs (Graphics Processing Units). It is also applicable to memories such as DRAMs (Dynamic Random Access Memory), HMCs (Hybrid Memory Cubes), MRAMs (Magnetoresistive Random Access Memory), PCMs (Phase-Change Memory), ReRAMs (Resistance Random Access Memory), FeRAMs (Ferroelectric Random Access Memory), and flash memories. It is also applicable to analog integrated circuits such as LEDs (Light Emitting Diodes), power devices, DC (Direct Current)-DC (Direct Current) converters, and insulated gate bipolar transistors (IGBTs). The present invention is also applicable to MEMS (Micro Electro Mechanical Systems) such as acceleration sensors, pressure sensors, vibrators, and gyro sensors.The present invention is also applicable to wireless elements such as GPS (Global Positioning System), FM (Frequency Modulation), NFC (Near field communication), RFEM (RF Expansion Module), MMIC (Monolithic Microwave Integrated Circuit), WLAN (Wireless Local Area Network), discrete elements, CMOS (Complementary Metal Oxide Semiconductor), CMOS image sensors, camera modules, passive devices, SAW (Surface Acoustic Wave) filters, RF (Radio Frequency) filters, IPDs (Integrated Passive Devices), etc. The metal-containing member of the present invention can be applied to these devices as, for example, a heat-conducting member, a heat-dissipating member, a reflecting member, a decorative member, or a conductive member.

[0078] The final products incorporating the semiconductor device of the present invention as described above are not particularly limited, and examples thereof include smart TVs, mobile communication terminals, mobile phones, smartphones, tablet terminals, desktop PCs, notebook PCs, network equipment (routers, switching), wired infrastructure equipment, digital cameras, game consoles, controllers, data centers, servers, mining PCs, HPC, graphic cards, network servers, storage, chipsets, in-vehicle equipment (electronic control equipment, driving assistance systems), car navigation systems, PNDs, lighting (general lighting, in-vehicle lighting, LED lighting, OLED lighting), televisions, displays, display panels (liquid crystal panels, organic EL panels, electronic paper), music playback terminals, industrial equipment, industrial robots, inspection equipment, medical equipment, white goods, space or aircraft equipment, and wearable devices.

[0079] When the metal-containing member of the present invention is a heat-conducting member, it can also be applied to, for example, a joint between a heat source such as a battery or a substrate and a component such as a cooling module (heat pipe or the like), a housing of an electronic device, etc. Furthermore, when the metal-containing member of the present invention is a heat-conducting member, it can also be applied to a joint between a component such as an in-vehicle electronic device, a battery, or a power conversion device and a cooling device using an air-cooling mechanism or a water-cooling mechanism. Furthermore, when the metal-containing member of the present invention is a heat-conducting member or a heat-dissipating member, it can also be used as, for example, a heat-dissipating fin. [Example]

[0080] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the examples, unless otherwise specified, "parts" and "%" are by mass, and the ambient temperature (room temperature) in each step is 23°C. Furthermore, hereinafter, "composition 1 for forming a metal-containing member" and the like will also be simply referred to as "composition 1" and the like.

[0081] <Preparation of Comparative Composition 1> Using a Schlenk flask equipped with a stirrer, 65.0 g (215 mmol) of 2-ethylhexylammonium 2-ethylcarbamate was dissolved in 150.0 g of isopropanol, and then 20.0 g (86.2 mmol) of silver oxide was added and the reaction was carried out at room temperature. The reaction solution was initially a black suspension, but as the reaction progressed and a complex compound was produced, it was observed that the color gradually lightened and became transparent. After the reaction was carried out for 2 hours, a colorless, transparent solution was obtained. To this solution, 2.5 g of 2-hydroxy-2-methylpropylamine, 85.0 g of n-butanol, and 50.0 g of amyl alcohol were added and stirred, and then hydrazine was added in an amount equivalent to 0.5% by mass of the total solution. The solution was filtered using a 0.45 micron membrane filter and subjected to thermal analysis to produce Comparative Composition 1 having a silver content of 5.0% by mass.

[0082] <Preparation of Composition 1 for Forming Metal-Containing Member> To 100 parts by mass of the above comparative composition 1, 12.5 parts by mass each of Seahoster KE-E30 (manufactured by Nippon Shokubai Co., Ltd., solid content 20%) and KE-E150 (manufactured by Nippon Shokubai Co., Ltd., solid content 20%) were added to obtain composition 1 for forming metal-containing components (composition 1).

[0083] <Preparation of composition 2 for forming metal-containing member> 3.8 g of cobalt chloride was dissolved in 50 g of water, and 24.6 g of 35% by mass hydrochloric acid was added to prepare a solution. A solution of 15.8 g of trioctylamine mixed with 40 g of xylene was added to the above solution, and the mixture was heated to 60°C with stirring. The aqueous layer and the solvent layer were separated, and only the solvent layer was taken out, and the xylene solvent was distilled off to obtain a precursor composition. Seven parts by mass of Zircostar ZP-153 (manufactured by Nippon Shokubai Co., Ltd., solid content 70%) was added to 100 parts by mass of the precursor composition to prepare a composition 2 for forming a metal-containing member (composition 2).

[0084] <Preparation of Compositions 3 to 17 for Forming Metal-Containing Members> The materials were blended to the blending ratio (parts by mass) shown in the "Composition" column in the following table. Specifically, the metal precursor, solvent, and additives shown in the table were mixed and stirred, and then the granular filler and reducing agent shown in the table were added and further mixed to obtain compositions 3 to 17 for forming metal-containing members (compositions 3 to 17).

[0085] [Table 1]

[0086] [Table 2]

[0087] Details of the ingredients used in the table are as follows:

[0088] [Granular filler] Seahoster KE-W30 (20% solids): Silica particles, manufactured by Nippon Shokubai Co., Ltd., particle size 0.3 μm Seahoster KE-W50 (20% solids): Silica particles, manufactured by Nippon Shokubai Co., Ltd., particle size 0.5 μm Seahoster KE-W10 (15% solids): Silica particles, manufactured by Nippon Shokubai Co., Ltd., particle size 0.1 μm Eposter MX050W (10% solids): acrylic cross-linked resin, manufactured by Nippon Shokubai Co., Ltd., particle size 70 nm Baylar Al-L7 (solid content 7%): Alumina particles, manufactured by Taki Chemical Co., Ltd., particle size 5-10 nm DIF-AB-33W (solid content 60%): Zinc oxide particles, manufactured by Sakai Chemical Industry Co., Ltd., particle size 35 nm The particle size is the arithmetic mean value of the diameter of the granular filler when calculated according to the method described in JIS Z 8901:2006. Additionally, Seahoster, Eposter, and DISPAL are registered trademarks.

[0089] (evaluation) <Stress resistance evaluation> [Examples 1, 3 to 13 and Comparative Example 1] An aluminum plate was used as the substrate. The metal-containing member-forming composition in each example and the comparative composition in each comparative example were each applied to the aluminum plate by spin coating to form a metal precursor-containing layer. By repeating the application, a metal precursor-containing layer having a thickness of 2 μm was produced. The aluminum plate with the obtained metal precursor-containing layer was heat-treated (heat-baked) for 2 minutes in an oven at the temperature listed in the "Baking temperature (°C)" column in the table to form an aluminum plate with a metal layer 2.0 μm thick. The aluminum plate with the metal layer was cut into a rectangular shape measuring 1 cm x 10 cm, and then the aluminum plate was immersed in hydrochloric acid to remove the metal layer, thereby obtaining a rectangular thin film of the metal layer. The obtained rectangular thin film was slid at a constant speed in the longitudinal direction on a flat, low-friction table that was nearly horizontal to the ground, and the length of the part of the rectangular thin film that protruded from the edge of the table when the tip of the part protruding from the edge was sunk 1 cm below the table was compared with the length when a similar test was performed in Comparative Example 1, and the relative ratio was calculated. The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "Stress resistance evaluation" column in the table. -Evaluation criteria- A: The relative ratio was 1.5 or more. B: The relative ratio was 1.3 or more and less than 1.5. C: The relative ratio was 1.1 or more and less than 1.3. D: The relative ratio was less than 1.1. Example 2 An aluminum plate was used as the substrate. The composition 2 for forming a metal-containing member in Example 2 was applied onto the aluminum plate by spin coating. By repeating the above application, a metal precursor-containing layer having a thickness of 2 μm was produced. The aluminum plate with the metal precursor-containing layer was fired for 20 minutes in an electric furnace at the temperature shown in the "Firing temperature (°C)" column to obtain a transparent thin film of high-purity cobalt oxide on the aluminum plate. This was further fired for 2 hours at 550°C in a hydrogen gas atmosphere to obtain a thin film (metal layer) of high-purity metallic cobalt on the aluminum plate. The stress resistance was evaluated in the same manner and with the same evaluation criteria as in Examples 1, 3 to 13 and Comparative Example 1, except that a member in which a thin film of high-purity metallic cobalt was formed on the aluminum plate was used instead of the aluminum plate with a metal layer in Examples 1, 3 to 13 and Comparative Example 1. <Warp resistance evaluation> In each example or comparative example, a silicon wafer having a metal layer was prepared in the same manner as in the stress resistance evaluation, except that a silicon wafer was used instead of an aluminum plate and the number of coating repetitions was changed to a thickness such that the thickness of the metal precursor-containing layer obtained was 10 μm. The silicon wafer used was thinned to a thickness of 100 μm by polishing. The warpage of the silicon wafer was compared with the warpage when a similar test was performed in Comparative Example 1, and the relative ratio was calculated. The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column "Warpage resistance evaluation" in the table. [Evaluation criteria] A: The relative ratio was less than 0.7. B: The relative ratio was 0.7 or more and less than 0.8. C: The relative ratio was 0.8 or more and less than 0.9. D: The relative ratio was 0.9 or more.

[0090] From the above results, it is clear that the metal-containing member obtained from the composition for forming a metal-containing member of the present invention is a member having excellent stress resistance and warp resistance, and excellent strength.

[0091] Furthermore, as an example of a device having a heat dissipation member, a device having the configuration shown in FIG. 2 was fabricated. FIG. 2 is a schematic cross-sectional view showing a part of the configuration of a device having a heat dissipation member produced in an example. The device 10 shown in FIG. 2 includes a heat dissipation member 22 in contact with the cover plate 20 in order to dissipate heat generated from the semiconductor chip 12 to the outside of the device 10. In this example, the composition for forming a metal member used in any of Examples 1 to 17 was applied to a cover plate 20 and heated to produce a metal member as a heat dissipation member 22. The heating temperature and heating time were the same as those in the stress resistance evaluation described above. The semiconductor chip 12 and the heat dissipation member 22 are bonded together by an adhesive member 24. The semiconductor chip 12 and other functional parts present in devices such as other semiconductor chips are electrically connected together by a circuit pattern 18 formed on the circuit board 14 or by another circuit pattern (not shown) formed on the opposite side of the circuit board 11 from the circuit pattern 18. The circuit pattern 18 and the semiconductor chip 12 are electrically connected together by bumps 16. When such devices were fabricated, none of the semiconductor devices had any problems with performance. [Explanation of symbols]

[0092] 1: Base material 2: Metal-containing parts 3: Granular filler 4: Heat conducting member 5: Laminate 10: Device 12: Semiconductor chip 14: Circuit board 16: Bump 18: Circuit pattern 20: Cover plate 22: Heat dissipation material 24: Adhesive material E Thermal energy (heat dissipation)

Claims

1. A composition for forming a metal-containing member, comprising: a metal precursor; a granular filler; a primary amine compound represented by the following formula (A-1); and a solvent; and containing, as the granular filler, multiple types of particles in which the ratio of arithmetic mean diameters of the granular filler is 0.5:1 to 0.8:1 when calculated according to the method described in JIS Z 8901:2006: R １１ -CHR １２ -CH ２ -NH ２ ・・・(A-1) In formula (A-1), R １１ and R １２ each independently represents a hydrocarbon group having 1 to 12 carbon atoms.

2. The R １１ and the R １２ The composition for forming a metal-containing member according to claim 1 , wherein at least one of the groups is an ethyl group.

3. The composition for forming a metal-containing member according to claim 1 or 2, wherein the particulate filler contains an inorganic compound.

4. The composition for forming a metal-containing member according to any one of claims 1 to 3, wherein the solvent comprises water.

5. The composition for forming a metal-containing member according to any one of claims 1 to 4, wherein the metal precursor comprises a silver precursor.

6. The composition for forming a metal-containing member according to any one of claims 1 to 5, which is used for film formation.

7. The composition for forming a metal-containing member according to any one of claims 1 to 6, further comprising a reducing agent.

8. The composition for forming a metal-containing member according to any one of claims 1 to 7, wherein the arithmetic mean value of the diameter of the particulate filler is 0.2 to 1 µm when calculated according to the method described in JIS Z 8901:2006.

9. The composition for forming a metal-containing member according to any one of claims 1 to 8, which is used to form a heat-conducting member, a heat-dissipating member, a reflecting member, a decorative member, or a conductive member.

10. A metal-containing member obtained by converting the metal precursor in the composition for forming a metal-containing member according to any one of claims 1 to 9 into a metal.

11. An application step of applying the composition for forming a metal-containing member according to any one of claims 1 to 9 to a substrate to form a metal precursor-containing layer; a conversion step of converting the metal precursor contained in the metal precursor-containing layer into a metal, A method for manufacturing a metal-containing member.

12. The method for producing a metal-containing member according to claim 11, wherein the converting step comprises heating the metal precursor-containing layer at a temperature of 80°C to 150°C.

13. The method for producing a metal-containing member according to claim 11 or 12, wherein the thickness of the obtained metal-containing member is 1 to 500 μm.

14. A laminate comprising a substrate and the metal-containing member according to claim 10 disposed on the substrate.

15. A device comprising the metal-containing member according to claim 10 or the laminate according to claim 14.

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