JP2022138746A - Metal-containing member forming composition, metal-containing member, method for producing metal-containing member, laminate, and device - Google Patents

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 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 ART In recent years, metal-containing members have been used in electronic devices, for example, as heat conductive members, heat radiating members, reflective members, decorative members, conductive members, and the like.
It is expected that the demand for higher performance of electronic devices such as portable information terminals will increase in the future, and in order to meet this demand, there is a demand for further improvements in various physical properties of metal-containing members.

For example, in Patent Document 1, a solution of an alkylamine diluted with an organic solvent such as an aromatic hydrocarbon or other hydrocarbon and a group III to V group, VIII group, VIa group, VIIa group, or Ib group whose pH is adjusted in advance are described. , to extract the metal salt into an organic solvent layer by contacting it with an aqueous solution of a group IIb metal salt, and separate and remove the aqueous layer to obtain an organic solvent solution containing a metal alkylamine complex; The resulting organic solvent is evaporated away, and to the solution is added an organic solvent for substitution such as hydrocarbons, alcohols, esters, β-diketoesters, ethers, β-diketones, glycols, or a mixture thereof. A method for producing a thin film-forming composition is described.
Patent Document 2 discloses a film mirror manufacturing method for manufacturing a film mirror in which a reflective layer is provided on a film substrate, comprising a base layer on which the reflective layer is formed, and a coating liquid containing a silver complex compound. A reducing agent is contained in at least one of the above, and the coating liquid is applied to the base layer to form a coating film; and the coating film is heated and baked to form the reflective layer. A method of manufacturing a featured film mirror is described.

JP-A-11-269656 Japanese Patent Publication No. 2012-181301

The present invention provides a metal-containing member-forming composition capable of obtaining a metal-containing member having excellent strength, a metal-containing member obtained by converting the above-mentioned metal-containing member-forming composition into a metal, and the above-mentioned metal-containing member-forming composition. An object of the present invention is to provide a method for manufacturing a metal-containing member using a material, and a laminate and a device provided with the metal-containing member.

Examples of representative embodiments of the present invention are provided below.
<1> A composition for forming a metal-containing member, comprising a metal precursor, a particulate filler and a solvent.
<2> The composition for forming a metal-containing member according to <1>, wherein the particulate filler contains an inorganic compound.
<3> The composition for forming a metal-containing member according to <1> or <2>, wherein the solvent contains water.
<4> The composition for forming a metal-containing member according to any one of <1> to <3>, wherein the metal precursor contains a silver precursor.
<5> The composition for forming a metal-containing member according to any one of <1> to <4>, which is used for film formation.
<6> The composition for forming a metal-containing member according to any one of <1> to <5>, which contains a reducing agent.
<7> Any one of <1> to <6>, wherein the arithmetic mean value of the diameter of the particulate filler is 0.2 to 1 μm when calculated by the method described in JIS Z 8901: 2006 A composition for forming a metal-containing member as described.
<8> A plurality of types of particles having a ratio of arithmetic mean values of diameters of the above-mentioned particulate filler of 0.1:1 to 0.8:1 as calculated by the method described in JIS Z 8901:2006, The composition for forming a metal-containing member according to any one of <1> to <7>, including as the particulate filler.
<9> The composition for forming a metal-containing member according to any one of <1> to <8>, which is used for forming 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 <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 <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 <11>, wherein the converting step includes heating the metal precursor-containing layer at 80°C to 150°C.
<13> The method for producing a metal-containing member according to <11> or <12>, wherein the resulting metal-containing member has a thickness of 1 to 500 μm.
<14> A laminate comprising a substrate and the metal-containing member according to <10> disposed on the substrate.
<15> A device comprising the metal-containing member according to <10> or the laminate according to <14>.

According to the present invention, there is provided a metal-containing member-forming composition capable of obtaining a metal-containing member having excellent strength, a metal-containing member obtained by converting the above-mentioned metal-containing member-forming composition into a metal, and the above-mentioned metal-containing member-forming composition. Provided are a method for producing a metal-containing member using a composition for a metal-containing member, and a laminate and a device comprising the metal-containing member.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of the thermally-conductive member of this invention, and a laminated body. FIG. 4 is a schematic cross-sectional view showing a part of the configuration of a device having a heat dissipation member produced in Examples.

Hereinafter, representative embodiments of the present invention will be described. Each component is described based on this representative embodiment for convenience, but the present invention is not limited to such an embodiment.
In this specification, a numerical range represented by the symbol "to" means a range including the numerical values before and after "to" as lower and upper limits, respectively.
As used herein, the term "process" is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or unsubstituted means that not only those not having substituents but also those having substituents are included. For example, when simply describing an "alkyl group", this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). Meaning. Further, when simply described as an "alkyl group", it may be chain or cyclic, and in the case of chain, it may be linear or branched.
As used herein, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic", or , and “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.
As used herein, the solid content in the composition means other components excluding the solvent, and the solid content (concentration) in the composition is, unless otherwise stated, relative to the total mass of the composition, It is represented by the mass percentage of other components excluding the solvent.
In this specification, the temperature is 23° C. and the pressure is 101325 Pa (1 atm) unless otherwise specified.
Combinations of preferred aspects are more preferred aspects herein.

<Composition for Forming Metal-Containing Member>
A composition for forming a metal-containing member of the present invention comprises 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 metal obtained by converting a metal precursor and a particulate filler is formed.
Moreover, the composition for forming a metal-containing member of the present invention is preferably used for film formation. Preferably, the film contains a metal and a particulate filler obtained by converting a metal precursor.
Details of a method for forming a metal-containing member (for example, the above-described film) using the composition for forming a metal-containing member of the present invention will be described later.
The metal-containing member-forming composition is not particularly limited, but is preferably used for forming 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 metal-containing member-forming composition is not particularly limited, but is preferably a heat conductive member, a heat radiating member, a reflective member, a decorative member, or a conductive member.

Here, it is known to form a metal-containing member using a composition containing a metal precursor and a solvent, as described in Patent Documents 1 and 2, for example.
The inventors have found that when a metal-containing member is formed using a conventional composition comprising a metal precursor and a solvent, the resulting member is susceptible to stress, e.g. It has been found that there is a problem that warping due to shrinkage occurs in a mode with a large thickness.
As a result of intensive studies, the inventors of the present invention have found that a metal-containing member with 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 effect is obtained are unknown, when the member contains the particulate filler, the stress resistance of the metal-containing member itself increases, making it difficult to bend when the thickness is small. Warping due to shrinking is thought to be suppressed because the effect of volume change during conversion to metal is reduced.
In addition, conventionally, for the purpose of improving the strength of a member containing a metal, it is also known to form a hybrid material, such as using a metal-containing member in combination with another member, but the composition of the present invention is used. As a result, there is also the advantage that damage to the adherend due to heat or the like can be suppressed.
Here, neither Patent Documents 1 nor 2 describes or suggests the use of a granular filler.
Details of each component contained in the composition for forming a metal-containing member of the present invention are described below.

[Metal precursor]
The metal precursor is not particularly limited as long as it is a compound that can be converted into a metal by chemical or physical treatment, but is preferably a compound that can be converted into a metal by heating. salt.
The ligand preferably has a boiling point of 150° C. or lower, more preferably 120° C. or lower, at 1 atm of the conjugate acid of the ligand.
Examples of the ligands 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; fluorine, chlorine, bromine, and iodine; halogen atoms such as, oxygen atoms, and the like.

The metal contained in the metal precursor is not particularly limited, and examples thereof include silver, copper, gold, platinum, cobalt, palladium, nickel, zinc, aluminum, tin, and iron.
These metal species may be selected according to the use of the metal-containing member, and silver, for example, is preferable.
That is, the metal precursor is preferably a silver precursor.

Metal precursors include organic acid salts of metals such as acetates, formates, oxalates, lactates, trifluoroacetates and acetylacetates, carbonates, phosphates, nitrates, nitrites and cyanates. , thiocyanates, and perchlorates, metal halides such as fluorides, chlorides, bromides, 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, chloride Silver, silver bromide, silver iodide, silver phosphate, silver trifluoroacetate, silver acetylacetate, silver sulfate, silver oxide and the like.
Among these, silver carbonate, silver acetate and silver oxide are preferred.

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

[Granular filler]
The composition for forming a metal-containing member of the present invention contains a particulate filler.
The shape of the particulate filler is not particularly limited, and may be fibrous, plate-like, scale-like, rod-like, spherical, tube-like, curved plate-like, or needle-like. There may be.
In addition, the particulate filler may be hollow or solid, and may have a multi-layered structure such as a core-shell structure, or a porous structure.

The particulate filler may be an inorganic compound, an organic compound, or hybrid particles of an inorganic compound and an organic compound, but an inorganic compound is preferred.
Granular fillers that are inorganic compounds include silicon compounds such as silica, silicates, and silicates; alumina, zinc oxide, magnesium oxide, antimony oxide, titanium oxide, beryllium oxide, zirconium oxide, copper oxide, cuprous oxide, Metal oxides, 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, etc. is mentioned.
Also, a structure in which a semiconductor or conductive thermally conductive particles are coated or surface-treated with an electrically insulating material such as silica may be used. According to such an aspect, it becomes easier to control the thermal conductivity and the electrical insulation individually, so it may be easier to adjust the thermal conductivity and the electrical insulation. For example, methods for forming a silica film on the surface include a water glass method and a sol-gel method.
Among these, the particulate filler is preferably a compound containing no metal, more preferably a silicon compound, and more preferably silica particles.
Granular fillers that are organic compounds include polystyrene, polystyrene/divinylbenzene copolymer, polymethyl (meth)acrylate, crosslinked polymethyl (meth)acrylate, styrene/acrylic copolymer, melamine/formaldehyde condensate, and benzoguanamine/formaldehyde condensation. benzoguanamine/melamine/formaldehyde condensates and the like.
Examples of hybrid particles of an inorganic compound and an organic compound include, for example, an organic polymer layer (for example, the resins exemplified as the above organic compounds) on the surface of particles made of an inorganic compound such as silica particles or metal particles (such as the metal oxides described above). and particles forming a layer containing.

Further, the granular filler may be subjected to surface treatment such as silane coupling treatment, titanate coupling treatment, epoxy treatment, urethane treatment, and oxidation treatment. Surface treatment agents used for surface treatment include, for example, polyol, aluminum oxide, aluminum hydroxide, silica (silicon oxide), hydrated silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, silane coupling agent, Titanate coupling agents and the like.

Commercially available products may be used as the granular filler, and commercially available products include Seahoster (registered trademark) KE-E10, KE-E30, KE-E150, KE-W10, KE-W30, KE-W50, and 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, Eposter (registered trademark) MX020W, MX030W, MX050W, MX100W, MX200W, MX300W, MS, M05, L15, M30, SS, S, FS, S6, S12 (above, all Nippon Shokubai ( Co., Ltd.) and the like.

From the viewpoint of improving the strength of the obtained metal-containing member, the arithmetic mean value of the diameter of the particulate filler when calculated by the method described in JIS (Japanese Industrial Standards) Z 8901: 2006 is 0.05 to It is preferably 20 μm, more preferably 0.1 to 10 μm, 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, one of them may be within the above range, and all of them are within the above range. is one of

Further, from the viewpoint of improving the strength of the obtained metal-containing member, when the composition for forming a metal-containing member of the present invention contains two or more kinds of particulate fillers, the ratio of the arithmetic mean values of the diameters of the particulate fillers is It is preferable that a plurality of types of particles with a ratio of 0.1:1 to 0.8:1 be included as the particulate filler.
The ratio is preferably 0.3:1 to 0.8:1, more preferably 0.5:1 to 0.8:1.
By adopting such a configuration, it is speculated that small particles are embedded between large particles and the strength is further improved. In addition, it is believed that the distance between the particulate fillers is reduced and the number of contact points is increased compared to the case where only particulate fillers having a single diameter are included, so that, for example, the thermal conductivity of the metal-containing member is improved.
When the composition for forming a metal-containing member of the present invention contains three or more kinds of particulate fillers, at least one combination in which the ratio of the arithmetic mean values of the diameters of the particulate fillers is within the above range is sufficient.

The Vickers hardness of the material of the granular filler is preferably 0.1 to 100 GPa, more preferably 1 to 50 GPa, even more preferably 5 to 30 GPa.

For example, when the metal-containing member is used as a heat-conducting member, a heat-dissipating member, or the like, the particulate filler is preferably heat-conducting.
The thermal diffusivity of the granular filler is, for example, 1.0×10 ⁻⁶ m ² s ⁻¹ or more, preferably 2.0×10 ⁻⁶ m ² s ⁻¹ or more, and 3.0× 10 ⁻⁶ m ² s ⁻¹ or more is particularly preferred. Although the upper limit of the thermal diffusivity of the granular filler is not particularly limited, it is practically 1.0×10 ⁻⁴ m ² s ⁻¹ or less.

The density (true specific gravity) of the granular filler is, for example, 10.0 g/cm ³ or less, more preferably 5.0 g/cm ³ or less. Although the lower limit of the density of the granular filler is not particularly limited, it is preferably 1.0 g/cm ³ or more, for example. In addition, in the case where the granular filler has voids or cavities such as porous or hollow particles, in this specification, the density of the granular filler means means density of solids.

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

〔solvent〕
The composition for forming a metal-containing member of the present invention contains a solvent.
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 -pyrrolidone, 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.), alkyloximes (acetone oxime, dimethylglyoxime, 2-butanone oxime, 2,3-butadione monoxime, etc.), Acetonitrile, dimethylsulfoxide, or a mixed solvent thereof can be used.
Among these, the composition for forming a metal-containing member of the present invention preferably contains water as a solvent.

The content of the solvent in the composition for forming a metal-containing member is preferably such that the ratio of the total solid content to the total weight of the composition for forming a metal-containing member is 5 to 70 mass%, preferably 10 to 60 mass. %, more preferably 20 to 50% by 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.
Also, the content of water 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. An embodiment in which the content of water is 90% by mass or more (further, 95% by mass or more) relative to the total mass of the solvent is also one of the preferred embodiments of the present invention. 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.

[Reducing agent]
The composition for forming a metal-containing member of the present invention preferably further contains a reducing agent.
Inclusion of a reducing agent may facilitate conversion of the metal precursor to metal.
The reducing agent may be inorganic compounds such as metal salts such as sodium, potassium borohydride, ferrous chloride and iron sulfate, hydrogen iodide and carbon monoxide, or organic compounds. , 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, glucose, ascorbic acid, salicylic acid, and tannic acid. organic compounds such as acid), pyrogallol, hydroquinone; metal salts such as sodium, potassium boron hydroxide, ferrous chloride, iron sulfate; and inorganic compounds such as hydrogen iodide and carbon monoxide.

式（Ｒ－１）中、Ｒ^１は水素原子、又は、１つ以上のアルデヒド基を有する１価の有機基を表す。
Ｒ^１としては、水素原子、アルデヒド基、１つ以上のアルデヒド基を有する炭素数１～２０のアルキル基、１つ以上のアルデヒド基を有する炭素数５～２０のアリール基、１つ以上のアルデヒド基を有するアミノ基、１つ以上のアルデヒド基を有する炭素数５～２０のヘテロ環基等が挙げられる。好ましくは、水素原子、アルデヒド基、１つ以上のアルデヒド基を有するメチル基、１つ以上のアルデヒド基を有するエチル基、１つ以上のアルデヒド基を有するベンゼン環であり、より好ましくは水素原子である。
式（Ｒ－１）で表される化合物としては、ギ酸、２－メチル－３－オキソプロパン酸、３－オキソプロパン酸、フタルアルデヒド酸、イソフタルアルデヒド酸、テレフタルアルデヒド酸等が挙げられる。 It is also preferable to use a compound represented by the following formula (R-1) as the reducing agent.

In formula (R-1), R ¹ represents a hydrogen atom or a monovalent organic group having one or more aldehyde groups.
R ¹ is a hydrogen atom, an aldehyde group, an alkyl group having 1 to 20 carbon atoms having one or more aldehyde groups, an aryl group having 5 to 20 carbon atoms having one or more aldehyde groups, and one or more aldehydes. an amino group having a group, a heterocyclic group having 5 to 20 carbon atoms having one or more aldehyde groups, and the like. 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, more preferably a hydrogen atom. be.
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.

The content of the reducing agent with respect to the total solid content of the composition for forming a metal-containing member is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.5 to 5% by mass. More preferably, it is 3% by 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.

[Amine compound]
The composition for forming a metal-containing member of the present invention preferably contains an amine compound.
At least part of the amine compound may form a complex with the metal precursor described above in the metal-containing member-forming composition.
By including the 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 composition for forming a metal-containing member can be stored stably. may improve performance.

As the amine compound, organic amines are preferable, and alkylamines are more preferable.

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 number of carbon atoms in the alkyl group is, for example, preferably 1-20, preferably 1-10, more preferably 2-10.
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, isobutyl group, sec-butyl group, pentyl group, isopentyl group, cyclohexyl group and cyclopentyl group. be done.
The alkylamine may be a primary, secondary or tertiary amine, preferably a primary or secondary amine, more preferably a primary amine.
The number of carbon atoms in the alkylamine is preferably 1-20, more preferably 2-10, even more preferably 3-8.

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

Amine compounds include, but are not limited to, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, isoamylamine, n-hexylamine, 2-ethylhexylamine, n-heptylamine, n-octyl Amine, isooctylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, docodecylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, arylamine, hydroxylamine, ammonium hydroxide, methoxyamine, 2-ethanol Amine, propanolamine, butanolamine, hexanolamine, dimethylethanolamine, methoxyethylamine, ethoxyethylamine, 2-hydroxypropylamine, 2-hydroxy-2-methylpropylamine, methoxypropylamine, cyanoethylamine, ethoxyamine, n-butoxy Amine, 2-hexyloxyamine, methoxyethoxyethylamine, methoxyethoxyethoxyethylamine, dimethylamine, diethylamine, dipropylamine, diethanolamine, hexamethyleneimine, morpholine, piperidine, N-methylpiperidine, piperazine, N,N'-dimethylpiperazine , 1-amino-4-methylpiperazine, pyrrolidine, N-methylpyrrolidine ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, 2,2-(ethylenedioxy)bisethylamine, triethylamine, triethanolamine, pyrrole, imidazole, pyridine , aminoacetaldehyde dimethylacetal, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aniline, anisidine, aminobenzonitrile, benzylamine and its derivatives, polymeric compounds such as polyarylamine and polyethyleneimine, and Derivatives thereof and the like can be mentioned.

Among them, as the amine compound, a primary amine compound represented by the following formula (A-1) branched at the β-position is preferable.
R ¹¹ —CHR ¹² —CH ₂ —NH ₂ (A-1)
In formula (A-1), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 12 carbon atoms.

The hydrocarbon group having 1 to 12 carbon atoms represented by R ¹¹ and R ¹² 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, such as methyl group, ethyl group, propyl group, butyl group and the like.
Examples of substituents of the substituted alkyl group include aryl groups (eg, phenyl group, naphthyl group), alkoxy groups (methoxy group, ethoxy group, etc., preferably having 1 to 4 carbon atoms), halogen atoms (eg, chlorine atom, bromine atom). etc.), cyano group, amino group, heterocyclic group (e.g., nitrogen-containing heterocyclic groups such as pyrrolidine ring, pyrrole ring and imidazole ring, and cyclic groups such as oxygen-containing heterocyclic groups such as furan ring and tetrahydrofuran ring), etc. is mentioned.
Examples of substituted alkyl groups include arylalkyl groups (1 to 4 carbon atoms in the alkyl moiety), cyanoalkyl groups (1 to 4 carbon atoms in the alkyl moiety), and halogenated alkyl groups (1 to 4 carbon atoms in the alkyl moiety). , cycloolefin-linked alkyl are preferred.
Among the above, at least one of R ¹¹ and R ¹² is preferably an ethyl group. The reason for this point is not necessarily clear and is speculated, but the two carbon atoms of the ethyl group and the nitrogen and hydrogen atoms of the amino group form a six-membered ring, so that the HOMO extends from the nitrogen atom to the ethyl group. It is believed that the widening stabilizes the complex formation.
More preferably, R ¹¹ is a butyl group and R ¹² is an ethyl group.

Examples of compounds represented by general formula (A-1) include the following compounds.
Among them, isobutylamine, 2-ethylbutylamine and 2-ethylhexylamine are preferred, and 2-ethylbutylamine and 2-ethylhexylamine are more preferred.

The molecular weight of the primary amine compound represented by formula (A-1) is preferably in the range of 70-400, more preferably in the range of 80-300, and particularly preferably in the range of 90-200. 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.

The content of the amine compound with respect to the total solid content of the composition for forming a metal-containing member may be appropriately determined in consideration of the solubility of the metal precursor and the like. % by mass is more preferred, and 30 to 80% by mass is even more preferred.
The composition for forming a metal-containing member may contain two or more amine compounds, and when two or more amine compounds are contained, the total amount thereof is preferably within the above range.

式（Ｃ－１）～式（Ｃ－３）において、Ｒ^１～Ｒ^６は、それぞれ独立に、水素原子、炭素数１～３０の脂肪族アルキル基、脂環族アルキル基、アリール基又はアラルキル基、官能基が置換されたアルキル、官能基が置換されたアリール基、ヘテロ環化合物基と高分子化合物及びその誘導体から選択される置換基を表す。 [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 amine compound described above.
At least part of the other complexing agent may form a complex with the metal precursor described above in the metal-containing member-forming composition.
Other complexing agents include ammonium carbamate compounds and ammonium carbonate compounds.
As the ammonium carbamate-based compound or the ammonium carbonate-based compound, compounds represented by any of the following formulas (C-1) to (C-3) are preferred.

In formulas (C-1) to (C-3), R ¹ to R ⁶ each independently represents a hydrogen atom, an aliphatic alkyl group having 1 to 30 carbon atoms, an alicyclic alkyl group, an aryl group or an aralkyl represents a substituent selected from a group, a functional group-substituted alkyl group, a functional group-substituted aryl group, a heterocyclic compound group, a polymer compound, and derivatives thereof.

Specific examples of the compounds represented by formulas (C-1) to (C-3) include ammonium carbamate, ammonium carbonate, ammonium bicarbonate, and ethylammonium ethylcarbamate. , isopropylammonium isopropylcarbamate, n-butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate, 2-ethylhexylammonium 2-ethylcarbamate, octadecylammonium octadecyl carbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimine ammonium hexamethyleneimine carbamate, morpholinium morpholine carbamate, pyridium ethylhexylcarbamate, triethylenediaminium isopropyl bicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate, ethylammonium ethyl carbonate, isopropylammonium isopropyl carbonate, isopropylammonium bicarbonate, n-butylammonium n-butylcarbonate, isobutylammonium isobutylcarbonate, t-butylammonium t-butylcarbonate, t-butylammonium bicarbonate, 2-ethylhexylammonium 2-ethylhexylcarbonate, 2-ethylhexylammonium bicarbonate, 2-methoxyethyl ammonium 2-methoxyethyl carbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium 2-cyanoethyl carbonate, 2-cyanoethylammonium bicarbonate, octadecylammonium octadecyl carbonate, dibutylammonium dibutyl carbonate, dioctadecylammonium dioctade Silic carbonate, dioctadecylammonium bicarbonate, methyldecylammonium methyldecyl carbonate, hexamethyleneimine ammonium hexamethyleneimine carbonate, morpholine ammonium morphocarbonate, 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. Moreover, the present invention is not limited to the above specific examples.

In addition, the type and manufacturing method of the ammonium carbamate-based compound or the ammonium carbonate-based compound are not particularly limited. For example, US Pat. No. 4,542,214 describes that ammonium carbamate compounds can be prepared from primary amines, secondary amines, tertiary amines, or mixtures of at least one or more thereof and carbon dioxide. ing. If 0.5 mol of water is further added to 1 mol of amine, an ammonium carbonate-based compound can be obtained, and if 1 mol or more of water is added, an ammonium bicarbonate-based compound can be obtained. At this time, it can be directly prepared without using a special solvent under normal pressure or pressurized state, or it can be prepared using a solvent. When using a solvent, 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, diethyl ether, tetrahydrofuran, dioxane, etc. Ethers, ketones such as methyl ethyl ketone and acetone, hydrocarbons such as hexane and heptane, aromatics such as benzene and toluene, halogen-substituted solvents such as chloroform, methylene chloride, and carbon tetrachloride, or mixed solvents thereof. be able to.
Carbon dioxide can be bubbling in the gas phase, or solid phase dry ice can be used, and can participate in the reaction even in supercritical conditions.
In addition to the above methods, any known method may be used for the production of the ammonium carbamate derivative or the ammonium carbonate derivative as long as the structure of the final substance is the same. That is, the solvent, reaction temperature, concentration, catalyst, etc. for production do not need to be particularly limited, and do not affect the production yield.

[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.

Stabilizers include, for example, phosphorus compounds such as phosphines, phosphites, phosphates, sulfur compounds such as thiols and sulfides, and mixtures thereof.
Phosphorus compounds include, for example, phosphorus compounds represented by general formulas R ₃ P, (RO) ₃ P, and (RO) ₃ PO. Here, R represents an alkyl group or an aryl group having 1 to 20 carbon atoms, and specific examples thereof include tributylphosphine, triphenylphosphine, triethylphosphite, triphenylphosphite, dibenzylphosphate, triethylphosphate and the like. .
Specific examples of sulfur compounds include butanethiol, n-hexanethiol, diethylsulfide, tetrahydrothiophene, aryldisulfide, 2-mercaptobenzazole, tetrahydrothiophene, and octylthioglycolate.
The content of the stabilizer is not particularly limited, but it is preferably in a molar amount of 0.1 to 90% with respect to the molar amount of the metal precursor content.
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.

Thin film auxiliaries 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 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. , 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, Th, manganese oxalate, gold acetate, palladium oxalate, silver 2-ethylhexanoate, silver octanoate, silver neodecanoate , cobalt stearate, nickel naphthalate, and cobalt naphthalate.
Although the content of the thin film auxiliary agent is not particularly limited, it is preferably in a molar amount of 0.1 to 25% with respect to the molar amount contained in the metal precursor.
The composition for forming a metal-containing member may contain two or more thin film auxiliary agents, and when two or more kinds are contained, the total amount thereof is preferably within the above range.

Specific examples of thermal decomposition reaction accelerators include polyhydric phenol compounds, phenolic resins, alkyd resins, pyrroles, and oxidative polymerizable resins such as ethylenedioxythiophene (EDOT).
The content of the thermal decomposition reaction accelerator with respect to the total solid content of the composition for forming a metal-containing member is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and 0 .2 to 5% by mass is more preferable.
The composition for forming a metal-containing member may contain two or more thermal decomposition reaction accelerators, and when it contains two or more, the total amount thereof is preferably within the above range.

As the surfactant, various surfactants such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants and silicone surfactants can be used.

By including a surfactant in the composition for forming a metal-containing layer of the present invention, it is possible to further improve the uniformity and liquid-saving properties of the metal precursor-containing layer to be formed. 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 surface to be coated and the composition decreases, The wettability to the coating surface is improved, and the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.

The surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
Only one type of surfactant may be used, 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.

[Method for preparing composition]
The compositions described above can be prepared by mixing the ingredients described above.
In preparing the composition, each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then blended successively. In addition, there are no particular restrictions on the order of addition or working conditions when blending.
For example, after forming a metal complex by reacting a metal precursor with an amine compound or other complexing agent in a solvent, other components such as particulate fillers and reducing agents may be added.

Moreover, you may perform the process of dispersing a granular filler. The step of dispersing the particulate filler includes a step of using compression, squeezing, impact, shearing, cavitation, etc. as mechanical force used for dispersing the particulate 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, ultrasonic dispersion, and the like. In addition, "Comprehensive Dispersion Technology, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion Technology Centered on Suspension (Solid/Liquid Dispersion System) and Actual Industrial Applications Comprehensive Materials Collection, Management Development Center Publishing ed., Oct. 10, 1978" can be suitably used.

Stirring of the composition can be performed using, for example, a stirrer (stirring element) or a stirring blade. The rotation speed is preferably 10 to 2000 rpm, for example. 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 a method such as bubbling or ultrasonic waves.

Conventionally known containers can be used as containers for the composition of the present invention. In addition, in order to suppress the contamination of raw materials and compositions with impurities, the storage container is a multi-layer bottle whose inner wall is made of 6 types and 6 layers of resin, and 6 types of resin are used in a 7-layer structure. It is also preferred to use a bottle that has been sealed. Examples of such a container include the container described in JP-A-2015-123351.

In preparing the composition, the composition may be filtered with a filter for the purpose of removing foreign substances and reducing defects. Any filter that is conventionally used for filtration can be used without particular limitation. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyethylene, polyolefin resins such as polypropylene (PP) (high density, ultra high molecular weight (including those of ) and the like. Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore size of the filter is suitably about 0.01-100 μm, preferably about 0.1-50 μm, more preferably about 1-30 μm. By setting the content within this range, it is possible to reliably remove fine foreign matter that hinders the preparation of a uniform composition in the subsequent steps. It is also preferable to use a fiber-like filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. As the fiber filter medium, for example, filter cartridges of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd. can be used.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once, or may be performed twice or more. For example, filtering with the first filter may be performed only on the dispersion containing the particulate filler, and the other components may be mixed before filtering with the second filter.

Also, the first filters having different pore diameters within the range described above may be combined. The pore size here can refer to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by Nippon Pall Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can do.

The second filter can be made of the same material as the first filter described above.

(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.
A method for converting a metal precursor into a metal is not particularly limited, but heating and the like can be mentioned.
Although the metal-containing member of the present invention is not particularly limited, it is preferably a heat conductive member, a heat radiating member, a reflective member, a decorative member, or an electrically conductive member.

<Heat conducting member, heat radiating member>
A case where the metal-containing member of the present invention is a heat-conducting member will be described below.
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, the heat-conducting member 4 of the present invention has a structure in which a particulate 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 thus has excellent strength.
Here, for example, when the heat source is on the side of the base material 1, the thermal energy E transmitted to the heat conducting member 4 is transmitted through the metal-containing member 2 to the side of the metal-containing member 2 opposite to the side on which the base material 1 exists. released to

The thermal diffusivity of the heat conducting member is preferably 3.0×10 ⁻⁷ m ² s ⁻¹ or more, particularly preferably 1.0×10 ⁻⁶ m ² s ⁻¹ or more. Although the upper limit of the thermal diffusivity of the heat conducting member is not particularly limited, it is, for example, 1.0×10 ⁻⁴ m ² s ⁻¹ or less.
Since such a heat conductive member has excellent thermal conductivity, it can be suitably used as a heat conductive member for devices such as LSI devices.
A heat conducting member similar to the heat conducting member shown in FIG. 1 can also be used as a heat radiating member. The preferred configuration and preferred thermal diffusivity of the heat radiating member in that case are the same as in the case of the heat conducting member.
When the metal-containing member of the present invention is a heat radiating member, it can be used as, for example, a conductive heat radiating member disclosed in JP-A-2012-231169, although it is not particularly limited.

A method for manufacturing 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 the metal precursor-containing layer. A conversion step is included to convert the metal precursor to the metal.
Details of each step will be described below.

<Applied process>
In the applying 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 of applying the metal-containing member-forming composition in the application step include spin coating, bar coating, spray coating, slit coating, spiral coating, screen printing, inkjet, cast coating, and roll coating. method and drop method (drop casting). Among these, the spin coating method, the bar coating method, the spray coating method or the slit coating method is preferable, and the spin coating method is more preferable.

The thickness of the metal precursor-containing layer (eg, coating thickness) is preferably 0.2 to 50 μm. The lower limit of this numerical range is more preferably 0.5 μm or more, further preferably 1.0 μm or more. Moreover, the upper limit of this numerical range is more preferably 35 μm or less, and even more preferably 20 μm or less.
The film thickness of the metal precursor-containing layer can be adjusted, for example, by selecting an application method or by performing multiple applications.

〔Base material〕
The base material is not particularly limited and is appropriately selected according to the application. Examples of substrates include transparent substrates used in liquid crystal display devices, light emitting devices, solid-state imaging devices, semiconductor memories, thermally conductive sheets, metal substrates, substrates having metal wiring, metal substrates, semiconductors used in ceramic substrates, etc. A substrate or the like can be used. Examples of the transparent substrate include quartz glass, alkali-free glass, soda glass, borosilicate glass, aluminosilicate glass, and resin. Other structures such as a transparent conductive film, a reflective film and a protective film may be formed on these transparent substrates. In addition, the semiconductor substrate includes, 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 and the like. Other structures such as PN junction layers, light emitting layers, photoelectric conversion layers, complementary metal oxide semiconductor (CMOS) layers and electrode layers may be formed on these semiconductor substrates. In addition, if necessary, an undercoat layer may be provided on these substrates for the purpose of improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface. In addition, the undercoat layer may contain the aforementioned reducing agent, amine compound, etc., in order to promote conversion of the metal precursor to metal.

The shape of the substrate may be planar, diffuse, concave, convex, or any other shape.
Further, the substrate may be surface-treated in advance.
Surface treatments include UV irradiation, ozone treatment, plasma treatment, corona treatment, flame treatment, and other treatments that decompose and activate the surface, and alkaline solutions such as hydrazine, N-methylpyrrolidone, sodium hydroxide solution, and potassium hydroxide solution. and treatment with acidic solutions such as sulfuric acid, hydrochloric acid, and nitric acid. Examples of the treatment for cleaning the substrate surface by removing stains include treatment with organic solvents such as methanol, ethanol, toluene, ethyl acetate and acetone, and water washing for removing adhering dust. These surface treatments may be performed in combination of multiple types.

Moreover, in the application step, the metal precursor-containing layer may be dried.
The drying method is not particularly limited, but drying by heating, reduced pressure, or the like can be mentioned.
A drying means is not particularly limited, and a known heating device, decompression device, or the like can be used.
Further, when the conversion step described later is performed by heating, drying may not be performed in the application step, and drying of the metal precursor-containing layer and conversion of the metal precursor to metal may be performed simultaneously in the conversion step.

<Conversion process>
In the conversion step, the metal precursor contained in the metal precursor-containing layer is converted into metal.
The conversion method is not particularly limited, but conversion by heating (firing) is preferred. That is, the converting 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 a metal.
The heating temperature may be determined in consideration of the types of components such as the metal precursor and the reducing agent, and is not particularly limited. °C is more preferred.
The heating time may be determined in consideration of the types of components such as the metal precursor and the 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, and examples thereof include hot plates, electric furnaces, infrared furnaces, electric heating ovens, hot air ovens, infrared ovens, and the like.

Heating may be done in stages. Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

<Other processes>
The method of manufacturing 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 performed after the converting step, but can also be performed before the converting step or after the applying step.
The overcoat layer includes, for example, a layer containing the aforementioned reducing agents, amine compounds, other complexing agents, etc. for promoting conversion of the metal precursor to metal.
Also, as the topcoat layer, a layer having functions such as insulation, conductivity, refractive index adjustment, and heat conduction may be formed.

In addition, the method for manufacturing the metal-containing member of the present invention may further include a step known in the art, such as a surface treatment step for the metal-containing member.

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

(Laminates and devices)
A laminate of the present invention comprises a substrate and a metal-containing member of the present invention formed on the substrate.
Other layers such as an undercoat layer may be provided between the substrate and the metal-containing member.
Further, the side of the metal-containing member opposite to the substrate may have another layer such as a topcoat layer.
The laminate may also include multiple layers of metal-containing members.
Moreover, when the metal-containing member is a heat-conducting member, the laminate of the present invention may further have a heat-absorbing portion in contact with the heat-conducting member. The heat absorbing part is a cooling module, such as a radiation fin, a heat pipe, a Peltier module, or a cooling plate.

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.

The present invention can also be applied to logic integrated circuits such as ASIC (Application Specific Integrated Circuit), FPGA (Field Programmable Gate Array), and ASSP (Application Specific Standard Product). The present invention is also applicable to microprocessors such as CPUs (Central Processing Units) and GPUs (Graphics Processing Units). Further, the present invention provides, for example, DRAM (Dynamic Random Access Memory), HMC (Hybrid Memory Cube), MRAM (Magnetoresistive Random Access Memory), PCM (Phase-Change Memory), ReRAM (Resistance Random Access Memory), FeRAM (Ferroelectric Random Access Memory), flash memory, and other memories. The present invention also applies 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). Applicable. The present invention is also applicable to MEMS (Micro Electro Mechanical Systems) such as acceleration sensors, pressure sensors, vibrators, and gyro sensors. Further, the present invention includes, for example, 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) Wireless elements, discrete elements, CMOS (Complementary Metal Oxide Semiconductor), CMOS image sensors, camera modules, passive devices, SAW (Surface Acoustic Wave) filters, RF (Radio Frequency) filters, IPD (Integrated Passive Devices), etc. Applicable.
The metal-containing member of the present invention can be applied to these devices, for example, as a heat conducting member, a heat radiating member, a reflecting member, a decorative member, or a conducting member.

The final product on which the semiconductor device of the present invention as described above is mounted is not particularly limited, and examples include smart TVs, mobile communication terminals, mobile phones, smartphones, tablet terminals, desktop PCs, notebook PCs, and 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 support systems) ), car navigation, PND, lighting (general lighting, vehicle lighting, LED lighting, OLED lighting), TV, display, display panel (liquid crystal panel, organic EL panel, electronic paper), music playback terminal, industrial equipment, industrial use Robots, inspection equipment, medical equipment, white goods, space or aircraft equipment, wearable devices, etc.

When the metal-containing member of the present invention is a heat-conducting member, it can be applied, for example, to a junction between a heat source such as a battery or a substrate and a component such as a cooling module (heat pipe or the like) or the housing of an electronic device. Furthermore, when the metal-containing member of the present invention is a heat-conducting member, it can be applied to joining parts such as automotive electronic devices, batteries, and power converters to cooling devices using an air-cooling mechanism or a water-cooling mechanism. be.
Moreover, when the metal-containing member of the present invention is a heat-conducting member or a heat-dissipating member, it can be used as a heat-dissipating fin, for example.

EXAMPLES The present invention will be described in more detail below with reference to examples. Materials, usage amounts, proportions, treatment details, treatment procedures, etc. shown in the examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In the examples, "parts" and "%" are based on mass unless otherwise specified, and the environmental temperature (room temperature) in each step is 23°C.
Further, hereinafter, "composition 1 for forming a metal-containing member" and the like are also simply referred to as "composition 1" and the like.

<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. The reaction was carried out at room temperature. This reaction solution was initially a black suspension, but it was observed that as the reaction proceeded and a complex compound was formed, the color gradually faded and turned transparent. After reacting for 2 hours, a colorless and transparent solution was obtained.
After adding 2.5 g of 2-hydroxy-2-methylpropylamine, 85.0 g of n-butanol and 50.0 g of amyl alcohol to this solution and stirring, hydrazine was added in an amount corresponding to 0.5% by mass of the total solution. was added, filtered using a 0.45 micron membrane filter, and thermally analyzed to produce Comparative Composition 1 with a silver content of 5.0% by weight.

<Preparation of composition 1 for forming metal-containing member>
Seahoster KE-E30 (manufactured by Nippon Shokubai Co., Ltd., solid content 20%) and KE-E150 (manufactured by Nippon Shokubai Co., Ltd., solid content 20%) are added to 100 parts by mass of the comparative composition 1. 12.5 parts by mass was added to obtain composition 1 for forming a metal-containing member (composition 1).

<Preparation of composition 2 for forming metal-containing member>
A solution was prepared by dissolving 3.8 g of cobalt chloride in 50 g of water and adding 24.6 g of 35% by mass hydrochloric acid therein. A solution of 15.8 g of trioctylamine in 40 g of xylene was added to the above solution and heated to 60° C. while stirring.
A water layer and a solvent layer were separated, only the solvent layer was taken out, and the xylene solvent was distilled off to obtain a precursor composition.
To 100 parts by mass of the precursor composition, 7 parts by mass of Zircostar ZP-153 (manufactured by Nippon Shokubai Co., Ltd., solid content 70%) was added to form a metal-containing member-forming composition 2 (composition 2). did.

<Preparation of Compositions 3 to 17 for Forming Metal-Containing Member>
Each material was blended so as to achieve the blending ratio (parts by mass) described in the "Composition" column of the table below. Specifically, after mixing and stirring the metal precursor, solvent and additive described in the table, the granular filler and reducing agent described in the table are added and further mixed to obtain a composition for forming a metal-containing member. 3-17 (compositions 3-17) were obtained.

Details of the components used in the table are as follows.

[Granular filler]
・ Seahoster KE-W30 (solid content 20%): silica particles, manufactured by Nippon Shokubai Co., Ltd., particle size 0.3 μm
・ Seahoster KE-W50 (solid content 20%): silica particles, manufactured by Nippon Shokubai Co., Ltd., particle size 0.5 μm
・ Seahoster KE-W10 (solid content 15%): silica particles, manufactured by Nippon Shokubai Co., Ltd., particle size 0.1 μm
Eposter MX050W (solid content 10%): acrylic crosslinked resin, manufactured by Nippon Shokubai Co., Ltd., particle size 70 nm
・Bilar Al-L7 (solid content 7%): alumina particles, manufactured by Taki Chemical Co., Ltd., particle size 5 to 10 nm
・ DIF-AB-33W (solid content 60%): zinc oxide particles, manufactured by Sakai Chemical Industry Co., Ltd., particle size 35 nm
As described above, the particle diameter is the arithmetic mean value of the diameter of the particulate filler calculated by the method described in JIS Z 8901:2006.
Seahoster, Eposter, and DISPAL are registered trademarks.

(evaluation)
<Stress resistance evaluation>
[Examples 1, 3 to 13 and Comparative Example 1]
An aluminum plate was used as the base material. The composition for forming a metal-containing member in each example and the comparative composition in the comparative example were each applied to the aluminum plate by a spin coating method to form a metal precursor-containing layer. By repeating the coating, a metal precursor-containing layer having a thickness of 2 μm was produced.
The aluminum plate provided with the obtained metal precursor-containing layer is heat-treated (heated and baked) for 2 minutes in an oven at the temperature described in the "Baking temperature (° C.)" column of the table to form a metal layer having a thickness of 2.0 μm. to form an aluminum plate.
The aluminum plate provided with the metal layer was cut into a rectangular shape with a size of 1 cm×10 cm. After that, by removing the aluminum plate by immersion in hydrochloric acid, a rectangular thin film of a metal layer was obtained.
The resulting rectangular thin film was slid in the long axis direction at a constant speed on a flat, low-friction table that was almost horizontal to the ground. The length of the portion protruding from the end was compared with the length when the same test was conducted 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 of the table.
-Evaluation criteria-
A: The above relative ratio was 1.5 or more.
B: The above relative ratio was 1.3 or more and less than 1.5.
C: The above relative ratio was 1.1 or more and less than 1.3.
D: The above relative ratio was less than 1.1.
[Example 2]
An aluminum plate was used as the base material. The metal-containing member-forming composition 2 in Example 2 was applied onto an aluminum plate by spin coating. By repeating the coating, a metal precursor-containing layer having a thickness of 2 μm was produced.
The aluminum plate provided with the metal precursor-containing layer was fired in an electric furnace at the temperature described in the column "Baking temperature (°C)" for 20 minutes to obtain a transparent thin film of high-purity cobalt oxide on the aluminum plate. . Furthermore, it was baked at 550° C. for 2 hours in a hydrogen gas atmosphere to obtain a thin film (metal layer) of high-purity metallic cobalt on the aluminum plate.
Examples 1 and 3 except that a member having a thin film of high-purity metallic cobalt formed on the aluminum plate was used instead of the aluminum plate having a metal layer in Examples 1, 3 to 13 and Comparative Example 1. The stress resistance was evaluated by the same method and evaluation criteria as in 13 and Comparative Example 1.
<Warpage resistance evaluation>
In each example or comparative example, the thickness of the metal layer obtained by using a silicon wafer instead of an aluminum plate and changing the number of repetitions of coating is 10 μm. A silicon wafer provided with a metal layer was produced in the same manner as in the evaluation of stress resistance, except that the thickness was set to . As the silicon wafer, a wafer thinned to a thickness of 100 μm by polishing was used.
The warpage of the silicon wafer was compared with the warpage in the same test 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 "warpage resistance evaluation" column of the table.
〔Evaluation criteria〕
A: The above relative ratio was less than 0.7.
B: The above relative ratio was 0.7 or more and less than 0.8.
C: The above relative ratio was 0.8 or more and less than 0.9.
D: The above relative ratio was 0.9 or more.

From the above results, it can be seen that the metal-containing member obtained from the composition for forming a metal-containing member of the present invention is a member excellent in stress resistance and warpage resistance and in strength.

Also, as an example of a device having a heat dissipation member, a device including the configuration shown in FIG. 2 was produced.
FIG. 2 is a schematic cross-sectional view showing a part of the configuration of a device having a heat dissipation member produced in Examples.
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 metal member-forming composition used in any one of Examples 1 to 17 was coated on the cover plate 20 and heated to fabricate a metal member as the heat dissipation member 22 . The heating temperature and heating time were the same as the heating temperature and heating time in the stress resistance evaluation described above.
The semiconductor chip 12 and the heat dissipation member 22 are adhered by an adhesive member 24 . In addition, the semiconductor chip 12 and other functional units existing in devices such as other semiconductor chips are connected to a circuit pattern 18 formed on the circuit board 14 or on the opposite side of the circuit board 11 to the circuit pattern 18 . They are electrically connected by another formed circuit pattern (not shown). The circuit pattern 18 and the semiconductor chip 12 are electrically connected by bumps 16 .
When such devices were produced, none of the semiconductor devices had any problem in performance.

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

Claims (15)

A composition for forming a metal-containing member comprising a metal precursor, a particulate filler and a solvent. 2. The composition for forming a metal-containing member according to claim 1, wherein said particulate filler comprises an inorganic compound. 3. The composition for forming a metal-containing member according to claim 1, wherein said solvent comprises water. The composition for forming a metal-containing member according to any one of claims 1 to 3, wherein the metal precursor comprises a silver precursor. 5. The composition for forming a metal-containing member according to claim 1, which is used for film formation. The composition for forming a metal-containing member according to any one of claims 1 to 5, comprising a reducing agent. The metal-containing member according to any one of claims 1 to 6, wherein the arithmetic mean value of the diameter of the particulate filler is 0.2 to 1 μm when calculated by the method described in JIS Z 8901:2006. Forming composition. A plurality of types of particles having a ratio of the arithmetic mean value of the diameter of the granular filler of 0.1: 1 to 0.8: 1 when calculated by the method described in JIS Z 8901: 2006 is used as the granular filler. The composition for forming a metal-containing member according to any one of claims 1 to 7, which contains the composition as an agent. 9. The composition for forming a metal-containing member according to any one of claims 1 to 8, which is used for forming a heat-conducting member, a heat-dissipating member, a reflecting member, a decorative member, or a conductive member. 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. an applying 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 of manufacturing a metal-containing member according to claim 11, wherein said converting step comprises heating said metal precursor-containing layer at 80°C to 150°C. 13. The method for producing a metal-containing member according to claim 11 or 12, wherein the metal-containing member obtained has a thickness of 1 to 500 μm. A laminate comprising a substrate and the metal-containing member of claim 10 disposed on the substrate. A device comprising the metal-containing member according to claim 10 or the laminate according to claim 14.

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