TW201513137A - Light-emitting device using silver nanoparticles and method for producing same - Google Patents

Abstract

The objective of the present invention is to provide: a light-emitting device having a circuit pattern having superior electrical conductivity and thermal conductivity and has a suppressed deterioration of an optical semiconductor element during the production process; and a method for producing the light-emitting device stably and conveniently without imparting thermal damage to the optical semiconductor element. The light-emitting device has an optical semiconductor element, a circuit pattern, and an insulating substrate, and is characterized by the optical semiconductor element and the circuit pattern being electrically and/or thermally connected, the circuit pattern being provided on the insulating substrate, the circuit pattern being formed by means of sintering silver nanoparticles, and the silver nanoparticles being obtained by the thermal decomposition of a mixture containing an amine (A) having an amino group and an aliphatic hydrocarbon group, and a silver compound (B).

Description

Light-emitting device using silver nano particles and manufacturing method thereof

The present invention relates to a light-emitting device in which an optical semiconductor element such as a light-emitting diode (LED) is mounted, and a method of manufacturing the same. The present application claims priority from Japanese Patent Application No. 2013-143479, filed on Jan. 9, 2013.

As exemplified in Patent Document 1, a light-emitting device has been conventionally formed by mounting an optical semiconductor element on a circuit board. The circuit pattern of the circuit board is formed by etching a copper foil formed by lamination or plating on the surface of the insulating substrate by using a photoresist pattern by lithography or the like, by etching the surface of the copper foil pattern. Gold plating or the like is applied to form a glossy surface. By the glossy surface of the surface of the circuit pattern, the surface of the circuit pattern can reflect the light emitted from the optical semiconductor element mounted on the circuit board to obtain more light.

However, when a circuit pattern is formed by the lithography method, plating processing or photoresist pattern formation must be performed, and there are problems in that the manufacturing steps of the light-emitting device become large. Further, when the uneven portion is present on the circuit board, or when a high-density circuit pattern must be formed, there is a problem that circuit pattern formation is difficult. In addition, when the surface of the circuit pattern is made into a glossy surface, plating such as gold plating is necessary, and the manufacturing process becomes more complicated and complicated, and the manufacturing efficiency is lowered.

Patent Document 2 discloses a light-emitting device which is an light-emitting device having an optical semiconductor element and a circuit pattern electrically connected thereto, wherein the circuit pattern is formed by coating a metal paste on a surface of the insulating substrate, and the circuit is formed The surface of the patterned metal paste itself is formed as a glossy surface capable of reflecting light emitted by the optical semiconductor element. Thereby, the steps can be simplified, the high-density circuit pattern can be easily formed, and the surface of the circuit pattern can be efficiently formed into a glossy surface.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. Hei 8-32119

Patent Document 2 Japanese Patent Laid-Open Publication No. 2009-65219

However, in Patent Document 2, most of the metals can be used for the metal paste. However, metal particles such as copper which are highly oxidizable and are not suitable for the nanometer size are not disclosed, and the specific metal is selected as a standard. Further, it is required to have metal particles having a property of being mutually fused at a low temperature (150 to 220 ° C), and components such as silver particles, acrylic resin, alcohol, toluene, etc. are exemplified, but no specific combination or cooperation is disclosed. The ratio can be melted at low temperature (150~220 °C) to obtain a glossy surface or a mirror surface. Further, although the application by a dispenser or an inkjet printer is simply described, a method of applying while maintaining the dispersion state or storage stability of the metal paste is not disclosed. According to the above, in order to realize the method of applying the metal paste, a lot of trial errors are required.

Accordingly, an object of the present invention is to provide a light-emitting device having a circuit pattern excellent in conductivity or thermal conductivity while suppressing deterioration of an optical semiconductor element in a manufacturing process, and providing thermal damage to the optical semiconductor element without being damaged, and being simple and stable A method of manufacturing the light-emitting device is obtained.

The present inventors have found that by using specific silver nanoparticles having excellent stability, dispersibility, conductivity, and thermal conductivity as a material for forming a circuit pattern of a light-emitting element, thermal damage to the optical semiconductor element can be avoided (ie, In the state in which the deterioration of the optical semiconductor element in the manufacturing process is suppressed, a high-quality light-emitting device having a circuit pattern excellent in conductivity or thermal conductivity is easily and stably obtained, and the present invention has been completed.

That is, the present invention provides a light-emitting device comprising a light-emitting device, a circuit pattern, and an insulating substrate, wherein the optical semiconductor element is electrically and/or thermally connected to the circuit pattern, and the circuit is The pattern is formed on the insulating substrate, and the circuit pattern is formed by sintering silver nanoparticles, and the silver nanoparticle system comprises an amine (A) having an aliphatic hydrocarbon group and an amine group, and a silver compound. The silver nanoparticle obtained by thermally decomposing the mixture of (B).

Furthermore, the light-emitting device is provided, wherein the mixture contains an aliphatic hydrocarbon monoamine (A1) having a carbon number of 6 or more and an aliphatic hydrocarbon group and an amine group as the amine (A), and an aliphatic hydrocarbon group and An aliphatic hydrocarbon monoamine (A2) having a carbon number of 5 or less formed by one amine group, and an aliphatic hydrocarbon diamine (A3) having 8 or less carbon atoms formed from an aliphatic hydrocarbon group and two amine groups.

Furthermore, the foregoing light-emitting device is provided, wherein the aforementioned mixture An aliphatic hydrocarbon monoamine (A1) having 6 or more carbon atoms and an aliphatic group and an amine group formed of an aliphatic hydrocarbon group and an amine group as the amine (A), and a carbon number of 5, which is an aliphatic hydrocarbon group and an amine group The following aliphatic monoamine (A2) contains the aforementioned monoamine in a ratio of 5 mol% or more and less than 20 mol% based on the total of the monoamine (A1) and the monoamine (A2). A1), and the aforementioned monoamine (A2) is contained in a ratio of more than 80 mol% and 95 mol% or less.

Furthermore, the foregoing light-emitting device is provided, wherein the aforementioned mixture A branched aliphatic hydrocarbon monoamine (A4) comprising a branched aliphatic hydrocarbon group having 4 or more carbon atoms and one amine group as the amine (A).

Furthermore, the light-emitting device is provided, wherein the silver compound (B) is silver oxalate.

Furthermore, the light-emitting device is provided, wherein the silver nanoparticles have an average particle diameter of 0.5 nm to 100 nm.

Furthermore, the light-emitting device is provided, wherein all or a part of the optical semiconductor element and the circuit pattern are covered with a transparent protective material.

Furthermore, the light-emitting device is provided, wherein the protective material is an epoxy resin, a siloxane resin, an acrylic resin, a carbonate resin, or a lowering agent. One or more materials selected from the group consisting of an olefin resin, a cycloolefin resin, and a polyamide resin.

Moreover, the present invention provides a method of manufacturing a light-emitting device, comprising the step (a) of applying a composition containing silver nanoparticles on an insulating substrate; and comprising the composition Silver nanoparticle sintering step (b); on the aforementioned insulating substrate a step (c) of mounting an optical semiconductor element; a step (d) of electrically and/or thermally connecting the optical semiconductor element and the circuit pattern; and a step (e) of forming a protective material so as to cover the circuit pattern.

Furthermore, a method of manufacturing the above-described light-emitting device is provided, wherein step (b) and the aforementioned step (d) are simultaneously performed.

In more detail, the present invention relates to the following

[1] A light-emitting device comprising a light semiconductor device, a circuit pattern, and an insulating substrate, wherein the optical semiconductor element is electrically and/or thermally connected to the circuit pattern, and the circuit pattern is And being formed on the insulating substrate, wherein the circuit pattern is formed by sintering silver nanoparticles, and the silver nanoparticle system comprises an amine (A) having an aliphatic hydrocarbon group and an amine group, and a silver compound (B) Silver nanoparticle obtained by thermal decomposition of the mixture.

[2] The light-emitting device according to [1], wherein the mixture contains an aliphatic hydrocarbon monoamine (A1) having 6 or more carbon atoms formed from an aliphatic hydrocarbon group and an amine group as the amine (A). An aliphatic hydrocarbon monoamine (A2) having an aliphatic hydrocarbon group and one amine group having 5 or less carbon atoms; and an aliphatic hydrocarbon diamine having 8 or less carbon atoms formed by an aliphatic hydrocarbon group and two amine groups (A3) ).

[3] The light-emitting device according to [2], wherein the monoamine (A1) in the mixture is based on the total of the monoamine (A1), the monoamine (A2), and the diamine (A3). The content is from 10 mol% to 65 mol%.

[4] The light-emitting device according to [2], wherein the monoamine in the mixture is based on the total of the monoamine (A1), the monoamine (A2), and the diamine (A3). The content of (A2) is from 5 mol% to 50 mol%.

[5] The light-emitting device according to any one of [2], wherein, in the mixture, the total of the monoamine (A1), the monoamine (A2), and the diamine (A3) are used as a reference. The content of the aforementioned diamine (A3) is from 15 mol% to 50 mol%.

[6] The light-emitting device according to any one of [2], wherein the monoamine (A1) and the monoamine (A2) and the silver atom of the silver compound (B) are 1 mol. The total amount of the above diamines (A3) is from 1 mole to 20 moles.

[7] The light-emitting device according to [1], wherein the mixture contains an aliphatic hydrocarbon monoamine (A1) having 6 or more carbon atoms and an aliphatic group and an amine group as the amine (A), and The aliphatic hydrocarbon monoamine (A2) having 5 or less carbon atoms and having an aliphatic hydrocarbon group and one amine group is 5 mol based on the total of the monoamine (A1) and the monoamine (A2). The ratio of % or more and less than 20 mol% includes the aforementioned monoamine (A1), and the aforementioned monoamine (A2) is contained in a ratio of more than 80 mol% and 95 mol% or less.

[8] The light-emitting device according to [7], wherein the total amount of the monoamine (A1) and the monoamine (A2) is 1 mol to 72 with respect to 1 mol of the silver atom of the silver compound (B). Moor.

[9] The light-emitting device according to [1], wherein the mixture contains a branched aliphatic hydrocarbon monoamine (A4) which is a branched aliphatic hydrocarbon group having 4 or more carbon atoms and an amine group as the amine (A). .

[10] The light-emitting device according to [9], wherein the amount of the monoamine (A4) is from 1 mol to 15 mol with respect to 1 mol of the silver atom of the silver compound (B).

[11] The light-emitting device according to [9] or [10] wherein the ratio of the monoamine (A4) is from 80 mol to 100 mol% with respect to the total amount of the amine (A) (100 mol%).

[12] The light-emitting device according to any one of [1], wherein the silver compound (B) is silver oxalate.

[13] The light-emitting device according to any one of [1] to [12] wherein the mixture further comprises an aliphatic carboxylic acid (C).

[14] The light-emitting device according to [13], wherein the aliphatic carboxylic acid (C) is used in an amount of from 0.05 mol to 10 mol based on 1 mol of the silver atom of the silver compound (B).

[15] The light-emitting device according to any one of [1], wherein the silver nanoparticles have an average particle diameter of 0.5 nm to 100 nm.

[16] The light-emitting device according to any one of [1], wherein all or a part of the optical semiconductor element and the circuit pattern are covered with a transparent protective material.

[17] The light-emitting device according to [16], wherein the protective material is an epoxy resin, a siloxane resin, an acrylic resin, a carbonate resin, or a lowering One or more materials selected from the group consisting of an olefin resin, a cycloolefin resin, and a polyamide resin.

[18] A method of producing a light-emitting device, comprising: a step (a) of applying a composition containing silver nanoparticles on an insulating substrate; and a silver contained in the composition. a step (b) of sintering the nanoparticle; a step (c) of mounting the optical semiconductor element on the insulating substrate; a step (d) of electrically and/or thermally connecting the optical semiconductor element and the circuit pattern; and The step (e) of forming the protective material in the manner of the aforementioned circuit pattern.

[19] The method for producing a light-emitting device according to [18], wherein the step (b) and the step (d) are simultaneously performed.

According to the present invention, deterioration of the optical semiconductor element in the manufacturing process is suppressed, and a light-emitting device having a circuit pattern excellent in conductivity or thermal conductivity can be obtained. Further, the light-emitting device can be easily and stably manufactured without causing thermal damage to the optical semiconductor element. Since the circuit pattern in the light-emitting device of the present invention is formed by sintering specific silver nanoparticles, and is formed on a glossy surface without applying plating or etching, the light of the present invention The manufacturing method of the device is excellent in manufacturing efficiency. Further, the light-emitting device of the present invention obtained by the production method has a quality superior in luminosity emitted.

1‧‧‧Optical semiconductor components

2‧‧‧ circuit pattern

3‧‧‧Composition containing silver nanoparticles

4‧‧‧Insert substrate

5‧‧‧ Conductive paste

6‧‧‧bonding line

7‧‧‧Protective materials

Fig. 1 is a view showing an example of an embodiment of a light-emitting device and a method of manufacturing the same according to the present invention. (a) to (e) are cross-sectional views (schematic cross-sectional views) showing the respective manufacturing steps of the light-emitting device of the present invention.

Fig. 2 is a view showing an example of an embodiment of a light-emitting device and a method of manufacturing the same according to the present invention. (a) to (e) are cross-sectional views (schematic cross-sectional views) showing the respective manufacturing steps of the light-emitting device of the present invention.

Fig. 3 is a view showing an example of an embodiment of a light-emitting device and a method of manufacturing the same according to the present invention. (a) to (e) are cross-sectional views (schematic cross-sectional views) showing the respective manufacturing steps of the light-emitting device of the present invention.

Form of implementing the invention

Hereinafter, the form for carrying out the invention will be exemplified, but the invention is not limited thereto.

<Lighting device>

The light-emitting device of the present invention is a light-emitting device having an optical semiconductor element, a circuit pattern, and an insulating substrate, wherein the optical semiconductor element is electrically and/or thermally connected to the circuit pattern, and the circuit pattern is provided on the insulating substrate. And the circuit pattern is formed by sintering silver nanoparticle, and the silver nanoparticle is thermally decomposed by a mixture comprising an amine (A) having an aliphatic hydrocarbon group and an amine group and a silver compound (B). The obtained silver nanoparticle (also referred to as "the silver nanoparticle of the present invention").

[Optical Semiconductor Components]

The optical semiconductor element in the light-emitting device of the present invention is not particularly limited as long as it emits light by being energized, and examples thereof include an optical semiconductor element such as a light emitting diode (LED). The optical semiconductor element in the light-emitting device of the present invention has a terminal, and any metal can be used as a material for forming the terminal. For example, gold, silver, copper or aluminum, or an alloy thereof can be used. Among the above-mentioned metals, from the viewpoint of adhesion or oxidation resistance, gold or a gold alloy or a metal whose surface is coated with gold or a gold alloy is preferable. As the material for forming the terminal, a composition containing silver nanoparticles may be used (that is, the terminal may be formed by sintering the silver nanoparticles).

[Insulating substrate]

The insulating substrate in the light-emitting device of the present invention is not particularly limited as long as it is an electrically insulating flat plate or the like, and examples thereof include a glass substrate and a curable resin containing an epoxy resin or a silicone resin. A laminated sheet of a glass cloth substrate (prepreg) hardened, such as a poly a heat-resistant plastic substrate of a bismuth imide film; a polyester film such as a polyethylene terephthalate (PET) film or a polyethylene naphthalate (PEN) film, or a polyolefin film such as polypropylene A general-purpose plastic substrate having a low heat resistance, a ceramic plate, a metal plate in which a surface is insulated by a resin or a resin or ceramic in which an inorganic filler is mixed.

[circuit pattern]

The circuit pattern in the light-emitting device of the present invention is electrically and/or thermally connected to the optical semiconductor element and is provided on the insulating substrate. The circuit pattern in the light-emitting device of the present invention is formed by sintering the silver nanoparticles of the present invention. Specifically, as a material for forming the above-described circuit pattern in the light-emitting device of the present invention, the composition containing the silver nanoparticle of the present invention is used. Specifically, the composition is applied onto the insulating substrate in a desired pattern, and then the silver nanoparticles of the present invention in the composition are sintered by heating to form the circuit pattern.

(constituent composition of silver nanoparticles)

Examples of the composition containing the silver nanoparticles used in the light-emitting device of the present invention include silver nanoparticles (the silver nanoparticles of the present invention) which are mostly composed of components exhibiting conductivity or thermal conductivity. The silver nanoparticle is composed of an organic solvent or a dispersing agent in a dispersed state. The above composition is not particularly limited and can take various forms. For example, a silver coating composition called a silver ink can be produced by dispersing the silver nanoparticles of the present invention in a suspended state in a suitable organic solvent (dispersion medium). Alternatively, by dispersing the silver nanoparticles of the present invention in an organic solvent in a state of kneading, a so-called weigh A silver coating composition of silver paste. The organic solvent used for obtaining the silver coating composition is not particularly limited, and examples thereof include pentane, hexane, heptane, octane, decane, decane, undecane, dodecane, and ten. An aliphatic hydrocarbon solvent such as trioxane or tetradecane; an aromatic hydrocarbon solvent such as toluene, xylene or mesitylene; methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, An alcohol solvent such as n-octanol, n-nonanol, n-nonanol or terpineol. The type or amount of the organic solvent can be appropriately determined depending on the concentration or viscosity of the desired silver coating composition. The same applies to the other metal nanoparticles described later, the nano particles of the silver composite, and the like.

The average particle diameter of the silver nanoparticles of the present invention is not particularly limited, but is preferably 0.5 nm to 100 nm, more preferably 0.5 nm to 50 nm, still more preferably 0.5 nm to 25 nm, and particularly preferably 0.5 nm to 10 nm. .

The silver nanoparticle of the present invention comprises a mixture of an amine (A) having an aliphatic hydrocarbon group and an amine group (also referred to as "amine (A)") and a silver compound (B) (also referred to as "mixture"). Silver nanoparticle obtained by thermal decomposition (specifically, thermal decomposition of the silver compound (B) in the mixture). The silver nanoparticle of the present invention is in a state in which the surface is covered with a protective agent containing an amine (A), and is excellent in stability, and is lower than 200 ° C (for example, 150 ° C or lower, preferably 120 ° C or lower). In the short-time sintering at a low temperature of 2 hours or less (for example, 1 hour or less, preferably 30 minutes or less), excellent conductivity can be exhibited even when a silver film having a thick film of, for example, 1 μm or more is formed. (low resistance) silver nanoparticles.

The composition containing the silver nanoparticles may be obtained by a conventionally known method using a silver nanoparticle obtained by thermally decomposing the mixture (the silver nanoparticle of the present invention), and is not particularly limited. For example, the silver nanoparticles obtained as described above may be washed or the like in a solvent, or may be suspended or dispersed in a solvent by a conventional method.

1. Amine (A)

The amine (A) used in forming the silver nanoparticles of the present invention may be a conventionally used amine (amine compound) as long as it has an aliphatic hydrocarbon group and an amine group. The aliphatic hydrocarbon group contains a linear or branched aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group. Further, each of the aliphatic hydrocarbon groups includes a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group. Further, the amine group includes a primary amino group, a secondary amino group, and a tertiary amine group. Hereinafter, specific examples of the amine (A) used in forming the silver nanoparticles of the present invention are exemplified as the embodiment 1 to 3 of the amine, but the amine (A) is not limited by these aspects.

[Implementation of Amine 1]

The amine (A) is an aliphatic hydrocarbon monoamine (A1) (also referred to simply as "monoamine (A1)") having at least 6 or more carbon atoms formed from an aliphatic hydrocarbon group and one amine group. An aliphatic hydrocarbon monoamine (A2) having a carbon number of 5 or less formed of an aliphatic hydrocarbon group and one amine group (also referred to as "monoamine (A2)"), and an aliphatic hydrocarbon group and two amine groups The aspect of the aliphatic hydrocarbon diamine (A3) having a carbon number of 8 or less (also referred to as "diamine (A3)"). That is, as one aspect of the above mixture, a mixture containing at least a monoamine (A1), a monoamine (A2), and a diamine (A3) may be mentioned as the above amine (A).

Further, in the aspect (the embodiment 1 of the amine), the monoamine (A1), the monoamine (A2), and the diamine (A3) may be used without departing from the effects of the present invention. Other than amines.

The aforementioned monoamine (A1) constitutes a carbon atom of the monoamine (A1) The total number (carbon number) is 6 or more monoamine. The monoamine (A1) has a high function as a protective agent (stabilizing agent) on the surface of the produced silver nanoparticles due to its hydrocarbon chain. The monoamine (A1) is preferably an alkyl monoamine having 6 to 12 carbon atoms. The aforementioned monoamine (A1) contains a primary amine, a secondary amine, and a tertiary amine.

The monoamine (A1) as the primary amine may, for example, be hexylamine. Saturated aliphatic hydrocarbons of heptylamine, octylamine, decylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentaamine, hexadecylamine, heptadecylamine, octadecylamine, etc. Amine (ie alkyl monoamine). As the saturated aliphatic hydrocarbon monoamine, in addition to the above-mentioned linear aliphatic hydrocarbon monoamine, for example, branched (branched) aliphatic hydrocarbon monoamines such as isohexylamine, 2-ethylhexylamine, and trioctylamine may be mentioned. . Further, a cycloalkyl monoamine such as cyclohexylamine may also be mentioned. Further, an unsaturated aliphatic hydrocarbon monoamine (i.e., an alkenyl monoamine) such as oleylamine may be mentioned.

The monoamine (A1) as a secondary amine may, for example, be N,N-di Propylamine, N,N-dibutylamine, N,N-dipentylamine, N,N-dihexylamine, N,N-diheptylamine, N,N-dioctylamine, N, N-didecylamine, N,N-didecylamine, N,N-di(undecyl)amine, N,N-di(dodecyl)amine, N-propyl-N-butylamine A dialkyl monoamine. The monoamine (A1) which is a tertiary amine may, for example, be tributylamine or trihexylamine.

Within this, as the monoamine (A1), it is preferably a carbon number of 6 The above saturated aliphatic hydrocarbon monoamine. When the number of carbon atoms is 6 or more, the amine group can be separated from other silver nanoparticles by being adsorbed on the surface of the silver nanoparticles, and thus the effect of preventing aggregation of the silver nanoparticles is increased. There is no special rule on the upper limit of the carbon number, but considering the ease of availability, The ease of removal during sintering and the like are usually preferably a saturated aliphatic hydrocarbon monoamine before the carbon number of 18. In particular, an alkyl monoamine having 6 to 12 carbon atoms such as hexylamine, heptylamine, octylamine, decylamine, decylamine, undecylamine or dodecylamine is preferably used. The monoamine (A1) may be used alone or in combination of two or more.

In the above mixture, the monoamine (A1) is not particularly limited, but is based on the total of the monoamine (A1), the monoamine (A2), and the diamine (A3) (100 mol%). The best contains 10% to 65% by mole.

The monoamine (A2) is an aliphatic hydrocarbon monoamine having a carbon number of 5 or less and an aliphatic hydrocarbon group and one amine group. In other words, the monoamine (A2) is a monoamine having a total number of carbon atoms (carbon number) of the monoamine (A2) of 5 or less. In comparison with the above-mentioned monoamine (A1), since the carbon chain length is short, it is judged that the function itself as a protective agent (stabilizing agent) is low, but since the polarity is higher than the above-mentioned monoamine (A1), it is judged to be silver. The compound (B) has a high coordination ability of silver and is effective in promoting the formation of a complex. Moreover, since the carbon chain has a short length, it can be removed from the surface of the silver nanoparticles by a short time of 30 minutes or less or 20 minutes or less, even when it is sintered at a low temperature of, for example, 120 ° C or less or about 100 ° C or less. Silver nano particles have an effect on low temperature sintering.

Examples of the monoamine (A2) include ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, third butylamine, n-pentylamine, isoamylamine, and third pentane. A saturated aliphatic hydrocarbon monoamine having a carbon number of 2 to 5 such as an amine (i.e., an alkyl monoamine). Further, for example, a dialkyl group such as N,N-dimethylamine, N,N-diethylamine, N-methyl-N-propylamine or N-ethyl-N-propylamine may be mentioned. Monoamine.

Within this, as the monoamine (A2), preferably n-butylamine, Isobutylamine, second butylamine, third butylamine, n-pentylamine, isoamylamine, and tertiary pentylamine are particularly preferred as the above butylamines. The monoamine (A2) may be used alone or in combination of two or more.

In the foregoing mixture, the aforementioned monoamine (A2) is not particularly specific. Although it is limited, it is preferably 5 mol% to 50 mol% based on the total of the monoamine (A1), the monoamine (A2), and the diamine (A3) (100 mol%).

The aforementioned diamine (A3) constitutes a carbon atom of the diamine (A3) The total number (carbon number) is 8 or less diamine. The diamine (A3) has a high coordination ability for silver of the silver compound (B) and is effective in promoting formation of a complex compound. The aliphatic hydrocarbon diamine is generally more polar than the aliphatic hydrocarbon monoamine, and has a high coordination ability for silver of the silver compound (B). Further, the diamine (A3) is in the thermal decomposition step of the wrong compound, and has an effect of promoting lower temperature and thermal decomposition in a short period of time, and can more efficiently produce silver nanoparticles. Further, since the protective film of the silver nanoparticles containing the diamine (A3) has a high polarity, the dispersion stability of the silver nanoparticles in the dispersion medium containing a solvent having a high polarity is increased. In addition, since the diamine (A3) has a short carbon chain length, it can be used for a short period of time of 30 minutes or less or 20 minutes or less from silver nanoparticles even when it is sintered at a low temperature of, for example, 120 ° C or lower or about 100 ° C or lower. Since the particle surface is removed, it has an effect on the low-temperature and short-time sintering of the silver nanoparticle of the obtained silver nanoparticle.

The diamine (A3) is preferably a carbon number of 2 to 8. Alkyl diamine. More specifically, the diamine (A3) may, for example, be ethylenediamine, N,N-dimethylethylenediamine, N,N'-dimethylethylenediamine, N,N- Diethylethylenediamine, N,N'-diethylethylenediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, N,N-dimethyl -1,3-propanediamine, N,N'-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N'-diethyl -1,3-propanediamine, 1,4-butanediamine, N,N-dimethyl-1,4-butanediamine, N,N'-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N'-diethyl-1,4-butanediamine, 1,5-pentanediamine, 1,5-diamino-2 -methylpentane, 1,6-hexanediamine, N,N-dimethyl-1,6-hexanediamine, N,N'-dimethyl-1,6-hexanediamine, 1,7 - heptanediamine, 1,8-octanediamine, and the like. These are all alkylene diamines in which at least one of the two amine groups is a primary amino group or a secondary amine group having a carbon number (total carbon number) of 8 or less, and the silver compounding ability of the silver compound (B) is high. It has an effect on the formation of complex compounds.

Within the above, as the diamine (A3), N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dimethyl-1, 3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4- One of the two amine groups such as butanediamine and N,N-dimethyl-1,6-hexanediamine is a primary amine group (-NH ₂ ), and the other one is a tertiary amino group (-NR). ¹ R ² ) The alkylene diamine having a carbon number (total carbon number) of 8 or less. A preferred alkylene diamine is represented by the following structural formula.

R ¹ R ² NR-NH ₂

Here, R represents an alkylene group, and R ¹ and R ² may be the same or different and each represents an alkyl group. However, the sum of the carbon numbers of R, R ¹ and R ² is 8 or less. The alkylene group does not contain a hetero atom such as an oxygen atom or a nitrogen atom. Further, the alkyl group does not contain a hetero atom such as an oxygen atom or a nitrogen atom.

Among these, from the viewpoint of being able to remove the surface of the silver nanoparticles in a short time even under low-temperature sintering, the carbon number (carbon total) is preferred. The diamine having 6 or less is more preferably a diamine having 5 or less carbon atoms (total carbon number). The diamine (A3) may be used alone or in combination of two or more.

In the foregoing mixture, the aforementioned diamine (A3) is not particularly specific. Although it is limited, it is preferably 15 mol% to 50 mol% based on the total of the monoamine (A1), the monoamine (A2), and the diamine (A3) (100 mol%).

This aspect of the invention (embodiment 1 of the amine) is used The total amount of the monoamine (A1), the monoamine (A2), and the diamine (A3) is not particularly limited, but is 1 mol per silver atom of the silver compound (B) with respect to the raw material. The total amount of the amine component [(A1) + (A2) + (A3)] is preferably from about 1 mole to about 20 moles. When the total amount of the amine component is less than 1 mol with respect to the silver atom of 1 mol, the silver compound which is not converted to the wrong compound in the step of forming the wrong compound of the amine (A) and the silver compound (B) (B) The possibility of residue. In the subsequent thermal decomposition step, the uniformity of the silver nanoparticles is impaired, and the particles are enlarged or the silver compound (B) remains without being thermally decomposed. In order to produce a dispersion of silver nanoparticles in a solvent-free manner, it is preferred that the total amount of the amine components be, for example, about 2 mol or more. By setting the total amount of the amine components to about 2 mol or more, the step of forming a wrong compound and the step of thermally decomposing can be favorably performed. The lower limit of the total amount of the amine component is preferably 2 mol or more, and more preferably 6 mol or more, based on 1 mol of the silver atom of the silver compound (B).

[Implementation of Amine 2]

As another embodiment of the amine (A), at least a carbon having 6 or more carbon atoms derived from an aliphatic hydrocarbon group and one amine group can be used. a hydrocarbon monoamine (A1), an aliphatic hydrocarbon monoamine (A2) having a carbon number of 5 or less formed of an aliphatic hydrocarbon group and one amine group, and a total of the monoamine (A1) and the monoamine (A2) (100% by mole), based on the ratio of 5 mol% or more and less than 20 mol% (for example, 5 mol% or more and 19 mol% or less), the aforementioned monoamine (A1), and more than 80 mol The ratio of the ear % and 95 mol% or less (for example, 81 mol% or more and 95 mol% or less) is the ratio of the aforementioned monoamine (A2). That is, as one aspect of the above mixture, a monoamine (A1) and a monoamine (A2) are contained as the above-mentioned amine (A), and a total of monoamine (A1) and monoamine (A2) (100 mol) Based on the ear %), the monoamine (A1) is contained in a ratio of 5 mol% or more and less than 20 mol%, and the mixture of the monoamine (A2) is contained in a ratio of more than 80 mol% and 95 mol% or less. .

The proportion of the aforementioned monoamine (A1) and the aforementioned monoamine (A2), The monoamine (A1): 5 mol% or more and less than 20 mol% (for example, 5 mol% or more) based on the total of the monoamine (A1) and the monoamine (A2) (100 mol%). 19 mol% or less), and the aforementioned monoamine (A2): more than 80 mol% and 95 mol% or less (for example, 81 mol% or more and 95 mol% or less). In addition, in the aspect (the embodiment 2 of the amine), the amine other than the monoamine (A1) or the monoamine (A2) or the like can be used as long as the effect of the present invention is not impaired.

By making the content of the aforementioned monoamine (A1) 5 mol% The upper and lower than 20 mol% can obtain the protective stabilization function of the surface of the produced silver nanoparticle due to the carbon chain of the monoamine (A1). When the content of the aforementioned monoamine (A1) is less than 5 mol%, the performance of the protective stabilization function is weak. On the other hand, when the content of the monoamine (A1) is 20 mol% or more, although the protective stabilization function is sufficient, it is difficult to form a relatively thick film by burning. The monoamine (A1) is removed by low temperature sintering at the time of conjunctiva. The lower limit of the content of the monoamine (A1) is preferably 10 mol% or more, for example, 13 mol% or more. The upper limit of the content of the monoamine (A1) is preferably 19 mol% or less, for example, 17 mol% or less.

By making the content of the aforementioned monoamine (A2) more than 80 The ear % and 95% by mole or less can easily obtain a complex formation promoting effect, and itself contributes to low temperature and short time sintering. When the content of the monoamine (A2) is 80 mol% or less, the effect of promoting the formation of the complex is weak, or it may be difficult to remove from the surface of the silver nanoparticles when sintering is performed on a sintered film having a relatively thick film thickness. The aforementioned monoamine (A1). On the other hand, when the content of the monoamine (A2) exceeds 95 mol%, a complex formation promoting effect can be obtained, but the content of the monoamine (A1) is relatively small, and it is difficult to obtain the produced silver naphthalene. The protection of the surface of the rice particles is stable. The lower limit of the content of the monoamine (A2) is preferably 81 mol% or more, for example, 83 mol% or more. The upper limit of the content of the monoamine (A2) is preferably 90 mol% or less, for example, 87 mol% or less.

In this aspect of the invention (embodiment 2 of the amine), Since the monoamine (A2) having a high coordination ability for silver of the silver compound (B) is used in the above ratio, the amount of adhesion of the monoamine (A1) to the surface of the silver nanoparticles is small. Therefore, even in the case of sintering at a low temperature for a short period of time, it is easy to remove these amines from the surface of the silver nanoparticles, and the sintering of the silver nanoparticles is sufficiently performed.

This aspect of the invention (embodiment 2 of the amine) is used The total amount of the monoamine (A1) and the monoamine (A2) is not particularly limited, but is 1 mol with respect to the silver atom of the silver compound (B). The amount of the amine [(A1) + (A2)] may be from about 1 mole to about 72 moles. When the amount of the amine [(A1) + (A2)] is less than 1 mol with respect to the silver atom of 1 mol, the silver compound (B) remaining in the wrong compound is not converted to the wrong compound. In the subsequent thermal decomposition step, there is a possibility that the uniformity of the silver nanoparticles is impaired, the particles are enlarged, or the silver compound (B) remains without being thermally decomposed. On the other hand, it is judged that there is no advantage even if the amount of the above amine [(A1) + (A2)] exceeds about 72 mol with respect to the above-mentioned silver atom of 1 mol. In order to produce a dispersion of silver nanoparticles in a solvent-free manner substantially, the amount of the amine [(A1) + (A2)] can be, for example, about 2 mol or more. By setting the amount of the above amine [(A1) + (A2)] to about 2 to 72 moles, the step of forming a wrong compound and the step of thermally decomposing can be favorably performed. The lower limit of the amount of the above amine [(A1) + (A2)] is preferably 2 mol or more, more preferably 6 mol or more, more preferably 6 mol or more, relative to the silver atom of the silver compound (B). Good for more than 10 moles.

In the aspect of the invention (the embodiment 2 of the amine), the aforementioned diamine (A3) may be further used.

[Example 3 of the amine]

As another embodiment of the amine (A), at least a branched aliphatic hydrocarbon monoamine (A4) composed of a branched aliphatic hydrocarbon group having 4 or more carbon atoms and one amine group may be used (also referred to as "single" The aspect of the amine (A4)"). That is, as one aspect of the above mixture, a mixture containing a monoamine (A4) may be mentioned as the above amine (A). If a branched aliphatic hydrocarbon amine compound is used, it can be used for the surface of the silver nanoparticles due to the steric factor of the branched aliphatic hydrocarbon group as compared with the case of using the linear aliphatic hydrocarbon amine compound having the same carbon number. A larger area of the surface of the silver nanoparticles is coated with less adhesion. Therefore, moderate stabilization of the silver nanoparticle can be obtained by less adhesion to the surface of the silver nanoparticles. In this case, since the amount of the protective agent (organic stabilizer) to be removed at the time of sintering is small, the organic stabilizer can be efficiently removed even when sintered at a low temperature of 200 ° C or lower, and the sintering system of the silver nanoparticles is performed. Fully proceed.

The carbon number of the branched aliphatic hydrocarbon group in the aforementioned monoamine (A4) is 4 or more, for example, 4 to 16. In order to obtain the steric factor of the branched aliphatic hydrocarbon group, it is necessary to have a carbon number of 4 or more. Examples of the monoamine (A4) include isobutylamine, second butylamine, third butylamine, isoamylamine, third pentylamine, isohexylamine, 2-ethylhexylamine, and thixylamine. The primary amine having a carbon number of 4 to 16, preferably 4 to 8 carbon atoms.

Further, examples of the monoamine (A4) include N, N-di A secondary amine such as isobutylamine, N,N-diisoamylamine, N,N-diisohexylamine or N,N-bis(2-ethylhexyl)amine. Further, for example, a tertiary amine such as triisobutylamine, triisoamylamine, triisohexylamine or tris(2-ethylhexyl)amine can be mentioned. In the case of N,N-bis(2-ethylhexyl)amine, the carbon number of the 2-ethylhexyl group is 8, but the total amount of carbon contained in the monoamine (A4) is 16. In the case of tris(2-ethylhexyl)amine, the total amount of carbon contained in the aforementioned monoamine (A4) is 24.

In the branched aliphatic hydrocarbon monoamine, the monoamine (A4) is preferably a branched alkyl group having 4 to 6 carbon atoms in a main chain such as isoprene, isohexylamine or 2-ethylhexylamine. A monoamine compound. Further, the above-mentioned "main chain" means a chain having the longest length among the branched aliphatic hydrocarbon groups (a chain composed of carbon-carbon bonds). If the carbon number of the main chain is 4 to 6, it is easy to obtain moderate stabilization of the silver nanoparticles. Again, from the branch From the viewpoint of the steric factor of the aliphatic hydrocarbon group, it is more effective to branch on the second carbon atom from the N atom side. The monoamine (A4) may be used alone or in combination of two or more.

This aspect of the invention (embodiment 3 of the amine) is used The amount of the monoamine (A4) is not particularly limited, but is preferably from about 1 mol to about 15 mol with respect to 1 mol of the silver atom of the silver compound (B) of the raw material. When the amount of the monoamine (A4) is less than 1 mol with respect to the silver atom of 1 mol, the step of forming the wrong compound of the amine (A) and the silver compound (B) is not converted to the wrong compound. The possibility of residual silver compound (B). Further, in the subsequent thermal decomposition step, there is a possibility that the uniformity of the silver nanoparticles is impaired, the particles are enlarged, or the silver compound (B) remains without being thermally decomposed. In order to produce a dispersion of silver nanoparticles in a solvent-free manner, it is preferred that the amount of the monoamine (A4) is, for example, about 2 mol or more. By setting the amount of the monoamine (A4) to about 2 mol or more, the step of forming a wrong compound and the step of thermally decomposing can be favorably performed. The lower limit of the amount of the monoamine (A4) is preferably 2 mol or more, more preferably 6 mol or more, based on 1 mol of the silver atom of the silver compound (B).

This aspect of the invention (embodiment 3 of the amine) is used The ratio of the monoamine (A4) to the total amount (100 mol%) of the amine (A) is not particularly limited, but is preferably 80 mol to 100 mol%, more preferably 90 mol. Ears ~100% by mole (eg 90 moles to 98 moles %). By controlling the above ratio within such a numerical range, it is possible to efficiently produce silver nanoparticles having excellent dispersion stability in a dispersion medium, and it is possible to efficiently perform sintering of silver nanoparticles.

The aliphatic hydrocarbon amine compound used as the deforming agent and/or the protective agent function in the aspect of the present invention (the third embodiment of the amine) may be further independently selected in addition to the aforementioned monoamine (A4). An aliphatic hydrocarbon amine compound selected from the foregoing monoamine (A1), the aforementioned monoamine (A2), and the aforementioned diamine (A3) is used. The monoamine (A2) and the aforementioned diamine (A3) are effective in promoting the formation of a complex.

2. Silver compound (B)

As the silver compound (B), a silver compound which is easily decomposed by heating to form metallic silver is used. As such a silver compound, silver carboxylate such as silver formate, silver acetate, silver oxalate, silver malonate, silver benzoate or silver phthalate, silver fluoride, silver chloride, silver bromide, silver iodide or the like can be used. Silver halide, sulfate, silver nitrate, silver carbonate, etc., but silver oxalate is preferably used from the viewpoint of easily forming metal silver by decomposition and not easily generating impurities other than silver. The silver oxalate silver has a high content rate, and it is advantageous to obtain metallic silver directly by thermal decomposition without requiring a reducing agent, and it is difficult to leave impurities derived from the reducing agent.

Further, the composition containing the silver nanoparticle may include a nanoparticle of a metal other than silver (also referred to as "other metal"), and a composite of silver and other metals, in addition to the silver nanoparticle of the present invention. Other nano particles such as nano particles. These other nanoparticles, for example, can be substituted for the silver compound (B) in the method for producing silver nanoparticles of the present invention by using a compound (metal compound) of another metal, or with other compounds of the silver compound (B). The compound is manufactured.

For example, when producing a nanoparticle of a metal other than the above-mentioned silver, it is easy to decompose by heating, and other gold for the purpose of production is used. A metal compound of the genus is substituted for the aforementioned silver compound (B). As such a metal compound, a salt corresponding to the metal of the above-mentioned silver compound (B), for example, a metal salt compound of a metal carboxylate, a metal halide, a metal sulfate, a metal nitrate, a metal carbonate or the like can be used. Among these, it is preferable to use a metal oxalate from the viewpoint that metal is easily formed by decomposition and impurities other than metals are less likely to occur. Examples of the other metal include Al, Au, Pt, Pd, Cu, Co, Cr, In, and Ni.

Also, for example, in order to obtain the aforementioned complexion of silver and other metals The nanoparticle of the compound (also referred to as "silver composite") may be used in combination with the above-mentioned silver compound (B) and other metal compounds other than the above-mentioned silver. Examples of the other metal include Al, Au, Pt, Pd, Cu, Co, Cr, In, and Ni. The silver composite is composed of silver and one or more other metals, and examples thereof include Au-Ag, Ag-Cu, Au-Ag-Cu, and Au-Ag-Pd. The silver composite is not particularly limited, but the silver is at least 20% by weight (that is, 20% by weight or more) based on the entire metal, and usually accounts for 50% by weight (that is, 50% by weight or more), for example, 80%. % by weight (ie 80% by weight or more).

Silver nanoparticles used in the light-emitting device of the present invention, It can be produced by heating the aforementioned mixture (containing at least a mixture of the amine (A) and the silver compound (B)) (specifically, thermally decomposing the silver compound (B) by heating). The preparation method of the above mixture is not particularly limited. For example, when two or more kinds of the amines (A) are used, the mixture (amine mixture) can be prepared, and then the silver compound (B) can be added and mixed therein. And the aforementioned mixture was prepared. The addition of the silver compound (B) may also be carried out in batches or sequentially. When the silver compound (B) is added successively, it can be continuously It can also be carried out intermittently. Although it is not clear, it is presumed that the complex formation of the two is carried out in the stage of mixing the amine (A) with the silver compound (B).

Heating temperature of the aforementioned mixture when generating silver nanoparticles The (thermal decomposition temperature) is not particularly limited, and may be appropriately set, for example, in the range of 60 to 150 °C. For example, when silver oxalate is used as the silver compound (B), since it can be thermally decomposed efficiently by heating at 80 to 120 ° C, silver nanoparticles can be produced with high productivity. Further, the heating temperature may be fixed or may be controlled continuously or intermittently. Further, the time (heating time) for heating the mixture is not particularly limited, and may be appropriately set, for example, in the range of 5 to 360 minutes. Thereby, a composition containing silver nanoparticles is obtained.

3. Aliphatic carboxylic acid (C)

In the present invention, in order to further improve the dispersibility of the silver nanoparticles in the dispersion medium, the aliphatic carboxylic acid (C) may be further used as a stabilizer in the preparation of the silver nanoparticles. The above aliphatic carboxylic acid (C) may be used in the above-mentioned amine mixed liquid. By using the aforementioned aliphatic carboxylic acid (C), the stability of the silver nanoparticles, particularly the stability of the coating state dispersed in an organic solvent, is improved.

As the aliphatic carboxylic acid (C), a saturated or unsaturated aliphatic carboxylic acid is used. For example, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, palmitic acid, and ten Carbonic acid, oleic acid, linoleic acid, palmitoleic acid, etc. The number of unsaturated aliphatic monocarboxylic acids is 8 or more.

Within this, as the aliphatic carboxylic acid (C), it is preferred It is a saturated or unsaturated aliphatic monocarboxylic acid having 8 to 18 carbon atoms. When the number of carbon atoms is 8 or more, since the carboxylic acid group is adsorbed on the surface of the silver nanoparticles, the distance from the other silver nanoparticles can be ensured, so that the effect of preventing aggregation of the silver nanoparticles is increased. In view of ease of availability, ease of removal during sintering, and the like, a saturated or unsaturated aliphatic monocarboxylic acid having a carbon number of 18 or more is usually preferable. In particular, caprylic acid, oleic acid or the like is preferably used. The aliphatic carboxylic acid (C) may be used alone or in combination of two or more.

The amount of the aforementioned aliphatic carboxylic acid (C) used is not particularly It is limited, but is preferably 0.05 mol to 10 mol, more preferably 0.1 mol to 5 mol, and even more preferably 0.5 mol, relative to the silver atom of the silver compound (B) of the raw material. ~2 moor. When the amount of the aliphatic carboxylic acid (C) is less than 0.05 mol with respect to 1 mol of the silver atom, the effect of improving the stability of the dispersed state due to the addition of the aliphatic carboxylic acid (C) is weak. On the other hand, when the amount of the aliphatic carboxylic acid (C) exceeds 10 mol, the effect of improving the stability in a dispersed state is saturated, and removal of the aliphatic carboxylic acid (C) under low-temperature sintering becomes difficult.

The foregoing circuit pattern in the light-emitting device of the present invention is borrowed It is formed by sintering the silver nanoparticles of the present invention. The method of sintering the silver nanoparticles can be carried out by a conventional method of forming a metal structure (for example, a film) by sintering the metal nanoparticles, and is not particularly limited, but for example, The composition containing the silver nanoparticle of the present invention is applied onto an insulating substrate or the like in a desired thickness, shape (pattern) or the like, and heated to form. The heating conditions are not particularly limited, but can be utilized at less than 200 ° C by using the silver nanoparticles of the present invention. (for example, 150 ° C or less, preferably 120 ° C or less), a low temperature and a short time of heating of 2 hours or less (for example, 1 hour or less, preferably 30 minutes or less) is sintered. By such sintering, a silver film as the circuit pattern can be formed. Since the silver film has excellent electrical conductivity and thermal conductivity, the obtained light-emitting device (the light-emitting device of the present invention) has excellent quality. Further, since the silver nanoparticle of the present invention has high density and high dispersibility or uniformity, the circuit pattern obtained by sintering without special processing has a small surface roughness Ra (for example, preferably 1 μm or less, more preferably 0.1 μm or less, has excellent gloss (for example, the surface thereof is a mirror surface). Therefore, the light-emitting device of the present invention can be manufactured with excellent efficiency and has excellent quality (for example, high luminosity, etc.). More specifically, the circuit pattern can be formed by, for example, the method described in the following "Examples 1 to 3 of the light-emitting device".

The light emitting device of the present invention may also have an optical semiconductor component, Circuit patterns and components other than the insulating substrate. The member used for the light-emitting device which is conventionally known or conventionally used is not particularly limited, and examples thereof include a protective material covering the optical semiconductor element and all or a part of the circuit pattern. The protective material is used for physically and/or chemically protecting the optical semiconductor element and the circuit pattern, and has, for example, preventing the optical semiconductor element or the like due to dust, moisture, oxygen, corrosive gas, or the like in the air. The function of contamination or damage of the aforementioned circuit pattern. Further, the protective material has a function of, for example, mitigating deterioration or damage of the optical semiconductor element or the circuit pattern due to a physical load such as mechanical force or heat. The aspect of the protective material is provided in the light-emitting device of the present invention, as long as the above-mentioned protection can be achieved There is no particular limitation on the aspect of the protective function, and it is suitable for the selection of the self-study.

As the protective material, a conventional protective material (sealing material) can be used without particular limitation, and for example, a transparent protective material is preferably used. Examples of such a transparent protective material include an epoxy resin, a silicone resin, an acrylic resin, a carbonate resin, and a lowering agent. An olefin resin, a cycloolefin resin, a polyamide resin, or the like.

The method for producing the light-emitting device of the present invention is not particularly limited, and can be carried out in accordance with a conventional method for producing a light-emitting device. Specific examples of the production method include the following steps (a) to (e) (step (a), step (b), step (c), step (d), and step (e). ) as a method of necessary steps, etc.

Step (a): a step of coating a composition containing silver nanoparticles on an insulating substrate

Step (b): a step of sintering the silver nanoparticles contained in the composition

Step (c): a step of mounting an optical semiconductor element on the insulating substrate

Step (d): the step of electrically and/or thermally connecting the optical semiconductor component and the circuit pattern

Step (e): a step of forming a protective material in such a manner as to cover the aforementioned circuit pattern

The method of carrying out the steps in the above steps (a) to (e) is not particularly limited, and can be carried out in accordance with a conventionally used method. Further, the order in which the above steps (a) to (e) are carried out is not particularly limited, but For example, it can be carried out in the order of step (a), step (b), step (c), step (d), and step (e). Specifically, for example, it can be implemented in accordance with the method of implementing each step described in the first to third embodiments of the light-emitting device described later.

Each step in the method of producing a light-emitting device of the present invention can be carried out only once or twice. Further, the above steps (a) to (e) may be carried out sequentially, or two or more steps may be simultaneously performed. In particular, in the method of manufacturing a light-emitting device of the present invention, the steps (b) and (d) can be simultaneously performed. Thereby, the manufacturing efficiency of the light-emitting device can be remarkably improved. The steps (b) and (d) are not particularly limited, but may be applied to an insulating substrate in the shape of a circuit pattern. An optical semiconductor device (detailed in detail) is placed on a composition containing silver nanoparticles (unsintered state) directly or via a conductive paste (may be a composition containing silver nanoparticles) The silver nanoparticle in the above composition is sintered.

The method for producing a light-emitting device of the present invention may include other steps in addition to the above steps (a) to (e).

<Implementation of Light Emitting Device>

Hereinafter, examples of the embodiment of the light-emitting device and the method of manufacturing the same according to the present invention will be described, but the embodiment of the present invention is not limited thereto.

[Embodiment 1 of Light Emitting Device]

An embodiment of the light-emitting device is illustrated in Fig. 1. First, as shown in Fig. 1(a), a composition 3 containing silver nanoparticles (silver nanoparticle of the present invention) is applied to a predetermined position on the upper surface of the insulating substrate 4 which has been formed substantially flat. The above composition 3 is used to form the circuit pattern 2 having a glossy surface. The coating amount of the above-mentioned composition 3 is not particularly limited, but is preferably 0.002 to 0.02 g/cm ² . Further, the coating method of the composition 3 is not particularly limited, but examples thereof include spin coating, inkjet printing, screen printing, dispenser printing, letterpress printing (offset printing), sublimation printing, lithography, and thunder. Screen printer printing (toner printing), gravure printing, contact printing, micro contact printing, and the like.

Next, as shown in Figure 1 (b), the above composition will be applied. The insulating substrate 4 of the object 3 is heated by a heating furnace or the like to sinter the silver nanoparticles contained in the composition 3. The heating conditions can be appropriately adjusted according to the composition or coating amount of the above-mentioned composition 3, and can be adjusted, for example, to less than 200 ° C (for example, 150 ° C or less, preferably 120 ° C or less, more preferably 100 ° C or less, still more preferably 80). (C) or less and 2 hours or less (for example, 1 hour or less, preferably 30 minutes or less, more preferably 15 minutes or less, still more preferably 10 minutes or less). Thereby, the above-described composition 3 can be formed into a circuit pattern 2 having a dense shiny surface and having conductivity. Here, the light reflectance of the glossy surface is preferably from 10 to 100%. Further, when the light reflectance of the glossy surface is 50 to 100%, such a glossy surface is particularly referred to as a "mirror surface".

Next, as shown in FIG. 1(c), a circuit pattern is formed At a predetermined position on the insulating substrate 4 of 2, the optical semiconductor element 1 is mounted via the conductive paste 5. Thereby, the optical semiconductor element 1 is electrically and thermally connected to the circuit pattern 2. Subsequently, as shown in FIG. 1(d), the optical semiconductor element 1 and the other circuit patterns 2 are electrically connected by a bonding wire 6 such as a gold wire. Here, as the conductive paste 5, those skilled in the art of blending a metal powder such as copper powder with a resin binder such as an epoxy resin can be used.

Subsequently, as shown in Fig. 1(e), the protective material 7 is formed so as to cover the circuit pattern 2. Thereby, the light-emitting device of the present invention is completed. Here, the protective material 7 has a function of protecting the glossy surface of the optical semiconductor element 1 or the circuit pattern 2 to prevent dust, moisture, and corrosive gas in the air. The protective material 7 is not particularly limited, and for example, an epoxy resin, a siloxane resin, an acrylic resin, a carbonate resin, or a drop can be used. It is formed of a transparent resin material such as an olefin resin, a cycloolefin resin, or a polyamide resin. Further, as the protective material 7, any transparent material such as glass or inorganic plating may be used in addition to the resin material. Further, the protective material 7 may be formed in a lens shape. In this case, the light emitted from the optical semiconductor element 1 or the light reflected by the shiny surface of the circuit pattern 2 may be converged or diverged by the protective material 7.

[Embodiment 2 of Light Emitting Device]

Another embodiment of the light-emitting device is illustrated in Fig. 2. First, as shown in Fig. 2(a), the composition 3 is applied to a predetermined position on the upper surface of the insulating substrate 4 which has been formed substantially flat. The coating amount or coating method of the above-mentioned composition 3 is the same as that of the first embodiment.

Next, as shown in FIG. 2(b), the optical semiconductor element 1 is mounted at a predetermined position on the insulating substrate 4 to which the composition 3 is applied. Then, as shown in FIG. 2(c), the insulating substrate 4 on which the coating of the composition 3 and the optical semiconductor element 1 are mounted is heated by a heating furnace or the like to form the silver nanoparticles contained in the composition 3. sintering. The heating conditions are the same as in the first embodiment. Thereby, the above-described composition 3 can be formed into a circuit pattern 2 having a dense shiny surface and having conductivity. At the same time, the optical semiconductor element 1 is electrically and thermally connected to the circuit pattern 2. Since this method is different from the first embodiment, the optical semiconductor element 1 can be integrated with the circuit pattern 2 without using the conductive paste 5, so that it can be said to be a highly efficient manufacturing method.

Next, as shown in FIG. 2(d), the optical semiconductor element 1 and the other circuit patterns 2 are electrically connected by a bonding wire 6 such as a gold wire. Next, as shown in FIG. 2(e), in order to cover the circuit pattern 2, the protective material 7 is formed in the same manner as in the first embodiment.

[Embodiment 3 of Light Emitting Device]

Another embodiment of the light-emitting device is illustrated in Fig. 3. First, as shown in FIG. 3(a), an insulating substrate 4 for mounting a concave portion of the optical semiconductor element 1 is prepared. The shape of the concave portion is not particularly limited, and examples thereof include a mortar shape, a hemispherical shape, and an inverted ladder shape. The method of forming the concave portion is not particularly limited, and the flat insulating substrate 4 may be cut, or a concave portion may be formed when the insulating substrate 4 is formed. Further, when the insulating substrate 4 is a metal plate whose surface is subjected to insulation treatment, the flat metal may be subjected to a cutting process or the like to form a concave portion, and then the surface may be insulated, or the insulating substrate 4 may be formed by metal casting or the like. After the recess is formed, the surface is insulated.

Next, as shown in Fig. 3(b), the composition 3 is applied to a predetermined position. The composition 3 may be applied not only to the bottom surface of the concave portion but also to the periphery of the opening of the concave portion from the side surface. As a result, even in the insulating substrate 4 having a complicated shape, the circuit pattern 2 can be formed at an arbitrary position, so that the formation of the high-density circuit pattern 2 is easy.

Next, as shown in FIG. 3(c), the optical semiconductor element 1 is mounted at a predetermined position on the insulating substrate 4 to which the composition 3 is applied. In the third embodiment, the optical semiconductor element 1 is provided with a bump on the lower surface, and the bump is placed in contact with the composition 3, The flip chip assembly of the optical semiconductor element 1 is performed. Then, as shown in FIG. 3(d), the insulating substrate 4 on which the coating of the composition 3 and the optical semiconductor element 1 are mounted is heated by a heating furnace or the like to form the silver nanoparticles contained in the composition 3. sintering. The heating conditions are the same as in the first embodiment. Thereby, the above-described composition 3 can be formed into a circuit pattern 2 having a dense shiny surface and having conductivity. At the same time, the optical semiconductor element 1 is electrically and thermally connected to the circuit pattern 2.

Subsequently, as shown in FIG. 3(e), the same as the first embodiment The protective material 7 is formed in such a manner as to cover the circuit pattern 2. Since this method is different from the above-described first embodiment and the second embodiment, it is not necessary to electrically connect the optical semiconductor element 1 and the other circuit pattern 2 by the bonding wires 6 such as gold wires, so that it can be said to be a highly efficient manufacturing method.

In addition, in any of the embodiments 1 to 3 of the light-emitting device In the case where the silver nanoparticles contained in the composition 3 are dense and have high dispersibility or uniformity, the surface of the composition 3 is not pressed as shown in Patent Document 2, so that the molding die is pressed. The surface of the circuit pattern 2 can also be processed into a mirror surface by the operation of the close contact. Thereby, the light emission from the optical semiconductor element can be easily and efficiently improved. The surface roughness Ra of the obtained circuit pattern 2 is not particularly limited as long as it satisfies the light reflectance of the gloss surface, but is preferably 1 μm or less, and more preferably 0.1 μm or less.

Further, in any of the embodiments 1 to 3 of the light-emitting device In this case, since the silver nanoparticles contained in the composition 3 can be sintered at a low temperature for a short period of time, the light-emitting device can be easily and stably obtained without causing thermal damage to the optical semiconductor element 1.

Further, in any of the first to third embodiments of the light-emitting device, the silver nanoparticles contained in the composition 3 are excellent in stability or dispersibility, and are sintered at a low temperature for a short period of time. For example, when a silver sintered film of a relatively thick film of 1 μm or more is used, good conductivity or thermal conductivity can be imparted, so that production stability and production efficiency are excellent, and a light-emitting device excellent in energy efficiency and durability can be easily obtained.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited by the examples.

[Specific resistance value of silver sintered film]

The obtained silver sintered film was measured using a four-end method (Loresta GP MCP-T610). The measuring range limit of this device is 10 ⁷ Ωcm.

The following reagents were used in each of the examples and comparative examples.

N,N-dimethyl-1,3-propanediamine (MW: 102.18): manufactured by Tokyo Chemical Industry Co., Ltd.

2-ethylhexylamine (MW: 129.25): Tested by Wako Pure Chemical Co., Ltd.

N-butylamine (MW: 73.14): Tested by Tokyo Chemical Industry Co., Ltd.

n-Hexylamine (MW: 101.19): Tested by Tokyo Chemical Industry Co., Ltd.

N-octylamine (MW: 129.25): Tested by Tokyo Chemical Industry Co., Ltd.

Oleic acid (MW: 282.47): Tested by Tokyo Chemical Industry Co., Ltd.

Methanol: Wako Pure Chemicals Co., Ltd.

1-butanol: Tokyo Chemical Industry Co., Ltd.

Octane: Heguang Pure Pharmaceutical Co., Ltd.

Dihydroxyterpineol: manufactured by Japan Terpene Co., Ltd.

Silver oxalate (MW: 303.78): Synthesized by silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) and oxalic acid dihydrate (manufactured by Wako Pure Chemical Co., Ltd.)

[Example 1] (modulation of silver nanoparticles)

In a 50 mL flask, 1.28 g (12.5 mmol) of N,N-dimethyl-1,3-propanediamine, 0.91 g (12.5 mmol) of n-butylamine, 3.24 g (32.0 mmol) of n-hexylamine, 0.39 g ( 3.0 mmol) of n-octylamine and 0.09 g (0.33 mmol) of oleic acid were stirred at room temperature to prepare a homogeneous mixed solution (amine-carboxylic acid mixed solution).

To the prepared mixed solution, 3.04 g (10 mmol) of silver oxalate was added, and the mixture was stirred at room temperature, and the stirring was terminated at the time when it was considered that the change to the viscous white matter was observed.

Next, the obtained reaction mixture was heated and stirred at 105 ° C to 110 ° C. Immediately after the start of the agitation, the reaction accompanying the generation of carbon dioxide started, and then the stirring was continued until the carbon dioxide production was completed, and as a result, a suspension of silver nanoparticles in which the blue luster was suspended was obtained.

Next, 10 mL of methanol was added to the obtained suspension and stirred, and then the silver nanoparticles were sedimented by centrifugation to remove the supernatant. To the obtained silver nanoparticle, 10 mL of methanol was further added and stirred, and then the silver nanoparticles were sedimented by centrifugation to remove the supernatant. In this way, silver nanoparticles in a wet state were obtained.

(Modulation and sintering of silver nano coatings)

Subsequently, a mixed solution of 1-butanol/octane (volume ratio = 1/4) and stirring was added to the wet silver nanoparticles to obtain a silver concentration of 50% by weight to prepare a silver nanoparticle dispersion ( Silver nano paint). The silver nanoparticle dispersion liquid was applied onto an alkali-free glass plate by a spin coating method so as to have a film thickness after sintering of about 1 μm to form a coating film.

After the formation of the coating film, it was rapidly sintered in a blow drying oven at 120 ° C for 15 minutes to form a silver sintered film having a thickness of about 1 μm. The specific resistance value of the obtained silver sintered film was measured by a four-terminal method and found to be 8.4 μΩcm.

In addition, the silver nanoparticle dispersion liquid was subjected to [1] initial dispersion evaluation and [2] storage stability evaluation as follows.

[1] The silver nanoparticle dispersion immediately after the preparation was filtered with a 0.2 μm filter, and as a result, no filter clogging occurred. That is, the silver nanoparticle dispersion described above maintains a good dispersion state.

[2] The silver nanoparticle dispersion liquid immediately after preparation was placed in a sample bottle made of a transparent glass, and sealed in a dark place at 25 ° C for 7 days, and as a result, no silver mirror was observed. The silver nanoparticle dispersion after storage was filtered through a 0.2 μm filter, and as a result, no filter clogging occurred. That is, the silver nanoparticle dispersion after storage is kept in a good dispersion state.

(About silver oxalate-amine complex)

The white substance having a viscosity obtained by the preparation of the above silver nanoparticles was subjected to DSC (differential scanning calorimeter) measurement, and as a result, the average temperature value of the exothermic temperature due to thermal decomposition was 102.5 °C. On the other hand, the silver oxalate of the raw material was subjected to DSC measurement in the same manner, and as a result, the average exothermic temperature value due to thermal decomposition was 218 °C. As described above, the viscous white matter obtained by the preparation of the above-mentioned silver nanoparticles has a lower thermal decomposition temperature than the silver oxalate of the raw material. Accordingly, it is shown that the viscous white substance obtained by the preparation of the above silver nanoparticles is a combination of silver oxalate and an alkylamine, and it is presumed that the amine group of the alkylamine is bonded to the silver atom of silver oxalate. A silver oxalate-amine complex.

The DSC measurement conditions are as follows.

Device: DSC 6220-ASD2 (manufactured by SII Nano Technology Co., Ltd.)

Sample container: 15μL gold-plated sealed box (SII Nano Technology Co., Ltd.)

Heating rate: 10 ° C / min (room temperature ~ 600 ° C)

Ambient gas: inside the box, atmospheric pressure, enclosed air

Outside the box, nitrogen flow (50mL/min)

Further, the modulation of the silver nanoparticles in the resulting sticky white substance performs spectrometry IR, absorption was observed from a group of alkylamine (2900cm ^-1 vicinity near 1000cm ^-1). Accordingly, it has also been shown that the viscous white substance obtained by the preparation of the above silver nanoparticles is a combination of silver oxalate and an alkylamine, and it is presumed that the amine group is bonded to the silver atom of silver oxalate. Silver oxalate-amine complex.

[Embodiment 2]

In addition to the preparation of the silver nanoparticles, the composition of the amine-carboxylic acid mixed solution was changed to 1.28 g (12.5 mmol) of N,N-dimethyl-1,3-propanediamine and 0.91 g (12.5 mmol). A silver nanoparticle dispersion liquid was prepared in the same manner as in Example 1 except that butanamine, 3.24 g (32.0 mmol) of n-hexylamine, 0.39 g (3.0 mmol) of n-octylamine, and 0.13 g (0.45 mmol) of oleic acid were used. Formed and sintered.

The obtained silver sintered film had a film thickness of about 1 μm and a specific resistance value of 11.3 μΩcm.

[Example 3]

In addition to the preparation of the silver nanoparticles, the composition of the amine-carboxylic acid mixed solution was changed to 1.53 g (15.0 mmol) of N,N-dimethyl-1,3-propanediamine and 0.73 g (10.0 mmol). Butylamine, 3.24g (32.0mmol) is already A silver nanoparticle dispersion liquid was prepared in the same manner as in Example 1 except that the amine, 0.39 g (3.0 mmol) of n-octylamine, and 0.13 g (0.45 mmol) of oleic acid were used to form and sinter the coating film.

The obtained silver sintered film had a film thickness of about 1 μm and a specific resistance value of 14.2 μΩcm.

[Example 4]

In addition to the preparation of the silver nanoparticles, the composition of the amine-carboxylic acid mixed solution was changed to 1.02 g (10 mmol) of N,N-dimethyl-1,3-propanediamine and 1.10 g (15.0 mmol) of n-butyl. A silver nanoparticle dispersion liquid was prepared in the same manner as in Example 1 except that the amine, 3.24 g (32.0 mmol) of n-hexylamine, 0.39 g (3.0 mmol) of n-octylamine, and 0.13 g (0.45 mmol) of oleic acid were used to form a coating film. ,sintering.

The obtained silver sintered film had a film thickness of about 1 μm and a specific resistance value of 14.5 μΩcm.

[Example 5] (modulation of silver nanoparticles)

To a 50 mL flask, 10.84 g (150 mmol) of n-butylamine and 3.00 g (30 mmol) of n-hexylamine were added, and the mixture was stirred at room temperature to prepare a homogeneous mixed solution (amine mixed solution).

To the prepared mixed solution, 3.04 g (10 mmol) of silver oxalate was added, and the mixture was stirred at room temperature, and the stirring was terminated at the time when it was considered that the change to the viscous white matter was observed.

Next, the resulting reaction mixture was heated and stirred at 85 ° C to 90 ° C. After the heating and stirring were started, the color was slowly changed toward brown color, and the mixture was heated and stirred for 2 hours to obtain a suspension in which silver nanoparticles were suspended.

Next, 10 mL of methanol was added to the obtained suspension and stirred, and then the silver nanoparticles were sedimented by centrifugation to remove the supernatant. To the obtained silver nanoparticle, 10 mL of methanol was further added and stirred, and then the silver nanoparticles were sedimented by centrifugation to remove the supernatant. In this way, silver nanoparticles in a wet state were obtained.

(Modulation and sintering of silver nano coatings)

Subsequently, in the wet silver nanoparticles, dihydroxy terpineol was added and stirred so as to have a silver concentration of 70% by weight to prepare a paste containing silver nanoparticles (silver nano paint). The silver-containing nanoparticle-containing paste was applied onto an alkali-free glass plate by an applicator to form a coating film.

The coating film was sintered in a blow drying oven under the respective conditions shown below to form a silver sintered film of each thickness. The specific resistance value of the obtained silver sintered film was measured by a four-terminal method.

[1] Sintering conditions: 80 ° C, 30 minutes

Film thickness after sintering: 6.77μm

The specific resistance value of the sintered film: 1.70E-05 Ωcm (ie, 17 μΩcm)

[2] Sintering conditions: 80 ° C, 60 minutes

Film thickness after sintering: 4.96μm

Specific resistance of sintered film: 1.00E-05Ωcm

[3] Sintering conditions: 120 ° C, 15 minutes

Film thickness after sintering: 5.42 μm

The specific resistance of the sintered film: 6.03E-06Ωcm

[Embodiment 6]

A paste containing silver nanoparticles was prepared in the same manner as in Example 5 except that 3.00 g (30 mmol) of n-hexylamine was changed to 3.88 g (30 mmol) of n-octylamine in the composition of the amine mixed solution, and a coating film was formed. Sintering under the conditions shown below.

[1] Sintering conditions: 80 ° C, 30 minutes

Film thickness after sintering: 6.38μm

Specific resistance of sintered film: 6.23E-05Ωcm

[2] Sintering conditions: 80 ° C, 60 minutes

Film thickness after sintering: 4.70 μm

Specific resistance of sintered film: 2.21E-05Ωcm

[3] Sintering conditions: 120 ° C, 15 minutes

Film thickness after sintering: 4.73 μm

Specific resistance of sintered film: 8.34E-06Ωcm

[Reference Example 1]

In addition to the preparation of the silver nanoparticles, the composition of the amine-carboxylic acid mixed solution was changed to 2.55 g (25.0 mmol) of N,N-dimethyl-1,3-propanediamine, 3.24 g (32.0 mmo n-hexylamine). In the same manner as in Example 1, except that 0.39 g (3.0 mmol) of n-octylamine and 0.13 g (0.45 mmol) of oleic acid were used, a silver nanoparticle dispersion liquid was prepared. Then, in the same manner as in the first embodiment, the coating film was formed and sintered so that the film thickness after sintering was about 1 μm.

The obtained silver sintered film had a film thickness of about 1 μm and a specific resistance value of about 2.0E+08 μΩcm.

[Reference Example 2]

In addition to the composition of the amine mixed solution, 10.84 g (150 mmol) of n-butylamine and 3.00 g (30 mmol) of n-hexylamine were changed to 8.67 g (120 mmol) of n-butylamine and 6.00 g (60 mmol) of n-hexylamine, respectively, and Examples 5 A paste containing silver nanoparticles was prepared in the same manner to form a coating film and to be sintered under the conditions shown below.

[1] Sintering conditions: 80 ° C, 30 minutes

Film thickness after sintering: 6.14μm

Specific resistance of sintered film: 3.21E-05Ωcm

[2] Sintering conditions: 80 ° C, 60 minutes

Film thickness after sintering: 5.11μm

Specific resistance of sintered film: 1.72E-05Ωcm

[3] Sintering conditions: 120 ° C, 15 minutes

Film thickness after sintering: 4.63μm

Specific resistance of sintered film: 7.42E-06Ωcm

[Reference Example 3]

In addition to the composition of the amine mixed solution, 10.84 g (150 mmol) of n-butylamine and 3.88 g (30 mmol) of n-octylamine were changed to 8.67 g (120 mmol) of n-butylamine and 7.66 g (60 mmol) of n-octylamine, respectively. In the same manner as in Example 6, a paste containing silver nanoparticles was prepared, and a coating film was formed and sintered under the following conditions.

[1] Sintering conditions: 80 ° C, 30 minutes

Film thickness after sintering: 6.04μm

Specific resistance of sintered film: 2.17E-02Ωcm

[2] Sintering conditions: 80 ° C, 60 minutes

Film thickness after sintering: 6.45μm

The specific resistance of the sintered film: 2.88E-04Ωcm

[3] Sintering conditions: 120 ° C, 15 minutes

Film thickness after sintering: 7.15μm

Specific resistance of sintered film: 1.10E-04Ωcm

Industrial utilization possibility

The light-emitting device and the method for producing the same according to the present invention are applicable to a light-emitting device such as a light-emitting diode (LED) device which is excellent in conductivity or heat dissipation and has high light-emitting efficiency, and a method of manufacturing the same.

1‧‧‧Optical semiconductor components

2‧‧‧ circuit pattern

3‧‧‧Composition containing silver nanoparticles

4‧‧‧Insert substrate

5‧‧‧ Conductive paste

6‧‧‧bonding line

7‧‧‧Protective materials

Claims (10)

A light-emitting device comprising an optical semiconductor device, a circuit pattern and an insulating substrate, wherein the optical semiconductor component is electrically and/or thermally connected to the circuit pattern, and the circuit pattern is disposed on the light-emitting device Above the insulating substrate, the circuit pattern is formed by sintering silver nanoparticles, and the silver nanoparticle system comprises a mixture of an amine (A) having an aliphatic hydrocarbon group and an amine group and a silver compound (B). Silver nanoparticles obtained by thermal decomposition. The light-emitting device according to claim 1, wherein the mixture contains, as the amine (A), an aliphatic hydrocarbon monoamine (A1) having an aliphatic hydrocarbon group and an amine group of 6 or more, and an aliphatic hydrocarbon group and An aliphatic hydrocarbon monoamine (A2) having a carbon number of 5 or less formed by one amine group, and an aliphatic hydrocarbon diamine (A3) having 8 or less carbon atoms formed from an aliphatic hydrocarbon group and two amine groups. The light-emitting device according to claim 1, wherein the mixture contains, as the amine (A), an aliphatic hydrocarbon monoamine (A1) having an aliphatic hydrocarbon group and an amine group of 6 or more, and an aliphatic hydrocarbon group. The aliphatic hydrocarbon monoamine (A2) having a carbon number of 5 or less formed with one amine group is 5 mol% or more and less than the total of the monoamine (A1) and the monoamine (A2). The ratio of 20 mol% includes the monoamine (A1), and the monoamine (A2) is contained in a ratio of more than 80 mol% and 95 mol% or less. The light-emitting device according to claim 1, wherein the mixture contains a branched aliphatic hydrocarbon monoamine (A4) which is a branched aliphatic hydrocarbon group having 4 or more carbon atoms and an amine group as the amine (A). The light-emitting device of claim 1, wherein the silver compound (B) is silver oxalate. The light-emitting device according to any one of claims 1 to 5, wherein the silver nanoparticles have an average particle diameter of from 0.5 nm to 100 nm. The illuminating device of any one of claims 1 to 6, wherein the optical semiconductor component and all or a portion of the circuit pattern are covered with a transparent protective material. The light-emitting device of claim 7, wherein the protective material is an epoxy resin, a phthalic resin, an acrylic resin, a carbonate resin, or a lowering One or more materials selected from the group consisting of an olefin resin, a cycloolefin resin, and a polyamide resin. A method of manufacturing a light-emitting device according to any one of claims 1 to 8, comprising: a step (a) of coating a composition comprising silver nanoparticles on an insulating substrate; a step (b) of sintering the silver nanoparticles contained in the composition; a step (c) of mounting the optical semiconductor element on the insulating substrate; and a step of electrically and/or thermally connecting the optical semiconductor element and the circuit pattern ( d); and, step (e) of forming a protective material in such a manner as to cover the circuit pattern. A method of manufacturing a light-emitting device according to claim 9, wherein the step (b) and the step (d) are simultaneously performed.