TW201407641A - Silver-containing composition and substrate having silver element formed thereon - Google Patents

Abstract

Provided are a silver-containing composition exhibiting high storage stability and a silver component forming base material using the composition, according to which a silver component such as a metal silver film or wire which exhibits excellent conductivity and adhesion can be obtained by sintering at a low temperature of 120 DEG C or below for a short amount of time or sintering at 150 DEG C or higher for an extremely short amount of time. The composition of the present invention comprises a silver compound (A) represented by formula (1), an amine compound (B) represented by formula (2) and a silane coupling agent (C), where the silver compound (A), the amine compound (B) and the silane coupling agent (C) are included at a specific ratio. (R1: hydrogen, -(CY1Y2)a-CH3, or ((CH2)b-O-CHZ)c-CH3, R2: -(CY1Y2)d-CH3, -((CH2)e-O-CHZ)f-CH3, Y1, Y2: hydrogen or -(CH2)g-CH3, Z: hydrogen or -(CH2)h-CH3, a: 0 to 8, b: 1 to 4, c: 1 to 3, d: 0 to 8, e: 1 to 4, f: 1 to 3, g: 0 to 3, h: 0 to 2).

Description

Silver-containing composition and substrate forming silver component

The present invention relates to a silver-containing composition capable of producing a silver component such as a metallic silver film or a metallic silver wire which is excellent in adhesion and conductivity by low-temperature sintering, and a silver-forming composition obtained by heating the composition on the surface of a substrate. The substrate of the ingredients.

As a method of preparing a metal thin film or a wire, a method in which a metal is used as a liquid ink or a slurry ink, which is coated or printed on a substrate and then heated is known. As the metal to be used, gold, silver, copper, and aluminum are used as a raw material of a wiring material, and general silver is used. In the case of an ink using silver, an ink in which metal silver is dispersed in a dispersion solvent is generally used, a pattern is formed on a wiring substrate, and metallic silver in the ink is sintered to form a wiring. In the case where metallic silver is used as the conductive metal material, a method of sintering at a low temperature by using a decrease in melting point due to refinement of the dispersed metallic silver is known. However, since the fine metal silver particles which show a decrease in the melting point are in contact with each other, aggregation tends to occur. Therefore, in order to prevent aggregation, it is necessary to add a dispersing agent to the ink (for example, refer to Patent Document 1). Therefore, when the slurry containing the dispersant is used, the metal silver particles are sintered, and impurities from the dispersant remain, and good conductivity is not obtained at a low temperature of 120 ° C or lower, preferably 150 ° C or higher. height of Warm and long-term treatment to remove impurities.

In recent years, attempts have been made to prepare metallic silver for transparent resin substrates. However, generally, the transparent resin substrate has a low softening point as compared with glass or the like. Therefore, a low-temperature sinterable silver forming material capable of producing metallic silver by heating at less than 150 ° C is desired. In view of such a background, there is a need for a silver-containing composition capable of forming a silver component such as a metallic silver film or a wire which exhibits good conductivity by sintering at a low temperature of 120 ° C or lower or sintering for a very short time of 150 ° C or more. .

As a silver material capable of low-temperature sintering, a method of forming metallic silver by using a silver salt of an organic acid has been reported (Patent Document 2). The organic silver salt is a silver salt containing a monofunctional carboxylic acid and silver, so that the silver content in the compound is low, and the organic component remaining during sintering increases. In order to decompose or evaporate the organic component, it is necessary to extend the sintering time. Further, the organic silver salt exhibiting low-temperature sinterability has a problem of poor thermal stability and poor storage stability of the silver-containing composition.

Prior art literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2005-60824.

Patent Document 2: Japanese Laid-Open Patent Publication No. 2008-159535.

The technical problem of the present invention is to provide a silver-containing composition having high storage stability, which can be obtained by sintering at a low temperature and a short time below 120 ° C or sintering at a temperature of 150 ° C or more for a short time. A silver component such as a metallic silver film or a wire excellent in adhesion.

Another object of the present invention is to provide a substrate comprising a silver component such as a metallic silver film or a silver component which is excellent in conductivity and adhesion.

According to the present invention, there is provided a silver-containing composition comprising a combination of the silver compound (A) represented by the formula (1), the amine compound (B) represented by the formula (2), and a decane coupling agent (C). The silver compound (A), the amine compound (B), and the decane coupling agent (C) are contained in an amount of 10 to 50% by mass based on 100% by mass of the total amount of the silver compound (A) and 50 to 90% by mass. Amine compound (B) and 0.1 to 5% by mass of a decane coupling agent (C);

Wherein R ¹ represents a hydrogen atom, -(CY ¹ Y ² )a-CH ₃ or -((CH ₂ )bO-CHZ)c-CH ₃ , and R ² represents -(CY ¹ Y ² )d-CH ₃ or -((CH ₂ )eO-CHZ)f-CH ₃ . Here, Y ¹ and Y ² each independently represent a hydrogen atom or -(CH ₂ )g-CH ₃ , and Z represents a hydrogen atom or -(CH ₂ )h-CH ₃ . a is an integer of 0 to 8, b is an integer of 1 to 4, c is an integer of 1 to 3, d is an integer of 0 to 8, preferably an integer of 1 to 8, and e is an integer of 1 to 4, f is an integer of 1 to 3, g is an integer of 0 to 3, preferably an integer of 1 to 3, and h is an integer of 0 to 2, preferably an integer of 1 to 2.

Further, according to the present invention, there is provided a substrate for forming a silver component which is coated with a silver-containing composition on a substrate and which is heated to form a silver component.

Further, according to the present invention, as used for coating and heating on a substrate For the composition in which a silver component is formed on the substrate, the above silver-containing composition can be used.

Since the silver-containing composition of the present invention contains the silver compound (A), the amine compound (B), and the decane coupling agent (C) in a specific ratio, it can be formed at a low temperature and a short time of sintering at 120 ° C or lower. It has excellent conductivity and excellent silver adhesion to various substrates such as glass, enamel, ITO, and polyester, and is excellent in storage stability. Further, for example, the concentration of silver in the composition can be increased, and the silver component can be rapidly obtained at a low temperature of 120 ° C or lower without a catalyst. Since the metallic silver component can be formed at a low temperature, for example, a silver component can be formed on a resin substrate having low heat resistance in a short time. Further, since the metal silver component can be formed in a shorter time at a high temperature of 150 ° C or higher, productivity is expected to be improved. Since the silver component thus obtained has high adhesion to various substrates, the silver component obtained by applying or printing the composition and then heating is expected to be used in various technical fields such as wiring materials and reflective materials.

Hereinafter, the present invention will be described in further detail.

The silver-containing composition of the present invention (hereinafter sometimes referred to simply as a composition) contains the silver compound (A) represented by the above formula (1) and the amine compound (B) represented by the above formula (2) in a specific ratio. A decane coupling agent (C).

The silver compound (A) is silver acetone dicarboxylate, and its form is usually a powder. Public It is known that when the silver compound (A) is diluted into a solvent, its viscosity is increased, and it is difficult to form a pattern decoration such as printing.

However, by combining with the above-described amine compound (B), the composition having a high silver content can also be set to have a reduced viscosity, and can be sintered at a low temperature of 120 ° C or lower for a short time to form metallic silver.

On the other hand, a silver component such as a metallic silver film or a wire obtained by combining a silver compound (A) and an amine compound (B) is used for various substrates such as glass, ruthenium, ITO, and polyester. Poor attachment. Therefore, by further mixing the decane coupling agent (C) in the silver compound (A) and the amine compound (B) in a characteristic ratio, the formed silver component can be maintained even at a low temperature of 120 ° C or lower and a short time of sintering. Good electrical conductivity, while significantly improving the adhesion to a variety of substrates.

In the composition of the present invention, the silver compound (A) is contained in an amount of 10 to 50% by mass based on 100% by mass of the total of the silver compound (A), the amine compound (B) and the decane coupling agent (C). The content ratio of the amine compound (B) is 50 to 90% by mass, and the content of the decane coupling agent (C) is 0.1 to 5% by mass. When the content ratio of the amine compound (B) is less than 50% by mass, the solubility of the silver compound (A) is remarkably lowered. In addition, when the content ratio of the decane coupling agent (C) is less than 0.1% by mass, the adhesion of the obtained silver component to the substrate is insufficient, and when it is more than 5% by mass, Although adhesion can be obtained, conductivity is deteriorated. The content ratio of the decane coupling agent (C) is preferably from 0.3 to 5% by mass from the viewpoint of adhesion and conductivity.

The preparation method of the silver compound (A) used in the present invention is not limited at all.

The amine compound (B) used in the present invention is a compound represented by the above formula (2), wherein R ¹ represents a hydrogen atom, -(CY ¹ Y ² )a-CH ₃ or -((CH ₂ )bO- CHZ)c-CH ₃ , R ² represents -(CY ¹ Y ² )d-CH ₃ or -((CH ₂ )eO-CHZ)f-CH ₃ . Here, Y ¹ and Y ² each independently represent a hydrogen atom or -(CH ₂ )g-CH ₃ , and Z represents a hydrogen atom or -(CH ₂ )h-CH ₃ . a is an integer from 0 to 8, b is an integer from 1 to 4, c is an integer from 1 to 3, d is an integer from 0 to 8, e is an integer from 1 to 4, f is an integer from 1 to 3, and g is An integer from 0 to 3, where h is an integer from 0 to 2.

As the amine compound (B), for example, ethylamine, 1-propylamine, 1-butylamine, 1-pentylamine, 1-hexylamine, 1-heptylamine, 1-octylamine, 2-ethylhexylamine can be exemplified. , isopropylamine, isobutylamine, isoamylamine, sec-butylamine, tert-butylamine, tert-amylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-isopropoxypropylamine, diisopropylamine, dibutyl One or more of the amines.

In the case where the composition of the present invention exhibits low-temperature sinterability at less than 150 ° C, the amine compound (B) having a boiling point of less than 130 ° C is more preferably used. As such an amine compound (B), for example, 1-propylamine, 1-butylamine, 1-pentylamine, 1-hexylamine, 1-heptylamine, 1-octylamine, isopropylamine, isobutylamine can be suitably exemplified. One or more of isoamylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-isopropoxypropylamine, diisopropylamine, and dibutylamine.

The decane coupling agent (C) is a compound having two different functional groups of an organic functional group and an alkoxy group in one molecule. The organic functional group may, for example, be a vinyl group, an allyl group, a styryl group, an epoxy group, a (meth)acryl group, an amino group, a ureido group, a fluorenyl group, a thioether group or an isocyanate group.

As the decane coupling agent (C), for example, a compound represented by the formula (3) can be exemplified.

Wherein R ³ represents -(CH ₂ )i-CH=CH ₂ , -(CH ₂ )jR ⁶ , -C ₆ H ₄ -CH=CH ₂ , -(CH ₂ ) ₃ -O-(C=O )-CR ⁷ =CH ₂ , -(CH ₂ ) ₃ -NHR ⁸ , -(CH ₂ ) ₃ -R ⁹ , -(CH ₂ ) ₃ -SR ¹⁰ or -(CH ₂ ) ₃ -N=C=O Here, R ⁶ is an organic functional group represented by the formula (4) or the formula (5), R ⁷ represents a hydrogen atom or -CH ₃ , and R ⁸ represents a hydrogen atom, -(CH ₂ ) ₂ -NH ₂ , -C ₆ H ₅ or -(C=O)-NH ₂ , R ⁹ represents an organic functional group represented by the formula (6), and R ¹⁰ represents a hydrogen atom or -SSS-(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ . i is 0 or 1, and j is 2 or 3. R ⁴ represents a methyl group, a methoxy group, an ethoxy group or an ethyloxy group, and R ⁵ represents a methyl group, an ethyl group or an ethyl fluorenyl group.

As the decane coupling agent (C) represented by the above formula (3), for example, vinyl trimethoxy decane, vinyl ethoxy decane, vinyl triethoxy decane, allyl trimethoxy hydride can be exemplified. Baseline, p-styryltrimethoxydecane, 2-(3,4-epoxycyclohexane)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidol Etheroxypropyltriethoxydecane, 3-glycidyloxypropylmethyldimethoxydecane, 3-glycidyloxypropylmethyldiethoxydecane, 3-methylpropene Methoxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methyl C Alkyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N- 2-(Aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxymethylidene-N -(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-mercaptopropylmethylmethyl Oxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, bis(triethoxycarbamidopropyl)tetrasulfide, 3-isocyanatepropyltriethoxylate Base decane.

When the composition of the present invention is a composition in which the obtained silver component is particularly excellent in adhesion to a substrate, a decane coupling agent (C) having an amino group is preferably used. The decane coupling agent (C) having an amino group represented by the formula (3) is a compound wherein R ³ in the formula (3) is -(CH ₂ ) ₃ -NHR ⁸ or (CH ₂ ) ₃ -R ⁹ . Here, R ⁸ represents a hydrogen atom, -(CH ₂ ) ₂ -NH ₂ , -C ₆ H ₅ or (C=O)-NH ₂ , and R ⁹ represents an organofunctional group represented by the formula (6).

As the decane coupling agent having an amino group, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-amino group can be exemplified. Propyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxycarbamido-N-(1,3-dimethylbutylene) ) propylamine, N-phenyl-3-aminopropyltrimethoxydecane.

In the case of preparing the composition of the present invention, the order of mixing the silver compound (A), the amine compound (B) and the decane coupling agent (C) is not particularly limited. For example, a method of adding a decane coupling agent (C) to a mixture of the silver compound (A) and the amine compound (B), and adding silver to a mixture of the amine compound (B) and the decane coupling agent (C) may be mentioned. A method of the compound (A), a method of adding an amine compound (B) to a mixture of the silver compound (A) and the decane coupling agent (C).

In the composition of the present invention, in addition to the silver compound (A), the amine compound (B), and the decane coupling agent (C), a solvent may be appropriately added in order to improve the coating property to the substrate or to adjust the viscosity. The amount of the solvent is preferably from 20 to 80% by mass based on 100% by mass of the total of the silver compound (A), the amine compound (B), and the decane coupling agent (C) and the solvent. When the amount of the solvent exceeds 80% by mass, a uniform silver film may not be obtained because the amount of silver contained is lowered.

The kind of the solvent is not particularly limited, but is preferably a type which is easily removed when preparing a silver component, and the solvent may be used singly or in combination depending on the use. As the solvent, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propene may be exemplified. Alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl- 1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl- 3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 3,3-dimethyl-1 -butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, ethylene glycol, butoxyethanol, A Alcohols such as oxyethanol, ethoxyethanol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether; acetoxymethoxypropane, phenyl glycidyl ether, Ethers such as ethylene glycol glycidol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile, propionitrile, butyronitrile, and isobutyl nitrile; , 1-methyl-2-pyrrolidone or two or more.

Examples of the solvent for further improving the flatness and low-temperature sinterability of the formed silver component include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and 2-methyl. 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butene Alcohol, 2,2-dimethyl-1-propanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1- Butanol, 2,3-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl- 2-butanol, 2-ethyl-1-butanol, ethylene glycol, butoxyethanol, methoxyethanol, ethoxyethanol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether And one or more of dipropylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, propionitrile, butyronitrile, and isobutyronitrile.

In the case of using the above solvent, the order of mixing the silver compound (A), the amine compound (B), the decane coupling agent (C), and the solvent is not particularly limited. For example, a method of adding a solvent to a mixture of a silver compound (A), an amine compound (B), and a decane coupling agent (C), and a silver compound (A) and a mixture of the amine compound (B) and a solvent may be mentioned. a method of adding a amide coupling agent (C), a method of adding an amine compound (B) and a decane coupling agent (C) to a mixture of a silver compound (A) and a solvent, and a mixture of a decane coupling agent (C) and a solvent A method of adding a silver compound (A) and an amine compound (B).

In the composition of the present invention, if necessary, in order to adjust the leveling property to the substrate, for example, a hydrocarbon, an acetylene alcohol or an eucalyptus oil may be appropriately mixed, and in order to adjust the viscosity characteristics of the composition, for example, a resin or a resin may be appropriately mixed. Plasticizer. Further, other conductor powders, glass powders, surfactants, metal salts or other additives generally used for the silver-containing composition may be appropriately mixed as needed, for example.

In the composition of the present invention, in order to further shorten the sintering time, the composition may be heated in advance, or a generally known reducing agent may be acted upon to form a silver colloidal dispersion liquid which forms silver clusters and nanoparticles.

The reducing agent may, for example, be a boron hydride compound, a tertiary amine, a thiol compound, a phosphorus compound, ascorbic acid, an anthraquinone or a phenol. The amount of the reducing agent to be used can be appropriately selected within the range not impairing the conductivity or flatness of the obtained silver component.

The silver component-forming substrate of the present invention is a substrate having a silver component which is applied onto a substrate such as a substrate by a silver-containing composition, and the substrate is heated to form a metallic silver film or A silver component that is linear.

The material of the substrate to which the composition of the present invention is applied is not particularly limited, and examples thereof include glass, ruthenium, tantalum nitride, ITO, copper, aluminum, polyimine, polyester, and polycarbonate. From the viewpoint of productivity, it is preferably applied to a resin substrate such as a soft polyester of various printing methods.

The coating of the substrate of the composition of the present invention can be carried out by printing or the like. The heating temperature at the time of heat-treating the substrate is not particularly limited as long as it is room temperature or higher. However, in consideration of productivity, in order to perform baking in a short time, heating at 80 ° C or higher is preferable. In particular, when a silver component such as a metallic silver film or a silver wiring is formed on a resin substrate having low heat resistance such as polyester or polycarbonate, it is preferably heated at a temperature of 80 ° C or more and less than 150 ° C. Moreover, when using the base material excellent in heat resistance, it is preferable to carry out the heat processing of 120 degreeC or more and less than 170 degreeC from a viewpoint of productivity.

[Examples]

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

Synthesis Example 1 Synthesis of Silver Acetone Dicarboxylate

After weighing 43.8 g of acetone dicarboxylic acid into a 1000 ml beaker, 600 g was added. The solution was dissolved in deionized water, and ice-cooled, and 102 g of silver nitrate was further added and dissolved. After 48 g of hexylamine was added thereto, the mixture was stirred for 30 minutes. The obtained white solid was collected by filtration, washed with acetone, and dried under reduced pressure to obtain 88.2 g of silver succinate dicarboxylate (hereinafter, abbreviated as silver salt (A)). The yield was 82%.

Example 1-1

In a light-shielding bottle, 100 mg of the silver salt (A) prepared as Synthesis Example 1 of the silver compound (A) was dissolved in 896 mg of hexylamine (HA) as the amine compound (B), and 4 mg of a decane coupling agent was added and mixed. (C) N-2-(Aminoethyl)-3-aminopropyltrimethoxydecane gives 1000 mg of a silver-containing composition. The amount of the silver compound (A), the amount of the amine compound (B), the substituent in the above formula (2), the amount of the decane coupling agent (C), and the substituent in the above formula (3) are shown in Table 1. in.

Example 1-2~1-5

The same procedure as in Example 1-1 was carried out except that the amounts of the silver salt (A), HA and N-2-(aminoethyl)-3-aminopropyltrimethoxydecane were changed as shown in Table 1. Silver-containing composition.

Example 1-6

In a light-shielding bottle, 398 mg of the silver salt (A) prepared as Synthesis Example 1 of the silver compound (A) was dissolved in 597 mg of HA as the amine compound (B), and 5 mg of ethylene as a decane coupling agent (C) was added. Base triethoxy decane gives 1000 mg of the silver-containing composition. The amount of the silver compound (A), the amount of the amine compound (B), the substituent in the above formula (2), the amount of the decane coupling agent (C), and the substituent in the above formula (3) are shown in Table 1. in.

Example 1-7~1-21

The decane coupling agent (C) was changed to allyltrimethoxy in Examples 1-7. Decane, changed to 2-(3,4-epoxycyclohexane)ethyltrimethoxydecane in Example 1-8, and changed to 3-glycidoxypropylpropyl in Example 1-9 Dimethoxy decane, changed to 3-glycidoxypropylmethyldiethoxy decane in Examples 1-10, and changed to p-styryltrimethoxydecane in Examples 1-11 In Example 1-12, it was changed to 3-methacryloxypropyltrimethoxydecane, and in Example 1-13, it was changed to 3-propenyloxypropyltrimethoxydecane, in the Example. Changed to N-2-(aminoethyl)-3-aminopropyltrimethoxydecane in 1-14, and changed to 3-aminopropyltrimethoxydecane in Examples 1-15, in Example 1- Changed to 3-triethoxycarbamido-N-(1,3-dimethyl-butylene)propylamine in 16 and changed to N-phenyl-3-aminopropyltrimethyl in Example 1-17. Oxydecane, changed to 3-ureidopropyltriethoxydecane in Examples 1-18, changed to 3-mercaptopropyltrimethoxydecane in Examples 1-19, in Examples 1-20 Changed to bis(triethoxycarbamidopropyl) tetrasulfide, in Example 1-21. More 3-isocyanate propyl triethoxysilane Silane same manner as in Example 1-6 except for the above to obtain a silver-containing composition. The results are shown in Table 1.

Example 1-22

In a light-shielding bottle, 398 mg of the silver salt (A) prepared as Synthesis Example 1 of the silver compound (A) was dissolved in 597 mg of butylamine (BA) as the amine compound (B), and 5 mg was added as a decane coupling agent ( N-2-(Aminoethyl)-3-aminopropyltrimethoxydecane of C) gives a silver-containing composition. The amount of the silver compound (A), the amount of the amine compound (B), the substituent in the above formula (2), the amount of the decane coupling agent (C), and the substituent in the above formula (3) are shown in Table 1. in.

Example 1-23~1-28

The amine compound (B) was changed to propylamine (PA) in Example 1-23, changed to dibutylamine (DBA) in Example 1-24, and changed to 2-ethoxyl in Example 1-25. Ethylamine (2-EOEA), changed to 2-ethylhexylamine (2-EHA) in Example 1-26, changed to isoamylamine (IAA) in Example 1-27, and in Examples 1-28 The silver-containing composition was obtained in the same manner as in Example 1-22 except that it was changed to 199 mg of 2-EHA and 398 mg of 2-EOEA. The results are shown in Table 1.

Comparative Example 1-1

In a light-shielding bottle, 100 mg of the silver salt (A) prepared as Synthesis Example 1 of the silver compound (A) was dissolved in 900 mg of HA as the amine compound (B) to obtain a silver-containing composition. The amount of the silver compound (A), the amount of the amine compound (B), and the substituent in the above formula (2) are shown in Table 1.

Comparative Example 1-2

The silver-containing composition was obtained in the same manner as in Comparative Example 1, except that the amount of the silver salt (A) prepared in Synthesis Example 1 and the amount of HA were changed as shown in Table 1.

Examples 2-1 to 2-32, Comparative Examples 2-1 to 2-4

In the light-shielding bottle, the silver-containing composition obtained in any one of Examples 1-1 to 1-28, Comparative Examples 1-1 and 1-2 shown in Table 2 was added to the amount shown in Table 2. In the solvent, a solvent silver-containing composition is obtained.

In Table 2, IPA represents isopropyl alcohol, MeOH represents methanol, PGM represents propylene glycol monomethyl ether, n-HA represents 1-hexanol, and TAA represents tert-amyl alcohol.

Examples 3-1 to 3-32, Comparative Examples 3-1 and 3-2

The solutions prepared in Examples 1-1 to 1-28 and Comparative Examples 1-1 and 1-2 were applied to various kinds shown in Table 3 using a spin coater (manufactured by Sanken Co., Ltd.). On the substrate, heat treatment was carried out under the heating conditions shown in Table 3 to obtain a silver film. The conductivity, adhesion, and storage stability of the silver-containing composition as described below were evaluated for the obtained silver film. The results are shown in Table 3.

(Electrical evaluation)

This was carried out using a four-needle low resistivity meter (LORESTA GP: manufactured by Mitsubishi Chemical Corporation). Further, the volume resistivity is a value in the case where glass is used as a substrate, and the volume resistivity is 5.0 × 10 ^-5 Ω. The silver film below cm is marked as ○, and the evaluation as ○ is regarded as an effect satisfying the present invention.

(attachment evaluation)

The adhesion of the substrate was evaluated by attaching and peeling the cellophane tape on the obtained silver film. The evaluation was carried out by using the mechanical property-adhesion (cross-cut method) test method of the coating film specified in JIS K5600-5-6. The unpeeled one was marked as ◎, and it was marked as ○ when it was attached by using a cellophane tape and peeled off, and it was marked as Δ when it was attached and peeled off using a cellophane tape, and was attached and peeled off using cellophane tape. The total peeling is marked as ×, and the evaluation as ◎, ○ or Δ is considered to satisfy the effect of the present invention. Further, in the table, the copper substrate is abbreviated as Cu, the polyester substrate is abbreviated as PET, the polycarbonate substrate is abbreviated as PC, the ruthenium substrate is abbreviated as Si, and the tantalum nitride substrate is abbreviated as SiN.

(storage stability evaluation)

Each solution was allowed to stand at room temperature for two weeks and confirmed by precipitation. Evaluation Depending on the state of the precipitate, the absence of precipitation is indicated by ○, the observation of a small amount of precipitation is indicated by Δ, and the observation of a large amount of precipitation is indicated by ×, and the evaluation of ○ or Δ is considered to satisfy the effect of the present invention.

Examples 4-1 to 4-36, Comparative Examples 4-1 to 4-4

The solutions prepared in Examples 2-1 to 2-32 and Comparative Examples 2-1 and 2-4 were applied to various substrates shown in Table 4 using a spin coater (manufactured by Sanken Co., Ltd.). Heat treatment was carried out under the heating conditions shown in Table 4 to obtain a silver film. The conductivity, adhesion, and storage stability of the silver-containing composition of the obtained silver film were evaluated in the same manner as in Examples 3-1 to 3-30 and Comparative Examples 3-1 and 3-2. The results are shown in Table 4.

Claims (4)

A silver-containing composition comprising a composition of a silver compound (A) represented by the formula (1), an amine compound (B) represented by the formula (2), and a decane coupling agent (C), In particular, the silver compound (A), the amine compound (B), and the decane coupling agent (C) having a total amount of 100% by mass contain 10 to 50% by mass of the silver compound (A) and 50 to 90% by mass. Amine compound (B) and 0.1 to 5% by mass of a decane coupling agent (C); Wherein, in the formula (2), R ¹ represents a hydrogen atom, -(CY ¹ Y ² )a-CH ₃ or -((CH ₂ )bO-CHZ)c-CH ₃ , and R ² represents -(CY ¹ Y ² ) d-CH ₃ or -((CH ₂ )eO-CHZ)f-CH ₃ , where Y ¹ and Y ² each independently represent a hydrogen atom or -(CH ₂ )g-CH ₃ , and Z represents a hydrogen atom or - (CH ₂ )h-CH ₃ , a is an integer from 0 to 8, b is an integer from 1 to 4, c is an integer from 1 to 3, d is an integer from 0 to 8, and e is an integer from 1 to 4, f An integer from 1 to 3, g is an integer from 0 to 3, and h is an integer from 0 to 2. The silver-containing composition according to claim 1, wherein the decane coupling agent (C) is a compound represented by the formula (3); Wherein, in the formula (3), R ³ represents -(CH ₂ )i-CH=CH ₂ , -(CH ₂ )jR ⁶ , -C ₆ H ₄ -CH=CH ₂ , -(CH ₂ ) ₃ -O -(C=O)-CR ⁷ =CH ₂ , -(CH ₂ ) ₃ -NHR ⁸ , -(CH ₂ ) ₃ -R ⁹ , -(CH ₂ ) ₃ -SR ¹⁰ or -(CH ₂ ) ₃ - N = C = O, R ⁴ represents methyl, methoxy, ethoxy or acetyl group, R ⁵ represents methyl, ethyl or acetyl group, where, R ⁶ represents the formula (4) or the formula ( 5) The organic functional group shown, R ⁷ represents a hydrogen atom or -CH ₃ , and R ⁸ represents a hydrogen atom, -(CH ₂ ) ₂ -NH ₂ , -C ₆ H ₅ or -(C=O)-NH ₂ , R ⁹ represents an organic functional group represented by the formula (6), R ¹⁰ represents a hydrogen atom or -SSS-(CH ₂ ) ₃ -Si(OC ₂ H ₅ ) ₃ , i is 0 or 1, and j is 2 or 3; A silver-containing composition comprising 20 to 80% by mass of the silver-containing composition according to claim 1 or 2 and 20 to 80% by mass of a solvent. A substrate for forming a silver component, which is characterized in that the silver-containing composition according to any one of claims 1 to 3 is coated or printed on a substrate, and the substrate is heated to form a silver component.