JP2743962B2 - Organic silver palladium ink - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to the synthesis of an organic silver palladium ink for forming a silver palladium thin film as a material for electronic industry.

(Prior art and its problems) Conventionally, there are various resistors using a noble metal, and in particular, even a noble metal, inexpensive silver palladium is often used.

2. Description of the Related Art Application development utilizing characteristics of silver palladium by forming silver palladium thin films on various substrates has been actively performed.

As a method of forming a silver palladium thin film, a vapor deposition method,
Sputtering methods are used, but the disadvantages of each method are that sputtering and vapor deposition require time and expensive equipment to form thin films, making it difficult to form thin films on substrates with complex shapes. There is a disadvantage that it is.

In addition, the paste method as a thick film method is actively used in a method for compensating for the disadvantages of the above method, but is prepared by adding and mixing a fine powder of metallic silver and palladium, a glass frit, an organic binder, and a solvent. Therefore, it is difficult to uniformly disperse the added components, and it is also difficult to make the thickness of silver palladium formed by applying, drying and baking the paste 3 μm or less. Palladium has a large variation in film thickness and has the disadvantage that pinholes are likely to occur.It is difficult to prepare a silver palladium film with a stable sheet resistance value. There is a disadvantage that it is difficult.

In addition, when a fine electronic circuit of silver palladium film is formed with the conventional thick film paste, there is a limit to uniformly disperse the added fine powder, and it is extremely difficult to prevent local electromigration. It is.

In addition, since fine powder is used as a raw material, there is a disadvantage in storage stability that components are easily separated during storage.

(Object of the Invention) The present invention has been made to solve the drawbacks of the conventional method, and has no pinholes dense to various substrates by a simple method.
An object of the present invention is to provide a uniform organic silver palladium ink which can form a silver-palladium alloy thin film having a thickness of 0.3 μm to 0.8 μm, has a small thickness variation, and does not separate even after long-term storage.

(Means for Solving the Problems) The present invention is selected from the group consisting of silver resinate, palladium resinate, other metal components, and alkyd resins, urea resins, melamine resins, rosin derivative resins, and terpene resins as binders. An organic silver-palladium ink containing one or more resins and an organic solvent.

 Hereinafter, the present invention will be described in detail.

As a raw material component of the organic silver palladium ink of the present invention, a halide and an acetate of silver and palladium are reacted with a polynuclear fatty acid such as an aliphatic or aromatic carboxylic acid or abietic acid or a gum rosin containing abietic acid as a main component. Metal components other than silver and palladium (hereinafter referred to as "other metal components") include platinum, iridium, rhodium, lead, bismuth, silicon, chromium, boron One selected from the group consisting of, antimony, vanadium, calcium, magnesium, manganese, zinc, zirconium, barium, strontium, and lanthanum
A metal resinate synthesized by reacting a halide or an acetate or an oxide of one or more metals with a polynuclear fatty acid such as an aliphatic or aromatic carboxylic acid or abietic acid or a gum rosin containing abietic acid as a main component. Add any combination depending on the application.

As the binder, the alkyd resin is linseed oil and / or rosin-modified alkyd resin, the urea resin is n-butyl ether type butylated urea resin and / or the isobutyl ether type butyl urea resin, and the melamine resin is n-butyl ether type butylated melamine resin. And / or an isobutyl ether type butyl melamine resin, wherein the rosin derivative resin is glycine ester of rosin, pentaerythol ester of rosin, methyl ester of hydrogenated rosin, triethylene glycol ester of hydrogenated rosin, hydrogenated Glycerin ester of rosin, pentaerythritol ester of hydrogenated rosin, polymerized rosin, glycerin ester of polymerized rosin, pentaerythryl ester of polymerized rosin, rosin ester modified with maleic acid Pentaerythritol ester of maleic acid-modified rosin and glycerin ester of maleic acid-modified rosin, wherein the terpene resin is a terpene polymer, α-pinene It is selected from the group consisting of polymers, β-pinene polymers, d-limonene polymers, diterpene resins, aromatic modified terpene polymers, modified terpene polymers, and terpene phenol copolymers.

Organic solvents such as mentanol, terpineol, butyl carbitol, methyl ethyl ketone, propylene glycol, ethylene glycol, cyclohexanone, ethyl acetate, benzyl acetate, amyl acetate, cellosolve, butyl cellosolve, butanol, nitrobenzene,
One or a mixture of two or more of toluene, xylene, petroleum ether, 1,1,1-trichloroethane, chloroform, carbon tetrachloride, pinene, dipentene, dipentene oxide, and essential oil are used.

Silver resinate and palladium resinate preferably have a silver and palladium content of 20 to 35% by weight, and by adjusting the amount added to the organic silver palladium ink,
A silver-palladium thin film can be formed in any thickness and alloy ratio, and is dissolved in a common organic solvent with various resins added as metal resinate and binder as other metal components to form a uniform solution, and long-term storage There is a feature that can withstand.

The other metal components are added by stabilizing the silver-palladium thin film and by adding a metal resinate of the glass component to various base materials, for example, ceramics, by coating, drying, and firing, the silver-palladium thin film is made of ceramic. This is because a strong adhesion can be obtained, and the sheet resistance can be adjusted by adjusting the amount of addition.

The various resins added as binders have a proper viscosity, and especially when forming fine circuits by screen printing, etc., a high printable viscosity without dripping, warping etc. is required. In order to make
It is necessary to select from various resins according to the present invention.

The solvent is used because it dissolves the raw materials silver resinate, palladium resinate, resinate of other metal components and various resins, is easy to apply, has good printability, and can be volatilized in a relatively short time. It is.

 The representative component ratio in the present invention is shown below.

Silver resinate and palladium resinate total 30 ~
70% by weight, other metal components 1-25% by weight, various resins as binders 10-30% by weight, solvents 10-10%
In the case of mixing and preparing in the range of 30% by weight, one application,
The thickness of 0.3 to 0.6 micron can be obtained by drying and baking.

In addition, a general brush application method, a screen printing method, a stamp method, a spray method, a dipping method, a spin coating method can be used as a coating method, and drying is performed at room temperature first.
It may be dried for 10 to 20 minutes and then heated and dried at 100 to 250 ° C. for 5 to 15 minutes. A sintering temperature of 500 to 850 ° C. for 10 to 20 minutes can form a metal thin film.

In addition, the formed metal thin film has excellent characteristics of electromigration resistance, circuit gap 0.4 mm, DC1
Under the condition of 0 V, the time from the dropping of pure water to the occurrence of electromigration is 15 minutes or more.

Hereinafter, examples of the present invention will be described, but the examples do not limit the present invention.

(Example 1) 27% of silver resinate (Ag30%), 10% of palladium resinate (Pd20%), 16% of lead resinate (Pb30%), 5% of silicon resinate (Si14%), 5% of boron resinate (B7%)
4%, alkyd resin 10%, urea resin 4%, mentanol 15%, terpene resin 4%, modified gum rosin 5% are mixed to prepare an organic silver palladium ink, and screen printing is performed on five ceramic substrates. After applying, at room temperature
It was dried for 10 minutes, then heated and dried at 200 ° C. for 10 minutes, and then calcined at 850 ° C. for 10 minutes and gradually cooled.

After cooling, the thin film formed on the ceramic was enlarged and observed.
With a micron film thickness, the sheet resistance is 0.1 to 0.13 ohm /
It was □.

(Example 2) Silver resinate (Ag 35%) 60%, palladium resinate (Pd 20%) 8%, bismuth resinate (Bi 17%) 1%,
20% of terpineol and 10% of terpene resin are mixed to prepare an organic silver-palladium ink, applied to five ceramic substrates by screen printing, dried at room temperature for 10 minutes, and then at 200 ° C. for 10 minutes Heat drying, then 500
It was baked at ℃ for 10 minutes and gradually cooled.

After cooling, the thin film formed on the ceramic was enlarged and observed.
With a micron film thickness, the sheet resistance is 0.03-0.04 ohm /
It was □.

(Example 3) Silver resinate (Ag 35%) 45%, palladium resinate (Pd 20%) 15%, bismuth resinate (Bi 18%) 1%,
0.3% antimony resinate (Sb10%), 0.5% chromium resinate (Cr6%), 3% urea resin, mentanol 23
%, A terpene resin 5%, and a modified gum rosin 2%, to prepare an organic silver palladium ink, and apply it to five ceramic substrates by a screen printing method.
It was dried for 10 minutes, then heated and dried at 125 ° C. for 10 minutes, and then calcined at 700 ° C. for 10 minutes and gradually cooled.

After cooling, the thin films formed on the ceramics were magnified and observed to be dense, pinhole-free films with an average thickness of 0.5 microns and a sheet resistance of 0.07-0.08 ohm / square.

Example 4 Each of the silver palladium thin films 5 obtained in Examples 1 to 3 was formed.
500g / m when measuring the adhesion strength of two ceramic substrates
m ² or more.

Also, put the organic silver palladium ink prepared in Examples 1 to 3 in a closed container, and stored in a cool dark place for 3 months,
When the change of the ink was visually confirmed, a uniform solution state was maintained.

(Effect of the Invention) The present invention uses an organic silver palladium ink,
The sheet resistance can be freely adjusted within a range of 0.03 ohm / □ to 0.13 ohm / □ by a simple method.
A thin film of 0.3-0.8 microns is obtained.

In addition, since the ink of the present invention is a uniform solution that does not use metal powder, it can be used to form a circuit with a line width of 50 microns by direct screen printing, and can withstand long-term storage. It is of high value and greatly contributes to the development of technology.

(Embodiment) The present invention has the features described in the claims, and examples of the embodiment are as follows.

(1) Platinum, iridium, rhodium, lead, silicon, boron, bismuth, chromium, vanadium, antimony, aluminum, calcium, magnesium, as metal components other than silver and palladium (hereinafter referred to as “other metal components”) The method according to claim 1, wherein one or more metal resinates selected from the group consisting of manganese, zinc, zirconium, barium, strontium, and lanthanum are added in any combination depending on the application.

(2) As the binder, the alkyd resin is linseed oil and / or a rosin-modified alkyd resin, the urea resin is an n-butyl ether type butylated urea resin and / or an isobutyl ether type butyl urea resin, and the melamine resin is n-type.
Butyl ether type butylated melamine resin and / or isobutyl ether type butyl melamine resin, wherein the rosin derivative resin is glycine ester of rosin, pentaerythol ester of rosin, methyl ester of hydrogenated rosin, triethylene of hydrogenated rosin Glycol esters, glycerin esters of hydrogenated rosin,
Pentaerythritol ester of hydrogenated rosin,
A group consisting of polymerized rosin, polymerized rosin glycerin ester, polymerized rosin pentaerythol ester, maleic acid-modified rosin ester, maleic acid-modified rosin pentaerythritol ester, and maleic acid-modified rosin glycerin ester And a mixture of two or more selected from the group consisting of terpene resins, terpene polymers, α-pinene polymers, β-
Pinene polymer, d-limonene polymer, diterpene resin,
2. The method according to claim 1, wherein the organic solvent is selected from the group consisting of aromatic modified terpene polymers, modified terpene polymers, and terpene phenol copolymers. (3) Mentanol and terpineol as organic solvents ,
Butyl carbitol, methyl ethyl ketone, propylene glycol, ethylene glycol, cyclohexanone,
Ethyl acetate, benzyl acetate, amyl acetate, cellosolve, butyl cellosolve, butanol, nitrobenzene, toluene, xylene, petroleum ether, 1,1,1-trichloroethane, chloroform, carbon tetrachloride, pinene, dipentene, dipentene oxide, any of the essential oils The method according to claim 1, wherein one or a mixture of two or more of them is used as a mixture.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-54-121996 (JP, A) JP-A-63-278983 (JP, A) JP-A-1-3111180 (JP, A) JP-A-2- 10607 (JP, A) JP-B 38-12846 (JP, B1) JP-B 43-29441 (JP, B1)

Claims (1)

(57) [Claims] 1. One or more resins selected from the group consisting of silver resinates, palladium resinates, other metal components, and alkyd resins, urea resins, melamine resins, rosin derivative resins, and terpene resins as binders. And an organic solvent.