Compositions – Electrically conductive or emissive compositions – Free metal containing
Reexamination Certificate
2000-03-24
2001-11-13
Kopec, Mark (Department: 1751)
Compositions
Electrically conductive or emissive compositions
Free metal containing
C252S513000, C252S514000
Reexamination Certificate
active
06315927
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a photosensitive conductive paste used for forming, for example, a wiring pattern of a high-frequency electronic component.
2. Related Art
Recently, high-frequency electronic components used in mobile communication devices, satellite broadcasting receiving devices, computers and the like, have been required to have small size and high performance. Also, wiring patterns of high-frequency electronic components are required to have increased density and signal speed. In order to increase density and signal speed in the wiring pattern, the pattern must be made finer and yet form a thicker film.
Hitherto, a wiring pattern of a high-frequency electronic component has been formed as follows. Firstly, a wiring pattern is formed on an insulating substrate by use of a conductive paste comprising a conductive metallic powder of a multivalent metal such as copper and an organic vehicle containing an organic binder and an organic solvent. Subsequently, the resultant pattern is dried and fired. In this method, a wiring pattern is generally formed through screen printing, and the lower limit of the width and pitch of the thus-formed wiring pattern is approximately 50 &mgr;m.
Japanese Patent Application Laid-Open (kokai) Nos. 287221/1993 and 227153/1996 disclose a method for forming a fine thick-film wiring pattern through photolithography by use of a photosensitive conductive paste. According to the method, a photosensitive conductive paste is applied onto an insulating substrate and the paste is dried and subjected to patterning by means of photolithography, the paste containing a conductive metallic powder, an acrylic copolymer having a carboxyl group and an ethylenic unsaturated group in the side chains, a photoreactive compound, and a photopolymerization initiator.
In recent years, in consideration of environmental safety, it has been demanded that development be carried out by use of water or an aqueous alkali solution in photolithography making use of a photosensitive conductive paste. Therefore, an organic binder contains an acidic functional group such as a carboxyl group, which group has the property of releasing a proton.
However, in the case of employment of such an organic binder, ions of a multivalent metal, which ions are released into solution, may react with anions of the organic binder, which anions are formed after the protons are released, and a three-dimensional network structure may be formed by ionic cross-linking, to thereby form a gel. When a photosensitive conductive paste becomes a gel, application of the paste becomes difficult. Even if application of the paste can be carried out, development of the paste may be unstable, making employment of the paste difficult.
In order to prevent gelation of a photosensitive conductive paste, Japanese Patent Application Laid-Open (kokai) No. 218509/1997 discloses a method in which a phosphorous-containing compound such as phosphoric acid, serving as a gelation-suppressing agent, is incorporated into the paste; Japanese Patent Application Laid-Open (kokai) No. 218508/1997 discloses a method in which a compound having an azole structure such as benzotriazole, serving as a gelation-suppressing agent, is incorporated into the paste; and Japanese Patent Application Laid-Open (kokai) No. 222723/1997 discloses a method in which an organic compound having a carboxyl group such as acetic acid, serving as a gelation-suppressing agent, is incorporated in the paste. However, these methods enable only slight retardation of gelation of the paste, and even when the paste contains the gelation-suppressing agent, use of the paste is substantially difficult.
In addition, in order to prevent gelation of a photosensitive paste, Japanese Patent Application Laid-Open (kokai) No. 10171107 discloses a method in which 3-methyl-3-methoxybutanol serving as an organic solvent is incorporated into the paste. However, 3-methyl-3-methoxybutanol has a boiling point as low as 174° C., and thus, when the paste is dried after application, the organic solvent component completely vaporizes, and the effect of preventing gelation may not be exhibited. Thus, in the dried paste, a phenomenon similar to gelation may occur, i.e., a three-dimensional network structure may be formed by ionic cross-linking, and the molecular weight of the paste may become substantially high. As a result, problems may occur. For example, unexposed portions of the paste may fail to dissolve into a developer.
SUMMARY OF THE INVENTION
To overcome the above described problems, preferred embodiments of the present invention provide a photosensitive conductive paste which has excellent storage stability and which enables stable development.
The present inventors have conducted extensive studies, and have found that gelation of a photosensitive conductive paste can be effectively suppressed while the paste is in its original state before application and also while the paste is in a dried state after application, by incorporating a mono-ol compound having a boiling point of about 178° C. or higher into the paste which comprises an organic binder having an acidic functional group such as a carboxyl group and a conductive metallic powder containing a multivalent metal having two or higher valences.
One preferred embodiment of the present invention provides a photosensitive conductive paste comprising a mixture of: an organic binder having an acidic functional group; a photosensitive organic component; a conductive metallic powder containing a multivalent metal; and a mono-ol compound having a boiling point of about 178° C. or higher (hereinafter the paste may be referred to as the “first photosensitive conductive paste of the present invention”).
In the first photosensitive conductive paste of the present invention, the mono-ol compound may be contained in an amount by mol of at least twice that of ions of the multivalent metal released in a solution portion of the paste.
In the first photosensitive conductive paste of the present invention, an organic solvent may be further present, and the amount of the mono-ol compound may be about 10-92 wt. % based on the total amount of the mono-ol compound and the organic solvent.
In the first photosensitive conductive paste of the present invention, the material of the conductive metallic powder containing a multivalent metal may be at least one species selected from the group consisting of copper, aluminum, palladium, nickel and iron.
In the first photosensitive conductive paste of the present invention, the organic binder having an acidic functional group may be an acrylic copolymer having a carboxylic side chain.
The first photosensitive conductive paste of the present invention contains a mono-ol compound having a boiling point of about 178° C. or higher, and therefore gelation of the paste can be sufficiently suppressed while the paste is in its original state before application and while the paste is in a dried state after application, and storage stability of the paste is enhanced. In addition, the paste can be consistently developed through photolithography.
The reasons why gelation of the paste can be suppressed are described below. A hydroxyl group in a mono-ol compound has very high ability to bind to a multivalent metallic ion, as compared with an acidic functional group of an organic binder (particularly a carboxylic group). Therefore, the reaction between the mono-ol compound and the multivalent metallic ion precedes the reaction between the organic binder and the ion, and ionic cross-linking between the organic binder and the multivalent metallic ion and formation of a three-dimensional network structure are hindered. Since the mono-ol compound has only one hydroxyl group, when the mono-ol compound bonds to the multivalent metallic ion, no three-dimensional network structure is formed by ionic cross-linking.
In addition, the mono-ol compound in the first photosensitive conductive paste of the present invention has a boiling point of about 178° C. or higher, a
Iha Michiaki
Kubota Masahiro
Miyayama Satoshi
Oda Toshikazu
Watanbe Shizuharu
Kopec Mark
Murata Manufacturing Co. Ltd.
Ostrolenk Faber Gerb & Soffen, LLP
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