JP2009016320A - Electrode member manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode member manufacturing method for forming an inexpensive and highly accurate pattern which has a thin film on a ceramic, silicon or glass substrate and high adhering strength. <P>SOLUTION: The electrode manufacturing method comprises steps of forming an aluminum paste layer containing aluminum powder A and a binding resin C on the substrate and forming a resist film on the aluminum paste layer formed on the substrate to form a laminate with the aluminum paste layer and the resist film on the substrate, applying exposure treatment to the resist film of the laminate to form the latent image of a resist pattern, applying developing treatment to the resist film to actualize the resist pattern, applying etching treatment to the aluminum paste layer to form the pattern of the aluminum paste layer corresponding to the resist pattern, and then applying firing treatment to the pattern. The contained aluminum powder A is an aluminum powder of D50: 2-20 μm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an electrode member. More specifically, in the production of circuit boards having electrode patterns used for display panels such as flat panel displays, advanced mounting materials for electronic components, and solar cell materials, it is suitable for forming highly sensitive and accurate patterns. The present invention relates to a method for manufacturing an electrode member that can be used.

  In recent years, there is an increasing demand for higher density and higher definition for pattern processing in circuit boards and display panels. Among such display panels that have been increasing in demand, particularly flat panel displays (hereinafter referred to as “FPD”) such as plasma display panels (hereinafter also referred to as “PDP”) and field emission displays (hereinafter also referred to as “FED”). ) Is attracting attention.

  FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type PDP. In FIG. 1, reference numerals 101 and 102 denote opposing glass substrates, and reference numerals 103 and 111 denote partition walls. Cells are partitioned by the glass substrate 101, the glass substrate 102, the rear partition wall 103, and the front partition wall 111. 104 is a transparent electrode fixed to the glass substrate 101, 105 is a bus electrode formed on the transparent electrode 104 for the purpose of reducing the resistance of the transparent electrode 104, and 106 is an address electrode fixed to the glass substrate 102. It is. 107 is a fluorescent material held in the cell, 108 is a dielectric layer formed on the surface of the glass substrate 101 so as to cover the transparent electrode 104 and the bus electrode 105, and 109 is used to cover the address electrode 106. A dielectric layer is formed on the surface of the glass substrate 102, and 110 is a protective film made of, for example, magnesium oxide. In a color FPD, a color filter (red / green / blue) or a black matrix may be provided between the glass substrate and the dielectric layer in order to obtain a high contrast image.

  FPDs are becoming smaller and higher definition, and accordingly, improvement of pattern processing technology is demanded. The screen printing method, which is a conventional construction method, has a problem that the demand for pattern accuracy becomes very strict with the increase in size and definition of the panel, and the photolithography method is mainly used.

  Photosensitive silver paste is often used for electrode formation by the photolithography method, but such paste has insufficient sensitivity in the depth direction of the layer, and a pattern with a sharp edge or a high-definition pattern is not necessarily obtained. It was not what was obtained. Further, since silver itself is a noble metal, it has become an expensive conductive paste. As a defect of the photosensitive silver paste, migration is likely to occur in a high-temperature and high-humidity environment, and the silver surface is susceptible to sulfidation.

  In particular, a method for forming an electrode as an FPD member requires an inexpensive inorganic particle-containing photosensitive resin material and a material that can be patterned with high definition.

  The present invention is intended to solve the problems associated with the prior art as described above, can form a low-cost, high-precision pattern, and adheres to a ceramic, silicon, and glass substrate with a thin film. It aims at providing the manufacturing method of an electrode member with high intensity | strength.

  The above problem is that an aluminum paste layer containing an aluminum powder (A) and a binder resin (C) is formed on a substrate, and a resist film is formed on the aluminum paste layer formed on the substrate. Forming a laminate of an aluminum paste layer and a resist film, exposing the resist film of the laminate to form a latent image of the resist pattern, developing the resist film to reveal the resist pattern; An electrode manufacturing method comprising etching a paste layer to form a pattern of an aluminum paste layer corresponding to a resist pattern, and firing the pattern, wherein the aluminum powder (A) includes: D50: achieved by an electrode manufacturing method characterized by containing 2 to 20 μm aluminum powder That.

In the manufacturing method of the present invention, an inexpensive and high-definition pattern can be formed, formation of members constituting electrode wiring of a flat panel display, formation of members of highly mounting materials for electronic components, and formation of members of solar cells Can be suitably used.

Hereinafter, the manufacturing method of the electrode which concerns on this invention is demonstrated. Hereinafter, materials used in the manufacturing method, various conditions, and the like will be described.
[substrate]
A plate-like member made of an insulating material such as glass, silicon, polycarbonate, polyester, aromatic amide, polyamideimide, or polyimide as a substrate material. If necessary, the surface of the plate-like member may be subjected to chemical treatment with a silane coupling agent, plasma treatment, ion plating method, sputtering method, gas phase reaction method, vacuum deposition method, etc. Such an appropriate pretreatment may be performed.
[Transfer film]
The transfer film used in the production method of the present invention has a support film and an aluminum paste layer and / or a resist layer formed on the support film, and a protective film layer on the surface of the aluminum paste layer or resist layer. May be provided.
[Support film]
The support film constituting the transfer film is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film has flexibility, the paste-like composition can be applied by a roll coater, and the aluminum paste layer can be stored and supplied in a state of being wound in a roll. Examples of the resin forming the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose. The thickness of the support film is, for example, 20 to 100 μm.

[Aluminum composition]
The components used in the production method of the present invention are formed from an aluminum paste layer and a resist layer. The aluminum paste layer contains aluminum powder (A), glass powder (B), binder resin (C) and solvent (D). The resist layer contains a binder resin (a), a solvent (b), a polyfunctional (meth) acrylate (c), and a photopolymerization initiator (d).
[Aluminum paste layer]
The aluminum paste layer of the present invention is prepared by applying an aluminum paste composition containing aluminum powder, glass powder, an alkali-soluble resin and a solvent as essential components onto the substrate and / or supporting film, drying the coating film, It can be formed by removing part or all of it.
[Aluminum paste composition]
The aluminum paste composition used for producing the aluminum paste layer contains an aluminum powder (A), a glass powder (B), a binder resin (C) and a solvent (D).
[Aluminum powder (A)]
Examples of the inorganic powder contained in the composition for forming the “electrode” constituting the FPD include an aluminum powder and a metal powder composed of a compound thereof.

  The particle size of the aluminum powder is appropriately selected in consideration of the shape of the pattern to be produced, but the 50% by weight particle size (D50) of the aluminum powder is preferably 2.0 to 20.0 μm. More preferably, the 50% by weight particle diameter (D50) is 3.0 to 15.0 μm. When the average particle diameter of the aluminum powder is within this range, no residue is produced during development, and a high-definition pattern can be obtained.

As the shape of the aluminum powder, one or more of spherical or flaky shapes are used.
[Glass powder (B)]
Examples of the glass powder used in the aluminum paste composition of the present invention include a glass powder having a softening point in the range of 350 to 700 ° C. (preferably 400 to 600 ° C.). When the softening point of the glass powder is less than 350 ° C., the glass powder is not fully decomposed and removed in the baking process of the aluminum paste layer formed from the transfer film of the present invention. Since it melts, a part of the organic substance remains in the formed dielectric layer. As a result, the dielectric layer is colored and its light transmittance tends to decrease. On the other hand, when the softening point of the glass powder exceeds 700 ° C., the glass substrate needs to be baked at a temperature higher than 700 ° C., so that the glass substrate is likely to be distorted.

Specific examples of suitable glass powder include
1. A mixture of lead oxide, boron oxide, silicon oxide (PbO-B ₂ O ₃ —SiO ₂ system),
2. A mixture of zinc oxide, boron oxide, silicon oxide (ZnO-B ₂ O ₃ —SiO ₂ system),
3. A mixture of lead oxide, boron oxide, silicon oxide, aluminum oxide (PbO-B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ series),
4). A mixture of lead oxide, zinc oxide, boron oxide, silicon oxide (PbO-ZnO-B ₂ O ₃ —SiO ₂ system),
5). A mixture of bismuth oxide, boron oxide, silicon oxide (Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ system),
6). A mixture of zinc oxide, phosphorus oxide, silicon oxide (ZnO-P ₂ O ₅ —SiO ₂ system),
7). A mixture of zinc oxide, boron oxide, potassium oxide (ZnO-B ₂ O ₃ -K ₂ O system),
8). A mixture of phosphorus oxide, boron oxide, aluminum oxide (P ₂ O ₅ —B ₂ O ₃ —Al ₂ O ₃ system),
9. A mixture of zinc oxide, phosphorus oxide, silicon oxide, aluminum oxide (ZnO-P ₂ O ₅ —SiO ₂ —Al ₂ O ₃ series),
10. A mixture of zinc oxide, phosphorus oxide, titanium oxide (ZnO-P ₂ O ₅ -TiO ₂ system),
11. A mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide (ZnO-B ₂ O ₃ —SiO ₂ system—K ₂ O system),
12 A mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide (ZnO-B ₂ O ₃ —SiO ₂ —K ₂ O—CaO system),
13. 14. Mixture of zinc oxide, boron oxide, silicon oxide, potassium oxide, calcium oxide, aluminum oxide (ZnO—B ₂ O ₃ —SiO ₂ —K ₂ O—CaO—Al ₂ O ₃ system) A mixture of boron oxide, silicon oxide, aluminum oxide (B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ series),
15. Examples thereof include a mixture of boron oxide, silicon oxide, and sodium oxide (B ₂ O ₃ —SiO ₂ —Na ₂ O system).

  As for the said glass powder, Preferably content of the glass powder in the aluminum paste composition for obtaining an electrode member is 0.5 to 15 weight% with respect to the aluminum paste composition whole quantity. More preferably, it is 1.0 to 10% by weight.

The particle size of the glass powder is appropriately selected in consideration of the shape of the pattern to be produced, but it is preferable that the 50% by weight particle size (D50) of the glass powder is 0.2 to 4.0 μm. Further, it is preferable that the 10% by weight particle size (D10) is 0.05 to 0.5 μm and the 90% by weight particle size (D90) is 10 to 20 μm. More preferably, the 50% by weight particle diameter (D50) is preferably 0.5 to 3.8 μm. When the average particle diameter of the glass powder is within this range, the light during ultraviolet irradiation reaches the bottom of the coating sufficiently and a high-definition pattern can be obtained. In particular, lead-free glass considering the environment is preferable.
In the aluminum paste composition of the present invention, the inorganic particles refer to portions excluding organic components, that is, the entire inorganic particles. Inorganic particles refer to aluminum powder and glass powder. In addition, addition of alkali-soluble resins, solvents, polyfunctional (meth) acrylates, polymerization inhibitors, antioxidants, plasticizers, thickeners, organic solvents, dispersants, anti-settling agents, leveling agents, etc. to organic components Agent components can be added. The aluminum paste composition of the present invention preferably comprises 95 to 10% by weight of inorganic particles and 5 to 90% by weight of organic components.
[Binder resin (C)]
The binder resin (C) used in the composition of the present invention is preferably alkali-soluble. In the present invention, “alkali-soluble” refers to a property of being dissolved in an alkaline developer to such an extent that the intended development processing is possible. Such a binder resin can be obtained by copolymerizing the alkali-soluble functional group-containing monomer (C1) and the (meth) acrylic acid derivative (C2).

Examples of the alkali-soluble functional group-containing monomer (C1) include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, and succinic acid mono (2- (meth)). Acryloyloxyethyl), 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrophthalate, carboxyl group-containing monomers such as ω-carboxy-polycaprolactone mono (meth) acrylate;
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (α-hydroxymethyl) acrylate;
Examples thereof include monomers having an alkali-soluble functional group and an unsaturated bond, such as phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. Among these monomers, (meth) acrylic acid, 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyl Oxypropyltetrahydrohydrogenphthalate and 2-hydroxyethyl (meth) acrylate are preferred.

  By copolymerizing the alkali-soluble functional group-containing monomer (C1), alkali solubility can be imparted to the resin. The content of the structural unit derived from the alkali-soluble functional group-containing monomer (C1) is usually from 5 to 90% by weight, preferably from 10 to 80% by weight, particularly preferably from 15 to 70% by weight, based on all the structural units of the resin. It is.

  The (meth) acrylic acid derivative (C2) is not particularly limited as long as it is a (meth) acrylic acid derivative copolymerizable with the alkali-soluble functional group-containing monomer (C1). For example, methyl (meth) acrylate, Ethyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) Monomers (C2) such as acrylate, phenoxyethyl (meth) acrylate, trityl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. Etc. outside (meth) acrylates.

In the present invention, for example, styrene, methyl (meth) acrylate, ethyl (meth) acrylate instead of the (meth) acrylic acid derivative (C2) or in addition to the (meth) acrylic acid derivative (C2). Alternatively, a macromonomer having a polymerizable unsaturated group such as a (meth) acryloyl group, an allyl group, or a vinyl group may be used at one chain end of a polymer obtained from benzyl (meth) acrylate or the like.
(Radical polymerization initiator)
In the copolymerization, it is preferable to use a radical polymerization initiator. As the radical polymerization initiator, a radical polymerization initiator used for polymerization of a vinyl monomer can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutylnitryl), 2,2′-azobis (2,4-dimethylvaleronitryl), 1,1 ′ -Azo compounds such as azobis (1-cyclohexanecarbonitrile), dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis (4-cyanovaleric acid); t-butyl peroxybivalate, t -Organic peroxides of peroxyesters such as butylperoxy 2-ethylhexanoate and cumylperoxy 2-ethylhexanoate. These radical polymerization initiators may be used alone or in combination of two or more. The usage-amount of these radical polymerization initiators is about 0.1-10 weight with respect to 100 weight part of all the monomers used for the said copolymerization.

  The weight average molecular weight (hereinafter also referred to as “Mw”) of the alkali-soluble resin (C) thus obtained is a polystyrene conversion value measured by gel permeation chromatography (GPC), and preferably from 5,000 to It is 150,000, More preferably, it is 10,000-100,000. Mw can be controlled by appropriately selecting conditions such as the copolymerization ratio, composition, chain transfer agent, and polymerization temperature of the monomer. When Mw is lower than the above range, film roughness after development is likely to occur, and when Mw exceeds the above range, the solubility of the unexposed portion in the developer may be reduced and resolution may be reduced. .

The glass transition temperature (Tg) of the binder resin is −10 to 120 ° C., preferably 0 to 100 ° C. When the glass transition temperature is lower than the above range, the coating film tends to be tacky and is difficult to handle. On the other hand, when the glass transition temperature exceeds the above range, the adhesiveness with a glass substrate as a support is deteriorated, and transfer may not be possible. In addition, the said glass transition temperature can be suitably adjusted by changing the quantity of a monomer (C1) and a (meth) acrylic acid derivative (C2).
The acid value of the binder resin (C) is preferably 20 to 200 mgKOH / g, more preferably 30 to 160 mgKOH / g. When the acid value is 20 mgKOH / g or less, it is difficult to quickly remove it with an alkaline developer, and it tends to be difficult to form a high-definition pattern. On the other hand, when the acid value is 200 mgKOH / g or more, it tends to be eroded by the alkaline developer, and it tends to be difficult to form a high-definition pattern.
[Solvent (D)]
The aluminum paste composition of the present invention usually contains a solvent for imparting appropriate fluidity or plasticity and good film forming properties. The solvent used is preferably a solvent that has good affinity with inorganic powder and good solubility of the alkali-soluble resin, can adjust the viscosity of the aluminum paste, and can be easily evaporated by drying.

Examples of preferable solvents include ketones, alcohols, and esters having a normal boiling point (boiling point at 1 atm) of 100 to 300 ° C.
Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methoxypropyl acetate, dioxane, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, dimethyl sulfoxide, γ- Examples include butyrolactone, terpineol, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether. The said solvent may be used individually by 1 type, or 2 or more types may be mixed and used for it. Further, the content ratio of the solvent in the composition of the present invention can be appropriately selected within a range in which good film forming properties (fluidity or plasticity) can be obtained.
[Multifunctional (meth) acrylate]
In the aluminum paste composition of the present invention, polyfunctional (meth) acrylate may be used in an amount of 10 wt% or more, preferably 15 to 60 wt% in the organic component in order to impart plasticity to the paste.

Such polyfunctional (meth) acrylates include allylated cyclohexyl di (meth) acrylate, 2,5-hexanedi (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, methoxylated cyclohexyl di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate Of di (meth) methacrylate compounds;
Pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Polyfunctional (meth) acrylates such as monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, benzyl mercaptan (meth) acrylate;
A monomer in which 1 to 5 of the aromatic ring hydrogen atoms in the compound are substituted with chlorine or bromine atoms; and
Styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethyl Examples thereof include styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, γ-methacryloxypropyltrimethoxysilane, and 1-vinyl-2-pyrrolidone. The said polyfunctional (meth) acrylate may be used individually by 1 type, or may be used in combination of 2 or more type.
[Ultraviolet absorber]
In the present invention, it is also effective to add an ultraviolet absorber to the aluminum paste composition. By adding a compound having a high ultraviolet absorption effect, a high aspect ratio, high definition, and high resolution can be obtained. As the ultraviolet absorber, an organic dye or an inorganic pigment can be used, and among them, an organic dye or an inorganic pigment having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used.

  Specifically, organic dyes such as azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes Inorganic pigments such as dyes, zinc oxide, titanium oxide, and cerium oxide can be used. In these, since organic dye does not remain in the insulating film after firing, it is preferable because the deterioration of the insulating film characteristics can be reduced, but from the viewpoint of the reliability of the flat display panel, zinc oxide, titanium oxide, cerium oxide Such inorganic pigments are more preferred.

The inorganic pigment can be added in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, with respect to 100 parts by weight of the glass powder. When the amount is less than 0.001 part by weight, the effect of adding the ultraviolet absorber is reduced. When the amount exceeds 5 parts by weight, the effect of the ultraviolet absorber is so great that light does not reach the lower part of the film, making it impossible to form a pattern or increasing the film strength. Since it may not be kept, it is not preferable.
[Sensitizer]
A sensitizer may be added to the aluminum paste composition of the present invention. Examples of the sensitizer include 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethylthioxanthone, 2,3-bis (4 -Diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminibenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (Diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p- Dimethylaminopheny Vinylene) -isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin) ), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, Examples thereof include 1-phenyl-5-ethoxycarbonylthiotetrazole.

The above sensitizers may be used alone or in combination of two or more. Some sensitizers can also be used as photopolymerization initiators. The sensitizer can be added in an amount of usually 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, based on the inorganic component. If the amount of the sensitizer is too small, the effect of improving the photosensitivity may not be exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.
[Polymerization inhibitor]
In order to improve the thermal stability during storage, a polymerization inhibitor may be added to the aluminum paste composition of the present invention. Examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol, Examples include chloranil and pyrogallol. The polymerization inhibitor can be added to the composition in an amount usually ranging from 0.001 to 1% by weight [antioxidant].
An antioxidant may be added to the aluminum paste composition of the present invention in order to prevent oxidation of the acrylic copolymer during storage. Examples of the antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-4-ethylphenol, 2,2-methylene-bis- (4 -Methyl-6-tert-butylphenol), 2,2-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4-bis- (3-methyl-6-tert-butylphenol), 1, 1,3-tris- (2-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-tert-butylphenyl) butane, bis [3,3-bis- (4-Hydroxy-3-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like. The antioxidant can be added to the composition in an amount usually ranging from 0.001 to 1% by weight.
[Adhesion aid]
An adhesion aid may be added to the aluminum paste composition of the present invention in order to improve the adhesion to the support. As the adhesion assistant, a silane compound is preferably used. Specific examples of the silane compound include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-icosanedimethylmethoxysilane, and n-propyldiethylmethoxy. Silane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane, n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n- Hexadecyldipropylmethoxysilane, n-icosanedipropylmethoxysilane, n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n-hexadecyldimethyl Ruethoxysilane, n-icosanedimethylethoxysilane, n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxysilane, n-icosanediethylethoxysilane, n -Butyldipropylethoxysilane, n-decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane, n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethyl Propoxysilane, n-hexadecyldimethylpropoxysilane, n-icosanedimethylpropoxysilane, n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldie Lupropoxysilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxysilane, n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n-icosanedipropyl Propoxysilane, n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosanemethyldimethoxysilane, n-propylethyldimethoxysilane, n-butyl Ethyldimethoxysilane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, n-icosaneethyldimethoxysilane, n-butylpropyldimethoxysilane, n-decyl Propyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane, n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n-hexadecylmethyldi Ethoxysilane, n-icosanemethyldiethoxysilane, n-propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-icosaneethyl Diethoxysilane, n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-icosanepropyldiethoxysilane, n-propylmethyldipropoxysilane, n-butyl Tildipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosanemethyldipropoxysilane, n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decyl Ethyldipropoxysilane, n-hexadecylethyldipropoxysilane, n-icosaneethyldipropoxysilane, n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n- Icosanpropyl dipropoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-icosanetrimethoxysilane, n-propylto Ethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosanetriethoxysilane, n-propyltripropoxysilane, n-butyltripropoxysilane, n-decyltri Propoxysilane, n-hexadecyltripropoxysilane, n-icosanetripropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl)- Examples include 1-propanamine, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, and the like. These may be used alone or in combination of two or more.

The content of the adhesion assistant in the photosensitive aluminum paste composition is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 100 parts by weight with respect to the alkali-soluble resin (C). 10 parts by weight.
[Solution Accelerator]
The aluminum paste composition of the present invention preferably contains a dissolution accelerator for the purpose of exhibiting sufficient solubility in a developer described later. As the dissolution accelerator, a surfactant is preferably used. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and fatty acids.

  Examples of the fluorosurfactant include “BM-1000” and “BM-1100” manufactured by BM CHIMIE, “Megafac F142D”, “Same F172” and “Same F172” manufactured by Dainippon Ink & Chemicals, Inc. "F173", "F183", "Florard FC-135", "FC-170C", "FC-430", "FC-431" manufactured by Sumitomo 3M Ltd., "Asahi Glass Co., Ltd." “Surflon S-112”, “S-113”, “S-131”, “S-141”, “S-145”, “S-382”, “SC-101”, “Same” Commercial products such as “SC-102”, “SC-103”, “SC-104”, “SC-105”, and “SC-106” can be mentioned.

  Examples of the silicone surfactant include “SH-28PA”, “SH-190”, “SH-193”, “SZ-6032”, “SF-8428” manufactured by Toray Dow Corning Silicone Co., Ltd. ”,“ DC-57 ”,“ DC-190 ”,“ KP341 ”manufactured by Shin-Etsu Chemical Co., Ltd.,“ F-top EF301 ”,“ same EF303 ”,“ same EF352 ”manufactured by Shin-Akita Kasei Co., Ltd., etc. Can be mentioned.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether, polyoxyethylene octyl Examples include polyoxyethylene aryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate.

  Examples of commercially available nonionic surfactants include “Emulgen A-60”, “A-90”, “A-550”, “B-66”, and “PP-99” manufactured by Kao Corporation. “(Meth) acrylic acid copolymer polyflow No. 57” and “No. 90” manufactured by Kyoeisha Chemical Co., Ltd. can be mentioned.

  Among the above surfactants, nonionic surfactants are preferable, polyoxyethylene aryl ethers are more preferable, and in particular, the following formula (1) ) Is preferred.

上記式（１）中、Ｒ^１は炭素数１〜５のアルキル基、好ましくはメチル基であり、ｐは１〜５の整数であり、ｓは１〜５の整数、好ましくは２であり、ｔは１〜１００の整数、好ましくは１０〜２０の整数である。

In the above formula (1), R ¹ is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group, p is an integer of 1 to 5, s is an integer of 1 to 5, preferably 2. t is an integer of 1 to 100, preferably an integer of 10 to 20.

The content of the dissolution accelerator in the composition of the present invention is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, particularly 100 parts by weight of the alkali-soluble resin (C). Preferably it is 0.1-10 weight part. When the content of the dissolution accelerator is in the above range, a composition having excellent solubility in a developer can be obtained.
Fatty acid can be used as a dissolution accelerator, and may be used as a clathrate for aluminum powder. The fatty acids include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoyl acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid Examples include acids, linolenic acid, nonadecanoic acid, arachidic acid, arachidonic acid, behenic acid, lignoselenic acid, nervonic acid, serotic acid, montanic acid, and melicic acid.
[Additive]
The composition of the present invention may contain various additives such as thickeners and suspending agents as optional components. Although the viscosity of the said composition can be suitably adjusted with the addition amount of various additives etc., the range is 100-500,000 cps (centipoise).
[Resist layer (hereinafter also referred to as resist composition)]
In the manufacturing method of the present invention, a resist layer is formed on the aluminum paste layer transferred onto the substrate, and a resist layer pattern is formed on the aluminum paste layer by subjecting the resist layer to exposure processing and development processing. Is done.

The resist composition used for forming the resist layer contains a binder resin (a), a solvent (b), a polyfunctional (meth) acrylate (c), and a photopolymerization initiator (d). Hereinafter, these resist compositions will be described.
[Resist composition]
The resist composition contains a binder resin and a photosensitive component as essential components.

As a photosensitive component which comprises a resist composition, the combination of a polyfunctional (meth) acrylate (E) and a photoinitiator (F) etc. can be mentioned as an example, for example.
[Binder resin (a)]
The alkali-soluble resin (a) used in the resist composition of the present invention is not particularly limited as long as it is alkali-soluble. In the present invention, the term “alkali-soluble” means that the alkali-soluble resin (a) is alkaline to the extent that the intended development processing is possible. The property of being dissolved in a developer. Such a binder resin can be obtained by copolymerizing the alkali-soluble functional group-containing monomer (a1) and the (meth) acrylic acid derivative (a2).
Examples of the alkali-soluble functional group-containing monomer (a1) include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, and succinic acid mono (2- (meth)). Acryloyloxyethyl), 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrophthalate, carboxyl group-containing monomers such as ω-carboxy-polycaprolactone mono (meth) acrylate;
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (α-hydroxymethyl) acrylate;
Examples thereof include monomers having an alkali-soluble functional group and an unsaturated bond, such as phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. Among these monomers, (meth) acrylic acid, 2-methacryloyloxyethylphthalic acid, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyl Oxypropyltetrahydrohydrogenphthalate and 2-hydroxyethyl (meth) acrylate are preferred.

  By copolymerizing the alkali-soluble functional group-containing monomer (a1), alkali solubility can be imparted to the resin. The content of the structural unit derived from the alkali-soluble functional group-containing monomer (a1) is usually from 5 to 90% by weight, preferably from 10 to 80% by weight, particularly preferably from 15 to 70% by weight, based on the total structural units of the resin. It is.

  The (meth) acrylic acid derivative (a2) is not particularly limited as long as it is a (meth) acrylic acid derivative copolymerizable with the alkali-soluble functional group-containing monomer (a1). For example, methyl (meth) acrylate, Ethyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) Monomers (a2) such as acrylate, phenoxyethyl (meth) acrylate, trityl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. Etc. outside (meth) acrylates.

In the present invention, for example, styrene, methyl (meth) acrylate, ethyl (meth) acrylate instead of the (meth) acrylic acid derivative (a2) or in addition to the (meth) acrylic acid derivative (a2). Alternatively, a macromonomer having a polymerizable unsaturated group such as a (meth) acryloyl group, an allyl group, or a vinyl group may be used at one chain end of a polymer obtained from benzyl (meth) acrylate or the like.
(Radical polymerization initiator)
In the copolymerization, it is preferable to use a radical polymerization initiator. As a radical polymerization initiator, the thing similar to what is used for superposition | polymerization of the said binder resin (C) can be used. These radical polymerization initiators may be used alone or in combination of two or more. The usage-amount of these radical polymerization initiators is about 0.1-10 weight with respect to 100 weight part of all the monomers used for the said copolymerization.

  The weight average molecular weight (hereinafter also referred to as “Mw”) of the binder resin (a) thus obtained is a polystyrene conversion value measured by gel permeation chromatography (GPC), and preferably 5,000 to 150. 1,000, more preferably 10,000 to 100,000. Mw can be controlled by appropriately selecting conditions such as the copolymerization ratio, composition, chain transfer agent, and polymerization temperature of the monomer. When Mw is lower than the above range, film roughness after development is likely to occur, and when Mw exceeds the above range, the solubility of the unexposed portion in the developer may be reduced and resolution may be reduced. .

The binder resin has a glass transition temperature (Tg) of −10 to 120 ° C., preferably 0 to 100 ° C. When the glass transition temperature is lower than the above range, the coating film tends to be tacky and is difficult to handle. On the other hand, when the glass transition temperature exceeds the above range, the adhesiveness with a glass substrate as a support is deteriorated, and transfer may not be possible. In addition, the said glass transition temperature can be suitably adjusted by changing the quantity of a monomer (a1) and a (meth) acrylic acid derivative (a2).
The acid value of the binder resin (a) is preferably in the range of 20 to 200 mgKOH / g, more preferably 30 to 160 mgKOH / g. When the acid value is 20 mgKOH / g or less, the unexposed portion after exposure is not easily removed with an alkaline developer, and it tends to be difficult to form a high-definition pattern. On the other hand, when the acid value is 200 mgKOH / g or more, the portion cured by the exposure light is easily eroded by the alkali developer, and it tends to be difficult to form a high-definition pattern.

[Solvent (b)]
The composition of the present invention usually contains a solvent for imparting appropriate fluidity or plasticity and good film forming properties. The solvent used is preferably a solvent that has good affinity with inorganic powder and good solubility of the alkali-soluble resin, can adjust the viscosity of the aluminum paste, and can be easily evaporated by drying.

Examples of preferable solvents include ketones, alcohols, and esters having a normal boiling point (boiling point at 1 atm) of 100 to 200 ° C.
Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methoxypropyl acetate, dioxane, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, dimethyl sulfoxide, γ- Examples include butyrolactone, terpineol, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether. The said solvent may be used individually by 1 type, or 2 or more types may be mixed and used for it. Further, the content ratio of the solvent in the composition of the present invention can be appropriately selected within a range in which good film forming properties (fluidity or plasticity) can be obtained.
[Polyfunctional (meth) acrylate (c)]
In the composition of the present invention, the polyfunctional (meth) acrylate is used in an amount of 10% by weight or more, preferably 15 to 60% by weight in the organic component from the viewpoint of sensitivity to light. Here, the polyfunctional (meth) acrylate includes a light insolubilizing type and a light solubilizing type.

  As a photo-insoluble type, (1) containing a functional monomer or oligomer having one or more unsaturated groups in the molecule, (2) aromatic diazo compound, aromatic azide compound, organic halogen compound, etc. And (3) a so-called diazo resin such as a condensate of a diazo amine and formaldehyde.

  As a light-soluble type, (4) a complex of a diazo compound with an inorganic acid or an organic acid, a quinone diazo compound, (5) a quinone diazo compound combined with a suitable polymer binder, such as a phenol resin And naphthoquinone-1,2-diazide-5-sulfonic acid ester.

  As the radiation-sensitive component in the present invention, all of the above can be used, but the above-mentioned (1) is preferable in that it can be easily used by mixing with an inorganic component.

Examples of the photosensitive monomer include a compound containing a carbon-carbon unsaturated bond. Specifically,
Allylated cyclohexyl di (meth) acrylate, 2,5-hexanedi (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, Di (meth) taacrylates such as propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate;
Pentaerythritol tri (meth) acrylate, trimethylolpropane (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Polyfunctional (meth) acrylates such as monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, benzyl mercaptan (meth) acrylate;
A monomer in which 1 to 5 of the aromatic ring hydrogen atoms in the compound are substituted with chlorine or bromine atoms; and
Styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethyl Examples thereof include styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, γ-methacryloxypropyltrimethoxysilane, and 1-vinyl-2-pyrrolidone. The said photosensitive monomer may be used individually by 1 type, or may be used in combination of 2 or more type.
[Photoinitiator (d)]
Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl- 4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 2,4-diethylthioxanthone, benzyl Methyl ketanol, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4 -Azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o -Methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1- Phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2′-dimethoxy-1,2-diphenylethane-1-one, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, naphthalenesulfonyl chloride, quinolinesulfonyl chloride Rholide, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide, and And a combination of a photoreductive dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine.

  The said photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type. The photopolymerizable initiator is generally used in the range of 0.1 to 30 parts by weight, preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the inorganic particles. In particular, when a combination of a polyfunctional (meth) acrylate and a photopolymerization initiator is used, the content of the photosensitive monomer is usually 1 to 100 parts by weight, preferably 5 to 50 parts by weight with respect to 100 parts by weight of the inorganic particles. The content of the photopolymerization initiator is usually 1 to 50 parts by weight, preferably 2 to 40 parts by weight with respect to 100 parts by weight of the photosensitive monomer. When the content of the photosensitive component exceeds the above range, the shape of the display panel member after firing may be deteriorated.

[Other additives]
The resist composition of the present invention may contain various additives such as an adhesion assistant, a dissolution accelerator, an antifoaming agent, a thickener, and a precipitation inhibitor. These additives can use the same thing as the said aluminum paste composition.
[Electrode formation method I]
In the electrode forming method of the present invention, [1] an aluminum paste layer forming step, [2] a resist layer forming step, [3] a resist layer exposing step, [4] a resist layer developing step, [5] An electrode having an aluminum pattern is formed by an etching process of the aluminum paste layer and [6] a baking process of the aluminum paste layer pattern. Here, the electrode wiring having an aluminum pattern includes a member constituting an electrode wiring of a flat panel display, a member of an advanced mounting material of an electronic component, a member of a solar cell, and the like.
[Aluminum paste layer formation process]
3 and 4 are schematic cross-sectional views showing an example of a transfer film forming step in the production method of the present invention. In FIG. 3 [1], 11 is a glass substrate. An aluminum paste layer 21 is formed on this glass substrate. The specific composition will be described later. The aluminum paste layer 21 can be formed by applying the aluminum paste by various methods such as a screen printing method, a roll coating method, a spin coating method, a casting coating method, and then drying the coating film.

  Specifically, the aluminum paste composition of the present invention is prepared by mixing the aluminum powder (A), the glass powder (B), the alkali-soluble resin (C) and the solvent (D), and various additives as necessary. After that, the mixture is uniformly mixed and dispersed with a three roll or kneader.

  The obtained aluminum paste composition is coated on a support film (for example, width 200 mm, length 30 m, thickness 38 μm) made of a polyethylene terephthalate (PET) film, which has been subjected to release treatment in advance, using a knife coater, or using a roll coater. For electrode formation by removing all or part of the solvent by coating method, coating method by doctor blade, coating method by curtain coater, coating method by die coater, coating method by wire coater, screen coating method by printing device, etc. The transfer film of the aluminum paste layer by which the aluminum paste layer of this was formed on the support film was produced.

  The viscosity of the composition can be adjusted as appropriate depending on the amount of inorganic particles, thickener, solvent, plasticizer, precipitation inhibitor, etc., but the range is 50 to 10,000 cps (centipoise). .

  What is necessary is just to adjust suitably the drying conditions of the said coating film so that the residual ratio of the solvent after drying may be within 2 weight%, for example, is about 0.5 to 60 minutes at the drying temperature of 50-150 degreeC.

The thickness of the aluminum paste layer formed as described above is 3 to 100 μm, preferably 5 to 80 μm.
[Resist layer forming step]
In FIG. 3 [3], a resist layer 31 is formed on the aluminum paste layer 21. The resist constituting the resist layer 31 may be either a positive resist or a negative resist, and its specific composition will be described later. The resist layer 31 can be formed by applying a resist by various methods such as a screen printing method, a roll coating method, a spin coating method, and a casting coating method, and then drying the coating film.

  Specifically, the resist composition of the present invention was prepared by preparing the above-described alkali-soluble resin, polyfunctional (meth) acrylate, photopolymerization initiator, solvent and various additives, and then kneading them. .

  A coating method using a knife coater and a coating method using a roll coater on a support film (for example, width 200 mm, length 30 m, thickness 38 μm) made of a polyethylene terephthalate (PET) film obtained by subjecting the obtained resist composition to a release treatment in advance. The resist layer is formed on a support film by applying a doctor blade, a curtain coater, a die coater, a wire coater, etc. to remove the solvent to some extent. A transfer film was prepared.

  Although the viscosity of the said composition can be suitably adjusted with the addition amount of a solvent, a plasticizer, a precipitation inhibitor, etc., the range is 5-1,000 cps (centipoise).

  What is necessary is just to adjust suitably the drying conditions of the said coating film so that the residual ratio of the solvent after drying may be within 2 weight%, for example, is about 0.5 to 60 minutes at the drying temperature of 50-150 degreeC.

  The thickness of the resist layer formed as described above is 1 to 100 μm, preferably 2 to 50 μm.

As the thermocompression bonding conditions, the surface temperature of the heating roller is 60 to 120 ° C., the roller pressure is 0.5 to 10 kg / cm 2, and the laminator moving speed is 0.1 to 10 m / min.
[Resist layer exposure process]
In this step, as shown in FIG. 3 [4], the surface of the resist layer 31 formed on the aluminum paste layer 21 is irradiated with ultraviolet rays or the like through an exposure mask, so that a latent image of the resist pattern is obtained. Form. Here, the ultraviolet radiation apparatus is not particularly limited, such as an ultraviolet irradiation apparatus used in the photolithography method, an exposure apparatus used in the semiconductor and liquid crystal display industries.

  After the transfer film is formed on the substrate by the transfer step, exposure is performed using an exposure apparatus. As the exposure is performed by ordinary photolithography, a mask exposure method using a photomask can be employed. As a mask to be used, either a negative type or a positive type is selected depending on the type of organic component of the resist layer transferred onto the aluminum paste layer. The exposure pattern of the exposure mask varies depending on the purpose, but is, for example, a stripe or lattice having a width of 10 to 500 μm.

  Alternatively, a direct drawing method using a red or blue visible laser beam, an Ar ion laser, or the like without using a photomask may be used.

  The surface of the aluminum paste layer is selectively irradiated (exposed) with radiation such as ultraviolet rays through an exposure mask to form a pattern latent image on the resin layer. As the exposure apparatus, a parallel light exposure machine, a scattered light exposure machine, a stepper exposure machine, a proximity exposure machine, or the like can be used. Examples of the active light source used in the exposure include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferable, and as the light source, for example, Low pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, halogen lamp, etc. can be used. Among these, an ultra high pressure mercury lamp is preferable.

Exposure conditions vary depending on the coating thickness, but exposure is performed for 0.05 to 1 minute using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² . In this case, by using a wavelength filter to narrow the wavelength region of the exposure light, light scattering can be suppressed and pattern formation can be improved. Specifically, pattern formation can be improved by using a filter that cuts off i-line (365 nm) light or a filter that cuts off i-line and h-line (405 nm) light.
[Development process of resist layer]
In this step, the exposed resist layer is developed to reveal a resist pattern (latent image).

  Here, as development processing conditions, development methods (for example, dipping method, rocking method, shower method, spray method, paddle method, brush method, etc.) and development processing conditions (for example, the resist layer 31) The type / composition / concentration of developer, development time, development temperature, etc.) may be appropriately selected and set according to the type of resin layer. By this development process, as shown in FIG. 4 [5], a resist pattern 35 (pattern corresponding to the exposure mask M) composed of the resist remaining portion 35A and the resist removing portion 35B is formed.

  This resist pattern 35 acts as an etching mask in the next process (etching process), and the constituent material of the resist remaining portion 35A (photocured resist) is more resistant to the etching solution than the constituent material of the aluminum paste layer 21. A low dissolution rate is required.

  As the developer used in the development step, a solvent capable of dissolving the organic component in the resin layer can be used. Further, water may be added to the solvent as long as its dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the resin layer, development can be performed with an alkaline aqueous solution.

  The aluminum paste layer contains the aluminum powder (A) and the glass powder (B), and the aluminum powder (A) and the glass powder (B) are uniformly dispersed by the alkali-soluble resin (C). Therefore, the aluminum powder (A) and the glass powder (B) are simultaneously removed by dissolving the resin (C) with a developer and washing.

  Examples of the alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus Potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, boric acid Sodium, potassium borate, aqueous ammonia, tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Bruno isopropylamine, diisopropylamine, ethanolamine, diethanolamine, triethanolamine.

  The concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

The alkaline aqueous solution may contain additives such as nonionic surfactants and organic solvents. In addition, after the development process with an alkali developer is performed, a washing process is usually performed.
[Aluminum paste layer etching process]
In this step, the aluminum paste layer is etched to form an aluminum paste layer pattern corresponding to the resist pattern.

  That is, as shown in FIG. 4 [6], a portion of the aluminum paste layer 21 corresponding to the resist removal portion 35B of the resist pattern 35 is dissolved in the etching solution and selectively removed. Here, FIG. 4 [6] shows a state during the etching process.

  Here, as the etching process conditions, depending on the type of the aluminum paste layer 21 and the like, the type / composition / concentration of the etchant, the processing time, the processing temperature, the processing method (for example, dipping method, rocking method, shower method, spraying) Method, paddle method), processing apparatus, and the like can be selected as appropriate.

  In addition, the development process and the etching process are continuously performed by selecting the types of the resist layer 31 and the aluminum paste layer 21 so that the same solution as the developer used in the development process can be used as the etching liquid. Therefore, the manufacturing efficiency can be improved by simplifying the process.

  Even if a part or all of the remaining resist portion 35A remains after the etching process, the remaining resist portion 35A is removed in the next baking step.

  Specifically, the etching solution used in the etching process of the aluminum paste layer is preferably an alkaline solution. Thereby, the alkali-soluble resin contained in the aluminum paste layer can be easily dissolved and removed.

  Since the aluminum powder contained in the aluminum paste layer is uniformly dispersed by the alkali-soluble resin, the aluminum powder is simultaneously removed by dissolving and washing the alkali-soluble resin as a binder with an alkaline solution. .

  Here, examples of the alkaline solution used as the etching solution include a solution having the same composition as the developer.

In addition, after the etching process with an alkaline solution is performed, a washing process is usually performed.
Moreover, the organic solvent which can melt | dissolve the binder of an aluminum paste layer can also be used as etching liquid. Examples of the organic solvent include the solvents exemplified as those constituting the inorganic powder-dispersed paste composition.

In addition, after the etching process with an organic solvent is performed, the rinse process with a poor solvent is performed as needed.
[Baking process of aluminum paste layer pattern]
In this step, the aluminum paste layer pattern 31 is baked to form electrode wiring. As a result, the organic material in the material layer remaining portion is burned out to form a metal layer or the like, and an electrode material 50 in which the electrode wiring 40 is formed on the surface of the glass substrate as shown in FIG. Obtainable.

The firing atmosphere varies depending on the composition and the type of substrate, but firing is performed in an atmosphere of air, ozone, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.
Here, the temperature of the baking treatment needs to be a temperature at which the organic substance in the material layer residual portion 25A is burned off, and is usually set to 350 to 750 ° C. The firing time is usually 10 to 90 minutes.

By the pattern forming method of the present invention including these steps, a display panel member such as an electrode, a circuit pattern of an electronic component, a wiring pattern of a solar cell member, and the like can be formed. In addition, you may introduce | transduce a 50-300 degreeC heating process in each process of the said transfer, exposure, image development, and baking for the purpose of drying or preliminary reaction.
[Electrode formation method II]
The method for producing an electrode member according to the present invention comprises: forming a resist layer on a support film; then forming an aluminum paste layer on the support film; Workability is improved by using a layer transfer film. Here, when forming a resist layer on a support film and when forming an aluminum paste layer on a support film, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a coating using a die coater A method, a coating method using a wire coater, a screen coating method using a printing apparatus, and the like can be used, whereby a layer having excellent film thickness uniformity can be formed. The electrode member manufacturing method using the transfer film of the present invention includes: [1] resist layer forming step, [2] aluminum paste layer forming step, [3] transfer film forming step, and [4] transfer film transfer. [5] resist layer exposure step, [6] resist layer development step, [7] aluminum paste layer etching step, [8] aluminum paste layer pattern firing step to form an electrode wiring having an aluminum pattern To do.
[Resist layer forming step]
5 and 6 are schematic cross-sectional views showing an example of a transfer film forming step in the production method of the present invention. In FIG. 5 [1], 22 is a support film. A support film and a resist layer 31 formed on the support film are formed. The resist constituting the resist layer 31 may be either a positive resist or a negative resist, and its specific composition will be described later. The resist layer 31 can be formed by applying a resist by various methods such as a screen printing method, a roll coating method, a spin coating method, and a casting coating method, and then drying the coating film.
[Aluminum paste layer formation process]
In FIG. 5 [2], 22 is a support film. A support film and an aluminum paste layer 21 formed on the support film are formed. The specific composition will be described later. The aluminum paste layer 21 can be formed by applying the aluminum paste by various methods such as a screen printing method, a roll coating method, a spin coating method, a casting coating method, and then drying the coating film.
[Transfer Film Formation Process]
The production method of the present invention is characterized in that a transfer film is used and an aluminum paste layer and a resist layer constituting the transfer film are transferred from the aluminum paste layer side to the surface of the substrate. Here, the transfer film is produced by thermocompression bonding of a support film, an aluminum paste layer formed on the support film, a support film, and a resist layer formed on the support film. Here, as the transfer conditions, for example, the surface temperature of the heating roller is 50 to 120 ° C., the roller pressure by the heating roller is 0.5 to 10 kg / cm 2, and the moving speed of the heating roller is 0.1 to 10 m / min. be able to. Further, the glass substrate may be preheated, and the preheat temperature can be set to 40 to 100 ° C., for example.
[Transfer process of transfer film]
An example of the transfer process is as follows. In FIG. 5 [4], after peeling the 21 abutting protective film layer [22] of the transfer film [22 + 31 + 21 + 22] used as necessary, it is shown in FIG. 5 [5]. In this way, the transfer film [31 + 21] is superimposed on the surface of the glass substrate 11 so that the surface of the aluminum paste layer 21 is in contact with the surface, and the transfer film [31 + 21] is thermocompression bonded with a heating roller or the like. did. Here, as the transfer conditions, for example, the surface temperature of the heating roller is 50 to 120 ° C., the roller pressure by the heating roller is 0.5 to 10 kg / cm 2, and the moving speed of the heating roller is 0.1 to 10 m / min. be able to. Further, the glass substrate may be preheated, and the preheat temperature can be set to 40 to 100 ° C., for example.
[Resist layer exposure process]
In this step, as shown in FIG. 5 [6], the surface of the resist layer 31 formed on the aluminum paste 21 is irradiated with ultraviolet rays or the like through an exposure mask and a support film 22 to form a resist pattern. The latent image is formed. Here, the ultraviolet radiation apparatus is not particularly limited, such as an ultraviolet irradiation apparatus used in the photolithography method, an exposure apparatus used in the semiconductor and liquid crystal display industries.
[Development process of resist layer]
In this step, the exposed resist layer is developed to reveal a resist pattern (latent image).

  Here, as development processing conditions, development methods (for example, dipping method, rocking method, shower method, spray method, paddle method, brush method, etc.) and development processing conditions (for example, the resist layer 31) The type / composition / concentration of developer, development time, development temperature, etc.) may be appropriately selected and set according to the type of resin layer. By this development step, as shown in FIG. 6 [7], a resist pattern 35 (pattern corresponding to the exposure mask M) composed of the resist remaining portion 35A and the resist removing portion 35B is formed.

  This resist pattern 35 acts as an etching mask in the next process (etching process), and the constituent material of the resist remaining portion 35A (photocured resist) is more resistant to the etching solution than the constituent material of the aluminum paste layer 21. A low dissolution rate is required.

As the developer used in the development step, a solvent capable of dissolving the organic component in the resin layer can be used. Further, water may be added to the solvent as long as its dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the resin layer, development can be performed with an alkaline aqueous solution.
[Aluminum paste layer etching process]
In this step, the aluminum paste layer is etched to form an aluminum paste layer pattern corresponding to the resist pattern.

  That is, as shown in FIG. 6 [8], a portion of the aluminum paste layer 21 corresponding to the resist removal portion 35B of the resist pattern 35 is dissolved in the etching solution and selectively removed. Here, FIG. 6 [8] shows a state during the etching process.

  Here, as the etching process conditions, depending on the type of the aluminum paste layer 21 and the like, the type / composition / concentration of the etchant, the processing time, the processing temperature, the processing method (for example, dipping method, rocking method, shower method, spraying) Method, paddle method), processing apparatus, and the like can be selected as appropriate.

  In addition, the development process and the etching process are continuously performed by selecting the types of the resist layer 31 and the aluminum paste layer 21 so that the same solution as the developer used in the development process can be used as the etching liquid. Therefore, the manufacturing efficiency can be improved by simplifying the process.

Even if a part or all of the remaining resist portion 35A remains after the etching process, the remaining resist portion 35A is removed in the next baking step.
[Baking process of aluminum paste layer pattern]
In this step, the aluminum paste layer pattern 31 is baked to form electrode wiring. As a result, the organic material in the remaining portion of the material layer is burned out, a metal layer or the like is formed, and an electrode material 50 in which the electrode wiring 40 is formed on the surface of the glass substrate as shown in FIG. Obtainable.
The details of each step are in accordance with the above-mentioned “electrode formation method I”.
[Other methods for forming electrodes]
The electrode forming method in the present invention is not limited to the method shown in FIGS. 3 and 4, 5 and 6. Examples of other methods for forming the electrode include, but are not limited to, the formation methods according to the following formation methods II to V.
[Electrode formation method III]
In the method for producing an electrode member of the present invention, an aluminum paste layer is formed on a substrate, and then a resist layer formed on a support film is transferred onto the aluminum paste layer to form a laminate. When an aluminum paste layer is formed on a substrate and a resist layer is formed on a support film, a coating method using a knife coater, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, a die coater A coating method using a wire coater, a coating method using a wire coater, a screen coating method using a printing apparatus, and the like can be used, whereby a layer having excellent film thickness uniformity can be formed. In the electrode forming method of the present invention, [1] an aluminum paste layer forming step, [2] a resist layer forming step, [3] a resist layer transferring step, [4] a resist layer exposing step, [5] An electrode having an aluminum pattern is formed by a resist layer developing step, [6] an aluminum paste layer etching step, and [7] an aluminum paste layer pattern firing step. The details of each step are in accordance with the above-mentioned “electrode formation method I”.
[Electrode formation method IV]
In the method for producing an electrode member of the present invention, an aluminum paste layer is formed on a support film, the transfer film is transferred onto a substrate, a resist layer is formed on the support film, and then transferred onto the aluminum paste layer. And is formed by lamination. When forming an aluminum paste layer on a support film and when forming a resist layer on a support film, a coating method using a knife coater, a coating method using a roll coater, a coating method using a doctor blade, a coating method using a curtain coater, A coating method using a die coater, a coating method using a wire coater, a screen coating method using a printing apparatus, and the like can be used, thereby forming a layer having excellent film thickness uniformity. In the electrode forming method of the present invention, [1] an aluminum paste layer forming step, [2] an aluminum paste layer transferring step, [3] a resist layer forming step, [4] a resist layer transferring step, [5] An electrode having an aluminum pattern is formed by a resist layer exposure step, [6] a resist layer development step, [7] an aluminum paste layer etching step, and [8] an aluminum paste layer pattern firing step. The details of each step are in accordance with the above-mentioned “electrode formation method I”.
[Electrode formation method V]
The method for producing an electrode member of the present invention can improve workability by using the layer transfer film of the present invention, in which a resist layer is formed on a support film and then an aluminum paste layer is formed on the resist layer. It is to improve. Here, when forming a resist layer on a support film and when forming an aluminum paste layer on a resist layer, a coating method by a roll coater, a coating method by a doctor blade, a coating method by a curtain coater, a coating by a die coater A method, a coating method using a wire coater, a screen coating method using a printing apparatus, and the like can be used, whereby a layer having excellent film thickness uniformity can be formed. In the method for forming an electrode using the transfer film of the present invention, [1] a resist layer forming step, [2] an aluminum paste layer forming step, [3] a transfer film forming step, [4] transfer film transfer [5] resist layer exposure step, [6] resist layer development step, [7] aluminum paste layer etching step, [8] aluminum paste layer pattern firing step to form an electrode wiring having an aluminum pattern To do. The details of each step are in accordance with the above-mentioned “electrode formation method I”.

The manufacturing method of the flat display panel of this invention includes the process of forming an electrode member as mentioned above, and is suitable for the manufacturing method of the electrode member of a flat panel display.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by these Examples. In the examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

  First, a method for measuring and evaluating physical properties will be described.

[Method for Measuring Weight Average Molecular Weight (Mw) and Weight Average Molecular Weight (Mw) / Number Average Molecular Weight (Mn) (hereinafter referred to as Mw / Mn)]
Mw and Mw / Mn are values in terms of polystyrene measured by gel permeation chromatography (GPC) (“HLC-8220GPC” manufactured by Tosoh Corporation). The GPC measurement was performed using “TSK guard column Super HZM-M” manufactured by Tosoh Corporation as a GPC column under the conditions of a tetrahydrofuran (THF) solvent and a measurement temperature of 40 ° C.
[Method for evaluating pattern after firing]
A panel test piece (150 mm × 150 mm × 2.8 mm) was prepared by cutting the fired panel, and the pattern cut surface at the position shown in FIG. 2 was observed with a scanning electron microscope (“S4200” manufactured by Hitachi, Ltd.). The width and height of the pattern were measured, and each was evaluated according to the following criteria. The desired standard is a pattern width of 50 μm, a height of 10 μm, and an interval of 100 μm.
A: The desired standard.
B: Within ± 5% of desired standard.
C: A value exceeding ± 5% and within ± 10% from a desired standard.
D: More than ± 10% from the desired standard.
[Evaluation of pattern adhesion after firing]
A pattern was prepared and fired on a panel test piece (150 mm × 150 mm × 2.8 mm), and the adhesion between the fired pattern and the support was evaluated. The desired standard is a pattern width of 50 μm, a height of 10 μm, and an interval of 100 μm. Cello tape (manufactured by Nichiban Co., Ltd.) was thermocompression bonded with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 23 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. As a result, the cellophane tape was transferred to the surface of the support and brought into close contact. Evaluation was made by peeling the cellophane from the support.
○: No pattern peeling.
X: Pattern peeling occurred.
[Synthesis Example 1]
80 g of 2-ethoxyethyl methacrylate, 20 g of methacrylic acid, 1 g of azobisisobutyronitrile (AIBN), 5 g of pentaerythritol tetrakis (3-mercaptopropionic acid) (manufactured by Sakai Chemical Industry Co., Ltd.) are charged into an autoclave equipped with a stirrer and nitrogen The mixture was stirred in 150 parts of terpineol under an atmosphere until uniform. Next, polymerization was carried out at 80 ° C. for 4 hours, and the polymerization reaction was continued at 100 ° C. for 1 hour, followed by cooling to room temperature to obtain a methacrylic resin (1) having SH groups. The polymerization rate of this methacrylic resin (1) was 98%, and the weight average molecular weight of alkali-soluble resin (1) was 20000 (Mw / Mn 1.8).
[Synthesis Example 2]
A methacrylic resin (2) was obtained in the same manner as in Synthesis Example 1 except that 5 g of NOFMER NSD (manufactured by NOF Corporation) was used instead of pentaerythritol tetrakis (3-mercaptopropionic acid). The polymerization rate of the alkali-soluble resin (2) was 98%, and the weight-average molecular weight of the alkali-soluble resin (2) was 25000 (Mw / Mn 2.2).
[Synthesis Example 3]
A methacrylic resin (3) was obtained in the same manner as in Synthesis Example 1 except that 25 g of 2-hydroxyethyl methacrylate was used instead of methacrylic acid. The polymerization rate of the alkali-soluble resin (3) was 98%, and the weight-average molecular weight of the alkali-soluble resin (4) was 28000 (Mw / Mn 2.4).
[Examples 1 to 4]
In Example 1, 16 g of aluminum powder shown in Table 1, 2 g of glass powder shown in Table 2, and 82 g of binder composition shown in Table 3 were prepared, and then kneaded with a kneader to produce an aluminum paste composition (hereinafter referred to as “aluminum paste”). (Also called).

After preparing the organic components shown in Table 4, a resist composition (hereinafter also referred to as “resist layer”) was prepared by kneading with a kneader.
The aluminum paste was applied onto a support film (for example, width 200 mm, length 30 m, thickness 38 μm) made of a polyethylene terephthalate (PET) film which had been subjected to a mold release treatment in advance, and held at 100 ° C. for 10 minutes to dry. In any of Examples 1 to 15, it was in the range of 15 μm ± 1 μm.
The resist was coated on a support film (for example, width 200 mm, length 30 m, thickness 38 μm) made of a polyethylene terephthalate (PET) film which had been subjected to a release treatment in advance, and was dried at 100 ° C. for 10 minutes. In any of Examples 1 to 4, it was in the range of 10 μm ± 1 μm.
Next, the transfer films were superposed on the surface of the aluminum paste layer so that the resist layer was in contact, and the transfer film was thermocompression bonded with a heating roller. The pressure bonding conditions were such that the surface temperature of the heating roller was 23 ° C., the roll pressure was 4 kg / cm ² , and the moving speed of the heating roller was 0.5 m / min. After the thermocompression treatment, the support film in contact with the aluminum paste layer of the transfer film was peeled off, and the support film was removed. The transfer film on the aluminum paste layer side was thermocompression bonded onto the glass substrate. As a result, the aluminum paste layer was in close contact with the surface of the glass substrate.

Next, using a negative chrome mask (pattern width 50 μm, pattern interval 100 μm), the photosensitive resist layer was exposed to ultraviolet rays with an ultrahigh pressure mercury lamp having an output of 25 mJ / cm ² from the top surface. The exposure amount was 500 mJ / cm ² .

  Next, the resist layer after exposure was developed by applying a 0.5% aqueous solution of sodium carbonate maintained at 23 ° C. for 60 seconds in a shower. Then, it washed with water using shower spray, the space part which is not photocured was removed, and the pattern of width 50 micrometers and a space | interval of 100 micrometers was formed on the glass substrate for panels. The developed pattern was evaluated by the above evaluation method. The results are shown in Table 5.

  Next, the obtained aluminum paste layer pattern was baked at 580 ° C. for 30 minutes to form an electrode pattern. This fired pattern was evaluated by the above evaluation method. The results are shown in Table 5.

  Examples 2 to 4 were evaluated in the same manner as in Example 1. As shown in Table 5, Examples 1 to 4 were particularly excellent in pattern evaluation after development in Examples 1 to 4. In the pattern evaluation after baking, Examples 1-4 were excellent.

TMP: trimethylolpropane (propion oxide modified) triacrylate DMMPB: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1
PGMEA: Propylene glycol monomethyl ether acetate

TMP: trimethylolpropane (propion oxide modified) triacrylate TPDA: tripropylene glycol diacrylate DMMPB: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1
BHHD: 1,7-bis (4-hydroxyphenol) -1,6-heptadiene-3,5-dione PGMEA: propylene glycol monomethyl ether acetate

[Comparative Examples 1-4]
As shown in Table 6, Comparative Examples 1 to 4 were evaluated in the same manner as Example 1. In the pattern evaluation after development in Comparative Examples 1 to 4, Comparative Examples 1, 3 and 4 were defective. Comparative Example 2 was slightly poor. In the pattern evaluation after firing, Comparative Examples 1, 3 and 4 were defective, but no chipping or peeling of the pattern was observed. Although Comparative Example 2 was slightly defective, pattern chipping and peeling were observed.

It is a schematic diagram which shows the cross-sectional shape of an alternating current type plasma display panel. It is a schematic diagram which shows the cross-sectional shape of a general field emission display.

Explanation of symbols

101 glass substrate 102 glass substrate 103 rear partition 104 transparent electrode 105 bus electrode 106 address electrode 107 fluorescent material 108 dielectric layer 109 dielectric layer 110 protective layer 111 front partition 201 glass substrate 202 glass substrate 203 insulating layer 204 transparent electrode 205 emitter 206 Cathode electrode 207 Phosphor 208 Gate 209 Spacer

Claims (7)

An aluminum paste layer containing aluminum powder (A) and a binder resin (C) is formed on the substrate, and a resist film is formed on the aluminum paste layer formed on the substrate, thereby forming an aluminum paste layer on the substrate. Form a laminate of resist films, expose the resist film of the laminate to form a latent image of the resist pattern, develop the resist film to reveal the resist pattern, and etch the aluminum paste layer An electrode manufacturing method comprising a step of processing to form a pattern of an aluminum paste layer corresponding to a resist pattern, and firing the pattern,
A method for producing a flat panel display electrode, wherein the aluminum powder (A) contains D50: 2 to 20 μm aluminum powder. Aluminum on the substrate by including a step of transferring the aluminum paste layer containing the aluminum powder (A) and the alkaline binder resin (C) formed on the support film and / or the resist film formed on the support film An electrode manufacturing method characterized by forming a laminate of a paste layer and a resist film,
The method for producing a flat panel display electrode according to claim 1, wherein the aluminum powder (A) contains D50: 2 to 20 µm aluminum powder. An aluminum paste layer and a resist film are formed on the substrate by including a step of transferring a laminate of the aluminum paste layer containing the aluminum powder (A) and the binder resin (C) formed on the support film and the resist film. An electrode manufacturing method characterized by forming a laminate of:
The method for producing a flat panel display electrode according to claim 1, wherein the aluminum powder (A) contains an aluminum powder having a D50 of 2 to 20 µm. The glass paste (B) having a softening point of 350 to 700 ° C is further contained in the aluminum paste layer in an amount of 0.5 to 20% by weight with respect to the aluminum paste layer. Method for manufacturing flat panel display electrode A transfer film comprising an aluminum paste layer containing an aluminum powder (A) and a binder resin (C) formed on a support film, wherein the aluminum powder (A) is D50: 2 to 20 μm aluminum powder A transfer film comprising: 57. The transfer film according to claim 56, wherein the aluminum paste layer further comprises 0.5 to 20% by weight of glass powder (B) having a softening point of 350 to 700 [deg.] C. with respect to the aluminum paste layer. The transfer film according to claim 5, comprising a laminate of the aluminum paste layer and a resist film.

Images