JPH10144210A - Electrode formation method - Google Patents

Abstract

(57) [Problem] To provide an underlayer and an electrode layer on a glass substrate at the same time in a display such as a PDP, a FED, a fluorescent display, a liquid crystal display, or a multilayer printed wiring board. An object of the present invention is to provide an electrode forming method capable of shortening a PDP manufacturing time and improving a yield. SOLUTION: The electrode forming method of the present invention is characterized in that at least an inorganic component composed of glass frit and an inorganic component composed of at least glass frit are formed on a base forming layer 14 of a glass substrate 11 provided with a base forming layer 14 formed of a thermoplastic resin. A first step of coating and forming an electrode forming layer 12 made of a conductive powder and a photosensitive resin, a second step of exposing from the electrode forming layer side through a predetermined electrode pattern mask M, and developing the electrode forming layer. A third step of forming the electrode pattern 12 and a fourth step of sintering the whole to simultaneously sinter the base formation layer and the electrode formation layer are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display such as a plasma display panel (PDP), a field emission display (FED), a fluorescent display, and a liquid crystal display, or a base layer and an electrode layer in a multilayer printed wiring board. The present invention relates to a method for forming an electrode, which can form the electrodes simultaneously.

[0002]

2. Description of the Related Art In a display such as a PDP, a FED, a fluorescent display, a liquid crystal display, or a multilayer printed wiring board, electrodes are provided on a glass substrate. When formed, the electrode material is eluted due to the alkali component contained in the glass to cause a decrease in function such as conduction, so that the electrode is generally laminated on a glass substrate via a dielectric underlayer.

The structure of a PDP will be described with reference to an example of the structure of an AC PDP shown in FIG. FIG. 3 shows the front plate and the rear plate separated from each other. Two glass substrates 1 and 2 are arranged in parallel and opposed to each other, and both glass substrates 2 are used as a rear plate. It is held at a fixed interval by cell barriers 3 provided above and parallel to each other. On the back side of the glass substrate 1 serving as the front plate, composite electrodes composed of a transparent electrode 4 serving as a discharge sustaining electrode and a metal electrode 5 serving as a bus electrode are formed in parallel with each other. 6 is formed thereon, and a protective layer (M
gO layer). In addition, address electrodes 8 are formed on the front side of the glass substrate 2 serving as the back plate and between the cell barriers 3 so as to be perpendicular to the composite electrode with the address electrodes 8 formed in parallel with each other. A fluorescent screen 9 is provided so as to cover the wall surface and the cell bottom.

In this structure, as shown in FIG. 5, after an underlayer 10 is formed on a glass substrate 2 serving as a back plate, an address electrode 8 is provided, and a dielectric layer 6 'is further laminated thereon. Thereafter, a structure in which the cell barrier 3 and the phosphor surface 9 are provided is adopted. This AC type PDP is a surface discharge type,
In this structure, an AC voltage is applied between the composite electrodes on the front panel, and discharge is caused by an electric field leaking into the space. In this case, since the alternating current is applied, the direction of the electric field changes according to the frequency.
Then, the phosphor 9 is caused to emit light by the ultraviolet rays generated by the discharge, and the light transmitted through the front plate can be visually recognized by an observer. In the DC type PDP, the difference is that the electrode has a structure not covered with a dielectric layer.
The discharge phenomenon is the same.

[0005] The structure shown in FIG. 5 has a structure in which a base forming layer and an electrode forming layer are sequentially laminated on a glass substrate. In manufacturing the base forming layer and the electrode forming layer, the base forming layer is coated on the glass substrate by screen printing or the like. After being formed, after firing to form an underlayer, an electrode forming layer is similarly coated and formed on the underlayer, and patterned by photolithography or the like,
A method of forming an electrode by firing again is adopted, but at present, it takes a lot of time to manufacture the electrode.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a PD
In displays such as P, FED, fluorescent display, and liquid crystal display, or in multilayer printed wiring boards, an underlayer and an electrode layer can be simultaneously formed on a glass substrate, thereby shortening the PDP manufacturing time and increasing the yield. An object of the present invention is to provide a method for forming an electrode, which can improve the resistance.

[0007]

According to a first electrode forming method of the present invention, at least a glass is formed on an undercoating layer of a glass substrate provided with an undercoating layer made of an inorganic component made of glass frit and a thermoplastic resin. A first step of coating and forming an electrode forming layer made of an inorganic component composed of a frit, a conductive powder, and a photosensitive resin; a second step of exposing from the electrode forming layer side through a predetermined electrode pattern mask; A third step of developing to form an electrode pattern;
The method is characterized by comprising a fourth step of firing the entire structure and simultaneously sintering the underlayer forming layer and the electrode forming layer.

[0008] The invention is characterized in that the above-mentioned electrode forming layer further contains a thickener.

According to a second electrode forming method of the present invention, a transfer sheet for forming an electrode forming layer having an electrode forming layer comprising at least an inorganic component composed of glass frit, a conductive powder, and a photosensitive resin is provided on a base film. From the electrode forming layer side, a first step of laminating on a base forming layer in a glass substrate provided with a base forming layer made of at least an inorganic component made of glass frit and a thermoplastic resin, a predetermined electrode pattern mask is formed from the base film side. A second step of exposing through the base film, a third step of peeling off the base film and then developing the electrode forming layer to form an electrode pattern, and a fourth step of firing the whole and simultaneously sintering the base forming layer and the electrode forming layer. It is characterized by comprising a process.

[0010] In a third electrode forming method of the present invention, a transfer sheet for forming an electrode forming layer having an electrode forming layer made of at least an inorganic component made of glass frit, conductive powder, and photosensitive resin is formed on a base film. A first step of laminating from a side of the electrode forming layer on a base forming layer of a glass substrate provided with a base forming layer made of at least an inorganic component made of glass frit and a thermoplastic resin, and then peeling the base film; A second step of exposing from the layer side through a predetermined electrode pattern mask, a third step of developing the electrode forming layer to form an electrode pattern, and firing the whole to simultaneously sinter the base forming layer and the electrode forming layer 4th
It is characterized by comprising a process.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIGS. 1A to 1D show a continuous process chart of a first electrode forming method of the present invention, in which S denotes a transfer sheet for forming a base forming layer. , 11 is a base film, 12 is an electrode forming layer, 13 is a glass substrate, 14 is a base forming layer, and M is an electrode pattern mask. First, the transfer sheet for forming a base forming layer shown in FIG.

The base film 11 is not affected by the solvent in the coating liquid for forming the undercoat layer,
It is necessary not to shrink and stretch by the heat treatment in the transfer step, and polyethylene terephthalate, 1,4-polycyclohexylene dimethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polystyrene, polypropylene, polysulfone, aramid, polycarbonate, polyvinyl alcohol, cellophane And cellulose derivatives such as cellulose acetate, and various films and sheets such as polyethylene, polyvinyl chloride, nylon, polyimide, and ionomer, and metal foils such as aluminum and copper. The film thickness is 4 μm to 400 μm, and preferably 4.
It is 5 μm to 200 μm.

Next, the base forming layer 14 is composed of an inorganic component having at least a glass frit and a thermoplastic resin.

The glass frit has a softening point of 3
At 50 ° C. to 650 ° C., the coefficient of thermal expansion α ₃₀₀ is 60 × 10 ⁻⁷
/ ° C to 100 × 10 ^-7 / ° C. If the softening point of the glass frit exceeds 650 ° C., it is necessary to raise the firing temperature, and depending on the lamination object, it is not preferable because it is thermally deformed. If it is lower than 350 ° C., the thermoplastic resin and the like are decomposed and volatilized. It is not preferable because the glass frit is fused before and a void or the like is generated in the layer. The thermal expansion coefficient is 60 × 10 ⁻⁷ / ° C. to 100 × 10 ⁻⁷ /
If the temperature is out of the range, the PDP is not preferable because the difference from the thermal expansion coefficient of the glass substrate is large, causing distortion and the like.

As the inorganic component, two or more inorganic powders and two or more inorganic pigments may be used in addition to the glass frit.

The inorganic powder is an aggregate, and is added as needed. The inorganic powder is intended to prevent casting during firing and to improve the compactness, and has a softening point higher than that of the glass frit, such as aluminum oxide, boron oxide, silica, titanium oxide, magnesium oxide, and oxide. Inorganic powders such as calcium, strontium oxide, barium oxide, and calcium carbonate can be used, and examples thereof include those having an average particle size of 0.1 μm to 20 μm. The inorganic powder may be used in an amount of 0 to 30 parts by weight based on 100 parts by weight of the glass frit.

As the inorganic pigment, for example, it is added as necessary to reduce the reflection of external light from PDP and to improve the practical contrast. Co-Cr-F as a black pigment
e, Co-Mn-Fe, Co-Fe-Mn-Al, Co
-Ni-Cr-Fe, Co-Ni-Mn-Cr-Fe,
Co-Ni-Al-Cr-Fe, Co-Mn-Al-C
r-Fe-Si and the like. In addition, as a fire-resistant white pigment, titanium oxide, aluminum oxide, silica,
Calcium carbonate and the like.

Next, a thermoplastic resin is contained as a binder of an inorganic component and for the purpose of improving transferability. Examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, and the like. n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate,
tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, styrene, α-
Examples include polymers or copolymers composed of one or more of methylstyrene, N-vinyl-2-pyrrolidone, and the like, and cellulose derivatives such as ethylcellulose.

In particular, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert -Butyl acrylate,
polymers or copolymers of one or more of tert-butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and the like;
Ethyl cellulose is preferred.

The proportion of the inorganic component and the thermoplastic resin used is as follows:
3 parts by weight of thermoplastic resin based on 100 parts by weight of inorganic component
It comprises 50 parts by weight, preferably 5 to 30 parts by weight. If the amount of the thermoplastic resin in the ink layer is less than 3 parts by weight, the holding property of the ink layer is low, and in particular, the storage property in the wound state and the handling property are problematic, and the transfer sheet is cut into an appropriate shape. In the case of (slit), a problem occurs that the inorganic component becomes dust and hinders PDP production. On the other hand, if the amount exceeds 50 parts by weight, carbon remains in the film after sintering, and the quality is undesirably deteriorated.

Further, a polymerizable monomer and a photoinitiator are added to the ink layer as needed.

Examples of the polymerizable monomer include compounds having at least one polymerizable carbon-carbon unsaturated bond. For example, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate,
Glycerol acrylate, glycidyl acrylate,
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobonyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate,
Methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6
-Hexanediol diacrylate, 1,3-propanediol diacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylol Propane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanetriol triacrylate, 2,2,4-trimethyl-1,3-pentanediol Diacrylate, diallyl fumarate,
1,10-decanediol dimethyl acrylate, dipentaerythritol hexaacrylate, and the above acrylates converted to methacrylates, one or two of γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, etc. Mixtures of more than one species.

The polymerizable monomer is preferably contained in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin.

Examples of photoinitiators include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, α-aminoacetophenone, Dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,2-diethoxyacetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert
-Butyldichloroacetophenone, thioxanthone, 2
-Methylthioxanthone, 2-chlorothioxanthone,
2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketal, benzylmethoxyethylacetal, benzoinmethylether, benzoinbutylether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-
Chloroanthraquinone, anthrone, benzanthrone, dibensuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone,
-Phenyl-1,2-butadione-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- [4- (methylthio) phenyl]- 2-morpholino-1-propane, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphosphine, camphorquinone, tetrabromine A combination of a photoreducing dye such as carbon fluoride, tribromophenylsulfone, benzoyl peroxide, eosin, or methylene blue and a reducing agent such as ascorbic acid or triethanolamine; and one of these photoinitiators. Also It may be used in combination of two or more. Further, a plasticizer, a dispersant, an antisettling agent, an antifoaming agent, a release agent, and a leveling agent are added to the ink layer as needed.

The plasticizer is added for the purpose of improving the transferability and the fluidity of the ink. For example, normal alkyl phthalates such as dimethyl phthalate, dibutyl phthalate and di-n-octyl phthalate, and di-2-ethylhexyl phthalate Phthalic acid esters such as diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalethyl glycolate, butyl phthalyl butyl glycolate, tri-2-ethylhexyl trimellitate, tri-n-alkyl trimellitate, triiso Trimellitate esters such as nonyl trimellitate and triisodecyl trimellitate, dimethyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol adipate , Di-2-ethylhexyl acetate, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl malate, acetyl-tri- (2-ethylhexyl) citrate, acetyl-tri-n-butyl Aliphatic dibasic acid esters such as citrate and acetyl tributyl citrate, glycol derivatives such as polyethylene glycol benzoate, triethylene glycol di- (2-ethylhexoate) and polyglycol ether;
Glycerol derivatives such as glycerol triacetate and glycerol diacetyl monolaurate; polyesters composed of sebacic acid, adipic acid, azelaic acid, phthalic acid, etc .; low molecular weight polyethers having a molecular weight of 300 to 3,000; low molecular weight poly-α-styrene , The same low molecular weight polystyrene, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylendiphenyl Phosphate,
Orthophosphates such as 2-ethylhexyldiphenyl phosphate, ricinoleates such as methylacetyl ricinoleate, poly-1,3-butanediol adipate, polyester epoxidized esters such as epoxidized soybean oil, glycerin triacetate, Acetates such as 2-ethylhexyl acetate are exemplified.

The dispersant and anti-settling agent are intended to improve the dispersibility of the inorganic component and the anti-settling property, and examples thereof include a phosphate ester type, a silicone type, a castor oil ester type, and various interface lubricants. Examples of the defoaming agent include, for example, silicone type, acrylic type, various interfacial lubricating agents, etc., and examples of the release agent include silicone type, fluorine oil type, paraffin type, fatty acid type, fatty acid ester type, castor oil. Examples include a system, a wax, and a compound type, and examples of the leveling agent include a fluorine-based, silicone-based, and various interfacial lubricating agents, each of which is added in an appropriate amount.

The material for forming the underlayer is methanol,
Anones such as ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, xylene, cyclohexanone, methylene chloride, 3-methoxybutyl acetate, ethylene glycol monoalkyl ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol monoalkyl Ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ether acetates, dissolved in terpenes such as α- or β-terpionaire, Or disperse, die coat, blade coat, comma coat on base film , Roll coating, gravure reverse coating method, gravure direct method, slit reverse method and the like, and drying to obtain a predetermined film thickness.

In the transfer sheet for forming an undercoat layer, the undercoat layer may be laminated on the base film via a release layer. Thereby, excellent transferability can be obtained. As the release layer, polyethylene wax, amide wax, Teflon powder, silicone wax, carnauba wax, acrylic wax, wax such as paraffin wax, fluorine resin, melamine resin, polyolefin resin, ionizing radiation-curable polyfunctional acrylate resin , A polyester resin, an epoxy resin, an amino-modified, an epoxy-modified, an OH-modified, a COOH-modified, a catalyst curable type, a photocurable type, a thermosetting type silicone oil or a silicone resin.

Further, an adhesive layer may be provided on the underlayer forming layer as required for the purpose of improving transferability. The adhesive layer is softened by heating to bond the underlayer and the electrode forming layer, and is preferably burned at a low temperature in the firing step and does not leave carbide.For example, a cellulose resin containing a plasticizer, an acrylic resin, or the like is preferable. For example, the film thickness is 0.1 μm or more.
5 μm.

The transfer sheet S for forming an underlayer forming layer thus prepared is heat-pressed on a glass substrate using a heat roll, and as shown in FIG.
1 is peeled off.

In the above, the case where the underlayer is formed using the transfer sheet S for underlayer formation layer formation has been described as an example. However, screen printing, die coating, blade coating, dispensing using a coating solution for underlayer formation layer formation are described. It may be formed on a glass substrate by coating, roll coating, or the like.

Next, as shown in FIG. 1C, an electrode forming layer 12 is formed on the base forming layer 14 by coating.

The electrode forming layer 12 is composed of at least an inorganic component composed of glass frit, a photosensitive resin, a conductive powder, and, if necessary, a thickener. As the inorganic component,
The glass frit, the inorganic powder, and the inorganic pigment described as the inorganic component in the above-described base forming layer can be used. As the glass frit, those having an average particle size of 0.3 μm to 5 μm are preferably used. The body is preferably from 0 to 20 parts by weight based on 100 parts by weight of the glass frit.

The photosensitive resin comprises an alkali developable binder polymer and a polymerizable monomer, and, if necessary, comprises a photoinitiator, a sensitizer, a polymerization terminator, and a chain transfer agent. Examples of the alkali developing type binder polymer include acrylic acid, methacrylic acid, a dimer of acrylic acid (M-5600 manufactured by Toagosei Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, and acid anhydride of vinyl acetate. And at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, se
c-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-
Hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, styrene, α-methylstyrene, N-vinylpyrrolidone Copolymers and these copolymers
A polymer obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to these copolymers, and having an acid value of 50 to 50 or more.
Weight average molecular weight of 3,000 to 150 mgKOH / g
100,000, preferably 5,000 to 50,000
0.

Further, one or more kinds of non-alkali developing type polymers may be mixed with these copolymers.
Examples of the non-alkali development type polymer include polyvinyl alcohol, polyvinyl butyral, acrylate polymer, methacrylate polymer, polystyrene, α
-Methylstyrene polymer, 1-vinyl-2-pyrrolidone polymer, or a copolymer thereof.

As the polymerizable monomer, the polymerizable monomer described in the section of the undercoat layer can be used in the same manner, but the amount of the polymerizable monomer used is based on 100 parts by weight of the alkali-developable binder polymer. 20 to 200 parts by weight.

As the photoinitiator, the photoinitiator described in the section of the undercoat layer can be used in the same manner.

In addition, a sensitizer, a polymerization terminator and a chain transfer agent may be added. When the photosensitive resin is a negative type, the photosensitive resin may be contained in a proportion of 5 to 60 parts by weight, preferably 10 to 40 parts by weight based on 100 parts by weight of the total amount of the inorganic component and the conductive powder.

Next, as the conductive powder, gold, silver, copper,
Metal powders such as nickel and aluminum are exemplified, and spherical metal powders having an average particle size of 0.1 μm to 5 μm are preferable.
The ratio of the conductive powder to the glass frit is from 2 parts by weight to 100 parts by weight of the conductive powder.
20 parts by weight.

The thickener is added as necessary in the coating solution for forming the electrode forming layer for the purpose of increasing the viscosity thereof and suppressing the penetration into the base forming layer. Known ones can be used, for example, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose,
Sodium alginate, casein, sodium caseinate, xanthan gum, polyvinyl alcohol, modified polyether urethane, polyacrylate, polymethacrylate, montmoronite, aluminum stearate, zinc stearate, aluminum octylate, castor oil with water, Castor oil ester, fatty acid amide, polyethylene oxide, dextrin fatty acid ester, dibenzylidene sorbitol, vegetable oil-based polymerized oil, surface-treated calcium carbonate, organic bentonite, silica, titania, zirconia, fine powders of alumina and the like.

The amount of the thickener to be added is 0.1 to 20 parts by weight, preferably 0.1 part by weight, per 100 parts by weight of the conductive powder.
The amount is 1 part by weight to 10 parts by weight, and if it is less than 0.1 part by weight, there is no thickening effect, and if it is more than 20 parts by weight, an adverse effect such as disconnection is caused on the characteristics as an electrode.

The coating solution for forming the electrode forming layer may contain a plasticizer, a dispersant, an antisettling agent, an antifoaming agent, a release agent, and a leveling agent in order to improve the coating properties and the like. ,
In any case, those described in the above-described base forming layer can be used, and the mixture is mixed with the solvent described in the above-described base forming layer to form a coating solution. The coating solution is applied on the base forming layer 14 in the same manner, and dried. The electrode forming layer 12 has a predetermined thickness.

The second step will be described with reference to FIG.
As shown in FIG. 1D, in the second step, the electrode forming layer is exposed through a predetermined electrode pattern mask M. As a light source, ionizing radiation such as an electron beam, ultraviolet light, or X-ray is used. As a result, the unexposed portions 12a are formed in the electrode forming layer 12.
And an exposure portion 12b are formed. In addition, a protective film may be peelably stuck on the electrode forming layer and exposed,
The protective film is peeled off and subjected to development in a development step described later.

Next, in a third step, as shown in FIG. 1E, the electrode forming layer is developed to remove the unexposed portions 12a, and an electrode forming pattern is formed on the base forming layer 14. Finally, as a fourth step, the entire substrate is fired at 350 ° C. to 650 ° C. so that the underlying layer and the electrode layer are simultaneously
It can be formed on a panel.

In the first method for forming an electrode of the present invention, a transfer sheet is used to form a base formation layer, and the base formation layer is fired simultaneously with the electrode formation layer. In the preparation of the electrode, the operation time can be shortened, and an electrode forming layer having excellent surface smoothness, uniform thickness and high distribution accuracy can be formed with good yield.

Next, a second electrode forming method of the present invention will be described.

FIGS. 2 (a) to 2 (e) show a continuous process chart of the second electrode forming method of the present invention.
S 'is a transfer sheet for forming an electrode forming layer, 11 is a base film, 12 is an electrode forming layer, 13 is a glass substrate, 14 is a base forming layer, and M is an electrode pattern mask. The base film 11 in the transfer sheet S 'for forming an electrode forming layer
The electrode forming layer 12 described in the above first electrode forming method is used, and the electrode forming layer forming coating liquid described in the above first electrode forming method is applied by the same method. ,
It is applied on a base film 11 and dried to form an electrode forming layer 12 having a predetermined thickness. In the first electrode forming method described above, the thickener is added to the electrode forming layer forming coating liquid. However, when the electrode forming layer forming transfer sheet is used, the electrode forming layer forming coating liquid is used. Does not penetrate into the underlayer forming layer, so that it is not necessary to add a thickener to the coating liquid for forming the electrode forming layer.

Although not shown, the transfer sheet for forming an electrode forming layer also has a structure in which the electrode forming layer is laminated on the base film via the release layer as described in the first electrode forming method described above. Then, the transferability can be further improved, and an adhesive layer may be provided on the electrode forming layer as needed for the purpose of improving the transferability.

The first electrode in the second electrode forming method of the present invention
The steps will be described with reference to FIGS. FIG.
(B) shows a structure in which a base forming layer 14 is laminated on a glass substrate 13, and the transfer sheet for forming a base forming layer described in the first electrode forming method is used to form the glass substrate 13.
May be stacked on top of each other, or the first
The coating liquid for forming a base forming layer described in the above electrode forming method may be applied to a glass substrate by die coating, blade coating, roll coating, screen printing, or the like, and dried to a predetermined film thickness. Then, as shown in FIG.
The transfer sheet for electrode formation is superimposed on the base layer on the glass substrate, and is heated and pressed using a hot roll.

In the second step, as shown in FIG. 2D, a predetermined electrode pattern mask M is placed on the base film 11 from above.
The electrode forming layer 12 is exposed to light through. As a light source, ionizing radiation such as an electron beam, ultraviolet light, or X-ray is used. Thereby, the unexposed portion 12a and the exposed portion 1
2b is formed. By exposing the mask M in close contact without exfoliating the base film 11, the exposure time can be shortened by the effect of blocking oxygen, and the sensitivity can be improved.

In the third step, as shown in FIG. 2E, after peeling the base film 11, the electrode forming layer is developed to remove the unexposed portions 12a, and the electrode forming pattern is formed on the base forming layer. Form. Finally, as a fourth step, the entire substrate is baked at 350 ° C. to 650 ° C., so that the underlayer and the electrode layer can be simultaneously formed on the PDP panel.

Next, a third electrode forming method of the present invention will be described with reference to FIGS. In the above-described second electrode forming method, in the exposure step described with reference to FIG. 2D, the exposure is performed in a state where the base films 11 are stacked.
The third electrode forming method is the same as the above-described second electrode forming method, except that as shown in FIG. 3D, the exposure is performed with the base film 11 peeled off.

According to the second and third electrode forming methods of the present invention,
The electrode forming layer is laminated on the base layer on the glass substrate using a transfer sheet. However, since the solvent for forming the electrode forming layer has been dried and removed, the electrode forming material is applied to the base layer. The use of a transfer sheet makes it possible to reduce the amount of time required to work, and furthermore, the work time can be reduced, and furthermore, it is possible to form an electrode forming layer with excellent surface smoothness, uniform film thickness and good distribution accuracy with good yield. it can.

Hereinafter, the present invention will be described in detail with reference to examples.

[0055]

(Example 1) (Transfer sheet for forming undercoat layer) Composition Glass frit {main component: PbO, SiO ₂ , B ₂ O ₃ (alkali-free)} (softening point of glass frit 570 ° C., Tg 480) ° C, thermal expansion coefficient α ₃₀₀ = 83 × 10 ^-7 / ° C, average particle size 1 µm) ··· 65 parts by weight · Al ₂ O ₃ ··· 11 parts by weight · CuO ··· 4 parts by weight · n-butyl methacrylate / 2-hydroxyethyl methacrylate copolymer (8/2) 15 parts by weight Dibutyl phthalate 5 parts by weight Isopropyl alcohol 15 parts by weight Methyl ethyl ketone After mixing and dispersing 10 parts by weight using a bead mill, roll coating is applied on a polyethylene terephthalate film,
After drying at 100 ° C. to form an ink layer having a film thickness of 18 ± 2 μm, a polyethylene film was laminated to prepare a transfer sheet for forming a base formation layer.

Next, the polyethylene film is peeled off,
Auto cut laminator (Asahi Kasei Corporation, Model AC
L-9100) using a substrate preheat temperature of 60 ° C.
The laminate was laminated on a glass substrate under a transfer condition at a ramirole temperature of 100 ° C.

The polyethylene terephthalate film was peeled off to produce a glass substrate having a base forming layer.

(Formation of Electrode Forming Layer) The following composition: photosensitive resin (the following composition): 20 parts by weight; silver powder (average particle size: 1 μm); 70 parts by weight; glass frit (main component): Bi ₂ O ₃ , SiO ₂ , B ₂ O ₃ (alkali-free) Average particle size 1 μm, softening point 600 ° C. 5 parts by weight Dipropylene glycol monomethyl ether 20 parts by weight Thickener (castor oil with water) 1 part by weight (Breakdown of photosensitive resin-Alkaline developing binder polymer (methyl methacrylate / methacrylic acid copolymer, acid value 100 mgKOH / g)-100 parts by weight-Poly 60% by weight of oxyethylated trimethylolpropane triacrylate ··· 10 parts by weight of photoinitiator (“Irgacure 907” manufactured by Ciba Geigy) ··· 10 parts by weight The composition was applied on a glass substrate having a layer by screen printing, and an electrode forming layer having a dry film thickness of 15 μm was formed on the base forming layer.

Next, after irradiating with ultraviolet rays at 700 mJ / cm ² through a negative pattern mask of the address electrode of the PDP, unexposed portions were peeled off using a 0.5% aqueous solution of sodium carbonate and developed.

After development, the entire substrate was baked at 600 ° C. to form a 9 μm-thick underlayer and a 6 μm-thick and 70 μm-wide PDP address electrode pattern.

(Example 2) (Transfer sheet for forming electrode forming layer) The following composition: photosensitive resin (the following composition): 20 parts by weight; silver powder (average particle size: 1 μm); 70 parts by weight; Glass frit {main component: Bi ₂ O ₃ , SiO ₂ , B ₂ O ₃ (alkali-free) Average particle size 1 μm, softening point 600 ° C.} 5 parts by weight Propylene glycol monomethyl ether 20 100 parts by weight (Breakdown of photosensitive resin, alkali developing type binder polymer (methyl methacrylate / methacrylic acid copolymer to which 7 mol% of glycidyl acrylate is added, acid value 100 mgKOH / g) 100 parts by weight polyoxyethylated trime Chiropropane triacrylate ... 60 parts by weight Photoinitiator ("Irgacure 907" manufactured by Ciba Geigy) ... 10 parts by weight Was applied onto a polyethylene terephthalate film by a slit reverse coating method to prepare an electrode-forming transfer sheet having an electrode-forming layer having a dry film thickness of 15 μm.

The transfer sheet for forming an underlayer and the transfer sheet for forming an underlayer formed in Example 1
Lamination was performed using a hot roll at 0 ° C.

Next, the PDP is placed on the base film 11 from above.
After irradiating with 700 mJ / cm ^{2 of} ultraviolet light through a negative pattern mask of the address electrode, the base film was peeled off, and the unexposed portion was peeled off using a 0.5% aqueous solution of sodium carbonate and developed.

After the development, the entire substrate was baked at 600 ° C. to form a 9 μm-thick underlayer and a 6 μm-thick and 70 μm-wide PDP address electrode pattern.

Example 3 Composition: Glass frit {main component: PbO, SiO ₂ , B ₂ O ₃ (alkali-free)} (softening point of glass frit: 570 ° C., Tg: 480 ° C., coefficient of thermal expansion α ₃₀₀ = 83 × 10 ^-7 / ° C., an average particle diameter of 1 [mu] m) ... 65 parts by weight Al ₂ O ₃ ... 11 parts by weight CuO .... 4 parts by weight of ethyl cellulose .... 3 parts by weight Butyl cellosolve Acetate 10 parts by weight Terpionell 10 parts by weight was mixed and dispersed using a three-mill to prepare a coating solution for forming an undercoat layer. This coating solution was applied on a glass substrate by a die coater, dried at 140 ° C., and a base forming layer having a thickness of 20 μm ± 2 μm was provided.

The transfer sheet for forming an electrode formation layer prepared in Example 2 was laminated on the underlayer formation layer by using a hot roll at 90 ° C., and the polyethylene terephthalate film was peeled off.

Next, after irradiating with ultraviolet rays at 700 mJ / cm ² through a negative pattern mask of the address electrode of the PDP, unexposed portions were peeled off using a 0.5% sodium carbonate aqueous solution developer and developed.

After development, the entire substrate is baked at 600 ° C. to form a 10 μm-thick underlayer and a 6 μm-thick and 70 μm-wide PDP.
Address electrode pattern was formed.

Example 4 The coating solution for forming an electrode forming layer described in Example 1 was applied by screen printing on the underlayer forming layer prepared in Example 3 to form an electrode forming layer having a dry film thickness of 15 μm. After that, the film was irradiated with ultraviolet rays at 700 mJ / cm ² through a negative pattern mask of the address electrode of the PDP, and then the unexposed portion was peeled off using a 0.5% aqueous solution of sodium carbonate and developed.

After development, the entire substrate was baked at 600 ° C. to form a 9 μm-thick underlayer and a 6 μm-thick and 70 μm-wide PDP address electrode pattern.

Example 5 (Transfer Sheet for Forming Underlayer) Composition: Glass frit {main component: PbO, SiO ₂ , B ₂ O ₃ (alkali-free)} (softening point of glass frit: 570 ° C., Tg: 480 ° C.) , Thermal expansion coefficient α ₃₀₀ = 83 × 10 ⁻⁷ / ° C., average particle size 1 μm) ··· 65 parts by weight · Al ₂ O ₃ ··· 11 parts by weight · CuO ··· 4 parts by weight · n -Butyl methacrylate / 2-hydroxyethyl methacrylate copolymer (8/2) 15 parts by weight Polyoxyethylenated trimethylolpropane triacrylate 5 parts by weight Photoinitiator (Ciba Geigy Co., Ltd.) Irgacure 907 ") 2 parts by weight Dibutyl phthalate 3 parts by weight Isopropyl alcohol 15 parts by weight Methyl ethyl ketone 10 weights After parts mixed dispersion treatment using a bead mill and roll-coated on a polyethylene terephthalate film,
After drying at 100 ° C. to form an ink layer having a film thickness of 18 ± 2 μm, a polyethylene film was laminated thereon to prepare a transfer sheet for forming a base formation layer. A glass substrate was prepared, and the electrode formation layer described in Example 1 was formed on the base formation layer.

Next, after 700 mJ / cm ^{2 of} ultraviolet rays were irradiated through the negative pattern mask of the address electrode of the PDP, unexposed portions were peeled off using a 0.5% aqueous solution of sodium carbonate and developed.

After the development, the entire substrate was baked at 600 ° C. to form a 9 μm-thick underlayer and a 6 μm-thick and 70 μm-wide PDP address electrode pattern at the same time.

[0074]

According to the present invention, the base layer and the electrode layer can be simultaneously fired, the time for forming the electrodes can be shortened, and the transfer sheet is used in forming the electrodes, so that the surface is smoothed. It is possible to form an electrode layer having excellent uniformity, uniform thickness, and high distribution accuracy with high yield.

[Brief description of the drawings]

FIG. 1 is a view for explaining an electrode forming method of the present invention with a continuous process chart.

FIG. 2 is a view for explaining an electrode forming method of the present invention with a continuous process diagram.

FIG. 3 is a diagram for explaining the electrode forming method of the present invention with a continuous process diagram.

FIG. 4 is a diagram illustrating an AC type PDP panel.

FIG. 5 is a diagram for explaining an AC type PDP panel.

[Explanation of symbols]

1, 2 is a glass substrate, 3 is a cell barrier, 4 is a transparent electrode, 5
Is a metal electrode, 6 and 6 'are dielectric layers, 7 is a protective layer, 8 is an address electrode, 9 is a phosphor screen, 10 is a base layer, S is a transfer sheet for forming a base layer, and S' is a transfer sheet for forming an electrode formation layer. Transfer sheet 1
1 is a base film, 12 is an electrode forming layer, 13 is a glass substrate, 14 is a base forming layer, and M is an electrode pattern mask.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Satoshi Moriwaki 1-1-1 Ichigaya Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd.

Claims (4)

[Claims] A glass substrate provided with at least an inorganic component composed of at least glass frit and an underlayer formed of a thermoplastic resin, comprises at least an inorganic component composed of glass frit, a conductive powder, and a photosensitive resin. A first step of coating and forming an electrode forming layer, a second step of exposing from the electrode forming layer side through a predetermined electrode pattern mask, and a third step of developing the electrode forming layer to form an electrode pattern.
A method for forming an electrode, comprising the steps of: sintering the entire structure to simultaneously sinter the base forming layer and the electrode forming layer. 2. The electrode forming method according to claim 1, wherein the electrode forming layer further contains a thickener. 3. An electrode forming layer forming transfer sheet having an electrode forming layer made of at least an inorganic component made of glass frit, a conductive powder, and a photosensitive resin on a base film. A first step of laminating on a base forming layer in a glass substrate provided with a base forming layer made of an inorganic component made of frit and a thermoplastic resin, a second step of exposing from a base film side through a predetermined electrode pattern mask, An electrode, comprising: a third step of developing the electrode formation layer after peeling the film to form an electrode pattern, and a fourth step of firing the whole to simultaneously sinter the base formation layer and the electrode formation layer. Forming method. 4. An electrode forming layer forming transfer sheet having an electrode forming layer made of at least an inorganic component made of glass frit, a conductive powder, and a photosensitive resin on a base film. A first step of laminating on a base forming layer of a glass substrate provided with a base forming layer made of an inorganic component made of frit and a thermoplastic resin, and then peeling the base film, using a predetermined electrode pattern mask from the electrode forming layer side. A second step of exposing through the substrate, a third step of developing the electrode formation layer to form an electrode pattern, and a fourth step of firing the whole to simultaneously sinter the base formation layer and the electrode formation layer. Electrode forming method.