JP3239847B2 - Method for producing photosensitive conductive paste and electrode - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive conductive paste and a method for producing an electrode.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for miniaturization, high density, high definition, and high reliability in circuit materials and displays, and accordingly, pattern processing techniques are also required to be improved. In particular, various methods have been proposed as an essential requirement for miniaturization and high density of the conductor circuit pattern.

[0003] Plasma display panel (PDP)
Since they can display images at a higher speed than a liquid crystal panel and can be easily made larger, they have permeated fields such as OA equipment and information display devices. Further, progress in the field of high-definition television is highly expected.

[0004] With the expansion of such uses, PD
As P, a color PDP having a fine number of display cells is attracting attention. The PDP generates a plasma discharge between opposing anode and cathode electrodes in a discharge space provided between a front glass substrate and a rear glass substrate, and emits light from a gas sealed in the discharge space. The display is performed. In this case, the anode and the cathode electrode on the glass substrate are arranged with a plurality of linear electrodes in parallel, and the electrodes oppose each other through a small gap and cross each other. It is configured to be superimposed so as to face. Among the PDPs, a surface discharge type PDP having a three-electrode structure suitable for color display using a phosphor includes a plurality of pairs of display electrodes adjacent to each other in parallel and a plurality of address electrodes orthogonal to each pair of electrodes. And

The above-mentioned address electrodes are usually formed by printing a conductive paste such as a silver paste on a glass substrate by using a printing mask having a mask pattern corresponding to the address electrodes by a screen printing method, followed by firing. . However, the screen printing method does not allow the width of the electrode pattern to be reduced to 100 μm or less even if optimization of mask pattern accuracy, squeeze hardness, printing speed, dispersibility, etc. is not possible, and there is a limit to fine pattern formation. Was. Also,
In the screen printing method, the accuracy of the print mask is
Since it depends on the precision of the mask plate making, the size error of the mask pattern increases when the print mask becomes large.
Therefore, in the case of a PDP having a large area of 30 inches or more, it is increasingly technically difficult to produce a high-definition PDP.

Further, there are a transmission type and a reflection type in the PDP. In the reflection type, an address electrode and a partition (rib) of an insulating layer are provided on the light emitting layer side of the back glass, and a phosphor is formed thereafter. . After the address electrodes are printed with a conductive paste and dried, the insulating glass paste is printed at a predetermined height and width depending on the printing mask for the partition walls. I do. Thereafter, the conductive paste and the insulating paste are fired at a time to form address electrodes and partition walls. However, as the size of a PDP becomes larger, the position pitch of the conductive paste is already determined at the other end of the glass substrate (depending on the dimensional accuracy of the print mask). Since the pattern pitch of the printing mask for the partition is accumulated, a large displacement occurs between the address electrode and the partition.
For this reason, a high-definition electrode pattern cannot be obtained, and enlargement of the electrode is also very limited, and it is necessary to solve the problem.

As a method for improving the disadvantages of the screen printing, Japanese Patent Application Laid-Open Nos.
As described in JP-A-296534 and JP-A-63-205255, an insulating paste is baked, a conductive paste is printed and baked to improve the electrode shape, and photolithography is used for forming an anode electrode. Although a conductive paste using a technique and a photolithography technique using a photoresist have been proposed, a technique that simultaneously satisfies a low resistance and a large size in addition to the formation of a fine pattern was not sufficient.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive conductive paste and a method for producing an electrode which are capable of forming a fine pattern and which are suitable for obtaining a low-resistance circuit pattern. .

Another object of the present invention is to provide a high-definition,
Another object of the present invention is to provide a photosensitive conductive paste and a method for manufacturing an electrode which can be suitably used for an electrode of a large-sized plasma display panel.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
Spherical conductive powder, photosensitive organic component and 350 to 45
Organic dye having an integrated value of absorbance at 0 nm of 35 to 60
Containing fee as an ultraviolet light absorber, an average particle diameter of the conductive powder is 0.7～6Myuemu, the specific surface area of the conductive powder 0.15
At least ³ m ² / g, and a method for manufacturing an electrode, comprising applying a photosensitive conductive paste on a substrate, forming a pattern by photolithography, and firing. Is done.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS That is, the present invention imparts photosensitivity to a conductive paste and uses a photolithography technique to efficiently form fine and low-resistance electrodes.

The conductive powder used in the present invention comprises:
Any powder having conductivity may be used, but preferably Ag,
It contains at least one selected from the group consisting of Au, Pd, Ni, Cu, Al and Pt.
A low-resistance conductive powder that can be baked at a temperature of 0 ° C. or less is used. These can be used alone, as an alloy or as a mixed powder. As an example of the mixed powder, for example, A
g (30-80) -Pd (70-20), Ag (40-
70) -Pd (60-10) -Pt (5-20), Ag
(30-80) -Pd (60-10) -Cr (5-1
5), Pt (20-40) -Au (60-40) -Pd
(20), Au (75-80) -Pt (25-20),
Au (60-80) -Pd (40-20), Ag (40
~ 95) -Pt (60 ~ 5), Ag (80 ~ 98) -P
d (20-2), Ag (90-98) -Pd (10
2) -Pt (2-10), Ag (85-98) -Pt
(15 to 2) (the numbers in parentheses indicate weight%)
Binary or ternary mixed metal powder can be used.

The average particle size of these conductive powders is 0.7
And ~6μm. It is more preferably 1.3 to 5 μm, and still more preferably 1.6 to 4.0 μm. When the average particle size is smaller than 0.7 μm, light does not smoothly pass through the printed film during exposure to ultraviolet light, and it is difficult to form a fine pattern with a minimum line width of the electrode conductor of 60 μm or less. On the other hand, when the average particle diameter exceeds 6 μm, the surface of the printed circuit pattern becomes rough, and the pattern accuracy and dimensional accuracy decrease.

The specific surface area of the conductive powder is 0.15 to ³ m ^2.
/ And g. More preferably, 0.17 to 1.5 m ² /
g, more preferably 0.2 to 0.65 m ² /
g. If the specific surface area is less than 0.15 m ² / g, the accuracy of the electrode pattern is reduced. On the other hand, if it exceeds 3 m ² / g, the surface area of the powder becomes too large and the ultraviolet rays are scattered, and the exposure hardening is not sufficiently performed to the lower part, so that peeling occurs during development and the pattern accuracy is reduced.

There is a more preferable range of the conductive powder which satisfies the formation of the fine pattern and the reduction of the resistance. That is, in order to obtain a fine circuit pattern of 10 to 40 μm after development at a coating film thickness of 5 to 20 μm after the electrode pattern is printed, the light is sufficiently transmitted without being scattered when exposed to ultraviolet light, and effectively acts, to obtain a fine circuit pattern of 10 to 40 μm after development. It is preferable that the particle size of the conductive powder is 1 to 5 μm and the specific surface area is 0.4 to 2.5 m ² / g. More preferably, the particle size is 2.0 to 4.5 μm, and the specific surface area is 0.5 to 2.0 m ² / g. Within this range, no residual film of the electrode film is left in the unexposed portion during development, and a highly accurate electrode pattern can be obtained.

The shape of the conductive powder is a spherical shape. In this case, the spherical shape preferably has a sphericity of 90% by number or more. For the measurement of the sphericity, the powder was photographed with an optical microscope at a magnification of 300 times and counted, and the ratio of spheres was expressed. When the shape is spherical, the scattering of ultraviolet light during exposure is very small, a highly accurate pattern can be obtained, and the irradiation energy can be reduced.

In the present invention, the photosensitive organic component is an organic component containing a photosensitive compound in the photosensitive conductive paste.

Regarding the photosensitive conductive paste of the present invention,
It is preferable that the content of the photosensitive compound is 10% by weight or more of the photosensitive organic component in terms of sensitivity to light. Further, it is preferably at least 30% by weight.

The photosensitive compound includes a photo-insolubilizing type and a photo-solubilizing type. The photo-insolubilizing type includes: (1) a monomer having at least one functional group such as an unsaturated group in a molecule; (2) photosensitive compounds such as aromatic diazo compounds, aromatic azide compounds, and organic halogen compounds; and (3) so-called diazo resins such as condensates of diazo amines and formaldehyde. And others.

Examples of the photo-soluble type include (4) a complex of a diazo compound with an inorganic salt or an organic acid, and quinone diazos. (5) quinone diazos bonded to an appropriate polymer binder, for example, phenol or novolak. Examples of the resin include naphthoquinone 1,2-diazide-5-sulfonic acid ester.

In the present invention, all of the above can be used, but the above (1) is preferred in terms of ease of handling and quality design.

Specific examples of the photosensitive monomer having a functional group in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, sec-butyl acrylate, Isobutyl acrylate, tert-butyl acrylate, n-
Pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-
Hydroxyethyl acrylate, isobonyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl Acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate , Dipenta Risuri hexaacrylate,
Dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropanetetraacrylate,
Glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, Benzyl acrylate, 1-naphthyl acrylate, 2-
Acrylates such as naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, diacrylate of bisphenol A-propylene oxide adduct, thiophenol acrylate, benzyl mercaptan acrylate, styrene, p-methylstyrene, o Styrenes such as -methylstyrene, m-methylstyrene, α-methylstyrene, chloromethylstyrene, and hydroxymethylstyrene; and those in which some or all of the hydrogen atoms in these aromatic rings are chlorine, bromine, iodine, or fluorine. And methacrylate in which some or all of the acrylates in the molecule of the compound are substituted with methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2- And pyrrolidone.

In the present invention, one or more of these can be used. In addition to these, the developability after exposure can be improved by adding an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

On the other hand, examples of oligomers and polymers having a functional group in the molecule include oligomers and polymers having at least one functional group in the molecule, obtained by polymerizing at least one of the aforementioned monomers. Alternatively, an oligomer or polymer having no functional group and a functional group added to a side chain or a molecular terminal of a polymer can be used. By containing at least an alkyl acrylate or an alkyl methacrylate, and more preferably containing at least methyl methacrylate, a polymer having good thermal decomposability can be obtained.

Preferred functional groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryl group, and a methacryl group.

A method for adding such a functional group to an oligomer or a polymer is to use an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or an acrylic acid for a mercapto group, an amino group, a hydroxyl group or a carboxyl group in the polymer. There is a method in which chloride, methacrylic chloride or allyl chloride is added to make an addition reaction.

Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonate, and glycidyl isocrotonic acid.

Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate.

The ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is used in an amount of from 0.05 to 0.05 to the mercapto group, amino group, hydroxyl group and carboxyl group in the polymer. It is desirable to add 0.8 molar equivalent, more preferably 0.1 to 0.6.
It is a molar equivalent. If it is less than 0.05 molar equivalent, the allowable development width is narrow, and the cutting of the pattern edge tends to be poor,
On the other hand, if the molar ratio is larger than 0.8 molar equivalent, the solubility of the developer in the unexposed portion tends to decrease.

Further, by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid, the developability after exposure can be improved. Specific examples of the unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

The acid value (AV) of the thus obtained oligomer or polymer having an acidic group such as a carboxyl group in the side chain is preferably in the range of 50 to 180, more preferably 70 to 140. More preferably, it is in the range of 80 to 120. If the acid value is less than 50 or more than 180, the allowable development width is narrow, and the edge of the pattern tends to be poor. If it exceeds 180, the hardness of the coating film tends to decrease.

As a binder, non-photosensitive materials such as polyvinyl alcohol, polyvinyl butyral, methacrylate polymer, acrylate polymer, acrylate-methacrylate copolymer, α-methylstyrene polymer, butyl methacrylate resin, etc. A hydrophilic polymer may be added.

It is preferable to use the photosensitive monomer in an amount of 0.05 to 10 times the amount of the oligomer or the polymer. More preferably, the amount is 0.1 to 3 times. If the amount exceeds 10 times, the viscosity of the paste becomes small, and the uniformity of dispersion in the paste may be reduced. If the amount is less than 0.05 times, the solubility of the unexposed portion in the developer tends to be poor.

In the present invention, in order to form a fine pattern of the electrode, the integrated value of the absorbance at 350 to 450 nm is used.
It is necessary to add an ultraviolet light absorbing agent which is an organic dye having a size of 35 to 60 . As a result, the minimum line width is 5 to 50 μm when the electrode thickness after baking is 5 to 30 μm
m, a high-resolution pattern with a minimum line spacing of 10 to 50 μm between electrodes can be formed. Furthermore, an electrode pattern with excellent cutting performance and free from bleeding and edge curl can be obtained.

That is, usually, when only the conductive powder is used, ultraviolet rays are scattered by the conductive powder having a size of 1 μm or less or the conductive powder having a non-uniform shape, and light is hardened to an excessive part, so that a pattern as an exposure mask cannot be formed. For this reason, it is likely that portions other than the mask cannot be developed. The present inventors have conducted intensive studies on the cause, and as a result, it has been found that the scattered ultraviolet light is absorbed or weakened and reaches the light-shielded portion by the exposure mask. Therefore, the scattered light is substantially prevented from being wrapped around by adding the ultraviolet light absorbing agent, the hardening of the photosensitive organic component in the mask portion is prevented, and a pattern corresponding to the exposure mask is formed.

As the ultraviolet absorber , 350 to 450 n
an organic dye having a high UV absorption coefficient in the wavelength range of m
It is necessary to use . As organic dyes, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, aminoketone dyes, anthraquinone dyes, benzophenone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes and the like can be used. Organic dyes, Ru possible to reduce the deterioration of the conductive film properties without remaining in the electrode conductor films after firing. Among these, azo dyes and benzophenone dyes are preferred.

As typical azo dyes,
Sudan Blue _{(Sudan Blue, C 22 H 18} N 2 O
₂ = 342.4), Sudan R (C ₁₇ H ₁₄ N ₂ O ₂ = 27
8.31), Sudan _{II (C 18 H 14 N 2} O = 276.3
4), Sudan _{III (C 22 H 16 N 4} 0 = 352.4), Sudan _{IV (C 24 H 2 0N 4} 0 = 380.45), Oil Orange _{SS (Oil Orange SS, CH 3} C 6 H
_{4 N: NC 10 H 6 OH} = 262.31) Oil Violet _{(Oil Violet, C 24 H 21} N 5 = 379.
46), Oil Yellow OB (Oil Yellow)
_{OB, CH 3 C 4 H 4} N: NC 10 H 4 NH 2 = 261.
33).

As benzophenone dyes, Ubinal D-50 (C ₁₃ H ₁₀ O ₅ = 246.22, 2,2 ′,
4,4′-tetrahydroxybenzophenone), ubinal MS40 (C ₁₄ H ₁₂ O ₆ S = 308, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid), ubinal DS49 (C ₁₅ H ₁₂ O ₁₁ S ₂ Na) ₂ =
478, 2,2-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-sodium disulfonate), and dyes that can absorb at 250 to 520 nm can be used.

The amount of the ultraviolet absorber added is 0.01 to 1
% By weight is preferred. More preferably 0.01 to 0.3
%, More preferably 0.02 to 0.1% by weight. If the amount is less than 0.01% by weight, the effect of addition is low, and the effect of eliminating cuts or bleeding of the pattern and curling of the edge is small. If it exceeds 1% by weight, the effect of absorbing ultraviolet rays becomes too large, so that the film is easily peeled off during development, and it is difficult to form a high-definition pattern.

A preferred example of the method for adding the ultraviolet light absorber is as follows. A solution is prepared by dissolving an ultraviolet absorber in an organic solvent in advance. Next, after mixing the conductive powder in the organic solvent, the mixture is dried. According to this method, a so-called capsule-like powder in which the surface of each of the conductive powders is uniformly coated with the film of the ultraviolet light absorber can be produced.

[0041] In the present invention, the integral value of the absorbance (wavelength measurement range; 350 to 450 nm) is intended to be measured in a powder state, it is measured for coated powder UV absorber.

In the present invention, the absorbance is defined as follows. That is, light is applied to the measurement sample in an integrating sphere using a commercially available spectrophotometer, and the light reflected there is collected and detected. In addition, all the light except for the light detected by the integrating sphere is regarded as absorption light and can be obtained from the following equation.

Before measuring the absorbance of the sample, Ir was used to measure the light intensity of the control light, and before measuring the absorbance of the sample, BaSO ₃ of the same material as the material applied to the inner surface of the integrating sphere was attached to the sample table, and the light intensity due to reflection was measured. If the light intensity of the light incident on the sample is I, and the light intensity of the absorption after irradiating the sample is Io, the light intensity of the reflection from the sample is represented by (I-Io), and the absorbance is It is defined as the following equation (1). The unit of the light intensity is represented by W / cm ² .

[0044]

(Equation 1)

The absorbance is measured as follows. 1. The powder to which the ultraviolet absorber was added was pressed with a pressing machine to a diameter of 20 mm.
mm and a thickness of 4 mm. 2. Next, the molded body of the powder is attached to the mounting hole of the reflecting sample of the integrating sphere using a spectrophotometer, and the absorbance due to the reflected light is measured in a wavelength range of 200 to 650 nm, whereby a graph as shown in FIG. 1 is obtained. The vertical axis indicates the absorbance of equation (1), and the horizontal axis indicates the measurement wavelength. 3. Next, in FIG.
The range of nm is divided into 10 sections every 10 nm, and the area of each section is obtained. The area is determined as follows.

For example, Assuming that the area of the 350 to 360 nm portion is (1) and is regarded as a trapezoid, (1) is calculated as follows.

[0047]

(Equation 2)

Similarly, the area (2) is

[0049]

(Equation 3)

[0050] Similarly, the area (10) is

[0051]

(Equation 4)

Is as follows. The integral value S of the area of ten sections is obtained as follows.

S = (1) + (2) + (3) +... + (10) The area S was defined as the absorbance.

[0054] The range of the integral value of the absorbance in the present invention 3
5 to 60 . If the absorbance is less than 30, light is scattered by the conductive powder before sufficiently transmitting to the lower part of the conductive film during ultraviolet exposure, and the unexposed portion is hardened, so that a high-resolution pattern cannot be formed. On the other hand, if the absorbance exceeds 70, the light is absorbed by the conductive powder before reaching the lower part of the conductive film, and the light cannot be cured because the light does not pass through to the lower conductive film. As a result, they come off during development, making it difficult to form electrodes.

In the photosensitive conductive paste used in the present invention, if necessary, a photopolymerization initiator, a glass frit, a sensitizer, a sensitization aid, a polymerization inhibitor, a plasticizer, a thickener,
Additive components such as organic solvents, antioxidants, dispersants, and suspending agents are added.

Specific examples of the photopolymerization initiator used in the present invention include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone,
α-aminoacetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone , 2-hydroxy-2
-Methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethylketanol, benzyl-methoxyethylacetal, benzoin, benzoin Methyl ether,
Benzoin butyl ether, anthraquinone, 2-t-
Butylanthraquinone, 2-amylanthraquinone, β
-Chloranthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-
Azidobenzylidene) -4-methylcyclohexanone,
2-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-propanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl Combination of photoreducing dyes such as disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide and eosin, and methylene blue with reducing agents such as ascorbic acid and triethanolamine And the like. In the present invention, one or more of these can be used.

Further, the photopolymerization initiator is usually used in an amount of 0.1 to 30% by weight, more preferably, of the photosensitive organic component.
Use 2 to 20% by weight. If the amount of the photopolymerization initiator is too small, the photosensitivity becomes poor, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion may be too small.

In the present invention, the photosensitive conductive paste preferably contains a glass frit. This is because glass frit has the effect of strongly baking the conductive powder on the glass substrate, the effect of a sintering aid for sintering the conductive powder, and the effect of lowering the conductor resistance. The glass transition temperature (Tg) and the glass softening point (Ts) of the glass frit are preferably lower from the viewpoint of lowering the baking temperature, and Tg is 300 to 500 ° C. and Ts is 350 to 45.
The temperature is preferably 0 ° C. More preferably, Tg is 350-4.
The temperature is preferably 50 ° C. If the Tg is too low, sintering starts before the organic components evaporate, which is not preferable. Tg is 50
A glass frit higher than 0 ° C. is not preferable because when it is performed at a baking temperature of 600 ° C. or less, the adhesiveness to the glass substrate becomes poor.

Further, when the glass frit is expressed in terms of oxides, the content of SiO _{2 is} 1 to 55% by weight, the content of Al ₂ O _{3 is} 1 to 5% by weight, the content of B ₂ O _{3 is} 8 to 65% by weight, the content of BaO is 2 to 20% by weight, and the content of K ₂ O 2 is It is preferred to contain 70% by weight or more of a composition having a composition range of 15% by weight. Within this range, a glass frit that can be baked on a glass substrate at 500 to 600 ° C. is obtained.

The composition of the glass frit is SiO ₂
Is preferably blended in the range of 1 to 55% by weight,
If it is less than the weight%, the adhesion when baked on the substrate,
Strength and stability decrease. On the other hand, if it exceeds 55% by weight, the heat resistance temperature increases, and it becomes difficult to bake on a glass substrate at 600 ° C or lower.

It is preferable that Al ₂ O ₃ is blended in a range of 1 to 5% by weight. If it is less than 1% by weight, the strength in the glass phase is reduced. If it exceeds 5% by weight, the heat-resistant temperature of the glass becomes too high, and it is difficult to bake the glass on a glass substrate.

It is preferable that B ₂ O ₃ is incorporated in the range of 8 to 65% by weight. B ₂ O ₃ has a baking temperature of 500-500 so as not to impair the electrical, mechanical and thermal properties such as electrical insulation, strength, and coefficient of thermal expansion even when the content of Al ₂ O ₃ is large.
It is blended to control in the range of 600 ° C. 8% by weight
If it is less than 65% by weight, the adhesion strength decreases, and if it exceeds 65% by weight, the stability of the glass frit decreases.

BaO is preferably blended in the range of 2 to 20% by weight. When the amount is less than 2% by weight, the effect of controlling the baking temperature is small when the conductive paste is baked on a glass substrate. If it exceeds 20% by weight, the heat-resistant temperature of the glass will be too low, and it will be difficult to bake it on a glass substrate.

It is preferable that K ₂ O is blended in the range of 2 to 15% by weight. When the amount is less than 2% by weight, the effect of controlling the baking temperature is small when the conductive paste is baked on a glass substrate. If it exceeds 15% by weight, the discharge characteristics of the plasma are undesirably deteriorated.

It is preferable that the glass frit powder does not contain an oxide metal such as Na ₂ O or Y ₂ O ₃ which deteriorates the discharge characteristics of the plasma. Even when it is contained, the content is preferably set to 5% by weight or less.

In the glass frit, Bi ₂ O ₃ , Zn
The thermal expansion coefficient, glass softening point, and insulation resistance can be controlled by containing O, CaO, TiO ₂ , ZrO ₂ , Li ₂ O, etc., but the amount is preferably less than 10% by weight.

The particle size of the glass frit to be used is preferably as small as possible because the particles are melted at a low temperature. 5
0% diameter is in the range of 0.5 to 2 μm, 90% diameter is in the range of 0.7 to 3
The range of μm is preferable, because it is melted at a low temperature and firmly adheres to a glass substrate.

The content of glass frit in the photosensitive conductive paste is preferably 1 to 5% by weight. More preferably, it is 1.5 to 3.5% by weight. In order to reduce the resistance of the anode and cathode electrodes of the PDP, it is preferable that the amount of glass frit is low. Since the glass frit is electrically insulating, its content exceeding 5% by weight is not preferred because the resistance of the electrode increases. If it is less than 1% by weight, it is difficult to obtain a strong adhesive strength between the electrode film and the glass substrate.

In the present invention, metals and oxides such as CaO, BaO, Fe ₂ O ₃ , K ₂ O, and Na ₂ O contained in a small amount in the glass frit react with the photosensitive organic component to gel the paste in a short time. In some cases, it becomes a lump and cannot be printed as a paste, or cannot be developed and cannot be patterned. This is presumed to be gelation due to an ionic cross-linking reaction, but in order to prevent such a reaction, it is preferable to add a stabilizer within a range that does not adversely affect the gelation. That is, the surface of the powder is treated with a compound having an effect of forming a complex with a metal or oxide powder causing a gelling reaction or forming a salt with an acid functional group, thereby stabilizing the photosensitive conductive paste. As such a stabilizer, a triazole compound is preferably used. Among the triazole compounds, benzotriazole works particularly effectively.

The surface treatment of the glass frit powder with benzotriazole used in the present invention is preferably performed as follows. That is, a predetermined amount of benzotriazole is dissolved in an organic solvent such as methyl acetate, ethyl acetate, ethyl alcohol, or methyl alcohol with respect to the glass frit, and then the solution is added to the solution in an amount of 3 to 24 so that these powders can be sufficiently immersed. Soak for hours. After immersion, preferably, the powder is naturally dried at 20 to 30 ° C. to evaporate the solvent, subjected to a triazole treatment, and vacuum dried at 50 to 80 ° C. for 5 to 12 hours to produce a powder.

The ratio of the stabilizer to the glass frit used in the present invention is preferably from 0.2 to 4% by weight, more preferably from 0.4 to 3% by weight. If it is less than 0.2% by weight, there is no effect in preventing the crosslinking reaction. On the other hand, if it exceeds 4% by weight, the amount of the stabilizer becomes too large, so that it becomes difficult to remove the binder such as polymer, monomer and stabilizer during firing of the conductive paste in a non-oxidizing atmosphere, and the characteristics of the conductive film become poor. descend.

In the above, when a small amount of water is present in the conductive paste, the gelation of the conductive paste is promoted. To prevent this, trace amounts are contained in photosensitive organic components (photosensitive polymer, photosensitive monomer, photopolymerization initiator, sensitizer, photopolymerization accelerator, plasticizer, thickener, organic solvent, organic dispersant, etc.) It is preferable to remove the moisture that forms. The removal of water depends on the type of solid or liquid, but is removed by vacuum drying, molecular sieve, rotary evaporator, or the like. Further, in the case of a glass frit, it is preferable to dry the glass frit at 150 to 200 ° C. for 5 to 15 hours to sufficiently remove water, since gelation can be prevented.

In the present invention, when a metal and / or metal oxide serving as a sintering aid is added in addition to the glass frit, the conductive powder can avoid abnormal grain growth during sintering, or can delay sintering. This has the effect of increasing the adhesive strength between the conductor film and the glass substrate. Cu, Cr, Mo, A as such sintering aids
Metals and / or metal oxides such as 1 or Ni can be used. Of these, metal oxides act as electrical insulators, so the smaller the amount of additive, the better.
% By weight or less is preferred. If it exceeds 3% by weight, the electric resistance of the conductor film increases, which is not good. It is also preferable to use a metal oxide and a metal together.

The sensitizer is added to improve the sensitivity. Specific examples of the sensitizer include 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) 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-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone,
2- (p-dimethylaminophenylvinylene) 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, 1-phenyl-5
-Ethoxycarbonylthiotetrazole and the like. In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators.

When a sensitizer is added to the conductive paste of the present invention, the amount added is usually 0.1 to the photosensitive organic component.
-30% by weight, more preferably 0.2-20% by weight. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.

In order to improve the thermal stability during storage in the conductive paste of the present invention, a thermal polymerization inhibitor is preferably added. Specific examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, phenothiazine,
pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol,
Chloranil, pyrogallol and the like. When a thermal polymerization inhibitor is added, its amount is usually 0.1 to 5% by weight in the photosensitive conductive paste, more preferably,
0.2 to 3% by weight. If the amount of the thermal polymerization inhibitor is too small, the effect of improving the thermal stability during storage is not exhibited, and if the amount of the thermal polymerization inhibitor is too large, the residual ratio of the exposed portion may be too small. is there.

As the plasticizer, for example, dibutyl phthalate (DBP), dioctyl phthalate (DOP), polyethylene glycol, glycerin and the like are used.

Further, an antioxidant can be added to the conductive paste of the present invention to prevent oxidation of the acrylic copolymer during storage. Specific examples of antioxidants include 2,6-
Di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-4-ethylphenol,
2,2-methylene-bis- (4-methyl-6-t-butylphenol), 2,2-methylene-bis- (4-ethyl-6-t-butylphenol), 4,4-bis- (3
-Methyl-6-t-butylphenol), 1,1,3-
Tris- (2-methyl-6-t-butylphenol),
1,1,3-tris- (2-methyl-4-hydroxy-
t-butylphenyl) butane, bis [3,3-bis-
(4-hydroxy-3-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like. When adding an antioxidant, the amount added is usually
It is 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, in the photosensitive conductive paste. If the amount of the antioxidant is small, the effect of preventing oxidation of the acrylic copolymer during storage cannot be obtained, and if the amount of the antioxidant is too large, the residual ratio of the exposed portion may be too small.

To adjust the viscosity of the solution, an organic solvent may be added to the photosensitive conductive paste of the present invention. Examples of the organic solvent used at this time include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, and the like. . These organic solvents can be used alone or in combination of two or more.

The preferred composition range of the photosensitive conductive paste is as follows: (a) conductive powder; 84 to 94% by weight based on the sum of (a), (b) and (c); (A) a photosensitive monomer;
15 to 3% by weight based on the sum of (b) and (c) (c) Glass frit; 1 to 5% by weight based on the sum of (a), (b) and (c) (d) Photopolymerization initiation 5% to 20% by weight with respect to (b) (e) UV absorber; 0.01 to 10% with respect to (a)
1% by weight More preferably, (a) 86 to 92% by weight, (b) 11
-5% by weight and (c) 2-4% by weight. Within this range, ultraviolet rays are well transmitted at the time of exposure, the photocuring function is sufficiently exhibited, the film strength of the exposed portion at the time of development is increased, and an electrode pattern having a fine resolution can be formed.

Further, if necessary, a photopolymerization accelerator, a dispersant, a thixotropic agent, a precipitation inhibitor and the like are added to form a slurry of the mixture. The slurry adjusted to have a predetermined composition is uniformly stirred and mixed with a stirrer such as a homogenizer, and then uniformly dispersed with a three-roller or kneader to produce a paste.

The viscosity of the paste is appropriately adjusted according to the composition and type of the conductive powder, the organic solvent and the glass frit, and the ratio of the plasticizer, the thixotropic agent, the suspending agent, the organic leveling agent, and the like. ~ 2
It is 10,000 cps (centipoise). For example, a glass substrate is coated once or twice with a screen printing method, a bar coater, a roller coater, or an applicator to form a film having a thickness of 10 to 20.
In order to obtain μm, 30,000 to 200,000 cps is preferable.

Next, a method for forming an electrode pattern of a PDP using the photosensitive conductive paste of the present invention will be described. That is, the photosensitive conductive paste of the present invention is usually applied on a glass substrate by a screen printing method or the like. The printing thickness can be arbitrarily controlled by adjusting the material of the screen (made of polyester or stainless steel), mesh and tension, and the viscosity of the paste, but is 5 to 30 μm. A more preferable range of the thickness is 8 to 20 μm.
When the thickness is less than 5 μm, it becomes difficult to obtain a uniform thickness by the printing method. On the other hand, if it exceeds 30 μm, the accuracy of the electrode pattern is reduced, the cross-sectional shape becomes inverted trapezoid, and a high-definition pattern having a minimum line width / minimum line interval of 30 μm / 30 μm or less, a pattern with good edge cuts and no bleeding is obtained. It becomes difficult.

When the photosensitive conductive paste is applied on a glass substrate, it is preferable to perform a surface treatment on the substrate in order to increase the adhesion between the substrate and the applied film. As the surface treatment liquid, a silane coupling agent such as vinyltrichlorosilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, tris- (2-methoxyethoxy) vinylsilane,
γ-glycidoxypropyltrimethoxysilane, γ-
(Methacryloxypropyl) trimethoxysilane, γ-
(2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, or the like, or an organic metal such as organic titanium, organic aluminum, or organic zirconium It is. A silane coupling agent or an organic metal diluted with an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol to a concentration of 0.1 to 5% is used. Next, the surface treatment liquid is uniformly applied on a substrate by a spinner or the like, and then dried at 80 to 140 ° C. for 10 to 60 minutes to perform surface treatment.

Next, the film obtained by applying such a photosensitive conductive paste on a substrate is dried by heating at 70 to 120 ° C. for 20 to 60 minutes to evaporate the solvents, and then the electrode pattern is formed by photolithography. The photosensitive paste is photo-cured by irradiating it with ultraviolet light using a film having the above or a mask such as a chrome mask. Examples of the active light source used in this case include ultraviolet rays, electron beams, and X-rays. Among them, ultraviolet rays are preferable, and examples of the light source include low-pressure mercury lamps, high-pressure mercury lamps, halogen lamps, and germicidal lamps. it can. Among these, an ultra-high pressure mercury lamp is preferred. Exposure conditions vary depending on the thickness of the conductive film, but it is preferable to perform exposure for 1 to 30 minutes using an ultra-high pressure mercury lamp having an output of 5 to 100 mW / cm ² .

Next, a part which is not cured by the exposure is removed by using a developing solution to form a (so-called negative type) electrode pattern. The development is performed by an immersion method, a spray method, or the like. As the developer, an organic solvent in which the mixture of the photosensitive organic components can be dissolved can be used. Water may be added to the organic solvent as long as the solvent does not lose its solubility. When a compound having an acidic group is present, development can be performed with an aqueous alkali solution. As the alkali aqueous solution, a metal alkali aqueous solution such as sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution or the like can be used. However, it is preferable to use an organic alkali aqueous solution since the alkali component can be easily removed at the time of firing. Specific examples of the organic alkali include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like. The concentration of the alkaline aqueous solution is usually 0.05 to 5% by weight, more preferably 0.1 to 2% by weight. If the alkali concentration is too low, the unexposed portions are not removed, and if the alkali concentration is too high, the exposed portions may be corroded, which is not good.

Next, the coating film after exposure and development is fired in air. Reactive components and binders, such as photosensitive polymers and photosensitive monomers, which are photosensitive organic components, photopolymerization initiators, ultraviolet light absorbers, sensitizers, sensitization aids, plasticizers, thickeners, organic solvents, and dispersions Organic substances such as agents and solvents are completely oxidized and evaporated. 500-600 ° C as temperature condition
More preferably, baking is performed at 520 to 580 ° C. for 15 minutes to 1 hour, and baking on a glass substrate is preferred. 50
If the temperature is lower than 0 ° C., it is difficult to sufficiently perform the sintering.
If the temperature exceeds 0 ° C., the substrate is liable to be deteriorated or to be thermally deformed.

The preparation, printing, exposure and development steps of the photosensitive conductive paste of the present invention need to be performed in a place where ultraviolet rays can be blocked. Otherwise, the paste or coating film will be photo-cured by ultraviolet rays, and a conductor film that can exhibit the effects of the present invention cannot be obtained.

When an electrode pattern is formed by using the photosensitive conductive paste of the present invention, for example, when the thickness of the conductor film after firing is 5 to 30 μm, the minimum line width of the conductor is 30 μm, and the minimum line interval between the conductors is about 30 μm. A high definition pattern can be obtained.

[0090]

The present invention will be described in detail with reference to the following examples. Electrodes were formed and evaluated according to the following materials A to K and a to g. In the following examples, all concentrations are expressed by weight% unless otherwise specified. A. Conductive powder Ag powder (1); spherical (spherical ratio 100%), average particle size 3.3 μm, specific surface area 0.82 m ² / g Ag powder (2); spherical (spherical ratio 100%), average particle size 2 0.2 μm, specific surface area 1.6 m ² / g Ag powder (3); spherical (spherical ratio 100%), average particle diameter 4.5 μm, specific surface area 0.25 m ² / g The particle size distribution is measured by a laser type particle size distribution analyzer. (HORIBA
LA-700). B. Photosensitive polymer (hereinafter abbreviated as polymer) 40% methacrylic acid (MAA), 30% methyl methacrylate (MMA) and 30% styrene (St)
A polymer obtained by adding 0.4 equivalent of glycidyl methacrylate (GMA) to MAA to a copolymer comprising D. Photosensitive monomer (hereinafter abbreviated as monomer) Trimethylolpropane triacrylate Glass frit Glass frit I; (component weight%) silicon dioxide (1.
5), aluminum oxide (3.6), boron oxide (6
1.3), barium oxide (19.1), potassium oxide (9.8), sodium oxide (4.7) glass frit II; (component weight%) silicon dioxide (4
8.3), aluminum oxide (4.8), boron oxide (21.8), barium oxide (5.6), potassium oxide (11.1), zinc oxide (6.4), lithium oxide (2. 0) E. UV absorbers UV absorber (1); azo dye; Sudan Chemical formula; C ₂₄ H ₂ ON ₄ O, molecular weight: 380.45 UV absorber (2): azo dye; oil yellow (Oi
l Yellow OB) _{formula; CH 3 C 4 H 4 N} : NC 10 H 4 NH 2, molecular weight: 2
61.33 F.R. Solvent γ-butyrolactone G. Photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2
Morpholino-1-propanone and 2,4-diethylthioxanthone are added to the sum of
0% was added. H. Plasticizer Dibutyl phthalate (DBP) was added at 10% of the polymer. I. Sensitizer 2,4-diethylthioxanthone was added in an amount of 20% based on the total amount of the polymer and the monomer. J. Sensitizing aid p-dimethylaminobenzoic acid ethyl ester (EPA)
Was added in an amount of 10% based on the total amount of the polymer and the monomer. K. SiO ₂ dissolved in the thickener 2- (2-butoxyethoxy) ethyl acetate (concentration 15%) was added 4% relative to the polymer. a. Preparation of Organic Vehicle The solvent and polymer were mixed and heated to 80 ° C. with stirring to dissolve all polymers homogeneously. Then, the solution was cooled to room temperature, and a photopolymerization initiator was added and dissolved. Thereafter, the solution was filtered through a 400 mesh filter. b. Preparation of Light Absorbing Agent-Added Powder A predetermined amount of the ultraviolet absorbing agent was weighed, a dispersing agent was added to a solution dissolved in isopropyl alcohol (IPA), and the mixture was homogeneously stirred with a homogenizer. Next, a predetermined amount of the conductive powder was added to this solution, and the mixture was uniformly dispersed and mixed, and then dried at a temperature of 150 to 200 ° C. using a rotary evaporator to evaporate IPA. In this way, a powder in which the surface of the conductive powder was uniformly coated with a film of the ultraviolet absorber (so-called encapsulated) was produced. c. Paste preparation Add conductive powder, monomer, plasticizer, sensitizer, sensitization aid, thickener, glass frit, and solvent to the above organic vehicle so as to have a prescribed composition. A paste was prepared by mixing and dispersing with three rollers. Table 1 shows the composition of the paste. d. Printing 400 g of the above paste was put on a glass substrate (430 mm square, 3 mm thick) using a 325 mesh screen.
The sheet was printed solid on a square of mm square, dried at 80 ° C. for 40 minutes. The thickness of the dried coating film varied depending on the composition, but was 12 to 15 μm. e. Exposure and development The above-prepared coating film was 500 mW / cm from the upper surface using a chromium mask on which an electrode for a plasma display panel having a fine pattern of 40 to 70 μm was formed.
^It was exposed to ultraviolet light from an ultra-high pressure mercury lamp with a power of ² . Then 25 ℃
The film was developed by immersing it in a 0.5% by weight aqueous solution of monoethanolamine held in, and then unexposed portions were washed with water using a spray. f. Firing The coating film printed on the glass substrate is heated in air at 580 ° C for 1 hour.
Baking was performed for 5 minutes to produce an electrode conductor film. g. Evaluation The electrode film after firing was measured and evaluated for film thickness, resolution, edge curl at the end of the electrode film, specific resistance, and adhesive strength.
The film thickness was determined by observing the cross section with a scanning electron microscope (SEM). The resolution was evaluated by observing the conductive film with a microscope and evaluating the line interval at which lines having a width of 40 μm did not overlap with a straight line and reproducibility was obtained. The edge curl was evaluated by observing the roughness and the cross section at the end of the electrode pattern with a surface roughness meter under a microscope.
The adhesive strength was evaluated by sticking an adhesive tape to the electrode surface and evaluating the degree of peeling. The specific resistance was obtained by measuring the sheet resistance and calculating from the film thickness. Tables 1 and 2 show the obtained results.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

As described above, high resolution pattern resolution was obtained by photolithography using a photosensitive conductive paste, and an electrode pattern having no edge curl and low resistance was formed. In particular, in screen printing, it is particularly advantageous for obtaining high definition and high reliability of a plasma display panel, which has been difficult to increase in size due to a limit of dimensional accuracy of a mask pattern and a problem of displacement caused by accumulation of pattern pitch. is there. In addition, the photosensitive conductive paste using the photolithographic method of the present invention, after exposure through a mask pattern on the solid printed surface, can be developed and formed a pattern, so that the problem of dimensional accuracy is greatly reduced, and a highly accurate mask Since the positioning can be performed by using the above, it is more advantageous to increase the size.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between measurement wavelength and absorbance.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI H01J 17/04 H01J 17/04 (56) References JP-A-5-206600 (JP, A) JP-A-6-228442 (JP) JP-A-6-242604 (JP, A) JP-A-5-271576 (JP, A) JP-A-5-287221 (JP, A) JP-A-6-290635 (JP, A) JP 58-123791 (JP, A) JP-A-1-206538 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/004 G03F 7/027 H01J 9/02 H01J 11 / 02 H01J 17/04

Claims (10)

(57) [Claims] 1. A spherical conductive powder, a photosensitive organic component and
When the integrated value of the absorbance at 350 to 450 nm is 35 to 60,
Photosensitivity containing certain organic dye as an ultraviolet absorber, an average particle diameter of the conductive powder is 0.7～6Myuemu, the specific surface area of the conductive powder characterized in that it is a 0.15~3m ² / g Conductive paste. 2. The photosensitive conductive paste according to claim 1, wherein the sphericity of the conductive powder is 90% by number or more. 3. The method according to claim 1, wherein the conductive powder is Ag, Au, Pd, Ni,
2. The photosensitive conductive paste according to claim 1, comprising at least one selected from the group consisting of Cu, Al and Pt. 4. The method according to claim 1, wherein the organic dye is an azo dye.
The photosensitive conductive paste according to claim 1, wherein 5. The surface of a conductive powder is coated with an organic dye.
2. The photosensitive conductive pen according to claim 1, wherein
Bust. 6. The photosensitive conductive paste according to claim 1, wherein the photosensitive organic component contains a photosensitive polymer or oligomer, a photosensitive monomer and a photopolymerization initiator. 7. The photosensitive conductive paste according to claim 1, wherein the photosensitive organic component contains an acrylic copolymer having an acidic group and an ethylenically unsaturated group. 8. A photosensitive conductive paste for a plasma display according to claim 1. 9. A method for manufacturing an electrode, comprising applying the photosensitive conductive paste according to claim 1 onto a substrate, forming a pattern by photolithography, and firing. 10. A method of manufacturing an electrode for a plasma display, comprising applying the photosensitive conductive paste according to claim 1 on a substrate, forming a pattern by photolithography, and firing. Method.