KR100581971B1 - An Ag paste composition for forming micro-electrode and the micro-electrode manufactured using the same - Google Patents

Abstract

The present invention relates to a high viscosity Ag paste composition and a fine electrode prepared using the composition, and more particularly, the composition according to the present invention comprises: a) 60 to 80% by weight of Ag powder; b) 1 to 10% by weight of the inorganic binder; c) 0.001 to 1 weight percent stabilizer; And d) 15 to 35% by weight of an alkali-soluble negative photoresist composition for fine conductive powder dispersion.

The Ag paste composition of the present invention is applicable to the firing process of 600 ° C. or lower, and is suitable for the manufacture of plasma display panels, and is suitable for the production of fine precision electrodes that could not be formed by conventional screen printing techniques due to its high viscosity. It is excellent in printability, and the process is simple, economical and environmentally friendly due to the absence of separate surfactants and organic solvents.

Ag paste composition, photoresist composition, fine electrode

Description

An Ag paste composition for forming micro-electrode and the micro-electrode manufactured using the same}

1 is a scanning electron micrograph after development of a 50 μm pattern formed using an Ag paste composition according to the present invention.

2 is a cross-sectional scanning electron micrograph after development of a 50 μm pattern formed using the Ag paste composition according to the present invention.

3 is a scanning electron micrograph after sintering of a 50 μm pattern formed using the Ag paste composition according to the present invention.

Figure 4 is a cross-sectional scanning electron micrograph after sintering of the 50㎛ pattern formed using the Ag paste composition according to the present invention.

The present invention relates to a high viscosity Ag paste composition for forming a fine electrode and a fine electrode prepared using the same.

In recent years, in the display devices, as the demand for larger size, higher density, higher precision, and higher reliability increases, various pattern processing techniques have been developed, and various fine electrode forming compositions suitable for such various pattern processing techniques have been developed. There is an active research on.

Plasma display panels (hereinafter referred to as 'PDP') are used in various fields at present because they have a faster response speed and easier size than those of liquid crystal panels. Conventionally, as a method of forming an electrode on such a PDP, the patterning method of the electrode material using the screen printing method has been generally used. However, the conventional screen printing method requires a high level of proficiency, has a low viscosity when performing screen printing, so that the paste can flow down on the substrate, and the precision of the screen is reduced, which is required by the PDP using the screen printing method. It is difficult to obtain a high precision large screen pattern. In addition, the conventional screen printing method may cause a short circuit or disconnection due to the screen during printing, there was a disadvantage that the firing temperature is high temperature 1000 ℃ or more.

Therefore, in recent years, the photolithography method using the photosensitive resin composition was developed in order to form the high precision electrode circuit suitable for a large area. This uses a photosensitive resin composition in which fine conductive powder is dispersed to form a uniform thick film through a printing method, and exposes the formed thick film using a mask having a desired shape, and then implements a necessary pattern using an alkaline developer. Way.

In this case, in order to form a high-precision electrode circuit, the miscibility between the photosensitive resin composition and the fine conductive powder to be used, the adhesion of the photosensitive resin composition to the glass substrate in the developing step, and the degree of heat resistance of the photosensitive resin in the firing step are very important. . In addition, in order to impart the shear stress for dispersing the inorganic fine conductive powder into the organic photosensitive resin composition appropriately, it has a high viscosity of 3000 cP or more, and in order to maintain a uniform dispersion state such as static electricity existing on the surface of the fine powder, etc. There is a need for a photosensitive resin composition which is stable against an acting force, does not have a high degree of crystallinity of a polymer resin, and has good adhesion to a glass surface and good thermal decomposition.

In addition, conventional photosensitive conductive pastes are subjected to a firing process at 800 ° C. or higher. In this case, since sodium carbonate glass is generally used, the photosensitive conductive pastes are not suitable for the production of PDP that should maintain a firing temperature of 600 ° C. or lower, and this is a temperature of 600 ° C. or lower. In the case of firing in a furnace, there are problems such as a calcination residue and deterioration of electrical conductivity.

Even in the conductive powder in which the photosensitive resin composition is dispersed, gold (Au) and copper (Cu) powders, which are widely used in the past, have a risk of causing environmental pollution in that they require a separate organic solvent treatment for post-exposure development. There is a problem that the price of the powder is expensive and economically, the sintering temperature is high.

In addition, since conventional commercial photosensitive resin compositions using Ag powder used plate-like Ag particles as low viscosity conductive pastes of about 500 to 1500 cP using plate-shaped Ag particles, the dispersion state of Ag powder was not good, and spherical Ag Even in the case of using the particles, there is a problem in that a fine pattern cannot be formed because large Ag particles having an average particle diameter of several μm to several tens of μm are used.

 An object of the present invention is applicable to the firing process of 600 ℃ or less, in order to solve the problems of the prior art as described above, and is suitable for the production of fine precision electrode that could not be formed by the conventional screen printing technology because of high viscosity and It is to provide a high viscosity Ag paste composition for the formation of fine electrodes, which is excellent in printability, and is simple in processing, economical and environmentally friendly due to the absence of separate surfactants and organic solvents.

One embodiment of the present invention to achieve the above technical problem,

a) 60 to 80 wt% Ag powder;

b) lead borosilicate frit, bismuth borosilicate frit, B ₂ O ₃ · SiO ₂ · MO and B ₂ O ₃ · SiO ₂ · M′O (where M is a divalent metal ion 1 to 10% by weight of an inorganic binder selected from the group consisting of M'1 is a metal ion);

c) 0.001 to 1 weight percent stabilizer; And

d) 15 to 35% by weight of alkali-soluble negative photoresist composition for fine conductive powder dispersion

It provides a high viscosity Ag paste composition for forming a fine electrode comprising a.

In the high viscosity Ag paste composition for forming a fine electrode according to an embodiment of the present invention, the alkali-soluble negative photoresist composition for fine conductive powder dispersion,

a) 30 to 70% by weight of an acrylate copolymer for photoresist represented by the following general formula (1) or (2);

b) 10 to 40% by weight of the photopolymerizable monomer;

c) 0.5 to 10% by weight photopolymerization initiator;

d) 0.1 to 10 weight percent antifoam; And

e) 0.1 to 10% by weight leveling agent

It includes.

Wherein R ₁ is hydrogen, a phenyl group, a benzyl group, a phenyl group substituted with a nitro group, a phenyl group substituted with halogen, a benzyl group substituted with a nitro group, an alkyl group substituted with a C1 to C10 hydroxy group, or a C1 to C10 hydroxy group; R ₂ is an ethylhexyl group, isobutyl group, tert-butyl group, octyl group, 3-methoxybutyl group, or methoxypropylene glycol group; R ₃ is hydrogen or a methyl group; R ₄ is hydrogen or a methyl group; n ₁ is an integer from 8 to 40; n ₂ is an integer of 1 to 2.

In which R ₅ is hydrogen or a carboxyl group; R ₆ is a phenyl group, a carboxyl group or an -OCOCH ₃ group; R ₇ is hydrogen or a —CH ₂ COOH group; R ₂ , R ₄ , n ₁ , and n ₂ are as defined above.

In addition, another embodiment of the present invention provides a fine electrode prepared using the Ag paste composition.

Hereinafter, the Ag paste composition according to the embodiment of the present invention will be described in detail.

 The present invention, a) 60 to 80% by weight of Ag powder; b) 1 to 10% by weight of the inorganic binder; c) 0.001 to 1 weight percent stabilizer; And d) 15 to 35% by weight of an alkali-soluble negative photoresist composition for dispersing fine conductive powder.

The conductive powder used in one embodiment of the present invention is Ag powder. The content of Ag powder in the Ag paste composition is 60 to 80% by weight, preferably 65 to 75% by weight.

When the content of Ag powder is 60 wt% or less, the density of Ag powder is small, so that the pores on the surface are increased after pattern formation and sintering, resulting in high electrical resistance, disconnection, and low viscosity, resulting in a glass substrate for printing. It is not desirable because it can flow in.

On the other hand, when the content of Ag powder is 80% by weight or more, the viscosity may be too high to print on the glass substrate, or the printing defect may occur such that the glass substrate is not separated from the screen mask, resulting in low smoothness after printing. This results in local differences in thickness and can result in mesh marks on the screen mask. In addition, due to the high density of Ag, the "under cut" phenomenon may be intensified.

Although there is no restriction | limiting in the shape of Ag powder used, When it considers dispersibility, it is preferable that it is spherical particle. It is preferable that the average particle diameter of particle | grains is 0.3-3 micrometers, More preferably, it is 0.5-2 micrometers, Most preferably, it is 0.6-1.3 micrometers.

The purity of the Ag particles is preferably 96% or more, more preferably 98% or more. This is because, when the purity of the particles is low, there is a fear that the electrical resistance increases after sintering due to impurities.

Ag paste composition according to an embodiment of the present invention is also, lead borosilicate frit, bismuth borosilicate frit, B ₂ O ₃ · SiO to fire and adhere the conductive powder on the glass substrate ₂ and MO · _{B 2 O 3 · SiO 2 ·} M'O includes an inorganic binder being at least one selected from the group consisting of (where, M is a divalent metal ion and, M'1 is a metal ion) . The content of the inorganic binder is 1 to 10% by weight, preferably 2 to 6% by weight based on the total weight of the Ag paste composition.

When the content of the inorganic binder is 1% by weight or less, the adhesion between the glass substrate and the electrode may be weakened after sintering, and the electrode may be separated. When the content of the inorganic binder is 10% by weight or more, the electrical resistance of the electrode after sintering may increase, It is not preferable because there is a risk of disconnection.

The shape of the inorganic binder particles does not necessarily need to be spherical, and the average particle diameter is preferably 0.3 to 3 µm, more preferably 0.5 to 2 µm, most preferably 0.6 to 1.3 µm.

delete

It is preferable that the glass transition temperature (Tg) of the said inorganic binder is 360-500 degreeC, and glass softening temperature (Ts) is 400-550 degreeC.

If the glass transition temperature and the glass softening temperature are below the above temperature range, there is a possibility that sintering of the inorganic binder starts in the state in which the organic matter is not completely decomposed, and that the organic matter that is not removed may exist in the pattern, and these impurities may cause the performance of the pattern. It will act to lower the.

On the other hand, when the glass transition temperature and the glass softening temperature exceeds the above temperature range, microparticles of the inorganic binder may occur, which causes poor adhesion between the microelectrode and the glass substrate and deteriorates the characteristics of the pattern as well as the pattern. It is not preferable because it may peel off.

The storage place of the inorganic binder is preferably a place where moisture can be avoided as much as possible. This is because when moisture is adsorbed on the inorganic binder powder, the gelation of the paste may be promoted. Therefore, the inorganic binder is preferably dried between 80 to 350 ° C. to prevent foreign matter from adhering to the surface of the inorganic binder. However, care should be taken when storing at temperatures exceeding 350 ° C., since the inorganic binder may lose the form of powder and cannot be used as a paste composition beyond the transition temperature.

The Ag paste composition according to one embodiment of the present invention also includes a stabilizer to prevent gelation of the paste and to control storage stability and development speed. The content of the stabilizer is 0.001 to 1% by weight, preferably 0.005 to 1% by weight, most preferably 0.01 to 0.6% by weight based on the Ag paste composition.

If the content of the stabilizer is less than 0.001% by weight, the paste tends to gel, and if it is more than 1% by weight, the viscosity of the composition may be lowered or a pattern may not be formed, which is not preferable.

As the stabilizer, a commonly used antioxidant may be used, and benzotriazole, ascorbic acid and phosphoric acid, phosphorous acid or salts thereof may be used, but is not limited thereto.

The Ag paste composition according to the embodiment of the present invention also exhibits high viscosity, so that it is easy to disperse conductive fine powder such as Ag powder, and alkali-soluble negative viscosity of high viscosity for fine conductive powder dispersion which can be developed at high speed in alkaline developer. Photoresist composition. The content of the photoresist composition is 15 to 35% by weight, preferably 20 to 35% by weight, most preferably 25 to 35% by weight based on the Ag paste composition.

When the content of the photoresist composition exceeds 35%, pores are present in the electrode when the electrode is formed. As a result, the electrode resistance increases, which may lead to electrode disconnection when driving the circuit. It becomes difficult to obtain an electrode pattern.

The photoresist composition is preferably,

a) 30 to 70% by weight of an acrylate copolymer for photoresist represented by the following general formula (1) or (2); b) 0.5 to 10% by weight photopolymerization initiator; c) 10 to 40% by weight of the photopolymerizable monomer; d) 0.1 to 10 weight percent antifoam; And e) 0.1 to 10% by weight leveling agent.

[Formula 1]

Wherein R ₁ is hydrogen, a phenyl group, a benzyl group, a phenyl group substituted with a nitro group, a phenyl group substituted with halogen, a benzyl group substituted with a nitro group, an alkyl group substituted with a C1 to C10 hydroxy group, or a C1 to C10 hydroxy group; R ₂ is an ethylhexyl group, isobutyl group, tert-butyl group, octyl group, 3-methoxybutyl group, or methoxypropylene glycol group; R ₃ is hydrogen or a methyl group; R ₄ is hydrogen or a methyl group; n ₁ is an integer from 8 to 40; n ₂ is an integer of 1 to 2.

[Formula 2]

In which R ₅ is hydrogen or a carboxyl group; R ₆ is a phenyl group, a carboxyl group or an -OCOCH ₃ group; R ₇ is hydrogen or a —CH ₂ COOH group; R ₂ , R ₄ , n ₁ , and n ₂ are as defined above.

The acrylate copolymer of Formula 1 preferably has a viscosity of 10000 to 20000 cP. In addition, the molecular weight of the formula (1) is preferably 15000 to 50000, more preferably 25000 to 30000. In addition, the glass transition temperature of the polymer is preferably at least 100 ℃ to use the printing method, if the glass transition point is less than 100 ℃ may cause problems due to the strong adhesion during printing.

The monomers used when preparing the acrylate copolymer include unsaturated carboxylic acids, aromatic monomers, monomers having self-plasticizing ability, and acrylic monomers except for the monomer having self-plasticizing ability.

The unsaturated carboxylic acids are used for alkali solubility, and specific examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid or their acid anhydride forms. The content of the unsaturated carboxylic acid is preferably 20 to 50% by weight in the polymer composition. When the content of the unsaturated carboxylic acid exceeds 50% by weight, it is easy to gelate during polymerization, difficult to control the degree of polymerization, and deterioration in the storage stability of the resin composition during photosensitive. In addition, when the content of unsaturated carboxylic acid is less than 20% by weight, there is a disadvantage that the developing time is long during the developing process.

The aromatic monomer is used for adhesion with the glass surface and stable pattern formation during development. Examples of the aromatic monomers include styrene, benzyl methacrylate, benzyl acrylate, phenyl acrylate, phenyl methacrylate, 2 or 4-nitrophenyl acrylate, 2 or 4-nitrophenyl methacrylate, 2 or 4-nitro Benzyl methacrylate, 2 or 4-chlorophenyl acrylate, 2 or 4-chlorophenyl methacrylate, and the like. The content of the aromatic monomer is preferably 15 to 45% by weight in the polymer composition, more preferably 20 to 40% by weight. When the content of the aromatic monomer exceeds 45% by weight, a disadvantage occurs that the development time is long during the development process, and the heat resistance is increased, so that the photosensitive resin is not removed during the firing process and remains fatal to inherent characteristics of the electrode. Problems will arise. In addition, when the content of the aromatic monomer is less than 15% by weight, adhesion to the glass surface is poor during the developing process, the tearing of the pattern is severe, and the straightness of the formed pattern is deteriorated, making it difficult to implement a stable pattern.

In particular, the monomer having its own plasticizing ability plays a role in controlling the degree of polymerization of polymers and weakening crystallinity. Examples of the monomer having the self-plasticizing ability include 2-ethylhexyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, octyl (meth) acrylate, and 3-methoxybutyl ( Meth) acrylate, methoxy propylene glycol (meth) acrylate, etc. are mentioned. The content of the monomer having its own plasticity is preferably 3 to 15% by weight, more preferably 5 to 10% by weight in the polymer composition. When the content of the monomer having the self-plasticization exceeds 15% by weight, the tearing of the pattern becomes worse during the developing process, and the straightness of the formed pattern is deteriorated. In addition, when the content of the monomer having its own plasticity is less than 3% by weight, the degree of polymerization is increased, and thus, even in the case of a polymer that is gelled or not gelated, a pattern formed after the developing process is easily damaged.

In addition, the acrylic monomers except for the acrylic monomer having self-plasticity control the glass transition temperature, adhesion to the substrate, and polarity of the polymer. Examples of such acryl monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxyoctyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl acrylate, and the like. Can be mentioned. The content of these monomers in the polymer is preferably used in 10 to 30% by weight of the polymer composition in consideration of the glass transition point and heat resistance of the polymer, hydrophilicity with the developer.

The acrylate copolymer can be obtained by polymerization in a solvent having a suitable polarity to prevent gelation of the four monomers. Preferred examples of the solvent include carbitol acetate, gamma butyrolactone, diethylene glycol butyl ether, trimethylpentane diol monoisobutyrate, dipropylene glycol monoethyl ether and the like.

The content of the acrylate copolymer resin of Formula 1 is used in 30 to 70% by weight. If the content of the copolymer resin is less than 30% by weight, there is a problem in pattern formation, and when the content of the copolymer resin is higher than 70% by weight, there is a problem in implementing the characteristics of the dispersed powder.

In addition, in the photoresist composition, the photopolymerization initiator may be used by mixing one or more compounds such as triazine-based, benzophenone-based, acetophenone-based, imidazole-based, thioxanthone-based. Specific examples thereof include 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine, 2 , 4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2,2-dichloro- 4-phenoxyacetophenone, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylproriophenone, pt-butyltrichloroacetophenone, pt-butyl Dichloroacetophenone, 4,4'-ethylaminobenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isobutyl thioxanthone, 2-dodecyl thioxanthone, 2,4 Dimethyl thioxanthone and 2,4-diethyl thioxanthone-2,2'-bis-2-chlorophenyl-4,5,4 ', 5'-tetraphenyl-2'-1,2'- Biimidazole compounds and the like. The content of the photopolymerization initiator is preferably used in 0.5 to 10% by weight, more preferably 2 to 4% by weight. If the amount of the photopolymerization initiator exceeds 10% by weight may cause a problem in storage stability, the pattern may be severely peeled during development due to the high degree of cure, whereas less than 0.5% by weight is a normal pattern implementation due to low sensitivity It is difficult and does not benefit the straightness of the pattern.

In the photoresist composition, the photopolymerizable monomer may be used by mixing one or more polyfunctional acrylate derivatives. Specific examples thereof include 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, di Pentaerythritol kisaacrylate, dipentaerythritol hydroxypentaacrylate, glycerol diacrylate, trimethol propane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol dimethacrylate, sorbitol trimethacrylate, bisphenol A diacrylate derivative, trimethyllopropane triacrylate, dipentaerythritol polyacrylate, and the like. The content of the photopolymerizable monomer is preferably 10 to 40% by weight, more preferably 20 to 30% by weight. If the content of the photopolymerizable monomer exceeds 40% by weight, the pattern is more severe due to the high degree of curing, and the straightness of the pattern is deteriorated.When the content of the photopolymerizable monomer is less than 10% by weight, it is difficult to realize a normal pattern due to the low sensitivity and the degree of curing. The straightness of the pattern is also worsened.

In the photoresist composition, the antifoaming agent prevents the microbubbles generated during the mixing process with the Ag powder in the thick film due to the high viscosity in the thick film due to the high viscosity to change into pinholes during the firing process to cause disconnection of the electrode do. The leveling additive is added to alleviate the phenomenon that the miscibility between the Ag powder and the photoresist composition is reduced due to the surface tension of the photoresist composition, and to reduce the defects that may be caused by the nonuniformity of the film.

Specific examples thereof include anionic copolymers and aralkyl modified polymethylalkylsiloxanes, and antifoaming agents include polyester-modified polymethylalkylsiloxanes, polysiloxanes, non-silicone polymers, modified urea solutions, and polyesters. Modified dimethylpolysiloxanes, polyester modified dimethylpolysiloxane copolymers, and the like.

The amount of the antifoaming agent and the leveling additive is preferably used 0.1 to 10% by weight of the defoaming agent, 0.1 to 10% by weight of the leveling additive. When the content of the antifoaming agent and the leveling additive is more than 10% by weight, the residual film is likely to be left during the development process, and if it is less than 0.1% by weight, it is difficult to expect desired properties.

The Ag paste composition according to the present invention is a mixture of Ag powder, an inorganic binder, a stabilizer, and an alkali-soluble negative photoresist composition for dispersing fine conductive powder, as described above, such as a planetary mixer. Pre-mixing with a mixer, and using a grinder such as a 3-roll mill to uniformly disperse Ag powder, inorganic binder and stabilizer in the photoresist composition to form a paste phase Are manufactured. The paste composition prepared as described above has a viscosity of 3000 to 60000 cP, has a behavior of pseudoplastic, and this characteristic has a low resistance to stress applied during printing, and has a high viscosity even though it has high viscosity. This improves and enables the production of a composition for producing a fine electrode having high smoothness after printing.

Another embodiment of the present invention also provides a fine electrode prepared using the Ag paste composition according to the present invention. The fine electrode is manufactured through the formation process and the firing process of the fine pattern.

In the process of forming the fine pattern, the Ag paste composition prepared as described above is printed on the surface of the substrate using a screen printing machine using a screen mask such as SUS 325 mesh or SUS 400 mesh, and the coated specimen is subjected to a convection oven. ), Dried at a temperature of 80 to 120 ° C. for 10 to 40 minutes, and then exposed to form a pattern with a mercury lamp having a 365 nm composite wavelength using a suitable light source on the formed Ag paste coating film, a Na ₂ CO ₃ solution, It is made by developing at a temperature of room temperature to 50 ° C. with a suitable alkaline developer such as KOH, TMA II and the like.

In addition, the firing process is performed by firing the fine pattern formed as described above in an electric furnace or the like for 10 to 60 minutes at 500 to 600 ° C. During this firing process, a holding process is performed for 10 to 60 minutes at a temperature of about 300 ° C. to 400 ° C. to completely remove the alkali-soluble negative photoresist composition for fine conductive powder dispersion, which is not completely removed. If the organic material in the photoresist composition is left carbonized, the Ag powder may not be completely sintered, and may have a high electrical resistance after sintering, or may serve as an insulator, and may have fine cracks in the pattern even after a fine pattern is formed after sintering. Because you can make.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples. On the other hand, in the following examples unless otherwise indicated, the numerical values represent weight percent.

EXAMPLE

Examples 1-4

(Production of Photoresist Acrylate Copolymer in Alkali Soluble Negative Photoresist Composition Component for Fine Conductive Powder Dispersion)

To polymerize the composition and content as shown in Table 1 to prepare an acrylate copolymer of Formula 1. In this case, 50 wt% of gamma butyrolactone (GBL) was used in Examples 1 to 3, and 50 wt% of dipropylene glycol monoethyl ether (DPGME) was used in Examples 1 to 3, respectively. .

Example 1 Example 2 Example 3 Example 4 Benzyl methacrylate (mol%) 35 30 41 41 Methacrylic acid (mol%) 50 45 45 45 2-hydroxyethyl methacrylate (mol%) 8 - 7 7 Ethylhexyl methacrylate (mol%) 7 7 7 7 Methyl methacrylate (mol%) - 18 - - Molecular Weight 30000 28000 28000 35000 Viscosity (cP) 15000 12000 12000 More than 20000

Examples 5-9

(Preparation of alkali-soluble negative photoresist composition for fine conductive powder dispersion)

To the acrylate copolymers of Examples 5 to 9 in the composition and content as shown in Table 2 below, the photopolymerization initiator, the antifoaming agent and the leveling additive were added to dissolve and stirred at room temperature for 2 hours, followed by the addition of a photopolymerizable monomer. Stirring at room temperature for a time to obtain an alkali-soluble negative photoresist composition for fine conductive powder dispersion. Impurities were removed by filtration using the obtained photoresist composition using 400 mesh.

Example 5 Example 6 Example 7 Example 8 Example 9 Acrylate copolymer Example 1 - - 60.1 51.1 - Example 2 - - - - 60.1 Example 3 - 68.0 - - - Example 4 71.7 - - - - Photopolymerization initiator 1.6 2.0 2.8 2.8 2.8 Photopolymerization monomer 14.3 28.1 30.8 40.9 30.8 Antifoam 3.7 0.1 4.0 3.1 4.0 Leveling agent 2 0.1 2.0 2.0 2.0 stabilizator 0.01 - 0.2 0.1 0.2 Etc 6.69 0.8 0.1 - 0.1

Example 10

(Preparation of Ag Paste Composition)

65 wt% Ag powder, 3 wt% inorganic binder, 0.05 wt% stabilizer, and 31.95 wt% alkali-soluble negative photoresist composition for dispersing fine conductive powder were mixed and premixed with a planetary mixer. Ag paste composition was prepared by pre-mixing and then evenly dispersed using a 3-roll mill.

Examples 11-14

(Characteristics of Ag Paste Composition According to Ag Powder Content)

Example 11 Example 12 Example 13 Example 14 Ag powder 63 67 71 73 Inorganic binder 2.95 2.95 2.95 2.95 stabilizator 0.05 0.05 0.05 0.05 Photoresist composition 34 30 26 24 Developability Good Good Good Good Pattern Formation (μm) 50 50 50 50 Thickness after development (㎛) 8 9 11 11 Thickness after sintering (㎛) 4 5 6 7 Viscosity (cP) 10000 13000 14000 20000

The average particle diameter of the Ag powder used was 1.2 μm, the inorganic binder was lead borosilicate lead frit, and the phosphorus acid was used as the stabilizer. The photoresist composition was 68% acryl-based copolymer, 28.2% photopolymerization monomer, 2% photopolymerization initiator and other additives 1.9. Contains%

An Ag paste composition was prepared in the same manner as in Example 10 except that the Ag powder content was changed to the content described in Examples 11 to 14 of Table 3. As a result of the characteristic test of the Ag paste composition according to the content of the Ag powder, the developability was excellent, it had a viscosity characteristic having pseudoplastic properties, and the printability and the pattern thickness after sintering were good.

Examples 15-18

(Characteristics of Ag Paste Composition According to Stabilizer Content)

Example 15 Example 16 Example 17 Example 18 Ag powder 67 67 67 67 Inorganic binder 2.95 2.95 2.95 2.95 stabilizator 0 - - - - 0.05 - - - - 0.3 - - - - One Photoresist composition 30 30 30 30 Developability Good Good Good usually Pattern Formation (μm) 50 50 50 - Gelation and Storage Stability Gelled Not gelled Not gelled Not gelled

The average particle diameter of the Ag powder used was 1.2 μm, the inorganic binder was lead borosilicate lead frit, and the phosphorus acid was used as the stabilizer. The photoresist composition was 68% acryl-based copolymer, 28.2% photopolymerization monomer, 2% photopolymerization initiator and other additives 1.9. Contains%

The test results according to the amount of stabilizer showed that if the amount of the stabilizer was very small or not included, it would affect the stability of the composition, whereas if too large amount was included, there was a problem in pattern formation.

Examples 19-22

(Characteristics of Ag Paste Composition According to Stabilizer Type)

Example 19 Example 20 Example 21 Example 22 Ag powder 67 67 67 67 Inorganic binder 2.95 2.95 2.95 2.95 stabilizator Phosphorous acid 0.05 - - - Phosphoric Acid - 0.05 - - Arcobic acid - - 0.05 - Benzotriazoles - - - 0.05 Photoresist composition 30 30 30 30 Developability Good Good Good Good Pattern Formation (μm) 50 50 50 50 Gelation and Storage Stability Not gelled Not gelled Not gelled Not gelled

The average particle diameter of the Ag powder used was 1.2 µm, the inorganic binder was lead borosilicate frit, the stabilizer was used the antioxidants listed above, the photoresist composition was 68% acrylic copolymer, 28.1% photopolymerization monomer, 2% photopolymerization initiator and 1.9% of other additives.

The composition test results according to the type of stabilizer showed good results regardless of the type of stabilizer.

Examples 23-26

(Characteristics of Ag Paste Composition According to Exposure Amount)

Example 23 Example 24 Example 25 Example 26 Ag powder 67 67 67 67 Inorganic binder 2.95 2.95 2.95 2.95 stabilizator 0.05 0.05 0.05 0.05 Photoresist composition 30 30 30 30 Exposure amount (mJ) 300 O - - - 400 - O - - 800 - - O - 1000 - - - O Developability Good Good Good Good Pattern Formation (μm) 50 50 50 50

The average particle diameter of the Ag powder used was 1.2 µm, the inorganic binder was lead borosilicate lead frit, and the phosphorus acid was used as the stabilizer. The photoresist composition was 68% acrylic copolymer, 28.1% photopolymerization monomer, 2% photopolymerization initiator and 1.9% other additives. It includes.

In the test results according to the exposure dose change, the Ag paste composition according to the present invention showed good results in developability, pattern formation, and the like despite the difference in the exposure dose.

Example 27

(Preparation of Fine Electrode)

The Ag paste composition prepared in the previous examples was printed on the surface of the glass substrate using a screen printer using a screen mask of SUS 325 mesh, and the coated specimen was dried at a temperature of 90 ° C. in a convection oven for 20 minutes. Next, exposure was performed so that a pattern was formed at a wavelength of 365 nm using an exposure machine using a mercury lamp on the formed Ag paste coating film, and developed at a temperature of 30 ° C. with a NaCO ₃ developer. The developed fine pattern was sintered at room temperature using an electric furnace and maintained for 30 minutes from the moment it reached 350 ° C. to burn the organic material, and then heated to 550 ° C. for 30 minutes to prepare a fine electrode.

According to the present invention, it can be applied to a firing process of 600 ° C. or less, which is suitable for PDP production, and because of its high viscosity, it is suitable for the production of fine precision electrodes that could not be formed by conventional screen printing technology and printability. It is excellent, it is possible to provide a composition for forming a simple electrode, the process is simple, economical, and environmentally friendly by not using a separate surfactant and organic solvents.

Claims (11)

a) 60 to 80 wt% Ag powder; b) lead borosilicate frit, bismuth borosilicate frit, B ₂ O ₃ · SiO ₂ · MO and B ₂ O ₃ · SiO ₂ · M′O (where M is a divalent metal ion And M'1 is a metal ion) 1 to 10% by weight of the inorganic binder; c) 0.001 to 1 weight percent stabilizer; And d) 15 to 35% by weight of alkali-soluble negative photoresist composition for fine conductive powder dispersion High viscosity Ag paste composition for forming a fine electrode comprising a. The Ag paste composition according to claim 1, wherein the Ag powder has an average particle diameter of 0.5 to 3 µm. delete The Ag paste composition of claim 1, wherein the inorganic binder has a glass transition temperature of 360 to 500 ° C and a glass softening temperature of 400 to 550 ° C. The Ag paste composition of claim 1, wherein the stabilizer is selected from the group consisting of benzotriazole, ascorbic acid and phosphoric acid, phosphorous acid, phosphorous acid or salts thereof. The alkali-soluble negative photoresist composition of claim 1, wherein a) 30 to 70% by weight of an acrylate copolymer for photoresist represented by the following general formula (1) or (2); b) 10 to 40% by weight of the photopolymerizable monomer; c) 0.5 to 10% by weight photopolymerization initiator; d) 0.1 to 10 weight percent antifoam; And e) 0.1 to 10% by weight leveling agent; Ag paste composition comprising: [Formula 1]

Wherein R ₁ is hydrogen, a phenyl group, a benzyl group, a phenyl group substituted with a nitro group, a phenyl group substituted with halogen, a benzyl group substituted with a nitro group, an alkyl group substituted with a C1 to C10 hydroxy group, or a C1 to C10 hydroxy group; R ₂ is an ethylhexyl group, isobutyl group, tert-butyl group, octyl group, 3-methoxybutyl group, or methoxypropylene glycol group; R ₃ is hydrogen or a methyl group; R ₄ is hydrogen or a methyl group; n ₁ is an integer from 8 to 40; n ₂ is an integer of 1 to 2. [Formula 2]

In which R ₅ is hydrogen or a carboxyl group; R ₆ is a phenyl group, a carboxyl group or an -OCOCH ₃ group; R ₇ is hydrogen or a —CH ₂ COOH group; R ₂ , R ₄ , n ₁ , and n ₂ are as defined above. The method of claim 6, wherein the photopolymerization initiator is 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl -s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone , 2,2-dichloro-4-phenoxyacetophenone, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylproriophenone, pt-butyltrichloro Loacetophenone, pt-butyldichloroacetophenone, 4,4'-ethylaminobenzophenone, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isobutyl thioxanthone, 2-dode Silthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethyl thioxanthone-2,2'-bis-2-chlorophenyl-4,5,4 ', 5'-tetraphenyl-2 Ag face, characterized in that at least one selected from the group consisting of '-1,2'-biimidazole compound Composition. The method of claim 6, wherein the photopolymerizable monomer is 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate , Polyethylene glycol diacrylate, dipentaerythritol chisa acrylate, dipentaerythritol hydroxypentaacrylate, glycerodiacrylate, trimethol propane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol dimethacrylate Ag paste composition, characterized in that at least one selected from the group consisting of latex, sorbitol trimethacrylate, bisphenol A diacrylate derivative, trimethyllopropane triacrylate, and dipentaerythritol polyacrylate. The method of claim 6, wherein the antifoaming agent and the leveling additive is an anionic copolymer, aralkyl modified polymethylalkylsiloxane, polyester modified polymethylalkylsiloxane, polysiloxane, non-silicone polymer compound, modified urea solution, polyester Ag paste composition, characterized in that at least one selected from the group consisting of modified dimethylpolysiloxane, and polyester-modified dimethylpolysiloxane copolymer. The Ag paste composition of claim 1, wherein the Ag paste composition has a viscosity of 3000 to 60000 cP. A fine electrode prepared using the Ag paste composition according to any one of claims 1, 2 and 4 to 10.

Images