JP2000082394A - Manufacture of plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a plasma display panel which enables a high aspect ratio and a pattern processing of high precision. SOLUTION: A photo-sensitive paste containing inorganic particulates and photo-sensitive organic component is applied onto a base board so that a coating film is formed, which is exposed to light and developed, and a bulkhead pattern is accomplished, and this method of manufacturing a plasma display is characterized by that the allowable width of photo-exposure in the exposing process is over 10%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method used for processing a partition pattern of a plasma display panel, a plasma addressed liquid crystal display panel and the like.

[0002]

2. Description of the Related Art In recent years, miniaturization and high definition of circuit materials and displays have been advanced, and accordingly, improvement of pattern processing technology has been desired. In particular, a technique capable of patterning an inorganic material such as glass with high precision and a high aspect ratio is desired for forming a partition wall of a plasma display panel.

Conventionally, screen printing using a paste composed of an inorganic powder and an organic binder has been often used for patterning a partition wall of an inorganic material. However,
Screen printing has a drawback that it is difficult to form a highly accurate partition pattern.

As a method for solving this problem, Japanese Patent Laid-Open No.
JP-A-296534, JP-A-2-165538 and JP-A-5-342929 propose a method of forming a partition pattern by a photolithography technique using a photosensitive paste.

[0005] Usually, the exposure used in the photolithography technique is performed using g-line (436 nm), h-line (405 nm) and i-line (365 nm) of an ultra-high pressure mercury lamp. At this time, a good partition pattern can be formed when the photosensitive paste is exposed at the optimum exposure amount. However, when large-area exposure is performed quickly and in large quantities, there is a problem that meandering due to insufficient curing is observed, a pattern is thickened, and a residual film is observed. In addition, the partition wall pattern for a plasma display formed by the photolithography technique is subjected to heat treatment together with a glass substrate carrying the same to thermally decompose and remove the organic components in the paste and to melt the glass particles in the inorganic particles to form a partition layer. To form This heat treatment is referred to as a baking process, but is performed at a temperature lower than that in consideration of the glass transition point of the glass substrate to be used. Under such conditions, it is preferable to use glass fine particles as a component of the inorganic fine particles in the paste.

Therefore, it has not been possible to form a partition pattern of a plasma display or a plasma addressed liquid crystal display having a high aspect ratio and a high definition with stability and high reproducibility.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of manufacturing a plasma display panel which can improve the disadvantages of the prior art and can process a partition pattern having a high aspect ratio and a high definition. It is.

[0008]

An object of the present invention is to form a coating film by applying a photosensitive paste containing inorganic fine particles and a photosensitive organic component on a substrate, and to expose and develop the coating film. This is achieved by a method of manufacturing a plasma display in which a partition pattern is formed through the following steps, wherein the allowable exposure amount in the exposure step is 10% or more.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive paste of the present invention contains inorganic fine particles and a photosensitive organic component, and forms a partition pattern by using a photolithography technique.

In the exposure operation for forming a pattern using the photosensitive paste of the present invention, various exposure apparatuses such as a proximity exposure machine can be used. However, when large-area exposure is performed quickly and in large quantities, slight illuminance unevenness of the exposure machine occurs.

The inventors of the present invention have found that meandering, pattern thickening and residual film due to insufficient curing are caused by a narrow allowable exposure amount.
This is because a slight difference in exposure due to uneven illuminance causes the exposure to become insufficient or excessive, and it has been found that it can be prevented by setting the allowable exposure to 10% or more. The allowable exposure amount is preferably 20% or more to ensure the pattern formation of the partition walls. If the exposure allowable width is narrow, the pattern may meander or fall due to the shortage of the exposure due to the uneven illuminance. On the other hand, when the exposure amount is excessive, the pattern shape becomes thick and the pattern is buried.

In the present invention, the allowable exposure amount means a value measured by the following method. That is, the photosensitive paste is applied to a desired thickness, and after drying, development is performed by changing the exposure amount at regular intervals.As a result, the partition wall cross section becomes rectangular or trapezoidal, and meandering and residual film are observed. When the range of the non-exposure amount is set as the exposure range and the center value of the exposure range is set as the optimum exposure amount, the allowable range of the exposure amount = (upper limit of the exposure range−lower limit of the exposure range) / optimal exposure Amount.

By designing the paste so that light necessary for photo-curing of the photosensitive paste is transmitted straight to the lowermost portion of the coating film, it is possible to form a residual film due to scattered light in the paste when the exposure amount is increased. It is possible to prevent pattern shape defects such as thickening of the pattern, and to increase the allowable exposure amount width. Therefore, using inorganic fine particles (fine particles including glass fine particles and glass fine particles / filler composite fine particles) having an appropriate particle size distribution to improve the particle filling property,
By matching the refractive indices of the glass fine particles and the photosensitive organic component, the total light transmittance and the straight transmissivity were increased. In addition, by adding an appropriate amount of an ultraviolet absorber, light near the h-line and i-line of the exposure wavelength is absorbed, and the amount of light absorbed by the photosensitive compound is reduced.
The g-line transmittance was increased. Furthermore, by adding an antioxidant, radicals generated at a small exposure dose due to scattered light were captured, polymerization was suppressed, and a contrast between dissolution and insolubility with a developer was given to increase the allowable exposure dose range. By using such a photosensitive paste and increasing the light transmittance to effectively utilize the active light, the allowable exposure amount in the exposure step can be made 10% or more.

The permissible exposure amount also changes depending on the thickness of the photosensitive paste coating film. Coating thickness is 50-200μm
Is preferred. If the coating film thickness exceeds 200 μm, a larger amount of exposure is required for photo-curing to the lowermost portion. However, the effect of scattered light inside the paste increases with this, and filling between patterns occurs. On the other hand, if the coating film thickness is less than 50 μm, a discharge space of the plasma display cannot be secured.

The allowable exposure amount also varies depending on the pitch, line width, and height of the partition pattern. If the pitch is too narrow, the partition walls are buried under the influence of scattered light inside the paste, and if the line width is too narrow, the partition walls meander or fall during the developing operation, and the allowable exposure amount narrows. Pitch is 100 ~
160 μm, line width 20-90 μm, height 120-2
The range of 00 μm is preferable because a partition wall having high definition and a high aspect ratio can be formed with a wide allowable exposure amount width.

Hereinafter, a preferred composition of the photosensitive paste of the present invention will be described.

The photosensitive paste of the present invention contains inorganic fine particles and a photosensitive organic component as essential components. The content of the inorganic fine particles in the photosensitive paste is preferably from 60/40 to 90/10% by weight, since the shrinkage during firing is small and the shape change due to firing can be reduced. Preferably, the inorganic fine particles are glass fine particles or are composed of 40 to 90% by weight of glass fine particles and 10 to 60% by weight of filler. When the inorganic fine particles contain a large amount of glass fine particles, the light transmittance at the time of exposure can be increased. Further, when a filler is contained, the volume shrinkage can be reduced, which is more preferable in view of the shape of the partition wall. By controlling the amount of the filler to be 10% by weight or more of the inorganic fine particles, it is possible to control volume shrinkage and to improve the shape retention. Further, when the content is 60% by weight or less, the adhesion strength to the substrate can be maintained.

In order to efficiently cause a chemical change to the light irradiation of the photosensitive paste containing a large amount of inorganic fine particles and to widen the allowable exposure amount, sufficient light energy is applied to a portion to be photoreacted. And the organic components must be fully photocured. For this purpose, the light transmittance of the photosensitive paste is high and it is necessary to allow light to reach the lower part.

The light transmittance can be evaluated by the total light transmittance and the straight light transmittance. Increasing these is an effective method for performing pattern processing with a high aspect ratio. In particular, a value T3 = (T1-T2) / T obtained by dividing the difference between the total light transmittance (T1) and the diffuse transmittance (T2) by the total light transmittance.
In the case where 1 is the straight transmittance, the higher the straight transmittance, the better the patterning of an excellent shape with a high aspect ratio.
That is, it is important to increase the ratio of light that transmits as linearly as possible inside the photosensitive paste.

In order to increase the total light transmittance, it is effective to use an organic component and glass fine particles having a high total light transmittance. Also, in order to increase the straight transmissivity,
It is effective that the glass particles are more uniformly dispersed in the photosensitive paste. Especially for glass particles,
In addition to high total light transmittance, it is important that the composition inside the fine particles is uniform and there is no composition unevenness such as bubbles.

Further, in order to increase the light transmittance of a dispersion of different components, it is desirable that the refractive indices of the respective components are made to match or approximate. For this reason, in the photosensitive paste of the present invention, the refractive indices of the glass fine particles and the organic component were made as close as possible. The refractive index of the glass particles can be controlled by the composition thereof, and the refractive index of the organic component can also be controlled by the composition of the photosensitive compound used. Therefore, it is possible to match the refractive indices of the two, and from such a viewpoint, the composition of the glass fine particles and the composition of the organic component including the photosensitive compound can be selected.

The glass fine particles of the present invention have a refractive index of 1.50.
It is preferably from 1.65 to 1.65 since the light transmittance of the photosensitive paste becomes close to the refractive index of the organic component and the light reaches the lower part of the coating film and is cured.

The measurement of the refractive index of the glass fine particles in the present invention can be performed by the Becke method. It is important to measure the wavelength of the light to be measured at the wavelength of the light to be exposed after applying the photosensitive paste in order to confirm the effect. In particular,
It is preferable to measure at a wavelength in the range of 350 to 650 nm. Further, i-line (365 nm) or g-line (4
(36 nm) is preferred.

As a method for producing glass fine particles, for example,
Raw materials such as lithium oxide, silicon oxide, aluminum oxide, boron oxide, barium oxide, and zinc oxide are mixed so as to have a predetermined composition, melted at 900 to 1200 ° C., rapidly cooled, made into glass frit, and then pulverized. Then 1
に す る 5 μm fine powder. The raw material is high purity carbonate,
Oxides, hydroxides and the like can be used. In addition, depending on the type and composition of the glass powder, ultra-high purity alkoxide or organometallic raw material of 99.99% or more is used. It is preferable because a high-strength insulating layer having few pores can be obtained.

In the present invention, a preferable composition of the glass fine particles includes the following composition. Lithium oxide: 3 to 10% by weight Silicon oxide: 10 to 30% by weight Boron oxide: 20 to 40% by weight Barium oxide: 2 to 15% by weight Aluminum oxide: 10 to 25% by weight

When the glass fine particles contain 3 to 10% by weight of lithium oxide, the softening point and the coefficient of thermal expansion can be easily controlled, and the refractive index of the glass fine particles can be lowered. It becomes easy to reduce the refractive index difference. Also, from the viewpoint of improving the stability of the photosensitive paste, the content is preferably 10% by weight or less, more preferably 8% by weight or less.

In the above composition, it is possible to use an alkali metal oxide such as sodium oxide or potassium oxide instead of lithium oxide, but lithium oxide is preferred in view of the stability of the photosensitive paste. Further, since potassium oxide has an advantage that the refractive index can be controlled even by adding a relatively small amount, it is preferable to use lithium oxide and potassium oxide at the same time. In that case, it is preferable that the total of both is contained in the glass powder in an amount of 3 to 10% by weight.

When the glass fine particles contain 10 to 30% by weight of silicon oxide, the density, strength and stability of the partition walls and the coefficient of thermal expansion are set to desired values, the softening point is lowered, and This is preferred in that it facilitates baking.

It is preferable that the glass fine particles contain 20 to 40% by weight of boron oxide in view of the strength of the partition walls and the stability of the glass. Boron oxide can reduce glass fine particles from 800 to
Since it is melted at a temperature of around 1200 ° C., even when the amount of silicon oxide is large, the material has electrical insulation, strength, thermal expansion coefficient,
The baking temperature is preferably adjusted to control the baking temperature in the range of 540 to 610 ° C. so as not to impair the electrical, mechanical and thermal properties such as the denseness of the partition walls.

It is preferable that the glass fine particles contain 2 to 15% by weight of barium oxide in terms of control of the baking temperature and electric insulation of the photosensitive paste, and stability and denseness of the partition walls.

The glass fine particles are made of aluminum oxide.
The content of 25% by weight is preferable in terms of the strength of the partition layer, the heat resistance temperature of glass, and the point that a dense partition can be easily obtained. The aluminum oxide is used to increase the strain point of the glass particles.

In the present invention, the glass fine particles preferably further contain zinc oxide, calcium oxide and magnesium oxide in addition to the above-mentioned metal oxide.

It is preferable that the glass fine particles contain zinc oxide in an amount of 1.5 to 10% by weight, since the denseness of the partition walls can be improved, the baking temperature on the substrate, and the insulation resistance can be appropriately maintained.

Calcium oxide facilitates the melting of the glass and controls the coefficient of thermal expansion, and is preferably contained in an amount of 2 to 10% by weight. If it is less than 2% by weight, the strain point tends to be low.

Magnesium oxide facilitates melting of the glass and controls the coefficient of thermal expansion, and is preferably contained at 1 to 10% by weight. If it exceeds 10% by weight, the glass tends to be devitrified.

In addition, the glass fine particles may contain titanium oxide, zirconium oxide and the like, but the amount is preferably less than 2% by weight. In particular, zirconium oxide is effective in controlling the softening point, glass transition point, and electrical insulation of glass.

For example, the metal oxide component is mixed with 20% by weight of silicon oxide, 4% by weight of barium oxide, 24% by weight of aluminum oxide, 31% by weight of boron oxide, 9% by weight of lithium oxide, 6% by weight of magnesium oxide, and calcium oxide. 4% by weight and 2% by weight of zirconium oxide. The glass particles have a transition point of 490 ° C. and a softening point of 52.
At 8 ° C., the refractive index at the g-line wavelength (436 nm) is 1.59, which satisfies the preferable conditions as the inorganic fine particles of the present invention.

The particle diameter of the glass fine particles is selected in consideration of the line width and height of the partition wall to be produced. The particle diameter is 50% by volume (average particle diameter D50) is 1 to 5 μm and the specific surface area is 1 to 5 μm. It is preferably 4 m ² / g. More preferably, 10% by volume particle diameter (D10) 0.4 to 2 μm, 50
Volume% particle size (D50) 1.5 to 5 μm, 90 volume% particle size (D90) 4 to 15 μm, maximum particle size 40
It is preferable to have a thickness of not more than μm.

Here, D10, D50 and D90 are respectively accumulated from the glass powder having a small particle diameter, and the particle diameter which becomes 10% by volume of the total amount is D10, similarly, 50% by volume.
The particle size at which 90% by volume is obtained is defined as D50 and D90.

By using glass fine particles having the above particle size distribution, the filling property of the fine particles is improved, and even if the ratio of the inorganic fine particles in the photosensitive paste is increased, the entrapment of air bubbles is reduced, and extra Since the light scattering is small, a preferable partition pattern can be formed with a wide allowable exposure amount width.

As the filler, it is preferable to use ceramics or high-melting glass particles which do not melt at the softening point of the glass particles. As the ceramic fine particles, at least one selected from the group consisting of alumina, zirconia, cordierite, mullite, spinel, titania, and silica can be used. As high melting point glass,
Glass transition point 500-1200 ° C, softening point 550-12
Those having a temperature of 00 ° C are preferred. Such a high-melting glass is made of silicon oxide and aluminum oxide,
Those having a composition containing not less than 50% by weight are preferable, and it is effective to obtain thermal characteristics that require the total content of these components to be not less than 50% by weight. It is preferable to use high melting glass particles containing the following oxide equivalent composition,
It is not limited to this. Silicon oxide 15 to 50% by weight Boron oxide 5 to 20% by weight Barium oxide 2 to 10% by weight Aluminum oxide 15 to 50% by weight It is also possible to use these high-melting glass fine particles and the above-mentioned ceramics simultaneously.

Since the filler having a softening point or a melting point higher than the heating temperature in the firing step remains in the partition walls or on the partition surface as it is, the average particle diameter and the maximum particle diameter are preferably smaller. That is, the average particle diameter of these fillers is preferably 1 to 4 μm, and the maximum particle diameter is preferably 25 μm or less. By using one having such a particle size distribution, it becomes possible to satisfy a filling property and a dispersing property and to constitute a photosensitive paste having excellent applicability and pattern forming property.

The ultraviolet absorber used in the present invention is 350
It absorbs a wavelength of about 400 nm and emits the absorbed light energy as harmless radiation (heat energy). By adding this ultraviolet absorber to the paste, the exposure wavelengths near the h-line and i-line are exposed. To reduce the amount of light near the h-line and i-line absorbed by the photosensitive compound (photopolymerization initiator or sensitizer), and to increase the g-line transmittance of the ultra-high pressure mercury lamp. Thereby, the allowable exposure amount width can be widened.

The ultraviolet absorber is particularly effective as long as it has excellent absorbance at wavelengths near the h-line and the i-line. Specific examples include benzophenone-based compounds, cyanoacrylate-based compounds, salicylic acid-based compounds, and benzotriazole-based compounds. Compounds, indole compounds, inorganic fine metal oxide particles, and the like. Of these, benzophenone-based compounds, cyanoacrylate-based compounds, benzotriazole-based compounds, and indole-based compounds are particularly effective. Specific examples of these include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy- 4-methoxy-2'-carboxybenzophenone, 2
-Hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxy Benzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl)
Benzotriazole, 2- (2′-hydroxy-3 ′,
5′-di-t-butylphenyl) benzotriazole,
2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-
(Hydroxy-4′-n-octoxyphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3
-Diphenyl acrylate, 2-ethyl-2-cyano-
3,3-diphenyl acrylate, BONASORB
UA-3901 (manufactured by Orient Chemical Co., Ltd.), BONASO
RB UA-3902 (manufactured by Orient Chemical Co., Ltd.), SOM
-2-0008 (manufactured by Orient Chemical Co., Ltd.) and the like, but are not limited thereto. Further, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

It should be noted that the ultraviolet absorber changes the transmission limit wavelength and the wavelength gradient width of the photosensitive paste film depending on the added amount.

The amount of the ultraviolet absorber added is 0.001 to 10% by weight in the paste, more preferably 0.005 to 10% by weight.
５5%. Beyond these ranges, the transmission limit wavelength and the wavelength gradient range change, the absorption capacity of h-line and i-line becomes insufficient, the transmittance of g-line decreases, and the sensitivity of the photosensitive paste decreases. It costs.

The organic components used in the present invention include:
It means an organic component (a portion obtained by removing an inorganic component from the paste) in the photosensitive paste, and occupies 10 to 40 parts by weight in the paste.

The organic component is a photosensitive component and a binder selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, the ultraviolet absorber and the antioxidant, an organic dye, a photopolymerization initiator, It is constituted by adding an additive component such as a sensitizer, a sensitization aid, a plasticizer, a thickener, an organic solvent, a dispersant, and an organic or inorganic suspending agent as required.

As the photosensitive monomer, a compound having an active carbon-carbon double bond is often used. As the functional group, monofunctional and polyfunctional compounds having a vinyl group, an allyl group, an acrylate group, a methacrylate group, and an acrylamide group can be applied. The present invention is characterized in that a polyfunctional acrylate compound and / or a methacrylate compound are contained in an organic component in an amount of 10 to 80% by weight. Since various kinds of compounds have been developed for the polyfunctional compound having an acrylate or methacrylate functional group, it is possible to select the compound in consideration of reactivity, refractive index, and the like.

As a method for controlling the refractive index of the organic component contained in the photosensitive paste, a method for controlling the refractive index of the photosensitive monomer is simple. In particular, the refractive index is 1.55-1.
By using the photosensitive monomer of No. 8, the refractive index of the organic component can be increased.

As the photosensitive monomer to be used, it is effective to use an acrylate monomer or a methacrylate monomer containing an aromatic ring such as a benzene ring or a naphthalene ring or a sulfur atom to increase the refractive index. In particular, in order to increase the crosslink density at the time of curing by photoreaction and to improve the pattern formability, it is effective to use a polyfunctional acrylate monomer or methacrylate monomer to increase the refractive index.

Specifically, pentaerythritol triacrylate or tetraacrylate, bisphenol A di (meth) acrylate, bisphenol A-ethylene oxide adduct di (meth) acrylate, bisphenol A-propylene oxide adduct di (meth) acrylate ) Acrylates, thiophenol (meth) acrylates, benzylmercaptan (meth) acrylates or compounds in which 1 to 5 hydrogen atoms in their aromatic rings have been replaced by chlorine or bromine atoms can be used.

As the monomer containing a sulfur atom in the molecule, a monomer having a thiol (meth) acrylate group or a monomer having a phenyl sulfide structure can be used. Various monomers can be used in combination with these monomers for improving the refractive index.

As an organic component constituting the photosensitive paste, an oligomer or a polymer is used as a component that plays a role in improving the physical properties of a cured product formed by a photoreaction and adjusting the viscosity of the paste. The oligomer or polymer is obtained by polymerization or copolymerization of a component selected from compounds having a carbon-carbon double bond.

As a monomer to be copolymerized, copolymerizability of an unsaturated acid such as an unsaturated carboxylic acid can improve the developability in an aqueous alkali solution after exposure.
Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

The acid value (A) of the polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained is obtained.
V) is preferably in the range of 50 to 180, more preferably 70 to 140. When the acid value exceeds 180, the allowable development width becomes narrow. Further, when the acid value is 50 or less, the solubility of the unexposed portion in the developing solution is reduced, so that the developing solution concentration is increased, peeling occurs up to the exposed portion, and it is difficult to obtain a high-definition pattern. Become.

By adding a photoreactive group to a side chain or a molecular terminal to the above-described polymer or oligomer, it can be used as a photosensitive polymer or photosensitive oligomer having photosensitivity.

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

A method for adding such a side chain to an oligomer or a polymer is based on a method in which an ethylenically unsaturated compound having a glycidyl group or an isocyanate group or an acrylic acid is added to 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 ether crotonic acid, glycidyl ether isocrotonic acid, and the like. .

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 0.05 to 0.05 to the mercapto group, amino group, hydroxyl group and carboxyl group in the polymer. It is preferable to add 1 molar equivalent.

The present invention is characterized in that an organic component contains 10 to 90% by weight of an oligomer or polymer having a weight average molecular weight of 500 to 100,000 containing a carboxyl group and an unsaturated double bond in the molecule. .

When a binder component is required, polyvinyl alcohol, polyvinyl butyral, methacrylate polymer, acrylate polymer, acrylate-methacrylate copolymer, butyl methacrylate resin, etc. may be used as the polymer. Can be. It is also effective to increase the refractive index of the binder component to increase the refractive index of the photosensitive organic component.

The organic component of the photosensitive paste of the present invention contains a photosensitive monomer, a photosensitive oligomer, a photosensitive polymer, or a binder, but none of these components has the ability to absorb active light energy. It is necessary to add a photopolymerization initiator and a sensitizer in order to start the reaction.

The pattern formation by the photosensitive paste is to polymerize and crosslink the photosensitive components (monomers, oligomers, and polymers) in the exposed portions to make them insoluble in a solvent. Is a radical polymerizable, and its photopolymerization initiator is selected from those generating radical species. In particular, those which generate radical species by light of 400 nm or more are preferable.
A photopolymerization initiator that generates a radical species by the following light also forms a charge transfer complex in combination with a sensitizer,
Attention must be paid to the fact that light of nm or more may be absorbed to generate radical species.

Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, and 4,4-dichlorobenzophenone. , 4-benzoyl-4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone , Pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethylketal, benzylmethoxyethylacetal, benzo Emissions, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-
t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibensuberone, methyleneanthrone, 4
-Azidobenzalacetophenone, 2,6-bis (p-
(Azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o-
Methoxycarbonyl) oxime, 1-phenylpropanedione-2- (o-ethoxycarbonyl) oxime,
1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, N-phenyl Thioacridone, 4,
Photoreducing dyes such as 4-azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoyl peroxide and eosin, methylene blue, and ascorbic acid And a combination of reducing agents such as triethanolamine.

In the present invention, one or more of these can be used. The photopolymerization initiator is added in a range of 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the photosensitive component. If the amount of the polymerization 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 reduced.

By using a sensitizer together with the photopolymerization initiator, the sensitivity can be improved and the wavelength range effective for the reaction can be extended.

Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone,
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) iso Naphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5 -Benzoi Thiotetrazole, such as 1-phenyl-5-ethoxycarbonyl-thiotetrazole 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 photosensitive paste of the present invention, the amount is usually 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the photosensitive component. 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 reduced.

In the present invention, an organic dye can be added as a mark for exposure and development. The organic dye is not particularly limited, but preferably does not remain in the insulating film after firing. The added amount of the organic dye is preferably 0.001 to 1% by weight.

An organic solvent is used to adjust the viscosity when applying the photosensitive paste to the substrate according to the application method. 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-butyl lactone, and propylene carbonate. For example, propylene glycol monomethyl ether acetate, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and an organic solvent mixture containing at least one of these are used.

Next, the pattern processing method using the photosensitive paste of the present invention will be described with reference to specific examples.

On a glass substrate or a ceramic substrate, the photosensitive paste is applied entirely or partially. As a coating method, a method such as a screen printing method, a bar coater, a roll coater, a die coater, or a blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, the screen mesh, and the viscosity of the paste.

Here, when applying the paste on the substrate,
It is preferable to perform a surface treatment on the substrate in order to increase the adhesion between the substrate and the coating film. Examples of the surface treatment liquid include silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tris (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacrylic acid). Roxypropyl) trimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like, or an organic metal such as , Organic titanium, organic aluminum, organic zirconium and the like.

A silane coupling agent or an organic metal is converted into an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol,
A solution diluted with butyl alcohol or the like to a concentration of 0.1 to 5% by weight is used. Next, the surface treatment liquid is uniformly applied on a substrate by a spinner or the like,
Surface treatment can be performed by drying for 60 minutes.

After the application of the photosensitive paste, exposure is performed using an exposure device. The exposure is generally performed through a photomask, as in the case of ordinary photolithography. Alternatively, a method of directly drawing with a laser beam or the like without using a photomask may be used.

As an exposure device, a stepper exposure device, a proximity exposure device, or the like can be used. Also,
In the case of performing exposure over a large area, a photosensitive paste is applied onto a substrate such as a glass substrate, and then exposed while being transported, so that a large exposure area can be exposed with an exposure machine having a small exposure area.

The active light source used at this time includes, for example, near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. Among these, ultraviolet rays are most preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp,
Halogen lamps, germicidal lamps and the like can be used. Among these, an ultra-high pressure mercury lamp is preferred. Although the exposure conditions vary depending on the coating thickness, it is preferable to perform exposure for 20 seconds to 30 minutes using an ultrahigh pressure mercury lamp having an output of 1 to 100 mW / cm ² .

It is to be noted that a pattern shape can be improved by further providing an oxygen blocking film on the surface of the applied photosensitive paste before exposure. As an example of the oxygen barrier film, a film such as polyvinyl alcohol or cellulose, or a film such as polyester can be given.

The polyvinyl alcohol film is formed by uniformly applying an aqueous solution having a concentration of 1 to 3% by weight on a substrate by a method such as a spinner and then drying at 70 to 90 ° C. for 10 to 60 minutes to evaporate water. It is good to do it.

The reason why the sensitivity is improved by the polyvinyl alcohol film or the like is estimated as follows. That is,
When the photosensitive component undergoes a photoreaction, the presence of oxygen in the air hinders the photocuring reaction, but the presence of a polyvinyl alcohol film or the like can block excess oxygen, which is considered to improve sensitivity during exposure.

When a transparent film such as polyester, polypropylene or polyethylene is used, it is advisable to apply these films after applying the photosensitive paste.

After exposure, development is carried out utilizing the difference in solubility between the cured exposed portion and the uncured unexposed portion in the developing solution. In this case, immersion, spraying or brushing is used. As the developer, an organic solvent in which an organic component in the photosensitive paste can be dissolved is used. Water may be added to the organic solvent as long as its solubility is not lost.

When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an aqueous alkali solution. As the alkaline aqueous solution, an aqueous solution of sodium hydroxide, sodium carbonate, calcium hydroxide, or the like can be used, but it is preferable to use an organic alkaline aqueous solution because the alkaline component can be easily removed during firing.

As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like.

If the concentration of the alkaline aqueous solution is too low, the soluble portion is not removed, and if it is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded.
% By weight, more preferably 0.1 to 1% by weight.
The development temperature is preferably from 20 to 50 ° C. in terms of process control.

In particular, after applying the photosensitive paste of the present invention on a substrate, exposure is carried out through a photomask, and a portion not irradiated with light is eluted by development to form a partition pattern. When the allowable amount width is 5% or more, a partition wall for a plasma display panel with high accuracy and a high aspect ratio can be easily manufactured.

[0090]

The present invention will be described below in more detail with reference to examples. However, the present invention is not limited to this. The concentration (%) in the examples is% by weight, and the abbreviations are as follows. X-4007: a weight average molecular weight of 43,000 obtained by addition-polymerizing 0.4 equivalent of glycidyl methacrylate to a carboxyl group of a copolymer composed of 40% methacrylic acid, 30% methyl methacrylate, and 30% styrene, and an acid value 9
5 photosensitive polymer MGP400: a compound represented by the following chemical formula X ₂ N-CH (CH ₃ ) -CH _2- (OCH ₂ CH (CH ₃ )) _n -NX ₂ X = -CH ₂ CH (OH)- CH ₂ O—CO—C (CH ₃ ) = CH ₂ n = 2 to 10 GX: Compound represented by the following chemical formula

[0091]

Embedded image

IC-369: Irgacure-369
(Manufactured by Ciba-Geigy) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 DETX-S: 2,4-diethylthioxanthone (Example 1) As inorganic fine particles, lithium oxide: 9 %,
Silicon oxide: 22%, aluminum oxide: 23%, boron oxide: 33%, barium oxide: 4%, zinc oxide: 2%,
Magnesium oxide: 7%, average refractive index 1.58
6, glass transition point 476 ° C., glass softening point 519 ° C., specific surface area 2.13 m ² / g, 50% by volume particle size 2.2 μm
m, 10 volume% particle size 0.8 μm, 90 volume% particle size 6.8 μm, and glass fine particles having a maximum particle size of 22.0 μm were prepared.

For 70 parts by weight of the glass fine particles, as an organic component, 15 parts by weight of a photosensitive polymer (X-4007), 15 parts by weight of a photosensitive monomer (MGP400), and a photopolymerization initiator (IC-369): 6.0 parts by weight of an antioxidant (1,6-hexanediol-bis [(3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]): 6.0 parts by weight, an ultraviolet absorber (2-ethylhexyl-2-cyano-3,3-diphenylacrylate): 2.5 parts by weight and an organic dye (Basic Blue 26) ) 0.02 parts by weight of each component was dissolved while heating to 50 ° C. Thereafter, the glass fine particles were added and kneaded with a kneader. The viscosity was adjusted by the amount of γ-butyrolactone, but the amount of solvent in the paste was 10 to
It was adjusted to be 40%.

On a glass substrate, by screen printing,
The obtained photosensitive paste was uniformly applied. Coating and drying were repeated several times or more in order to avoid pinholes or the like on the coating film, and coating was performed so that the dry thickness became 180 μm. Drying was performed at 80 ° C. for 10 minutes. Then, it dried at 80 degreeC for 60 minutes.

A photomask (stripe-shaped pattern,
Exposure is performed through a pattern pitch of 140 μm and a line width of 20 μm). Exposure was performed with an ultra-high pressure mercury lamp having an output of 50 mW / cm ² to perform an ultraviolet exposure of 1.0 J / cm ² . At this time, a gap of 100 μm was provided between the mask and the application surface in order to prevent the mask from being contaminated. Thereafter, a 0.2% by weight aqueous solution of monoethanolamine maintained at 35 ° C. is developed by spraying with a shower for 180 seconds, and then washed with water using a shower spray to remove a space portion that has not been photocured and glass. Striped partition walls were formed on the substrate. The glass substrate on which the processing of the partition pattern was completed was dried at 80 ° C. for 15 minutes. At this time, the allowable exposure amount was 30% (exposure amount: 1.0 ± 0.15 J / cm ² ).

The pattern of the photosensitive paste coating film formed by exposing and developing the entire surface was observed with an electron microscope. As a result, at a light exposure of 1.0 J / cm ² , the height was 180 μm, the half width was 47 μm, and the pitch was 140 μm. A rectangular partition wall was formed on the entire surface.

(Example 2) The same operation as in Example 1 was performed except that the thickness of the coating film was changed to 120 µm. At this time, the allowable exposure amount width was 50% (exposure amount: 0.9 ± 0.23 J / cm ² ). When the exposure amount is 1.0 J / cm ² , the height is 120
A rectangular partition wall having a thickness of 45 μm, a half width of 45 μm, and a pitch of 140 μm was formed on the entire surface.

Example 3 The same procedure as in Example 1 was carried out except that the thickness of the coating film was changed to 150 μm. At this time, the allowable exposure amount was 44% (exposure amount: 0.9 ± 0.20 J / cm ² ). When the exposure amount is 1.0 J / cm ² , the height is 150
A rectangular partition wall having a thickness of μm, a half width of 46 μm, and a pitch of 140 μm was formed on the entire surface.

(Example 4) The specific surface area of the glass fine particles is 1.15 m ² / g, the average particle diameter is 4.8 μm, and 10% by volume.
Example 1 was repeated except that the particle diameter was 1.3 µm, the particle size of 90% by volume was 12.2 µm, and the maximum particle size was 22.0 µm. At this time, the allowable exposure amount width is 18%.
(Exposure amount: 1.1 ± 0.1 J / cm ² ). At an exposure dose of 1.0 J / cm ² , a rectangular partition wall having a height of 180 μm, a half width of 43 μm, and a pitch of 140 μm was formed on the entire surface.

Example 5 The same procedure as in Example 1 was carried out except that the mixing ratio between the glass fine particles and the photosensitive organic component was changed to 80/20. At this time, the allowable exposure amount width is 20% (exposure amount:
0.8 ± 0.08 J / cm ² ). Exposure 0.8
In J / cm ² , height 180 μm, half width 42 μm
m, and a rectangular partition wall was formed on the entire surface at a pitch of 140 μm.

(Example 6) For the inorganic fine particles of Example 1, the following high melting glass powder was used as a filler.
Except for the addition of%, the preparation and evaluation of the partition walls were performed in the same manner as in Example 1. The average refractive index of the inorganic fine particles was 1.58.

<Filler: High-melting glass particles> Composition (analytical value): 38% silicon oxide, 10% boron oxide, 5.5% barium oxide, 34.5% aluminum oxide, 2.2% zinc oxide, magnesium oxide 4.8%, calcium oxide 4.4%, titanium oxide 0.6% Glass transition point: 655 ° C., softening point: 770 ° C., average refractive index: 1.58, average particle diameter: 2.4 μm, maximum particle diameter :
9.5 μm, tap density: 0.65 g / cm ³ , shape: non-spherical.

A rectangular partition wall having a height of 180 μm, a half width of 46 μm, and a pitch of 140 μm was formed on the entire surface. At this time, the allowable exposure amount width is 28% (exposure amount: 200 ± 28 m
J / cm ² ).

The height of the partition walls after baking was 152 μm, the baking shrinkage was 16%, and the top irregularities were 6 μm. Both the pattern formability, the tops of the partition walls, and the baking shrinkage were in good ranges.

(Example 7) Cordierite shown below was used as a filler in the inorganic fine particles of Example 1 as a filler.
Except for the addition of%, the preparation and evaluation of the partition walls were performed in the same manner as in Example 1. The average refractive index of the inorganic fine particles was 1.57.

<Filler: Cordierite> Average refractive index: 1.54, average particle diameter: 2.2 μm, maximum particle diameter: 7.2 μm, tap density: 1.0 g / cm ³ ,
Shape: spherical.

A rectangular partition wall having a height of 180 μm, a half width of 48 μm, and a pitch of 140 μm was formed on the entire surface. At this time, the allowable exposure amount width is 21% (exposure amount: 200 ± 21 m).
J / cm ² ).

The height of the partition walls after firing was 146 μm, the firing shrinkage was 19%, and the top irregularities were 8 μm. Both the pattern formability, the partition top unevenness, and the firing shrinkage were in good ranges.

(Comparative Example 1) The maximum particle size was 46.0.
The procedure was performed in the same manner as in Example 1, except that glass microparticles of μm were used. At this time, the allowable exposure amount width is 4% (exposure amount: 1.07
± 0.02 J / cm ² ). Exposure 1.0 J / c
As for the cross-sectional shape of the pattern at m ² , the pattern meandered at a height of 180 μm and a half width of 29 μm. Exposure 1.05
The cross-sectional shape of the pattern obtained at J / cm ² was 180
The pattern meandered at a width of 30 μm and a width of 30 μm. When the exposure amount was further increased to 1.1 J / cm ² , a residual film was formed. Further, the residual film could not be removed even if the developing time was added for 180 seconds.

(Comparative Example 2) Glass fine particles and photosensitive organic compound
The same as Example 1 except that the mixing ratio of
went. At this time, the allowable exposure amount width is 4% (exposure amount: 0.
56 ± 0.01 J / cm^Two)Met. Exposure 0.5J
/ Cm^TwoThe cross-sectional shape of the pattern is 180 μm in height,
The meandering occurred in the pattern when the half width was 51 μm. Exposure 0.
55J / cm ^TwoThe cross-sectional shape of the pattern obtained in
The pattern meandered at 80 μm and half width at 60 μm.
Further increase the exposure to 0.58 J / cm^TwoAnd leave
A film was formed. Also, even if the development time is added for 180 seconds,
The remaining film could not be removed.

[0111]

According to the method of manufacturing a plasma display of the present invention, even when large-area exposure is performed quickly and in large quantities, pattern processing with a high aspect ratio and high accuracy can be performed. The shape can be made better.

As a result, it becomes possible to process a thick film such as a display or a circuit material and a highly accurate pattern, thereby improving the definition and simplifying the process. Furthermore, since a high-precision partition can be easily formed, a plasma display panel can be manufactured efficiently.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G09F 9/30 320 G09F 9/30 320 H01J 11/02 H01J 11/02 B

Claims (14)

[Claims] 1. A plasma display, comprising: forming a coating film by coating a photosensitive paste containing inorganic fine particles and a photosensitive organic component on a substrate, exposing the coating film and developing the coating film; A method of manufacturing a plasma display, wherein an allowable exposure amount in an exposure step is 10% or more. 2. The photosensitive paste has a coating thickness of 50 to 200.
2. The method according to claim 1, wherein the thickness is μm. 3. The pitch of the partition pattern is 100 to 160 μm.
m, line width 20-90 μm, height 120-200 μm
The method according to claim 1, wherein: 4. The method according to claim 1, wherein the inorganic fine particles are glass fine particles, and
4. The method according to claim 1, wherein the photosensitive paste contains 60 to 90% by weight of glass particles and 40 to 10% by weight of a photosensitive organic component. 5. An inorganic fine particle comprising 40 to 90% by weight of glass fine particles and 10 to 60% by weight of a filler, and a photosensitive paste comprising 60 to 90% by weight of inorganic fine particles and 40 to 10% by weight of a photosensitive organic component. 2. The method according to claim 1, wherein
4. The method for manufacturing a plasma display according to any one of items 3 to 3. 6. A glass fine particle having a refractive index of 1.5 to 1.65.
6. The method according to claim 5, wherein
The manufacturing method of the plasma display according to the above. 7. The glass fine particles having a particle diameter of 50% by volume of 1 to 5%.
The method according to any one of claims 4 to 6, wherein the specific surface area is 1 m to ⁴ m2 / g. 8. The method according to claim 1, wherein the 10% by volume particle diameter of the glass fine particles is 0.4.
２2 μm, 50% by volume particle size 1.5-5 μm, 90% by volume particle size 4-15 μm, maximum particle size 40 μm
The method for manufacturing a plasma display according to claim 7, wherein m is equal to or less than m. 9. The glass fine particles are expressed in terms of oxide. Lithium oxide: 3 to 10% by weight Silicon oxide: 10R0% by weight Boron oxide: 20 to 40% by weight Barium oxide: 2 to 15% by weight Aluminum oxide: 10 to 25% by weight The method of manufacturing a plasma display according to any one of claims 4 to 8, further comprising: 10. The plasma display according to claim 5, wherein the filler contains at least one selected from the group consisting of alumina, zirconia, cordierite, mullite, spinel, titania, silica, and high-melting glass particles. Manufacturing method. 11. The high melting point glass particles have a glass transition point of 5
The method for manufacturing a plasma display according to claim 10, wherein the softening point is from 00 to 1200C and the softening point is from 550 to 1200C. 12. The method according to claim 1, wherein the photosensitive paste contains an ultraviolet absorber. 13. The method according to claim 12, wherein the ultraviolet absorber is selected from a benzophenone compound, a cyanoacrylate compound, a benzotriazole compound, and an indole compound. 14. The method of manufacturing a plasma display according to claim 1, wherein the method is used for forming a partition in a plasma display or a plasma addressed liquid crystal display.