JP2000347394A - Photosensitive paste, member for display and display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable good patterning, to enhance contrast by a cost-wise advantageous photolithography method and to form a black partition wall having a low reflectance by using a photosensitive paste which contains a low melting point glass and blackens after baking. SOLUTION: The photosensitive paste contains a low melting point glass and blackens after baking. Since the low melting point glass is used, patterning in exposure is not blocked and a partition wall is formed by baking. When lithium oxide is further incorporated into the low melting point glass powder, the control of the refractoriness of the glass under load and the coefficient of thermal expansion of the glass is facilitated, and since the average refractive index of the glass is lowered, the refractive index difference between the glass and an organic material is easily reduced. The blackening property is attained by incorporating a compound which is converted to a black oxide by baking into the paste.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive paste used for forming partition walls, and relates to a plasma display panel (PDP), a plasma addressed liquid crystal display, an electron emission device (FED, field emission), and an organic electroluminescence device (PDP). It can be used for an image display device using an organic EL, electroluminescence) or a fluorescent display tube element (VFD).

[0002]

2. Description of the Related Art Light and thin so-called flat panel displays have been receiving attention. Liquid crystal displays (LCDs) have been actively developed as flat panel displays, but have disadvantages such as dark images and narrow viewing angles. Image displays using PDPs and electron-emitting devices can provide brighter images than liquid crystal displays, have a wider viewing angle, and can respond to demands for larger screens and higher definition. It is getting.

The electron-emitting devices include a thermionic electron-emitting device and a cold cathode electron-emitting device. The cold cathode electron-emitting devices include a field emission type (FE type), a metal / insulating layer / metal type (MIM type), and a surface conduction type. An image forming apparatus using such a cold cathode electron source displays an image by irradiating a phosphor with an electron beam emitted from each type of electron-emitting device to generate fluorescent light. In this device, the front glass substrate and the rear glass substrate are used with their respective functions. The rear glass substrate is provided with a plurality of electron-emitting devices and a matrix-like wiring for connecting the electrodes of those devices. Since these wirings intersect at the electrode portion of the electron-emitting device, an insulating layer for insulation is provided. Further, a partition wall (spacer) is formed between the two substrates as an anti-atmospheric pressure support member.

The organic electroluminescent device is based on the application of emitting light by recombining electrons injected from a cathode and holes injected from an anode in an organic phosphor sandwiched between both electrodes. Attention has been paid to the fact that light emission is possible, that high-luminance light emission is possible under a low driving voltage, and that multicolor light emission is possible by selecting a fluorescent material. In the production of the organic electroluminescent device, a partition is also formed.

A PDP generates a plasma discharge between an anode electrode and a cathode electrode facing each other in a discharge space partitioned by partitions provided between a front glass substrate and a rear glass substrate, and is sealed in this space. The display is performed by irradiating the phosphors applied in the discharge space with the ultraviolet rays generated from the gas.

Conventionally, a partition wall in a PDP has been formed by repeating a process of printing an insulating glass paste in a pattern by a screen printing method and then drying the insulating glass paste to a predetermined height, followed by firing. However, in the screen printing method, especially when the panel size is increased, it is difficult to align the discharge electrode formed on the substrate in advance with the printing place of the insulating glass paste, and it is difficult to obtain positional accuracy. is there. In addition, a number of times of overlapping printing are performed to obtain a predetermined partition wall height, so that the partition walls and their side edges are wavy or distorted, and the accuracy of the height cannot be obtained, resulting in poor display quality. In addition, there are problems such as poor workability and low yield. Further, in the screen printing method, it is not possible to obtain a high-definition partition wall having a high aspect ratio, which is required with an increase in the area and resolution of a PDP.

As a method for solving such a problem, Japanese Patent Application Laid-Open No. 6-295676 discloses a method of forming a partition by a photolithography technique using a photosensitive paste. However, conventionally, the sensitivity and resolution of the photosensitive paste were low, and a high-definition partition having a high aspect ratio could not be obtained.

On the other hand, in the PDP, it is required to lower the reflectance of the partition walls. That is, when the reflectance of the partition walls is high, there is a problem that when external light is applied to the upper surface of the partition walls of the non-light-emitting pixels, the reflection reduces the contrast.

On the other hand, for example, Japanese Patent Laid-Open No. 6-14487
No. 1, JP-A-8-17345, JP-A-10-
No. 72240 discloses a method for manufacturing a partition wall using a photosensitive paste containing a black pigment. However, since the black pigment in the photosensitive paste absorbs light, the curing depth obtained by one exposure is insufficient, so that many exposures are required, or sufficient patterning property capable of coping with high definition is required. There was a problem that it could not be obtained.

[0010]

As described above, in forming a partition by photolithography using a photosensitive paste, it is necessary to use a photosensitive paste having high light transmittance in order to obtain good patterning properties. On the other hand, as a result, there is a problem that the characteristics of the partition wall required for improving the contrast cannot be obtained.

An object of the present invention is to provide a photolithography method that enables good patterning and is advantageous in cost.
An object of the present invention is to provide a photosensitive paste used for forming a black partition having a low reflectance which contributes to improvement of contrast.

[0012]

That is, the present invention is a photosensitive paste containing a low-melting glass and changing to black after firing.

According to the present invention, there is provided a display wherein a partition is formed by using the above-mentioned photosensitive paste.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the photosensitive paste of the present invention will be described. The photosensitive paste of the present invention contains low-melting glass as an essential component. By using the low-melting glass, the partitioning property can be formed by baking without hindering the patterning property at the time of exposure.

The low-melting glass powder has a glass transition point of 400 in consideration of the fact that partition walls are usually formed on a glass substrate.
~ 550 ° C, softening point under load (also referred to as yield point) 450 ~ 6
Preferably it is 00 ° C. By setting the softening point under load to 450 ° C. or higher, the partition walls are not deformed in the post-process of forming the display. By setting the softening point to 600 ° C. or lower, the partition walls can be melted at the time of firing and have high strength. . In addition, the average refractive index of the low-melting glass is in the range of 1.5 to 1.65 in order to match the average refractive index of the photosensitive organic component in the photosensitive paste and to suppress scattering of exposure light. Is preferred.

The low-melting glass powder satisfying the above characteristics is
The composition is as follows in terms of oxide. Lithium oxide 3 to 15 wt% Silicon oxide 10 to 30 wt% Boron oxide 20 to 40 wt% Barium oxide 2 to 15 wt% Aluminum oxide 10 to 25 wt%.

By containing 3 to 15% by weight of lithium oxide, not only is it easy to control the softening point under load and the coefficient of thermal expansion of the glass, but also the average refractive index of the glass can be lowered. Can be easily reduced. The amount of the alkali metal oxide such as lithium oxide is preferably 15% by weight or less, more preferably 8% by weight, in order to improve the stability of the paste.
% By weight or less.

It is preferable that silicon oxide is blended in the range of 10 to 30% by weight. When the content is 10% by weight or more, the denseness, strength, and stability of the glass layer are improved, and the coefficient of thermal expansion becomes close to the value of the glass substrate, and therefore, peeling due to mismatch with the glass substrate is prevented. Can be. By setting the content to 30% by weight or less, there is an advantage that the softening point under load is lowered and baking on a glass substrate becomes possible.

It is preferable that boron oxide is blended in the range of 20 to 40% by weight. When the content is 40% by weight or less, the stability of the glass can be maintained. When the content is 20% by weight or more, strength and stability of glass can be improved.

Preferably, barium oxide is used in the range of 2 to 15% by weight. When the content is 2% by weight or more, the glass baking temperature and the electrical insulation can be controlled. Also, 1
When the content is 5% by weight or less, the stability and the denseness of the partition layer can be maintained.

Aluminum oxide is preferably used in an amount of 10 to 25% by weight, and is added for increasing the strain point of the glass, stabilizing the glass composition, and extending the pot life of the paste. By setting the content to 10% by weight or more, the strength of the partition layer can be improved. By setting the content to 25% by weight or less, it is possible to prevent the heat resistance temperature of the glass from becoming too high and to make it difficult to bake on the glass substrate, and to obtain a dense partition wall layer at a temperature of 580 ° C or less.

Although not described in the above composition, calcium oxide or magnesium oxide is preferably added in some cases to facilitate melting of the glass and to control the coefficient of thermal expansion. It is preferable that the mixing range is 2 to 10% by weight of calcium oxide and 1 to 10% by weight of magnesium oxide.

The low-melting glass powder has good filling properties and dispersibility at the time of forming the paste, and can be applied with a uniform thickness of the paste. Is preferably 1 to 7 μm, and the maximum particle size is preferably 40 μm or less.

It is important that the photosensitive paste of the present invention turns black after firing. If the color does not change to black after firing, for example, even if a transparent photosensitive paste is used for high transparency at the time of exposure, the contrast of the display cannot be improved after firing even if a transparent photosensitive paste is used. Even if the conductive paste is used, it absorbs the exposure light and cannot obtain a good patterning property. The black color after firing is preferably 15 or less, more preferably 6 or less, and still more preferably 3 or less as the Y value in the XYZ color system. Further, the reflection OD value is preferably 1.3 or more, more preferably 1.5 or more, and further preferably 1.6 or more. Here, the reflection OD value is -log (I / I ₀ ) when the incident light intensity is I ₀ and the reflected light intensity is I.
Is defined by

The property of changing to black after firing can be achieved by including a compound that converts to a black oxide by firing into the photosensitive paste of the present invention. Such compounds include, for example, Ru, Mn, Ni, C
It is preferable to include at least one selected from the group of compounds of r, Fe, Co, and Cu. These compounds are thermally decomposed and oxidized to their respective oxides, namely, "ruthenium oxide, manganese oxide, nickel oxide, chromium oxide,
It can turn into black as iron oxide, cobalt oxide, and copper oxide.

These compounds are not particularly limited, but alkoxide derivatives of the above metals, complexes of β-diketones, complexes of β-keto acid esters, organic carboxylic acid derivatives and the like are used.

Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, n-
Pentoxy group, t-pentoxy group, n-hexoxy group,
An n-heptoxy group, an n-octoxy group, or the like can be used. Specific examples of β-diketones and β-keto acid esters include acetylacetone, benzoylacetone, dibenzoylmethane, methylacetoacetate, ethylacetoacetate, benzoylacetoacetate, ethylbenzoylacetate, methylbenzoylacetate, and the like. Can be

In the case of metal alkoxides, it is known that a gel formed through hydrolysis and polycondensation is converted into a metal oxide in a firing step to form glass or ceramics. It is presumed that the desired metal oxide is formed through the chemical change of

The content of the organometallic compound which is converted into a black oxide by firing is preferably 6 to 30% by weight based on the photosensitive paste from which the solvent has been removed. When the content is 6% by weight or more, the effect of lowering the reflectance after firing can be obtained. Further, by setting the content to 30% by weight or less, the patterning property can be maintained without inhibiting light transmission in the state of the paste applied film.

As the photosensitive organic component to be blended in the photosensitive paste, a photosensitive component which becomes insoluble in a solvent by being photo-cured by a polymerization and / or a cross-linking reaction caused by absorbing irradiation light is used. Is preferred. That is, a photosensitive monomer, a photosensitive or non-photosensitive oligomer or polymer can be preferably used as the photosensitive organic component.

As the photosensitive monomer, a compound having an active carbon-carbon double bond is preferable.
Monofunctional and polyfunctional compounds having a vinyl group, an allyl group, an acrylate group, a methacrylate group, and an acrylamide group are applied. In particular, a polyfunctional acrylate compound and / or a polyfunctional methacrylate compound may be contained in an organic component.
Those containing 0 to 80% by weight are preferred. Since various kinds of compounds have been developed for the polyfunctional acrylate compound and / or the polyfunctional methacrylate compound, it is possible to select from them in consideration of reactivity, refractive index, and the like. As a method for controlling the refractive index of the photosensitive organic component for matching with the refractive index of the glass component or the like, a method using a photosensitive monomer having a refractive index of 1.55 to 1.75 is simple. The photosensitive monomer having such a high refractive index can be selected from an aromatic ring such as a benzene ring or a naphthalene ring, or an acrylate or methacrylate monomer containing a sulfur atom.

The photosensitive oligomer and the photosensitive polymer are preferably used because they serve to improve the physical properties of a cured product formed by the photoreaction and to adjust the viscosity of the paste. In a preferred embodiment, the photosensitive oligomer and the photosensitive polymer have a carbon chain skeleton obtained by polymerization or copolymerization of a component selected from compounds having a carbon-carbon double bond. In particular, a weight average molecular weight having a carboxyl group and an unsaturated double bond in a molecular side chain of 2000
Up to 60,000, more preferably 3000 to 40,000 oligomers or polymers are used. By having a carboxyl group in the side chain, the solubility of the unexposed portion in an aqueous alkali solution can be obtained. The acid value of the oligomer or polymer having an acid group such as a carboxyl group in the side chain is preferably controlled so as to be in the range of 50 to 140, preferably 70 to 120.

In order to obtain a photosensitive oligomer or polymer, an unsaturated double bond is introduced by adding an ethylenically unsaturated compound having a glycidyl group or an isocyanate group to an oligomer or polymer having a carboxyl group in a side chain, or an acrylic compound. An acid chloride, methacrylic acid chloride or allyl chloride may be added.

In order to impart photosensitivity by introducing an unsaturated double bond into an oligomer or polymer having a carboxyl group in the side chain as described above, a salt bond must be formed between the carboxyl group and the amine compound. It is also possible to use a forming method. For example, a acrylate or methacrylate group can be used as a photosensitive group by forming a salt bond by reacting dialkylaminoacrylate or dialkylaminomethacrylate. The number of ethylenically unsaturated groups is
It can be appropriately selected depending on the reaction conditions.

Further, by adding a photopolymerization initiator, it is possible to impart an energy absorbing ability to actinic rays. Photopolymerization initiators are mechanically different types, such as a single-molecule direct cleavage type, an electron transfer between ion pairs, a hydrogen abstraction type, and a two-molecule composite type, and are used by selecting from them. Further, a sensitizer can be added to assist the effect of the photopolymerization initiator.

The compounding ratio of the above photosensitive organic component to the photosensitive paste is 10 to 40% by weight, and more preferably 15 to 3%.
5% by weight is preferred. If the amount of the photosensitive organic component is too small, it tends to be difficult to obtain good patterning properties,
If the amount is too large, the shrinkage after firing tends to be large, and it becomes difficult to control the shape of the partition walls.

In order to stabilize the shape of the partition wall during firing,
Fillers can be preferably added. The filler has an average refractive index of 1.45 to 1.65 in order to match the average refractive index with other components such as a photosensitive organic component and a low-melting glass in the photosensitive paste and to suppress scattering of exposure light.
Is preferably within the range. In order to keep the average refractive index of the filler within this range, it is preferable to use at least one selected from high melting point glass and cordierite.

As the high melting point glass, a glass transition point of 50
It is preferable that the high melting point glass has a composition containing 15% by weight or more of silicon oxide and aluminum oxide, respectively, and has a content of 0 to 1200 ° C and a softening point under load of 550 to 1200 ° C. It is effective to obtain the necessary thermal characteristics that the total should be 50% by weight or more. Although the composition of the high melting point glass is not limited to this, for example, the following oxide-converted composition can be used. 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.

Cordierite has a refractive index of 1.58, which is close to the average refractive indexes of the low-melting glass component and the photosensitive organic component, and thus is suitable as the filler component of the present invention.

The average particle diameter of the filler is preferably 1.5 to 5 μm. If the average particle size is too small, the agglomeration of the powder becomes large, so that the filling and dispersibility of the paste becomes poor, and it tends to be difficult to form a high-definition pattern. In addition, since the filler component is not melted in the firing step, if the average particle diameter is too large, the unevenness of the top of the formed partition wall becomes large, and crosstalk tends to occur.

The viscosity of the photosensitive paste is adjusted to about 10,000 to 100,000 cps (centipoise) with an organic solvent before use. Examples of the organic solvent used include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, and the like. 1
Organic solvent mixtures containing more than one species are included.

The photosensitive paste may further contain an ultraviolet absorber, a polymerization inhibitor, a plasticizer, a thickener, an antioxidant, a dispersant, and other additives.

The glass paste of the present invention is prepared by mixing various components so as to have a predetermined composition, and then uniformly mixing and dispersing the mixture by means of mixing and dispersing means such as a three-roller and a kneader.

The display including the display member and the plasma display of the present invention will be described below in accordance with the procedure for manufacturing the plasma display. However, the present invention is also preferably applied to a plasma addressed liquid crystal display and a display using an electron-emitting device, an organic electroluminescent device or a fluorescent display device.

As the substrate of the back plate of the plasma display, soda glass or a glass substrate for a plasma display (such as PD200 manufactured by Asahi Glass Co., Ltd.) can be used. An electrode is formed on a substrate using a conductive metal. As conductive metals, silver, copper, chromium, aluminum, nickel,
Etc. can be used. The electrodes are formed in a stripe shape having a width of 20 to 200 μm. Next, a dielectric layer is preferably formed so as to cover the electrodes.

Next, partition walls are formed on the dielectric layer or on the substrate on which the electrodes are formed. The partition walls are formed by applying the above-described photosensitive paste of the present invention, exposing, developing using the difference in solubility of the exposed portion and the unexposed portion in the developing solution, and then firing.

The above-mentioned glass paste of the present invention is applied on a substrate or a dielectric layer. Before applying the photosensitive paste, it is effective to perform surface treatment on the application surface to improve the adhesiveness. For such a surface treatment, a silane coupling agent, a metal alkoxy compound, or the like is used.

The application of the photosensitive paste can be performed by a general method such as a screen printing method, a bar coater method, a roll coater method, and a doctor blade method. The coating thickness can be determined in consideration of a desired height of the partition walls and a shrinkage ratio due to baking of the paste.

The coated and dried photosensitive paste film is exposed through a photomask to form a partition pattern. At the time of exposure, either a method in which the paste coating film and the photomask are brought into close contact or a method in which the paste is applied at a predetermined interval (proximity exposure) may be used. As a light source for exposure, a mercury lamp or a halogen lamp is suitable, but an ultra-high pressure mercury lamp is most often used. Although the exposure conditions vary depending on the thickness of the applied paste, the exposure is performed for about 20 seconds to 5 minutes using an ultra-high pressure mercury lamp having an output of 5 to 30 mW / cm ² .

The development is performed by an immersion method, a spray method, a brush method, or the like. The photosensitive organic component having a carboxyl group in the side chain as a preferred embodiment of the photosensitive paste of the present invention can be developed with an alkaline aqueous solution.
As the alkali, it is preferable to use an organic alkali aqueous solution because the alkali 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. The concentration of the alkaline aqueous solution is usually 0.05 to
It is 1% by weight, more preferably 0.1 to 0.5% by weight. If the alkali concentration is too low, the soluble portion tends to be difficult to completely remove, and if the alkali concentration is too high, the pattern of the exposed portion tends to peel off or erode. The development is preferably performed at a temperature of 20 to 50 ° C. in terms of process control.

The partition pattern formed by the development is then baked in a baking furnace to thermally decompose and remove the organic components, and at the same time, to melt the low melting point glass in the inorganic fine particle components to form inorganic partition walls. The firing atmosphere and temperature vary depending on the properties of the paste and the substrate, but are usually fired in air. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

In order to carry out batch-type firing, the temperature of the glass substrate on which the partition wall pattern is formed is raised from room temperature to about 500 ° C. at a substantially constant speed over several hours, and then the firing temperature is set to 520 to 580. The temperature is raised to 30 ° C. for 30 to 360 minutes and held for about 15 to 30 minutes for firing. Since the firing temperature must be lower than the glass transition point of the glass substrate used, there is naturally an upper limit. If the firing temperature is too high or the firing time is too long, defects such as sagging tend to occur in the shape of the partition walls.

A phosphor substrate that emits red, green, and blue light is applied to the cells sandwiched between the thus obtained partition walls to form a back substrate for a plasma display panel. After bonding the back substrate and the front substrate, sealing, gas sealing, and mounting of a driver IC for driving, a plasma display is manufactured.

[0054]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The concentration (%) is% by weight unless otherwise specified.

(Measurement method) (1) Total light transmittance The total light transmittance was measured using a spectrophotometer (UV-3101PC) manufactured by Shimadzu Corporation under the following conditions.

A sample for transmittance measurement was prepared by coating and drying a photosensitive paste by a screen printing method so that the thickness became 50 μm after drying on a quartz cell, and placing the quartz cell on the sample. The total light transmittance measured the total transmitted light of the light incident at an incident angle of 0 degree.

(2) Stimulus Value of XYZ Color System The tristimulus value XYZ of the light source color is JIS Z8701 (XY
Z color system and X_TenY _TenZ_TenColor display method by color system)
Can be determined by the method specified in

For the measurement, a color computer SM-7-CH manufactured by Suga Test Instruments Co., Ltd. (optical conditions; irradiation at 45 °,
0 ° light reception).

The measurement sample was 80 mm square and 1.3 mm thick.
Each of the glass pastes was applied to a soda glass substrate having a dry thickness of 50 μm.
It was produced by firing for 5 minutes. Using this sample, a C light (north window light) 2 degree field of view, a white plate as a reference (barium sulfate as a standard product, X = 91.06, Y = 93.01, Z = 10)
6.90). Prior to the measurement, a white plate was placed only on the soda glass substrate, and zero adjustment was performed on the sample table. The measurement sample was placed on a sample table having a measurement hole of 12 mmφ with the fired sample surface in the light irradiation direction, and a white plate was placed on the glass substrate side. The position of the measurement sample was changed, three points were measured, and the average value was taken as the measured value.

(3) Reflection OD value A Macbeth reflection densitometer RD-918 was used. For the measurement,
A photosensitive paste was applied on a glass substrate by screen printing at a dry film thickness of 140 μm and baked at 570 ° C. for 15 minutes to obtain a fired film having a thickness of about 100 μm. You. (Example 1) First, a photosensitive paste was prepared by the following procedure. The low-melting glass has an oxide-equivalent composition of 6.8% lithium oxide, 23% silicon oxide, and 33% boron oxide.
%, Barium oxide 4.5%, aluminum oxide 19.5
%, Zinc oxide 2.8%, magnesium oxide 5.8%, and calcium oxide 4.6%. The glass transition point of this low melting glass powder was 497 ° C., the softening point under load was 530 ° C., the coefficient of thermal expansion was 75 × 10 ⁻⁷ / K, and the refractive index was 1.58.

Nickel acetylacetonate and cobalt acetylacetonate were prepared as organometallic compounds that convert to black upon firing. These become nickel oxide and cobalt oxide by firing.

On the other hand, the photosensitive polymer was mixed with γ-butyrolactone so as to form a 40% solution, and stirred while stirring.
Heated to ° C. to dissolve all polymers. The photosensitive polymer used was obtained by subjecting a carboxyl group of a copolymer composed of 40% methacrylic acid, 30% methyl methacrylate and 30% styrene to an addition reaction of 0.4 equivalent of glycidyl methacrylate, and its weight average molecular weight Was 43,000 and the acid value was 95.

A photosensitive monomer (MGP400), a photopolymerization initiator (IC-369) and a sensitizer (2,4-diethylthioxanthone) were added to and dissolved in the photosensitive polymer solution at room temperature. Thereafter, this solution was filtered using a 400-mesh filter to produce an organic vehicle.

The low melting glass powder, the organometallic compound and the organic vehicle were mixed and dispersed by three rollers to obtain a photosensitive paste. The amount (parts by weight) of each component contained in the photosensitive paste is as follows: low melting point glass powder 60, a compound which converts to black by firing, nickel oxide 6.8, cobalt oxide 2.5, photosensitive polymer 19 in terms of oxide. , Photosensitive monomer 7.5, photopolymerization initiator 2.4, and sensitizer 2.4.
The mixing ratio (%) of the low melting point glass powder and the inorganic compound is 8
6.6: 13.4. Further, the ratio (%) between the inorganic material and the organic photosensitive component is 68.9: 31.1.

Thickness 5 for basic evaluation of this photosensitive paste
The total light transmittance of the coating film of 0 μm is 70%, and the coating film obtained by baking the coating film at 570 ° C. for 15 minutes is black, and its XY
The Y value in the Z color system was 3. The reflection OD value was 1.7.

Next, a plasma display panel was manufactured. An electrode layer was formed on a 100 mm square glass substrate. Using a spherical silver powder having an average particle size of 1.5 μm and a photosensitive silver paste containing a photosensitive organic component, a stripe pattern having a pitch of 150 μm and a line width of 40 μm is formed by photolithography, and the resultant is formed at 580 ° C. in air. Baking for 15 minutes, silver content 97.5%, glass frit amount 2.
A 5% electrode layer was formed. The thickness of this electrode layer is 2.6μ.
m.

Next, 30 g of a terpineol solution containing 5% of ethylcellulose, 5 g of rutile-type titanium oxide having an average particle diameter of 0.24 μm, glass powder (composition expressed as oxide: bismuth oxide 67%, silicon oxide 10%, boron oxide 12%, After mixing and pre-kneading 165 g of aluminum oxide (3%, zinc oxide 3%, zirconium oxide 5%), the mixture was passed through a three-roller to prepare a dielectric paste. This dielectric paste was applied on a glass substrate on which the above-mentioned electrode layer was formed, by a screen printing method using a 325-mesh screen so as to have a dry thickness of 18 μm. Then at 570 ° C
By firing for 5 minutes, a dielectric layer having a thickness of 9 μm was formed.

Next, the photosensitive glass paste of this example was applied by screen printing using a 325 mesh screen. Coating and drying were repeated several times to avoid generation of pinholes and the like on the coating film, and the film thickness was adjusted. Drying was performed at 80 ° C. for 10 minutes.
Then, it was kept at 80 ° C. for 1 hour and dried. The coating thickness after drying was 180 μm.

Subsequently, a pitch of 150 μm and a line width of 20 μm
20mW / from the top using a negative chrome mask
Proximity exposure was performed with an exposure amount of 500 mJ / cm ^{2 using} an ultra-high pressure mercury lamp with a cm ² output. After exposure, the pattern
A 0.2% aqueous solution of monoethanolamine maintained at 5 ° C. was developed by applying a shower for 300 seconds, and then washed with shower spray to form a stripe-shaped partition pattern on the glass substrate.

The partition wall pattern thus obtained was baked in air at 560 ° C. for 30 minutes to form black partition walls. When the cross-sectional shape of the formed partition wall was observed with an electron microscope, the height was 123 μm, the line width at the center of the partition wall was 30 μm,
The shape was good with a pitch of 150 μm.

Next, five 3 mm long needles each having a discharge port with a hole diameter of 150 μm and a nozzle (L / D = 20) press-fitted at the tip at a pitch of 420 μm are used to form red, green and blue colors between the partition walls. A phosphor paste containing a phosphor powder that emits light was applied and dried to form a phosphor layer, thereby obtaining a back plate for a plasma display panel as a display member of the present invention.

Next, the back plate and the front plate for a plasma display panel were combined, sealed, sealed with gas, and connected to a drive circuit to produce a plasma display. A display was performed by applying a voltage to this panel, and the luminance during full lighting was measured using a photometer MCPD-200 manufactured by Otsuka Electronics Co., Ltd., and the luminance was 350 cd / m ² and the contrast was 350: 1. The display characteristics of the present invention were satisfied.

(Example 2) As an organometallic compound, 2.5 parts by weight of cobalt oxide in terms of oxide, chromium (III) oxide
Example 1 was repeated except that the acetylacetonate derivative of each metal was used so as to be 2.9 parts by weight and 2.9 parts by weight of iron (III) oxide. A black partition having a good shape and without peeling was obtained.

The total light transmittance of the coating film for basic evaluation of the photosensitive paste of this example was 70%, the baked film was black, and the stimulus value Y in the XYZ color system was 4. The reflection OD value was 1.6.

In the production of the plasma display, a black partition having a good shape and without peeling was obtained. The brightness of the produced plasma display was 400 cd / m ² ,
The contrast was 350: 1, which satisfied the target display characteristics of the present invention.

Example 3 In preparing a photosensitive paste similar to that used in Example 1, the following materials were used.

As the photosensitive polymer, Cyclomer PCA 210 (acid value: 120, molecular weight: 28,000) manufactured by Daicel Chemical Industries, Ltd. was used.

As the low melting point glass, a glass having the following composition and characteristics was used. Oxide equivalent composition (analytical value):
9.1% lithium oxide, 21.3% silicon oxide, 32.9% boron oxide, 4% barium oxide, 21.9% aluminum oxide, 6.3% magnesium oxide, 4.5% calcium oxide. Characteristics: Glass transition point is 472 ° C., softening point under load is 515 ° C., coefficient of thermal expansion is 83 × 10 ⁻⁷ / K, refractive index is 1.59, average particle diameter is 2.3 μm, maximum particle diameter is 22 μm.
m.

As the organic metal compound, an acetylacetonate derivative of each metal, which is 8 parts by weight of cobalt oxide and 2 parts by weight of nickel oxide in terms of oxide, was used.

A mixture of the above photosensitive polymer, 70 parts by weight of low melting glass powder and an inorganic compound was blended. A black partition having a good shape and without peeling was obtained. Mixing ratio of low-melting glass and inorganic compound in inorganic material (%)
Was 87.5: 12.5, and the mixing ratio (%) of the inorganic material and the photosensitive organic component was 71.8: 28.2. Thereafter, Example 1 was repeated.

The total light transmittance of the coating film for basic evaluation of the photosensitive paste of this example was 60%, the baked film was black, and the stimulus value Y in the XYZ color system was 2. The reflection OD value was 1.7.

In the production of the plasma display, a black partition having a good shape and without peeling was obtained. The brightness of the produced plasma display was 420 cd / m ² ,
The contrast was 350: 1, which satisfied the target display characteristics of the present invention.

Example 4 The acetylacetonate of each metal was adjusted so that the organic metal compound was 4.0 parts by weight of cobalt oxide, 3.5 parts by weight of chromium oxide and 2.5 parts by weight of iron oxide in terms of oxide. Example 3 was repeated except that the derivative was used.

The total light transmittance of the coating film for basic evaluation of the photosensitive paste of this example was 74%, the baked film was black, and the stimulus value Y in the XYZ color system was 5.1.
The reflection OD value was 1.5.

In the production of the plasma display, a black partition having a good shape and without peeling was obtained. The brightness of the produced plasma display was 400 cd / m ² ,
The contrast was 350: 1, which satisfied the target display characteristics of the present invention.

Description of Abbreviations MGP400: X ₂ N-CH (CH ₃ ) -CH _2- (OCH ₂ CH (CH ₃ )) _n -NX ₂ X: -CH ₂ CH (H) -CH ₂ O-CO -C (CH ₃ ) = CH ₂ n: 2 to 10 IC-369: Irgacure 369 (product of Ciba-Geigy) 2-pentenyl-2-dimethylamino-1- (4-morpholinophenyl) phthalanone-1

[0087]

According to the present invention, a good patterning property can be obtained by forming a partition by a photolithography method using a photosensitive paste, and a black partition having a low reflectance which contributes to an improvement in contrast is formed. can do.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01J 11/02 H01J 11/02 B F term (Reference) 2H025 AA00 AB17 AC01 AD01 BC31 BC51 CA00 CC14 FA03 FA17 FA29 5C040 FA01 FA02 FA09 GF18 JA22 KA04 MA02 5C094 AA06 BA21 BA27 BA31 EA04 EC00 FB02 GA10 GB01

Claims (9)

[Claims] 1. A photosensitive paste containing a low-melting glass and turning black after firing. 2. The photosensitive paste according to claim 1, further comprising a compound which is converted into a black oxide by firing. 3. The compound which is converted into a black oxide after firing includes at least one selected from the group consisting of compounds of Ru, Mn, Ni, Cr, Fe, Co, and Cu. Or the photosensitive paste according to 2. 4. A member for a display, wherein a partition is formed by using the photosensitive paste according to claim 1. 5. A plasma display, wherein a partition is formed by using the photosensitive paste according to claim 1. 6. A plasma-addressed liquid crystal display, wherein a partition is formed by using the photosensitive paste according to claim 1. 7. A display using an electron-emitting device, wherein a partition is formed by using the photosensitive paste according to claim 1. 8. A display using an organic electroluminescent element, wherein a partition is formed using the photosensitive paste according to claim 1. 9. A display using a fluorescent display tube element, wherein a partition is formed by using the photosensitive paste according to claim 1.