JP2001117220A - Photosensitive paste, member for display and display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive paste capable of forming a fine pattern and capable of producing a member for a display and a display excellent in luminance and contrast. SOLUTION: The photosensitive paste contains a low melting point glass and turns chromatic after baking.

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 a partition, and relates to a plasma display panel (PDP), a plasma addressed liquid crystal (PAL).
C) It can be used for a display, an image display device using an electron-emitting device (FED, field emission), an organic electroluminescent device (organic EL, electroluminescence), a fluorescent display tube device (VFD), and the like.

[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.

The structure and electrical operation mechanism of a fluorescent display (VFD) are similar to those of a triode, and the electro-optical effect of the display operation is the same cathode luminescence as that of a CRT. C
Unlike RT, VFD excites a phosphor with a low-speed electron flow of several tens mA at a voltage of several tens of volts. Even in a display using such a VFD element, a partition wall such as a grid is formed to separate a light emitting region.

[0006] A plasma addressed liquid crystal (PALC) display is a thin film transistor liquid crystal display (TF).
A thin film transistor (TFT) array portion of a T-LCD is replaced with a plasma channel, and the structure is basically the same as the TFT-LCD except for the plasma portion. The plasma generation part has a height of about 200 μm and a pitch of 480.
Each cell is separated by a partition having a thickness of about μm, and a cell in which an anode electrode and a cathode electrode each made of nickel and having a thickness of about 30 μm are opposed to each other is used.
The technology in PDP is applied to these fabrications.

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 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, the partition walls not only divide the light emitting area but also affect display characteristics such as light emission luminance, color purity and contrast.

In this connection, for example, Japanese Patent Laid-Open No. 10-172
442 etc., for the purpose of improving the reflection efficiency of light emission of the phosphor, a white pigment may be contained in the photosensitive paste.
On the other hand, JP-A-10-182185 and the like disclose that a black pigment is contained in a photosensitive paste for the purpose of suppressing reflection of external light to a display surface and improving contrast.

[0012] However, it has been difficult to achieve both objectives with the same paste. In addition, when such an opaque pigment is contained in the photosensitive paste, at the time of exposure in photolithography, scattering or absorption of exposure light occurs in the paste coating film, and it becomes more difficult to form a fine pattern. .

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a display member and a display capable of forming a fine pattern and having excellent light emission luminance and contrast, and a photosensitive paste capable of manufacturing the same. Aim.

[0014]

That is, the present invention is a photosensitive paste containing a low melting point glass, which changes into a chromatic color after firing.

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

[0016]

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-point glass powder has a glass transition point of 400 in consideration of the fact that partitions 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.

As a glass powder which satisfies both the above thermal characteristics and the above range of the average refractive index, those containing the following composition in terms of oxide are preferable. Further, the content of each component is preferably the content in parentheses. Lithium oxide, sodium oxide or potassium oxide: 3 to 15% by weight Silicon oxide: 5 to 30% by weight (10 to 30% by weight) Boron oxide: 20 to 45% by weight (20 to 40% by weight) Barium oxide or strontium oxide: 2 to 15% by weight (3 to 15% by weight) Aluminum oxide: 10 to 25% by weight Magnesium oxide or calcium oxide: 2 to 15% by weight.

Lithium oxide (Li ₂ O), sodium oxide (Na ₂ O) or potassium oxide (K ₂ O) is used in a total of 3
Preferably, it is contained in an amount of from 15 to 15% by weight. By setting the content of these alkali metal oxides to 3% by weight or more, the glass softening point can be lowered, the coefficient of thermal expansion can be easily controlled, and the average refractive index of the glass can be lowered. Further, these alkali metal oxides are contained in 15% by weight.
The stability of the paste can be improved by adjusting the content to 10% by weight or less. Of these alkali metal oxides, lowering the refractive index of glass,
Lithium oxide (Li ₂ O) is preferable in order to reduce the influence of migration due to a conductive metal such as silver.

The silicon oxide is 5 to 30% by weight, more preferably 10 to 30% by weight.
It is preferable to mix in the range of ３０30% by weight. Silicon oxide is effective as a glass network former,
It is also effective for lowering the refractive index. By setting the content to 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, so that separation and the like due to mismatch with the glass substrate can be prevented. it can. By making it 30% by weight or less,
There are advantages such as a lower softening point and baking on a glass substrate.

The boron oxide (B ₂ O ₃ ) is preferably added in an amount of 20 to 45% by weight, more preferably 20 to 40% by weight. Boron oxide is an important component for lowering the melting point of glass containing no heavy metals such as lead and bismuth, and is also very effective for lowering the refractive index. When the content is 20% by weight or more, the strength and the stability of the glass can be improved while lowering the glass transition point and the softening point.
When the content is 40% by weight or less, chemical durability and stability of the glass can be maintained.

Strontium oxide (SrO) and barium oxide (BaO) are preferably used in a total amount of 2 to 15% by weight. These components are effective in expanding the vitrification range, that is, the stable melting temperature range of the glass, and are effective components for lowering the melting point of the glass and controlling the thermal expansion coefficient.
When the content is 2% by weight or more, the effect of lowering the melting point can be obtained, and the glass baking temperature and the electrical insulation can be controlled. Further, devitrification due to crystallization can be prevented. Also,
By setting the content to 15% by weight or less, it is possible to prevent the coefficient of thermal expansion from becoming too large, and thus prevent the occurrence of cracks during baking, thereby maintaining the stability and denseness of the glass layer.

Aluminum oxide is preferably used in an amount of 10 to 25% by weight. Addition increases the vitrification range,
It has the effect of increasing the strain point, stabilizing the glass composition, and extending the pot life of the paste. When the content is 10% by weight or more, devitrification due to crystallization can be suppressed. Further, the strength of the glass layer can be improved.
When the content is 25% by weight or less, the glass transition point of the glass,
It is possible to prevent the heat resistance temperature, such as the softening point, from becoming too high, so that baking on a glass substrate becomes difficult, and a dense insulating layer can be obtained at a temperature of 600 ° C. or lower.

In addition to these components, it is preferable to add zinc oxide, calcium oxide, or magnesium oxide in oxide notation.

It is preferable that zinc oxide is blended in the range of 2 to 15% by weight. Zinc oxide is effective in lowering the melting point without greatly changing the thermal expansion coefficient of glass. When the content is 2% by weight or more, it is effective in improving the denseness of the insulating layer. By setting the content to 15% by weight or less, it is possible to prevent the temperature for baking on the glass substrate from becoming too low, and to keep the insulation resistance high. By setting the content to 15% by weight or less, it is possible to prevent the refractive index from becoming too large and the difference from the refractive index of the organic component from becoming too large, and to maintain good pattern formability.

Magnesium oxide and calcium oxide are effective components for suppressing the devitrification of glass and expanding the vitrification range. The total amount of magnesium oxide and calcium oxide is preferably 2 to 15% by weight. When the content is 2% by weight or more, the effect of lowering the melting point can be obtained, and devitrification can also be prevented. By setting the content to 15% by weight or less, it is possible to prevent the coefficient of thermal expansion from becoming too large, suppress the occurrence of cracks during printing, and prevent the refractive index from increasing.

2 to 13% by weight of calcium oxide
It is preferable to mix in the range of. By adding in this range, the glass can be easily melted and the coefficient of thermal expansion can be controlled.

The magnesium oxide is preferably blended in the range of 1 to 15% by weight. By adding 1% by weight or more, the glass can be easily melted and the coefficient of thermal expansion can be controlled. When the content is 15% by weight or less, devitrification of the glass can be suppressed.

Further, the total amount of magnesium oxide, calcium oxide, strontium oxide, and barium oxide is determined in consideration of a balance between a stable glass structure, a glass transition point, a yield point, a coefficient of thermal expansion, a refractive index, and chemical durability. And 4 to 30% by weight are preferred.

The glass powder may contain titanium oxide, zirconium oxide and the like, but the amount is preferably 5% by weight or less. Zirconium oxide is effective in controlling the softening point, transition point, and electrical insulation of glass.

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 changes to a chromatic color after firing. Changing to a chromatic color after firing means that an achromatic color before firing changes to a chromatic color after firing, that a chromatic color before firing changes to another chromatic color after firing, This means that the chromatic coloring chemical species (coloring source) differs before and after firing.
By changing to a chromatic color after baking, it is possible to obtain a partition wall which maintains high transparency to exposure light at the time of exposure and improves the color development efficiency of a desired color after baking.

The chromatic color after firing preferably has a saturation of 20 or more, more preferably 30 or more. Saturation C ^* is JIS
It is calculated by the formula of C ^* = [(a ^* ) ² + (b ^* ) ² ] ^{1/2 according to} the L ^* a ^* b ^* color system adopted in Z8729. When the saturation is 20 or more, an effect of improving the luminance of a specific color can be obtained.

As the chromatic color after firing, for example, blue,
Available in brown, green, red, purple, yellow-green, and yellow.
No. It is preferable to adopt blue, green, or even blue as the chromatic color after firing. When external light is applied to the display, the red reflected light tends to give a sense of deterioration,
Further, since the visibility of green reflected light is high for human eyes, by selectively absorbing red or green as a blue partition, high quality and high contrast can be obtained. For PDP, FED, VFD, R
The problem is that the luminance of blue light emission among the phosphors of GB is weak. However, by setting the partition walls to blue, the reflectance of blue light can be selectively increased to increase the luminance of blue light. .

For the blue color of the partition walls, the chromaticity a ^* is −25 to
It is preferable that +20 and b ^* are -30 or less in order to improve contrast by absorbing red and green ^.
Is −15 to +15 and b ^* is −30 or less, which enables display with further improved blueness.

The property of changing to blue after firing can be achieved by incorporating a compound which converts to a blue oxide upon firing into the photosensitive paste of the present invention. Such a compound preferably contains at least one selected from the group of compounds of Co and Cr. These compounds are thermally decomposed and oxidized to form respective oxides, that is, cobalt oxide and chromium oxide, which can be changed to blue.

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 a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group and an 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

With respect to 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, but these components are also similar. 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 chromatic 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, an effect of exhibiting a chromatic color can be obtained also as a partition wall. 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 of a type which becomes insoluble in a solvent by being photocured by a polymerization and / or a crosslinking 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 a 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 can be 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 the 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-mentioned photosensitive organic component to the photosensitive paste is 10 to 40% by weight, and more preferably 15 to 3% by weight.
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 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 index 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 size 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 (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 fired in a firing furnace to remove organic components by thermal decomposition, 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 perform the 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 set at 520 to 580 set as the firing temperature. 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 paste which emits red, green and blue light is applied to the cells sandwiched between the partition walls thus obtained to form a back plate for a plasma display panel as a display member of the present invention. Is done.

Next, a front plate for a plasma display can be manufactured by forming a transparent electrode, a bus electrode, a dielectric, and a protective film (MgO) on a substrate in a predetermined pattern. A color filter layer may be formed in a portion corresponding to the RGB phosphor layers formed on the rear substrate. Further, a black stripe may be formed to improve the contrast.

After sealing the back plate and the front plate thus obtained, helium and helium are added to the space formed between the substrates between the two members.
After charging a discharge gas composed of neon, xenon, or the like, the driving circuit is mounted to manufacture the plasma display of the present invention.

[0067]

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.

(Color Measurement Method After Firing) (1) Firing A glass substrate is dried to a thickness of 5 by a screen printing method.
The coating film of 0 μm was baked at 590 ° C. for 15 minutes.

(2) Colorimetry Using the above calcined sample, the chromaticity and chroma were measured by using a Minolta “color difference meter ICR-300”.

Example 1 First, a photosensitive paste was prepared according to the following procedure.

As the low-melting glass, the composition in terms of oxide is as follows:
Lithium oxide 6.8%, silicon oxide 23%, boron oxide 33%, barium oxide 4.5%, aluminum oxide 1
9.5%, zinc oxide 2.8%, magnesium oxide 5.8
% And 4.6% calcium oxide. The glass transition point of this low melting glass is 497 ° C., and the softening point under load is 5
At 30 ° C., the coefficient of thermal expansion was 75 × 10 ⁻⁷ / K. The glass component was previously made into fine powder with an attractor, and had an average particle size of 2.6 μm, a maximum particle size of 22 μm, and a tap density of 0.75.
g / cm ³ , used as a non-spherical powder having a refractive index of 1.59. This was prepared in an amount of 50 parts by weight.

As a filler, a high-melting glass having an oxide equivalent composition of 38% silicon oxide, 10% boron oxide, 5% barium oxide, 4% calcium oxide, 36% aluminum oxide, 2% zinc oxide, and 5% magnesium oxide. Powder was used. The glass transition point of this high melting glass powder is 652 ° C.
The softening point under load is 746 ° C., the coefficient of thermal expansion is 43 × 10 ⁻⁷ / K,
The average particle diameter was 2.4 μm and the average refractive index was 1.59. This was prepared in 12 parts by weight.

Cobalt acetylacetonate and chromium (III) acetylacetonate were used as compounds to be converted to oxides by firing. This is converted to oxide to 10
It was prepared to be parts by weight.

0.08 parts by weight of the azo organic dye sudan was added to 100 parts by weight of the low melting glass and filler.
The IV was dissolved in acetone, a dispersing agent was added thereto, and the mixture was uniformly stirred with a homogenizer. Glass powder was added to this solution, and the mixture was uniformly dispersed and mixed.The acetone was evaporated using a rotary evaporator, and the mixture was heated to 150 to 200 ° C. At a temperature of.

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 32,000 and the acid value was 95.

A photosensitive monomer (MGP400), a photopolymerization initiator (IC-369),
An anti-gelling agent (benzotriazole), a dispersant (Nopcosperse), a polymerization inhibitor (hydroquinone monomethyl ether) and a plasticizer (dibutyl phthalate) were added and dissolved. Thereafter, this solution was filtered using a 400-mesh filter to produce an organic vehicle. The average refractive index of the photosensitive organic component was 1.56.

The compounding ratio of the organic components excluding the solvent is as follows: photosensitive polymer 38%, photosensitive monomer 38%, photopolymerization initiator 9.2%, gelling inhibitor 8.5%, dispersant 1.6%. ,
0.5% of polymerization inhibitor and 4.2% of plasticizer.

A low-melting glass powder, a filler, tetraethoxysilane, and an organic vehicle were mixed and dispersed with three rollers to obtain a photosensitive paste. The components (parts by weight) contained in the photosensitive paste were 50 low melting point glass powder, 12 fillers, 10 compounds converted to oxides after firing, in terms of oxides, and 35 organic vehicles. The mixing ratio of the low-melting glass powder, the filler, and the compound that converts to a chromatic color in the inorganic material in terms of oxide is 69.4: 16.7: 13.9.
Becomes

Although the obtained photosensitive paste was red due to the added organic dye, the film after baking was blue,
Its chromaticity a ^* was -35.21 and b ^* was -5.46. The saturation C ^* was 35.63.

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 diameter of 1.5 μm and a photosensitive silver paste containing a photosensitive organic component, a stripe pattern having a pitch of 140 μm and a line width of 40 μm is formed by photolithography at 580 ° C. in air. Fifteen
After baking for minutes, an electrode layer having a silver content of 97.5% and a glass frit amount of 2.5% was formed. The thickness of this electrode layer is 2.
It was 6 μm.

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 10 μm was formed.

Next, the photosensitive glass paste of this example was applied by a screen printing method using a 325 mesh screen. Coating and drying were repeated several times to avoid pinholes and the like in 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 175 μm.

Subsequently, a pitch of 140 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 250 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 pattern thus obtained was baked in air at 570 ° C. for 15 minutes to form a blue partition. When the cross-sectional shape of the formed partition was observed with an electron microscope, the height was 120 μm, the line width at the center of the partition was 33 μm,
The shape was good with a pitch of 140 μm.

Next, five 3 mm long needles having a discharge port with a hole diameter of 150 μm, and a nozzle (L / D = 20) press-fitted into the tip at a pitch of 420 μm were used to color red, green, and blue 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.

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 obtain a plasma display. A display was performed by applying a voltage to the panel, and the luminance during full lighting was measured using a photometer MCPD-200 manufactured by Otsuka Electronics Co., Ltd., and the luminance was 420 cd / m ^2. The characteristics were satisfied.

Example 2 Example 1 was repeated except that 5 parts by weight of cobalt acetylacetonate in terms of oxide was used as the compound that changes to a chromatic oxide upon firing. The refractive index of the used cobalt acetylacetonate was 1.49.

The obtained photosensitive paste had a red color due to the added organic dye, but had a purple color after firing,
The chromaticity a ^* was +24.35, b ^* was 36.20, and the chroma C ^* was 43.63. The porosity of the fired film was 3.2%.

Example 3 Example 1 was repeated except that a low-melting glass having the following oxide equivalent composition and thermal characteristics was used. Low melting glass powder composition: lithium oxide 8.6%, silicon oxide 20.1%, boron oxide 31
%, Aluminum oxide 20.6%, barium oxide 3.8
%, Magnesium oxide 5.9%, calcium oxide 4.2
%, Zinc oxide 2.1%. Characteristics of low melting point glass: glass transition point 472 ° C, softening point under load 515 ° C, coefficient of thermal expansion 83 ×
10 ^-7 / K, refractive index 1.59.

The obtained photosensitive paste was prepared by adding
Although it was red due to the dye, it was blue after firing,
Chromaticity a^*Is −20.24, b^*Is -34.17, and
Degree C ^*Was 39.71. Also this photosensitive paste
Plasma display panels manufactured using
Is 420 cd / m^TwoMet.

Example 4 As a compound to be converted into a chromatic color, nickel acetylacetonate and chromium acetylacetonate were used in an amount of 5 parts by weight in terms of oxide.
Was repeated. The refractive index of the chromium acetylacetonate used was 1.48.

The obtained photosensitive paste had a red color due to the added organic dye, but had a green color after firing,
Chromaticity a ^* was -42.55, b ^* was -8.93, and chroma C ^* was 43.48.

Example 5 Example 1 was repeated except that 5 parts by weight of chromium acetylacetonate in terms of oxide was used as the compound that changes to a colored oxide upon firing.

The obtained photosensitive paste was mixed with the added organic paste.
Red color due to dye, but pale green after firing
And chromaticity a^*Is -28.33, b^*Is 34.78,
Saturation C ^*Was 44.86.

Example 6 A display using an electron-emitting device is manufactured by sealing a back substrate for fixing an electron source on which an electron-emitting device is formed, and a front substrate on which a phosphor layer and a metal back are formed. did. Between the front substrate and the rear substrate, a support frame and a partition wall (spacer) as an anti-atmospheric pressure support member were produced.

On the substrate on which the surface conduction electron-emitting device and the wiring between the electrodes were formed, the photosensitive paste used in Example 1 was applied and dried by screen printing on the entire surface, and this was repeated to obtain a dried thickness of about 1.0 mm. Was formed. In this coating film, a stripe-shaped opening having a width of 2 mm was formed by 1 cm.
15m output by contacting the photomask with pitch
It was exposed to ultraviolet light using a W / cm ² ultrahigh pressure mercury lamp. The exposure amount was 1.2 J / cm ² .

Next, a second application and drying of the photosensitive paste is performed to form a second coating film having the same thickness as that of the first application, and a photomask having an opening width of 1.6 mm is applied to the first application. Alignment was performed so as to correspond to the exposed portion, and exposure was performed similarly. This method is repeated up to the third stage, where the width 1.
A photomask having a 2 mm opening was used. The coating film thus exposed is developed and washed with the same means as in Example 1, and has a platform-like height of three steps 2.3.
A stripe-shaped partition (spacer) pattern having a width of mm was formed. This was fired in air at 560 ° C. for 30 minutes to obtain a back substrate for a display using an electron-emitting device.

On the other hand, a front substrate provided with a black matrix and a phosphor layer which emits light in three primary colors and provided with a metal back was separately prepared and sealed with the rear substrate to obtain a display using electron-emitting devices. The resulting display has improved brightness due to the effect of the blue partition walls.

(Example 7) The photosensitive paste used in Example 1 was applied to a glass substrate on which a transparent electrode film of indium tin oxide (ITO) was patterned in a stripe shape.
A coating film having a thickness of 10 μm was obtained. Exposure and development using a striped photomask perpendicular to the ITO electrode
A 5 μm partition pattern was formed. Baking this to width 2
A white partition having a thickness of 0 μm and a height of 7 μm was formed. While rotating the substrate, N, N′-diphenyl-N, N′-di (3-methylphenyl) -1,1′-diphenyl-4,
After depositing 4′-diamine (TPD) at 70 nm and 8-hydroxyquinoline aluminum complex (Alq3) at 55 nm, the rotation of the substrate was stopped and aluminum was deposited at 100 nm from a direction perpendicular to the substrate surface. An organic electroluminescent device was obtained by forming a silicon oxide film as a protective layer on the entire surface.

(Example 8) As a photosensitive polymer, a cyclomer PCA210 manufactured by Daicel Chemical Industries, Ltd. (acid value 1)
20, molecular weight 28,000). A low melting glass powder having the following composition and properties was used.

Composition in terms of oxide (analytical value): 9.1% of lithium oxide, 21.3% of silicon oxide, 32.9% of boron oxide
%, Barium oxide 4%, aluminum oxide 21.9%,
6.3% magnesium oxide, 4.5% calcium oxide.

Properties: glass transition point 472 ° C., softening point under load 515 ° C., coefficient of thermal expansion 83 × 10 ⁻⁷ / K, refractive index 1.5
9, average particle diameter 2.3 μm, maximum particle diameter 22 μm.

As oxides to be colored in a chromatic color after firing, acetylacetonate derivatives of 8 parts by weight of cobalt oxide and 2 parts by weight of chromium oxide were used.
Example 1 was repeated with a mixture of the above photosensitive polymer, 70 parts by weight of low melting glass powder and an acetylacetonate derivative. A blue partition having a good shape and without peeling was obtained.

(Example 9) As low melting glass powder, lithium oxide 10%, silicon oxide 25%, boron oxide 30
%, Zinc oxide 15%, aluminum oxide 5%, and calcium oxide 15%, each having an average particle diameter of 2 μm. Cobalt acetylacetonate was used as a compound that colored blue after firing. Example using 50 parts by weight of the low melting point glass described in this example, 12 parts by weight of the high melting point glass described in Example 1, 10 parts by weight of a cobalt compound in terms of oxide, and cyclomer P as a photosensitive polymer. 1 was repeated.

The obtained photosensitive paste exhibited a red color due to the added organic dye, but exhibited a blue color after firing,
Chromaticity a ^* was -2.05, b ^* was -43.11, and chroma C ^* was 43.19.

(Explanation of Abbreviations) MGP400: 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 IC-369: Irgacure369 (a product of Ciba-Geigy) 2-pentenyl-2-dimethylamino-1- (4-morpholinophenyl) phthalanone-1

[0108]

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 display excellent in light emission luminance and contrast can be manufactured. .

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AB17 AC01 AD01 CC11 CC12 CC14 CC20 DA40 FA29 FA39 2H096 AA27 AA30 BA05 EA02 HA01 HA09 5C027 AA09 5C040 FA01 FA02 FA09 GF18 JA21 KA01 KA04 KA08 KA16 KB03 KB14 KB19 MA02

Claims (10)

[Claims] 1. A photosensitive paste containing low-melting glass and changing to a chromatic color after firing. 2. The photosensitive paste according to claim 1, further comprising a compound which is converted into a chromatic oxide by firing. 3. The photosensitive paste according to claim 1, wherein the chromatic color is blue. 4. The photosensitive material according to claim 1, wherein the compound converted into a chromatic oxide after firing includes at least one selected from the group consisting of compounds of Co and Cr. paste. 5. A display member, wherein a partition is formed by using the photosensitive paste according to claim 1. 6. A plasma display, wherein a partition is formed by using the photosensitive paste according to claim 1. 7. A plasma-addressed liquid crystal display, wherein a partition is formed by using the photosensitive paste according to claim 1. 8. A display using an electron-emitting device, wherein a partition is formed by using the photosensitive paste according to claim 1. 9. A display using an organic electroluminescent device, wherein a partition is formed using the photosensitive paste according to claim 1. Description: 10. A display using a fluorescent display tube element, wherein a partition is formed by using the photosensitive paste according to claim 1.