JPH11135025A - Plasma display and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasma display preventing the bouncing and the swelling of a barrier rib end portion, allowing no erroneous charge at the end portion, and having a uniform luminescence characteristic over the whole surface. SOLUTION: In a plasma display having an dielectric layer and a stripe-like barrier rib formed on a substrate, a slope portion is formed at the end portion in the lengthwise direction of the barrier rib. This manufacturing method is composed of a process forming the stripe-like barrier rib having the slope portion at its end portion on the substrate using paste for the barrier rib comprising inorganic material and an organic component, a process burning the barrier rib pattern, and a process forming the stripe-like barrier rib.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plasma display and a method for manufacturing the same. The plasma display can be used for a large television or a computer monitor.

[0002]

2. Description of the Related Art Plasma displays (PDPs) are used in fields such as OA equipment and public information display devices because they can display at a higher speed than liquid crystal panels and can be easily made larger. In addition, progress in the field of high-definition television is highly expected.

[0003] With the expansion of such uses, a color plasma display having a large number of fine display cells has attracted attention. To explain using an AC type plasma display as an example, a plasma discharge is generated between opposing anode and cathode electrodes in a discharge space provided between a front glass substrate and a back glass substrate, and sealed in the discharge space. The display is performed by irradiating the phosphors provided in the discharge space with the ultraviolet rays generated from the gas. FIG. 1 shows a simple configuration diagram of an AC type plasma display. In this case, a partition (also referred to as a barrier or a rib) is provided to suppress the spread of the discharge to a certain area and perform display in a specified cell, and to secure a uniform discharge space. In the case of the AC type plasma display, the partition is formed in a stripe shape.

The above-mentioned partition has a width of about 30 to 80 μm,
Although the height is 70 to 200 μm, usually, an insulating paste containing glass powder is printed and dried on the front glass substrate and the rear glass substrate by a screen printing method, and the printing and drying process is repeated several times for a predetermined height. Formed.

[0005] JP-A-1-296534 and JP-A-2
JP-A-165538, JP-A-5-34292, JP-A-6-295676, JP-A-8-508
Japanese Patent Application Laid-Open No. 11 proposes a method for forming a partition by a photolithography technique using a photosensitive paste.

In any of the above methods, after forming an insulating paste containing glass powder in the shape of a partition pattern, the partition is formed by firing. At that time, the end of the partition wall,
Due to the difference in firing shrinkage between the upper part and the lower part of the partition wall, there was a problem that the partition wall was peeled off from the base as shown in FIG. 4 or jumped up as shown in FIG. .

If the swelling or swelling is at the end of the partition, a gap is formed between the top of the partition of the back plate and the front plate when the front plate and the back plate are combined to form a panel. Due to this gap, crosstalk occurs at the time of discharge, and there is a problem that the image is disturbed.

As a countermeasure against this, Japanese Patent Laid-Open Publication No.
In Japanese Patent Application Laid-Open Publication No. H11-163, a method is proposed in which the partition has a multilayer structure, the composition of the upper layer and the lower layer is changed, and glass having a lower melting point than the upper layer is provided in the lower layer. Japanese Patent Application Laid-Open No. H6-150831 proposes a method in which an under glass layer is provided as a base on an end portion. However, none of these methods was sufficient to prevent climax. Also, Japanese Patent Application Laid-Open No. 6-150
No. 832 describes a method of making the end of the partition wall step-like, but it is not enough to prevent swelling.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-definition plasma display having no edge swelling or swelling and a method of manufacturing the same.
Another object of the present invention is to provide a high-definition plasma display with less erroneous discharge and a method for manufacturing the same. Incidentally, the plasma display in the present invention,
Refers to a display that performs display by discharging in a discharge space partitioned by partition walls, and includes various discharge-type displays such as a plasma-addressed liquid crystal display in addition to the AC-type plasma display.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a plasma display having a dielectric layer and a stripe-shaped partition formed on a substrate, wherein the partition has an inclined portion at a longitudinal end. This is achieved by a plasma display.

Another object of the present invention is a method of manufacturing a plasma display in which a dielectric layer and stripe-shaped partition walls are formed on a substrate, wherein a paste for a partition wall made of an inorganic material and an organic component is used. Manufacturing a plasma display characterized by forming a partition having a slope at a longitudinal end of the partition through a step of forming a stripe-shaped partition pattern having a slope on a substrate and a step of firing the partition pattern. Achieved by the method.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The plasma display of the present invention needs to have a slope at the end of the partition. Here, having an inclined portion at the end of the partition means that at least a part of the longitudinal end of the partition is tapered as shown in FIG. By having an inclined portion at the end of the partition wall, the contraction stress at the upper portion of the partition wall and the stress caused by the adhesive force can be reduced as shown in FIG.

When there is no inclined portion at the end of the partition wall, the lower portion of the partition wall is adhered to the base as shown in FIG. It is presumed that the phenomenon of jumping (FIG. 4) or swelling (FIG. 5) occurs due to the difference in contraction stress.

The inclined portion is (1) linear, (2) an upwardly convex curve,
Any shape, such as (3) a downwardly convex curve and (4) a plurality of connected straight lines, may be used as long as it has a slope.

Further, it is preferable to form the inclined portions at both ends of the partition wall in order to eliminate gap unevenness between the front plate and the back plate when the panel is sealed.

Further, the inclined portion may be combined with a step shape as shown in FIG. However, the height of the portion other than the inclined portion is preferably 50 μm or less. In a stepped shape having a right-angled portion, since the contraction stress cannot be balanced, the higher the height, the greater the degree of jumping or swelling. When it is 50 μm or less, the swelling is small,
When a panel having a size of 20 inches or more is formed, the front plate and the partition wall come into close contact with each other, and crosstalk hardly occurs. When combining the step shape and the inclined portion, it is more preferable to provide the inclined portion at the uppermost portion of the partition wall. Since the inclined portion is at the uppermost portion, the swelling can be eliminated.

It is preferable that the height (Y) of the inclined portion and the length (X) (FIG. 7) of the base of the inclined portion are within the following ranges.

0.5 ≦ X / Y ≦ 100 The length (X) of the base of the inclined portion is 0.05 to 50 mm.
It is preferred that Since the inclined portion is lower than the desired partition height and causes image disorder, it is not preferable that X exceeds 50 mm. More preferably, it is 10 mm or less, still more preferably 5 mm or less. On the other hand, when the thickness is less than 0.05 mm, the effect of suppressing the jumping and the swelling by forming the inclined portion is small.

Further, in the present invention, the inclination angle of the inclined portion of the partition wall is preferably 0.5 to 60 degrees. If the inclination is not on a straight line, the angle of the portion where the inclination is maximum as shown in FIG. 8 is defined as the inclination angle. 0.5 inclination
When the angle is less than 60 degrees, the inclined portion becomes too long, which is not preferable in panel design. When the angle of inclination is 60 degrees or more, peeling during firing cannot be sufficiently suppressed. The preferred range is 2
0 to 50 degrees.

Since swelling and bouncing occur during firing, it is preferable to form the inclined portion before firing the partition walls.

Assuming that the shrinkage ratio of the partition wall paste during firing is r, firing shrinkage is remarkable in the height direction, but hardly occurs in the longitudinal direction of the partition walls. , When the length of the inclined portion is X ′, Y = r × Y ′,
X〓X ′. Therefore, in order to keep the shape of the partition wall after firing within the range of the present invention, the preferable shape of the end of the partition pattern before firing is in the range of 0.5 ≦ X ′ / (Y ′ × r) ≦ 100.

At this time, the height Y 'of the inclined portion before firing is preferably 0.2 to 1 times the height of the partition pattern before firing.
This is effective for preventing the end of the partition from rising. 0.2
If it is less than twice, the difference in firing shrinkage stress between the upper part and the lower part of the partition cannot be alleviated, and the protrusion cannot be prevented. Further, when the ratio is set to 1, the dielectric or the electrode provided on the substrate may be damaged depending on the process of forming the inclined portion. More preferably 0.3 to
It is 0.8 times.

The method of measuring the shape of the inclined portion is not particularly limited, but it is preferable to use an optical microscope, a scanning electron microscope, or a laser microscope.

For example, a scanning electron microscope (HITACH)
When (IS-2400) is used, the following method is preferable. It is cut so that the end of the partition wall comes out accurately, and processed into a size that allows observation. The measurement magnification is selected where the inclined part enters the field of view. Then, after calibrating the scale with a standard sample having the same size as the inclined portion, a photograph is taken. The lengths of X and Y are measured by a method as shown in FIG. 7, and the shape is calculated from the scale.

When a nondestructive measurement is desired, a laser focus displacement meter (for example, LT-8010 manufactured by Keyence Corporation) may be used. In this case as well, it is preferable to perform the measurement after the calibration is similarly performed using the standard sample.
At this time, it is preferable to confirm that the laser measurement surface is parallel to the stripe direction of the partition wall for accurate measurement.

In the method of manufacturing a plasma display according to the present invention, a step of forming a stripe-shaped partition pattern having an inclined portion at an end on a substrate using a partition paste comprising an inorganic material and an organic component, and the partition pattern Is formed to form a stripe-shaped partition having an inclined portion at the longitudinal end of the partition. The method of forming the inclined portion at the end of the partition is not particularly limited, but the following method can be used.

One method is to apply a glass paste for a partition so that the end of the coating film forms an inclined surface when the glass paste for a partition is formed on the substrate, and the inclined surface of the coating film is formed in the longitudinal direction of the stripe-shaped partition pattern. This is a method of forming a partition pattern so as to be an end. The application method is not particularly limited, but it is preferable to use screen printing, a roll coater, a doctor blade, or a slit die coater that discharges from a die.

A screen printing method, a sand blast method, a lift-off method, a photolithography method, or the like can be used as a method for forming a partition pattern.

In particular, when the partition pattern is formed by a photolithography method, the coating film having the inclined surface is exposed through a photomask having a stripe pattern and developed to form a stripe partition pattern. However, at this time, by exposing through a photomask having a stripe pattern longer than the length of the coating film with the inclined surface as an end, a stripe-shaped partition pattern having an inclined portion at the end can be obtained. This method does not require any post-processing, and can form the inclined portion without increasing the number of steps.

Another method is to apply a glass paste for barrier ribs on a substrate, and then process the coating film to form an inclined surface, and the inclined surface of the applied film is in contact with the longitudinal end of the stripe-shaped barrier rib pattern. This is a method of forming a partition pattern in such a manner.

The method of forming the inclined surface by processing the coating film may be any method, but it is preferable to form the inclined surface by spraying a fluid onto the coating film. More specifically, a fluid is sprayed onto a flowable remaining coating film that has not been completely dried and hardened, thereby forming an inclined surface as shown in FIG.

The fluid used in this method may be any substance as long as it is a liquid or gas at the working temperature, but it is a substance that does not remain on the substrate after the firing step and can perform the work cleanly. It is preferred that The fluid is preferably a gas because of its cleanliness and no need for a recovery operation. The gas component is not particularly limited, but air or nitrogen is preferably used in terms of cost. When a gas is used as the fluid, it is preferable that the inclined surface is formed by injecting the gas into the fluid coating film that has not yet been completely dried and hardened. It is also preferable to use a solvent as the fluid. When a solvent is used as the fluid, precise processing can be performed by spraying the solvent onto the dried and cured coating film to form an inclined surface.

It is preferable to use a nozzle or a slit for jetting the fluid. The inner diameter of the nozzle and the gap between the slits are preferably 0.01 mm to 3 mm, respectively. If the thickness is less than 0.01 mm, a required flow rate cannot be obtained at the time of fluid ejection, and a slope cannot be formed. If it exceeds 3 mm, it becomes difficult to control the ejection position of the fluid.

As a method of forming the inclined surface by processing the coating film, a method of mechanically cutting and processing may be used. The term "cutting" as used herein includes cutting with a blade, a grindstone or the like, cutting with sand blast, baking by laser irradiation, and the like. The cutting amount depends on the thickness of the coating film, and is preferably 10 to 90%, more preferably 50 to 80% of the coating film thickness.
Is preferred. If the amount of cutting is too large, the substrate may be shaved. If the amount of cutting is too small, a portion that cannot be cut due to the influence of unevenness in the coating film thickness occurs. After drying and curing the coating film, cutting is
This is preferable because no swelling due to cutting occurs.
This method may be applied after curing with heat or ultraviolet rays. The present invention can also be applied to a case where a pattern is exposed to ultraviolet rays on a coating film by a photolithography method to form a partially cured portion.

The cutting speed may be determined by checking the condition of the cutting section, but is preferably 0.05 to 10 m / min.

As for materials such as cutting tools and grindstones, any material used as a cutting material such as ceramics, high speed steels and super steels can be applied.

When the coating film is formed by applying a photosensitive paste and a partition pattern is formed by a photolithography method, it is preferable that the film is removed in a step after exposure and before development. The shavings are washed away in the developing step, so that defects caused by the shavings can be easily prevented.

When a lift-off method is used for forming the partition pattern, it is preferable to fill the resin mold with the paste for the partition, dry and cure the resin mold, and simultaneously cut the resin mold and the paste-coated film for the partition. Simultaneous cutting can prevent the partition wall pattern from falling down. Furthermore, since shavings can be removed together in the step of removing the resin mold, it is also advantageous for preventing defects. With the lift-off method, a resin mold is formed on a glass substrate as a matrix of a partition pattern by a photosensitive resin,
It is filled with the partition wall paste. Subsequently, the partition wall paste is dried, the resin mold is removed, a partition wall pattern is formed, and the partition wall pattern is baked to form a partition wall.

In the case where the sand blast method is used for forming the partition pattern, unnecessary portions may be removed by sand blast and then cut together with the resist layer. Since shavings can be removed at the same time when the resist layer is removed, it is advantageous in preventing defects. The sand blast method is to form a partition pattern mask by applying a resist layer on the partition paste application film, exposing and developing the resist layer, and forming a partition pattern by removing unnecessary portions by sand blast. And removing the resist layer and baking the partition pattern to form partition walls.

FIG. 10 shows an example of a preferable shape of the end portion of the coating film on which the inclined surface is formed by cutting. Assuming that the height of the portion other than the inclined surface is t1, the thickness of the coating film is t2, and the inclination angle of the inclined surface is φ, t1 / t2 = 0.1 to 0.8, φ = 0.1
A range of 60 degrees is preferred. For this purpose, a molding blade or a grindstone having a shape corresponding to the shape of the target inclined surface (for example, FIG. 1)
0 (shape indicated by a broken line). At the time of cutting, the substrate may be fixed and the cutting means such as a blade or a grindstone may be moved, or the cutting means may be fixed and the substrate may be moved.
FIGS. 11 and 12 show a side view of FIG. 10 when a blade is used. Here, the blade is fixed and the substrate is moved in the direction of the arrow. The angle of the blade with respect to the substrate may be opposed to the substrate as shown in FIG. 11, or the blade may be covered by the substrate as shown in FIG. What is necessary is just to select according to the characteristic of a coating film.
In both cases, the angle の between the blade and the substrate is 10 to 80 degrees,
Particularly, 15 to 60 degrees is preferable.

When cutting by sandblasting or baking by laser, the injection angle of the sandblast and the laser irradiation angle are important, but the angle may be set so as to match the desired inclined surface shape. The preferable angle is 0.1 to 60 degrees as described above.

Further, it is preferable to forcibly remove shavings generated by cutting the coating film. It is preferable to forcibly remove the shavings by sucking the shavings. This prevents the scum from re-adhering to the surface of the coating film, thereby preventing panel defects. The suction pressure of the device used for suction is preferably 10 to 500 hPa.

Further, the relative position of the cutting tool or the grindstone with respect to the coating film may be changed according to the coating film profile so that the film thickness is always constant. When a partition pattern is formed on a glass substrate having a diagonal of 20 inches or more, the substrate has undulations on the order of several tens of μm. By keeping the distance between the blade or the grindstone and the substrate constant, it is possible to prevent a dielectric or an electrode from being cut and prevent defects.

As means for forming a slope by processing the coating film, it may be processed by dissolving with a solvent. Specifically, an inclined surface is formed by rubbing the coating film with a cloth or the like containing a solvent. Alternatively, a wedge-shaped press may be applied to the coating film to form an inclined surface.

In particular, when the partition pattern is formed by photolithography, a photomask having a stripe pattern longer than the length of the coating film with the inclined surface at the end is used, as described above. A stripe-shaped partition pattern having a portion can be obtained.

Here, the coating film length with the inclined surface as the end means the coating film length when the inclined surface is regarded as the end. In processing the coating film, if an unnecessary part of the coating film (hereinafter, referred to as a coating film residue) remains outside the formed inclined surface, the coating film residue is coated with the inclined surface as an end. It is not included in the film length. The coating film residue is removed from the substrate in a later step such as a developing step. For example, FIG. 9 shows a state in which an inclined surface is formed in the coating film, and the left side of the drawing is the coating film and the right side is the outside of the coating film.
In the present invention, the dotted line on the left side of the drawing is regarded as the end of the coating film length. On the right side of the dotted line on the right side of the drawing, unnecessary coating film residues are shown. Here, a photomask having a length longer than the coating film length with the inclined surface as an end and not including the coating film residue, that is, a length in which the end of the pattern exists between the dotted line on the left and the dotted line on the right in the drawing. By using this, since the coating film residue is not exposed, it is removed at the time of development, and only a partition pattern having an inclined portion at an end is obtained.

Further, after forming the partition pattern, the end portion may be processed to form the inclined portion. However, the inclined portion is formed as described above because the process is easy and the number of steps can be reduced. Thereafter, it is preferable to form a partition pattern.

Another method of forming an inclined portion at the end of the partition wall is as follows.
A step of filling a partition wall paste formed of an inorganic material and an organic component into a partition wall matrix having striped grooves, a step of transferring the partition wall paste filled in the partition wall mold onto a substrate, the partition wall paste And baking at 400 to 600 ° C. in this order.

That is, a groove corresponding to the partition wall pattern is formed in advance in the partition wall matrix, a glass paste for the partition wall is filled therein, and the paste is transferred from the partition wall matrix onto the glass substrate to form a partition wall pattern. Is the way. In this method, after filling the glass paste into the partition matrix,
The partition pattern is formed by transferring the pattern onto a glass substrate. However, by transferring the pattern by applying pressure during the transfer, transfer defects are less likely to occur. In addition, the transfer while heating facilitates detachment of the paste from the partition wall matrix. Furthermore, when the organic component in the glass paste contains a component that is thermally polymerized, the volume changes due to polymerization shrinkage, so that the partition wall type can be easily separated.

In this method, after the partition pattern is formed, an inclined portion may be formed at the end of the partition pattern by the above-described inclined surface forming method. If the inclined portion is formed in advance, the post-processing is not required, and the inclined portion can be formed without increasing the number of steps, which is preferable.

Still another method is a step of applying a partition wall paste composed of an inorganic material and an organic component to a substrate to form a coating film, and pressing a partition matrix having striped grooves formed in the coating film. This is a method including, in this order, a step of forming a partition pattern by contacting and a step of firing the partition pattern at 400 to 600 ° C.

In this method, the glass paste for the partition is
This is a method of forming a partition pattern by applying a uniform coating on a part or the entire surface of a glass substrate in advance, and pressing a partition matrix onto the paste applied layer. The method of uniformly applying the glass paste to the glass substrate is not particularly limited,
A screen printing method and a coating method using a die coater or a roll coater are preferably exemplified.

Also in this method, similarly to the above, it is preferable to form an inclined portion in advance at the end of the groove formed in the partition matrix.

FIG. 13 is a cross-sectional view of a partition matrix that is preferably used in each of the above-described manufacturing methods, and has an inclined portion at a longitudinal end of a groove formed in the partition matrix. As a material constituting the partition wall mold, a polymer resin or a metal is preferably exemplified.In the former manufacturing method, a silicone rubber partition wall mold can be preferably used, and in the latter manufacturing method, It is preferable to use a partition wall mold in which a metal plate is manufactured by pattern etching, pattern grinding using an abrasive, or the like.

In addition to having an inclined portion at the end, it is also preferable to form the partition into a multilayer structure and use a glass having a low softening point in the lower layer than the upper layer because the adhesive strength can be increased.
By improving the adhesive strength to the base, it is possible to prevent splashing.

The partition for a plasma display of the present invention comprises:
When the lower surface width is Lb, the half value width is Lh, and the upper surface width is Lt, it is preferable that Lt / Lh = 0.65 to 1 Lb / Lh = 1 to 2. Note that Lb indicates the width of the partition bottom, Lh indicates the half-value width (when the partition height is 100, the line width at a height of 50 from the bottom), and Lt indicates the width of the partition upper part.

When Lt / Lh is greater than 1, the shape of the partition wall becomes constricted, and the ratio of the discharge space to the pitch of the partition walls, that is, the aperture ratio is reduced, so that the luminance is reduced. In addition, coating unevenness, that is, thickness unevenness and non-uniformity occur during the formation of the phosphor. On the other hand, if it is less than 0.65, the upper surface becomes too thin, the strength to withstand the atmospheric pressure applied during panel formation is insufficient, and the tip is easily crushed. When Lb / Lh is less than 1, the strength is low, and the partition walls may fall down or meander, which is not preferable. On the other hand, if it is larger than 2, the discharge space is reduced and the luminance is reduced.

More preferably, Lt / Lh = 0.8-
1, the range of Lb / Lh = 1 to 1.5 is preferable because it is excellent in securing the aperture ratio. Where Lt = L
In the case of h = Lb, the strength becomes weak, and it is easy to fall down, which is not preferable. As the shape, a trapezoid or rectangular shape having no constriction on the lower surface of the partition wall is preferable from the viewpoint of strength.

By forming the partition pattern before firing into the above-mentioned shape, the contact area particularly with the substrate glass or the dielectric layer is increased, and the shape retention and stability are improved. As a result, peeling and disconnection after firing are eliminated.

In the present invention, the porosity of the partition wall is 1 since it prevents the partition wall from falling down and has excellent adhesion to the substrate.
0% or less is preferable, and 3% or less is more preferable. The porosity (P) is defined as P = (dth−dex) / dth × 100, where dth is the true specific gravity of the partition wall material and dex is the measured density of the partition wall.

The true specific gravity of the partition wall material is preferably calculated using the so-called Archimedes method as follows. Using a mortar, crush the partition wall material to about 325 mesh or less so as not to be felt at the fingertips. Then, the true specific gravity is obtained as described in JIS-R2205.

Next, the measurement of the measured density is carried out using the Archimedes method in the same manner as described above, except that the partition wall is cut off so as not to lose its shape, and pulverization is not performed.

When the porosity is more than 10%, the adhesion strength is reduced, and in addition, the strength is insufficient, and the light emission characteristics such as the luminance lowered due to the adsorption of gas and moisture discharged from the pores during discharge are reduced. . Considering the light emission characteristics of the panel, such as discharge life and luminance stability, it is more preferably 1% or less.

When used for a partition of a plasma display or a plasma addressed liquid crystal display, a pattern is formed on a glass substrate having a low glass transition point and softening point.
It is preferable to use a glass material having a softening point of 470 to 580 ° C. Glass transition point 500 ° C, softening point 58
If the temperature is higher than 0 ° C., firing must be performed at a high temperature, and the substrate will be distorted during firing. The glass transition point is 430
If the material has a softening point lower than 470 ° C., a dense partition wall layer cannot be obtained, which causes peeling, disconnection and meandering of the partition wall.

The glass transition point and the softening point are preferably measured as follows. Using a differential thermal analysis (DTA) method, about 100 mg of a glass sample was heated in air at 20 ° C./min,
A DTA curve is drawn by plotting the temperature on the horizontal axis and the amount of heat on the vertical axis. The glass transition point and the softening point are read from the DTA curve.

Since the thermal expansion coefficient of general high strain point glass used for the substrate glass is 80 to 90 × 10 ⁻⁷ / K, it is necessary to prevent warpage of the substrate and cracking at the time of panel sealing. Has a coefficient of thermal expansion at ₅₀ to ₄₀₀ ° C. (α ₅₀ to ₄₀₀ ) of 50 to 90 × 10 ⁻⁷ / K, and more preferably 60 to 90 × 10
It is preferable to use a glass material of ^-7 / K for the partition walls and the dielectric layer. By using a glass material having the above characteristics, peeling or disconnection of the partition can be prevented.

As the composition of the partition wall material, it is preferable that silicon oxide is blended in the glass in the range of 3 to 60% by weight. If the content is less than 3% by weight, the denseness, strength and stability of the glass layer decrease, and the coefficient of thermal expansion deviates from desired values, so that the glass layer is likely to be inconsistent with the glass substrate. Further, when the content is set to 60% by weight or less, there is an advantage that the heat softening point is lowered and baking on a glass substrate becomes possible.

The boron oxide is contained in the glass in an amount of 5 to 50% by weight.
The electrical, mechanical and thermal properties such as electrical insulation, strength, coefficient of thermal expansion, and denseness of the insulating layer can be improved by blending in the range. If it exceeds 50% by weight, the stability of the glass will decrease.

By using a glass powder containing at least one of lithium oxide, sodium oxide and potassium oxide in an amount of 2 to 15% by weight, a photosensitive paste having a temperature characteristic capable of patterning a glass substrate can be obtained. . Alkali metal oxides such as lithium, sodium and potassium are added in an amount of 15% by weight or less,
Preferably, by setting the content to 15% by weight or less, the stability of the paste can be improved.

The glass composition containing lithium oxide includes:
It is preferable that the composition contains lithium oxide 2 to 15% by weight, silicon oxide 15 to 50% by weight, boron oxide 15 to 40% by weight, barium oxide 2 to 15% by weight aluminum oxide 6 to 25% by weight in terms of oxide. In the above composition,
Sodium oxide or potassium oxide may be used instead of lithium oxide, but lithium oxide is preferred in terms of paste stability.

Further, the glass containing both a metal oxide such as lead oxide, bismuth oxide and zinc oxide and an alkali metal oxide such as lithium oxide, sodium oxide and potassium oxide can be softened at a lower alkali content. Point and linear thermal expansion coefficient can be easily controlled.

When a dielectric layer is provided between the substrate and the partition, the adhesion of the partition is increased and peeling is suppressed as compared with the case where the dielectric layer is formed directly on the substrate.

The thickness of the dielectric layer is preferably 5 to 20 μm, more preferably 8 to 15 μm, in order to form a uniform dielectric layer. If the thickness is more than 20 μm, it is difficult to remove the solvent during firing and cracks are easily generated, and the substrate is warped due to a large stress applied to the substrate. If the thickness is less than 5 μm, it is difficult to maintain the uniformity of the thickness.

If a partition pattern is formed on the dielectric layer coating film and then the partition pattern and the dielectric layer coating film are baked simultaneously, the binder removal of the dielectric layer coating film and the partition pattern occurs simultaneously. Shrinkage stress due to debinding of the pattern is reduced, and peeling and disconnection can be prevented.
On the other hand, after baking only the dielectric layer coating film,
When a partition pattern is formed thereon and firing is performed, peeling or disconnection is likely to occur during firing due to insufficient adhesion between the partition and the dielectric layer. Further, when the partition pattern and the dielectric layer coating film are baked simultaneously, there is an advantage that the number of steps can be reduced.

In the case of the simultaneous firing method, it is preferable to cure the film after forming the coating film for the dielectric layer because the coating film is not eroded by the developing solution in the step of forming the partition wall pattern. In order to cure the dielectric layer coating film, a photosensitive layer paste is used as the dielectric layer paste, applied on a glass substrate, dried, exposed, and photocured is a simple and suitable method. Used for

Further, the coating film can be cured by thermal polymerization. In this case, there is a method of adding a radical polymerizable monomer and a radical polymerization initiator to the dielectric layer paste, applying the paste, and then heating the paste.

Although it is possible not to cure the dielectric layer coating film, the dielectric layer is more likely to be eroded and cracked in the dielectric layer in the partition pattern forming step, as compared to the case where the curing is performed. Therefore, a polymer that is insoluble in the developer must be selected.

The dielectric layer according to the present invention has a coefficient of thermal expansion α ₅₀ to ₄₀₀ in the range of ₅₀ to ₄₀₀ ° C., 70 to 85 × 10 ^-7.
/ K, more preferably 72 to 80 × 10 ⁻⁷ / K, as the main component, is preferable in terms of matching the coefficient of thermal expansion of the substrate glass and reducing the stress applied to the glass substrate during firing. . The main component is 60% by weight in all components
It is said that the content is preferably 70% by weight or more.
If it exceeds 85 × 10 ⁻⁷ / K, a stress that warps the substrate will be applied to the surface on which the dielectric layer is formed, and if it is less than 70 × 10 ⁻⁷ / K, the substrate will warp to the surface without the dielectric layer. Such stress is applied. Therefore, the substrate may be cracked when the substrate is repeatedly heated and cooled. In addition, when sealing with the front substrate, the substrates may not be parallel and cannot be sealed due to warpage of the substrates.

Since the amount of warpage of the substrate for a plasma display of the present invention is inversely proportional to the radius of curvature R of the substrate, it can be defined by the reciprocal (1 / R) of the radius of curvature of the substrate. Here, the positive or negative value of the amount of warpage indicates the direction in which the substrate warps. Although the radius of curvature of the glass substrate can be measured by various methods, a surface roughness meter (Tokyo Seimitsu Co., Ltd .: Surfcom 1500A)
The simplest method is to measure the undulation of the substrate surface using the above method. The warpage amount 1 / R can be calculated from the obtained maximum deviation H of the undulation curve and the measured length L using the following equation.

1 / R〓8H / L2 When the substrate is warped, a gap is formed between the head of the partition and the surface of the front plate when the front plate and the rear plate are sealed. As a result, erroneous discharge occurs or the substrate is damaged during sealing. In order to avoid these problems, the absolute value of the amount of warpage needs to be 3 × 10 ⁻³ m ⁻¹ or less. That is, the amount of warpage of the substrate needs to be within the range of the following equation.

-3 × 10 ⁻³ m ⁻¹ ≦ 1 / R ≦ 3 × 10 ^-3 m
^-1 (R represents the radius of curvature of the substrate) In the present invention, warping of the substrate at the time of firing and cracking at the time of panel sealing can be prevented by substantially not containing an alkali metal in the dielectric layer. . In the present invention, "substantially not contained" means that the content of the alkali metal is 0.5% by weight or less, preferably 0.1% by weight or less based on the inorganic material. Even though the coefficient of thermal expansion matches that of the substrate glass, an alkali metal such as Na (sodium), Li
When the content of (lithium), K (potassium) or the like exceeds 0.5% by weight, ion exchange occurs with the glass component in the glass substrate or the electrode during firing, so that the heat of the surface portion of the substrate or the dielectric layer is increased. The coefficient of expansion changes and does not match the coefficient of thermal expansion of the dielectric layer and the substrate, causing tensile stress on the substrate and causing substrate cracking. It is more preferable that the alkaline earth metal is not substantially contained.

The dielectric layer of the present invention is preferably at least two layers. A two-layer structure of a dielectric layer (referred to as dielectric layer A) formed on the electrode on the glass substrate and a dielectric layer (referred to as dielectric layer B) formed on the dielectric layer A is preferable. For example, when silver is used as an electrode, a problem may occur in that components in the dielectric layer A and silver ions or components on the glass substrate cause a reaction such as ion exchange, and the dielectric layer A is colored. is there. In particular, when an alkali metal and its oxide are contained in the dielectric layer A, the ion exchange reaction occurs remarkably, and the dielectric layer A may become yellow. To solve this problem, the dielectric layer A of the present invention is used.
And B are preferably inorganic materials substantially free of alkali metals.

The dielectric layer of the present invention is made of a glass containing at least one of bismuth oxide, lead oxide and zinc oxide, more preferably 10 to 60% by weight of bismuth oxide. It is preferable because control becomes easy. In particular, when bismuth oxide is
Use of glass containing 60% by weight has advantages such as stability of the paste. If the added amount of bismuth oxide, lead oxide, or zinc oxide exceeds 60% by weight, the heat resistance temperature of the glass becomes too low, and it becomes difficult to bake the glass substrate.

Specific examples of glass compositions include those containing the following compositions in terms of oxides, but the present invention is not limited to these glass compositions.

Bismuth oxide 10-60% by weight Silicon oxide 3-50% by weight Boron oxide 10-40% by weight Barium oxide 5-20% by weight Zinc oxide 10-20% by weight Inorganic material contained in the dielectric layer of the present invention For example, white fillers such as titanium oxide, alumina, silica, barium titanate, and zirconia are used. 50 to 9 glass
An inorganic material containing 5% by weight and a filler of 5 to 50% by weight is used. By including the filler in the above range, the reflectance of the dielectric layer is improved, and a high-luminance plasma display can be obtained.

The dielectric layer of the present invention can be formed by applying or laminating a dielectric paste composed of an inorganic material powder and an organic binder on a glass substrate, and firing it. The amount of the inorganic material powder used for the dielectric layer paste is preferably 50 to 95% by weight based on the sum of the inorganic material powder and the organic component. If it is less than 50% by weight, the denseness of the dielectric layer and the flatness of the surface are lacking, and if it exceeds 95% by weight, the paste viscosity increases, and the thickness unevenness during application becomes large.

The method for producing the partition wall of the present invention is not particularly limited, but a photosensitive paste method which has a small number of steps and can form a fine pattern is preferable.

In the photosensitive paste method, a coating film is formed using a photosensitive paste composed of an inorganic material containing glass powder as a main component and a photosensitive organic component, and the coating film is exposed through a photomask and developed. In this method, a partition pattern is formed, and then the partition pattern is fired to obtain a partition.

The amount of the inorganic material used in the photosensitive paste method is 65 to 85% by weight based on the sum of the inorganic material and the organic component.
It is preferred that

If it is less than 65% by weight, the shrinkage during firing becomes large, which causes disconnection and peeling of the partition walls.
Not preferred. Further, drying as a paste becomes difficult, stickiness occurs, and printing characteristics deteriorate. Further, the pattern is likely to be thickened and a residual film is likely to occur during development. When the content is more than 85% by weight, the photosensitive component is small, so that the photocuring is not performed to the bottom of the partition wall pattern, and the pattern formability tends to be deteriorated.

When this method is used, it is preferable to use the following glass powder as the inorganic material.

By adding aluminum oxide, barium oxide, calcium oxide, magnesium oxide, zinc oxide, zirconium oxide and the like, particularly aluminum oxide, barium oxide and zinc oxide to the glass powder, the softening point,
The coefficient of thermal expansion and the refractive index can be controlled, but the content is preferably 40% by weight or less, more preferably 25% by weight or less.
% By weight or less.

Further, glass generally used as an insulator has a refractive index of about 1.5 to 1.9.
When using the photosensitive paste method, if the average refractive index of the organic component is significantly different from the average refractive index of the glass powder, the reflection / scattering at the interface between the glass powder and the organic component increases,
A fine pattern cannot be obtained. Since the refractive index of a general organic component is 1.45 to 1.7, in order to match the refractive index of the glass powder with that of the organic component, the average refractive index of the glass powder is set to 1.5 to 1.7. Is preferred. Still more preferably, it is good to be 1.5-1.65.

A total of 2 to 10% by weight of alkali metal oxides such as sodium oxide, lithium oxide and potassium oxide
By using the glass contained, not only the softening point and the thermal expansion coefficient can be easily controlled, but also the average refractive index of the glass can be lowered, so that the difference in the refractive index from the organic substance can be easily reduced. Become. If it is less than 2%, it becomes difficult to control the softening point. When it is more than 10%, the brightness is reduced due to evaporation of the alkali metal oxide during discharge. Further, the addition amount of the alkali metal oxide is preferably less than 8% by weight, more preferably 6% by weight or less, in order to improve the stability of the paste.

In particular, among the alkali metals, it is preferable to use lithium oxide because the stability of the paste can be relatively increased. Further, when potassium oxide is used, there is an advantage that the refractive index can be controlled by adding a relatively small amount.

As a result, it has a softening point that can be printed on a glass substrate, can have an average refractive index of 1.5 to 1.7, and can easily reduce the difference in refractive index from an organic component. Become.

Glasses containing bismuth oxide are preferred from the viewpoint of improving the softening point and water resistance, but glasses containing 10% by weight or more of bismuth oxide often have a refractive index of 1.6 or more. Therefore, by using bismuth oxide in combination with an oxide of an alkali metal such as sodium oxide, lithium oxide, and potassium oxide, the softening point, the coefficient of thermal expansion, the water resistance,
Control of the refractive index becomes easy.

The measurement of the refractive index of the glass material in the present invention is accurate at the wavelength of the light exposed by the photosensitive glass paste method in order to confirm the effect. In particular, 35
It is preferable to measure with light having a wavelength in the range of 0 to 650 nm. Further, i-line (365 nm) or g-line (4
(36 nm) is preferred.

The partition walls of the present invention may be colored black because they are excellent in increasing the contrast. By adding various metal oxides, the partition walls after firing can be colored. For example, by containing 1 to 10% by weight of a black metal oxide in the photosensitive paste,
A black pattern can be formed.

As the black metal oxide used at this time,
By including at least one, and preferably three or more of the oxides of Ru, Cr, Fe, Co, Mn, and Cu, blackening becomes possible. In particular, a black pattern can be formed by containing 5 to 20% by weight of each of Ru and Cu oxides.

Further, a pattern of each color can be formed by using a paste to which an inorganic pigment which develops a color such as red, blue, green or the like in addition to black is added. These coloring patterns can be suitably used for a color filter of a plasma display and the like.

The dielectric constant of the partition wall glass material is preferably 4 to 10 at a frequency of 1 MHz and a temperature of 20 ° C. in view of excellent power consumption and discharge life of the panel. In order to reduce the value to 4 or less, a large amount of silicon oxide having a dielectric constant of about 3.8 must be contained, and the glass transition point is increased and the firing temperature is increased. If it is 10 or more, power loss due to an increase in the amount of charge occurs, which causes an increase in power consumption, which is not preferable.

The specific gravity of the partition wall of the present invention is preferably from 2 to 3.3. In order to reduce the content to 2 or less, the glass material must contain a large amount of an oxide of an alkali metal such as sodium oxide or potassium oxide, which is unfavorable because it evaporates during the discharge and lowers the discharge characteristics. . When it is 3.3 or more, the display becomes heavy when the screen is enlarged, or the substrate is distorted by its own weight, which is not preferable.

The particle diameter of the glass powder used in the above is selected in consideration of the line width and height of the partition wall to be produced, but the particle diameter of 50% by volume (average particle diameter D50) is 1 to 5.
It is preferable that the particle size is 6 μm, the maximum particle size is 30 μm or less, and the specific surface area is 1.5 to 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 6 μm, 90 volume% particle size (D90): 4 to 15 μm, maximum particle size 2
It preferably has a specific surface area of not more than 5 μm and a specific surface area of 1.5 to 3.5 m ² / g. More preferably, D50 is 2
It is 3.5 μm and the specific surface area is 1.5 to 3 m ² / g.

Here, D10, D50 and D90 are glass particle diameters of 10% by volume, 50% by volume and 90% by volume, respectively, of glass powder having a small particle diameter.

If the particle size is smaller than the above-mentioned particle size distribution, the specific surface area increases, so that the agglomeration of the powder increases, and the dispersibility in the organic component decreases. For this reason, light scattering increases, the central part of the partition wall becomes thicker, and the bottom part is insufficiently cured, and a desirable shape cannot be obtained. On the other hand, if the particle size is large, the bulk density of the powder is reduced, so that the filling property is reduced, and the amount of the photosensitive organic component is insufficient, so that air bubbles are easily entangled and light scattering is apt to occur.

Therefore, there is an optimum region in the particle size distribution, and by using the glass powder having the above particle size distribution, the filling property of the powder is improved, and even if the powder ratio in the photosensitive paste is increased, the air bubbles are reduced. Is reduced, and since the extra light scattering is small, the partition pattern formation is maintained. In addition, since the powder filling ratio is high, the firing shrinkage ratio is reduced, the pattern accuracy is improved, and a preferable partition shape is obtained.

The method for measuring the particle size is not particularly limited, but it is preferable to use a laser diffraction / scattering method because it can be measured easily. For example, the measurement conditions when the particle size distribution analyzer HRA9320-X100 manufactured by Microtrac Co., Ltd. is used are as follows.

Sample amount: 1 g Dispersion conditions: Ultrasonic dispersion in purified water for 1 to 1.5 minutes. If dispersion is difficult, perform in a 0.2% aqueous sodium hexametaphosphate solution.

Particle refractive index: changed depending on glass type (lithium-based 1.6, bismuth-based 1.88) Solvent refractive index: 1.33 Number of measurements: 2 times The partition walls of the present invention have a softening point of 550 to 1200 ° C., and A filler having a temperature of preferably 650 to 800 ° C. may be contained in an amount of 3 to 60% by weight. Thereby, in the photosensitive paste method, the shrinkage ratio at the time of baking after pattern formation is small, the pattern formation is easy, and the shape retention at baking is improved.

As the filler, titania, alumina,
A high melting point glass powder containing 15% by weight or more of ceramics such as barium titanate and zirconia, silicon oxide and aluminum oxide is preferable. As an example, it is preferable to use a glass powder containing the following composition.

Silicon oxide: 25 to 50% by weight Boron oxide: 5 to 20% by weight Aluminum oxide: 25 to 50% by weight Barium oxide: 2 to 10% by weight When a high melting glass powder is used as a filler, the base glass material (low If the difference in refractive index from the glass (melting point glass) is large, matching with the organic component becomes difficult, and the pattern formability deteriorates.

Therefore, the average refractive index N of the low melting glass powder is
1. When the average refractive index N2 of the high melting point glass powder is in the following range, the refractive index matching with the organic component becomes easy.

-0.05≤N1-N2≤0.05 The small variation in the refractive index of the inorganic powder is also important for reducing the light scattering. ± 0.05 variation in refractive index
(95% by volume or more of the inorganic powder has an average refractive index N1 ±
0.05) is preferable for reducing light scattering.

The filler preferably has an average particle diameter of 1 to 6 μm. D10 (10
Volume% particle diameter) 0.4 to 2 μm, D50 (50 volume% particle diameter): 1 to 3 μm, D90 (90 volume% particle diameter): 3
It is preferable to use one having a particle size distribution of about 8 μm and a maximum particle size of 10 μm or less from the viewpoint of pattern formation.

Still more preferably, D90 is 3-5 μm.
m, and the maximum particle size is preferably 5 μm or less. D90 is 3
Fine powder having a size of from 5 μm to 5 μm is preferable because it is excellent in that a shrinkage ratio of firing can be reduced and a partition having a low porosity is produced. In addition, it is possible to make the unevenness in the longitudinal direction of the upper part of the partition wall less than ± 2 μm. It is not preferable to use a powder having a large particle diameter as the filler, because not only the porosity increases, but also the irregularities on the upper part of the partition wall become large, causing erroneous discharge.

As an organic component contained in the glass paste, a cellulose compound represented by ethyl cellulose, an acrylic polymer represented by polyisobutyl methacrylate, and the like can be used. In addition, polyvinyl alcohol, polyvinyl butyral, methacrylate polymer, acrylate polymer, acrylate-methacrylate copolymer, α-methylstyrene polymer, butyl methacrylate resin, and the like can be given.

In addition, various additives can be added to the glass paste as needed, and an organic solvent may be added when the viscosity is to be adjusted. As the organic solvent used at this time, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone,
Isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, terpineol, and an organic material containing at least one of these A solvent mixture is used.

When a photosensitive paste method is used as the partition wall forming method, the following organic components are used.

The organic component contains a photosensitive component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer. If necessary, a binder, a photopolymerization initiator, an ultraviolet absorber, Additive components such as a sensitizer, a sensitization aid, a polymerization inhibitor, a plasticizer, a thickener, an organic solvent, an antioxidant, a dispersant, and an organic or inorganic precipitation inhibitor may also be added.

The photosensitive component includes a photo-insolubilizing type and a photo-solubilizing type. The photo-insolubilizing type includes: (A) a functional monomer having at least one unsaturated group in the molecule. (B) those containing photosensitive compounds such as aromatic diazo compounds, aromatic azide compounds, and organic halogen compounds. (C) So-called diazo resins such as condensates of diazo amines and formaldehyde. And others.

Examples of the photo-soluble type include (D) a complex of a diazo compound with an inorganic salt or an organic acid, and a compound containing a quinone diazo compound. (E) a quinone diazo compound combined with an appropriate polymer binder. For example, phenol, naphthoquinone-1,2-diazide-5-sulfonic acid ester of a novolak resin, and the like.

As the photosensitive component used in the present invention, all of the above can be used. As the photosensitive component which can be easily used as a photosensitive paste by being mixed with inorganic fine particles, (A) is preferred.

The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and sec-butyl. Acrylate, sec-
Butyl acrylate, iso-butyl acrylate, te
rt-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate Heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobonyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafuro Pentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene Glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, Polypropylene Glycol diacrylate, triglycerol diacrylate,
Trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct,
Diacrylates of bisphenol A-propylene oxide adducts, acrylates such as thiophenol acrylate and benzyl mercaptan acrylate, and monomers in which 1 to 5 hydrogen atoms of these aromatic rings have been substituted with chlorine or bromine atoms, or Styrene, p-
Methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethyl Styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, and those obtained by changing some or all of the acrylate in the molecule of the above compound to methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, etc. No. In the present invention, one or more of these can be used.

In addition to the above, the developability after exposure can be improved by adding an unsaturated acid such as an unsaturated carboxylic acid. 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 content of these monomers is preferably 5 to 30% by weight based on the sum of the glass powder and the photosensitive component.
Outside of this range, the pattern formability deteriorates and the hardness becomes insufficient after curing.

Examples of the binder include polyvinyl alcohol, polyvinyl butyral, methacrylate polymer, acrylate polymer, and acrylate ester.
Examples include methacrylate copolymers, α-methylstyrene polymers, and butyl methacrylate resins.

Further, an oligomer or a polymer obtained by polymerizing at least one of the compounds having a carbon-carbon double bond described above can be used. During the polymerization, the copolymer may be copolymerized with another photosensitive monomer so that the content of the photoreactive monomer is 10% by weight or more, more preferably 35% by weight or more.

As a monomer to be copolymerized, the developability after exposure can be improved by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid. 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 polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained preferably has an acid value (AV) of 30 to 150, more preferably 70 to 120. If the acid value is less than 30, the solubility of the unexposed portion in the developing solution is reduced. Therefore, if the developing solution concentration is increased, peeling occurs up to the exposed portion, making it difficult to obtain a high-definition pattern. On the other hand, when the acid value exceeds 150, the allowable development width becomes narrow.

In the case where the developability is imparted by a monomer such as an unsaturated acid, it is preferable that the acid value of the polymer be 50 or less since gelation due to the reaction between the glass powder and the polymer can be suppressed.

By adding a photoreactive group to a side chain or a molecular terminal of the polymer or oligomer described above, it can be used as a photosensitive polymer or a photosensitive oligomer having photosensitivity. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryl group, and a methacryl group.

A method for adding such a side chain to an oligomer or a polymer is based on an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, an acrylic acid, or 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 from 0.05 to 0.05 to the mercapto group, amino group, hydroxyl group and carboxyl group in the polymer. It is preferable to add one molar equivalent.

The amount of the polymer component comprising the photosensitive polymer, the photosensitive oligomer and the binder in the photosensitive glass paste is excellent in terms of pattern formability and shrinkage ratio after firing. It is preferably 5 to 30% by weight based on the sum of the components. Outside this range, it is not preferable because pattern formation is impossible or the pattern becomes thick.

As specific examples of the photopolymerization initiator,
Benzophenone, methyl o-benzoylbenzoate, 4,
4-bis (dimethylamine) benzophenone, 4,4-
Bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,
2-diethoxyacetophenone, 2,2-dimethoxy-
2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl Ketanol, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-
Chloranthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-
Azidobenzylidene) -4-methylcyclohexanone,
2-phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3
-Diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-
Propanetrione-2- (o-benzoyl) oxime,
Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, naphthalenesulfonyl chloride, quinoline Sulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile,
Photoreducing dyes such as diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide and eosin, and methylene blue and reducing agents such as ascorbic acid and triethanolamine Combinations and the like are given. In the present invention, one or more of these can be used.

The photopolymerization initiator is added in an amount of 0.1 to the photosensitive component.
In the range of 0.5 to 20% by weight, more preferably
0.1 to 15% by weight. 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 too small.

It is also effective to add an ultraviolet absorber. By adding a compound having a high ultraviolet absorption effect, a high aspect ratio, high definition, and high resolution can be obtained. UV absorbers composed of organic dyes, especially 35
Organic dyes having a high UV absorption coefficient in the wavelength range of 0 to 450 nm are preferably used. Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, anthraquinone dyes, benzophenone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes and the like can be used. Even when the organic dye is added as a light absorbing agent, it is preferable because deterioration of the insulating film characteristics due to the light absorbing agent can be reduced without remaining in the insulating film after firing. Among these, azo dyes and benzophenone dyes are preferred.

The addition amount of the organic dye is preferably 0.05 to 1 part by weight based on the glass powder. If the content is less than 0.05% by weight, the effect of adding the ultraviolet absorber is low, and if it exceeds 1% by weight, the properties of the insulating film after firing are deteriorated, which is not preferable. More preferably, it is 0.1 to 0.18% by weight.

An example of a method for adding an ultraviolet light absorbing agent comprising an organic dye will be described. A solution in which an organic dye is dissolved in an organic solvent in advance is prepared, and the solution is kneaded when preparing a paste. Alternatively, there is a method in which glass fine particles are mixed into the organic dye solution and then dried. By this method, so-called capsule-shaped fine particles in which the surface of each of the glass fine particles is coated with an organic dye film can be produced.

In the present invention, C contained in inorganic fine particles
Metals and oxides such as a, Fe, Mn, Co, and Mg may react with the photosensitive components contained in the paste, causing the paste to gel in a short time, making it impossible to apply the paste. In order to prevent such a reaction, it is preferable to add a stabilizer to prevent gelation. As the stabilizer used,
Triazole compounds are preferably used. As the triazole compound, a benzotriazole derivative is preferably used. Among them, benzotriazole works particularly effectively. As an example of surface treatment of glass fine particles with benzotriazole used in the present invention, a predetermined amount of benzotriazole with respect to inorganic fine particles was dissolved in an organic solvent such as methyl acetate, ethyl acetate, ethyl alcohol, and methyl alcohol. Thereafter, the particles are immersed in the solution for 1 to 24 hours so that the particles can be sufficiently immersed. After immersion, preferably, the particles are naturally dried at 20 to 30 ° C., and the solvent is evaporated to produce triazole-treated fine particles. The ratio of the stabilizer used (stabilizer / inorganic fine particles) is preferably 0.05 to 5% by weight.

The sensitizer is added to improve the sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone,
2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone,
4,4-bis (diethylamino) -benzophenone,
4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylvinylene)- Isonaphthothiazole, 1,3-bis (4-
Dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylaminobenzal) acetone,
3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N
-Phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. Can be 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 too small.

As the sensitizer, one having absorption at the exposure wavelength is used. In this case, the refractive index becomes extremely high near the absorption wavelength. In addition, the refractive index of the organic component can be improved. In this case, the sensitizer may be added in an amount of 3 to 10% by weight.

The polymerization inhibitor is added to improve the heat stability during storage. Specific examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone,
N-nitrosodiphenylamine, phenothiazine, p-
t-butylcatechol, N-phenylnaphthylamine,
2,6-di-t-butyl-p-methylphenol, chloranil, pyrogallol and the like.

Further, the addition increases the threshold value of the photo-curing reaction, reduces the pattern line width, and eliminates the thickening of the upper portion of the pattern due to the gap.

The amount added is usually 0.01 to 1% by weight in the photosensitive paste. If the amount is less than 0.01% by weight, the effect of addition is difficult to obtain, and if the amount is more than 1% by weight, the sensitivity decreases, so that a large amount of exposure light is required to form a pattern.

Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.

An antioxidant is added to prevent oxidation of the acrylic copolymer during storage. Specific examples of antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, and 2,6-di-t.
-4-ethylphenol, 2,2-methylene-bis-
(4-methyl-6-t-butylphenol), 2,2-
Methylene-bis- (4-ethyl-6-t-butylphenol), 4,4-bis- (3-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-6
-T-butylphenol), 1,1,3-tris- (2
-Methyl-4-hydroxy-t-butylphenyl) butane, bis [3,3-bis- (4-hydroxy-3-t-
[Butylphenyl) butyric acid] glycol ester, dilaurylthiodipropionate, triphenylphosphite and the like. When adding an antioxidant, the addition amount is usually 0.01 to 1% by weight in the paste.

When the viscosity of the solution is to be adjusted, an organic solvent may be added to the photosensitive paste of the present invention. The organic solvent used at this time includes methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, Chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and an organic solvent mixture containing at least one of these are used.

The refractive index of the organic component is the refractive index of the organic component in the paste at the time when the photosensitive component is exposed by exposure. In other words, when the paste is applied and the exposure is performed after the drying step, it refers to the refractive index of the organic component in the paste after the drying step. For example, there is a method of applying a paste on a glass substrate, drying the paste at 50 to 100 ° C. for 1 to 30 minutes, and measuring the refractive index.

The measurement of the refractive index in the present invention is preferably performed by a generally performed ellipsometry method or V-block method, and the measurement is performed at the wavelength of the light to be exposed, which is accurate for confirming the effect. In particular, it is preferable to measure with light having a wavelength in the range of 350 to 650 nm. Further, it is preferable to measure the refractive index at the i-line (365 nm) or the g-line (436 nm).

In order to measure the refractive index after the organic component is polymerized by light irradiation, it can be measured by irradiating only the organic component with the same light as when irradiating light in the paste.

The photosensitive paste is usually prepared by mixing various components such as inorganic fine particles, an ultraviolet absorber, a photosensitive polymer, a photosensitive monomer, a photopolymerization initiator, a glass frit and a solvent so as to have a predetermined composition. The mixture is uniformly mixed and dispersed with three rollers or a kneading machine.

The viscosity of the paste is appropriately adjusted by the addition ratio of inorganic fine particles, a thickener, an organic solvent, a plasticizer, a suspending agent, etc., but the range is from 2000 to 200,000 cp.
s (centipoise). For example, when the coating on the glass substrate is performed by the spin coating method, 200 to 5000 c
ps is preferred. In order to obtain a film thickness of 10 to 20 μm by applying once by a screen printing method, 10,000 to 100,000 cps is preferable.

Next, an example of performing pattern processing using a photosensitive paste will be described, but the present invention is not limited to this.

A photosensitive paste is applied on the entire surface or on a glass substrate, a ceramic substrate, or a polymer film. As the application method,
Methods such as screen printing, a bar coater, a roll coater, a die coater, and a blade coater can be used. The coating thickness is determined by the number of coatings, screen mesh,
It can be adjusted by choosing the viscosity of the paste.

When applying the paste on the substrate,
Surface treatment of the substrate can be performed to enhance the adhesion between the substrate and the coating film. Examples of the surface treatment liquid include silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and tris-silane.
(2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like, or organic metals such as organic titanium, organic aluminum and organic zirconium. The silane coupling agent or the organic metal is dissolved in an organic solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol or the like.
Use the one diluted to a concentration of 1 to 5%. Next, after applying this surface treatment liquid uniformly on the substrate with a spinner or the like, 8
Surface treatment can be performed by drying at 0 to 140 ° C. for 10 to 60 minutes.When applied on a film, after drying on the film, performing the next exposure step,
There is a method in which an exposure step is performed after affixing on a glass or ceramic substrate.

After application, exposure is performed using an exposure device. The exposure is generally performed by a mask exposure using a photomask, as is performed by ordinary photolithography. As the mask to be used, either a negative type or a positive type is selected depending on the type of the photosensitive organic component. Alternatively, a method of directly drawing with a red or blue laser beam without using a photomask may be used.

As an exposure apparatus, a stepper exposure machine, a proximity exposure machine or the like can be used. In the case of performing a large-area exposure, after applying a photosensitive paste on a substrate such as a glass substrate, and performing the exposure while transporting, it is possible to expose a large area with an exposure machine having a small exposure area. it can.

The active light source used at this time is, for example,
Visible light, near-ultraviolet light, ultraviolet light, electron beam, X-ray, laser light, etc. are preferable. Among them, ultraviolet light is preferable. Etc. can be used. Among these, an ultra-high pressure mercury lamp is preferred.
Exposure conditions vary depending on the coating thickness, but 3 to 50 mW /
Exposure is performed for 20 seconds to 30 minutes using an ultrahigh pressure mercury lamp having an output of cm ² .

After the exposure, development is performed utilizing the difference in solubility between the photosensitive portion and the non-photosensitive portion in the developing solution.
The immersion method, the shower method, the spray method, and the brush method are used.

As the developer used, an organic solvent in which the organic components in the photosensitive paste can be dissolved can be used. Water may be added to the organic solvent as long as the solvent does not lose its solubility. When a compound having an acidic group 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, a metallic alkaline aqueous solution such as sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution, etc. can be used, but it is preferable to use an organic alkaline aqueous solution since the alkaline component can be easily removed during firing.

As the organic alkali, an 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 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded, which is not preferable. The development temperature during development is preferably from 20 to 50 ° C. from the viewpoint of process control.

Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of the paste and the substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

When processing a pattern on a glass substrate,
The baking is performed at a temperature rising rate of 200 to 400 ° C./hour and a temperature of 540 to 610 ° C. for 10 to 60 minutes. The firing temperature is determined by the glass powder to be used, but it is preferable to fire at an appropriate temperature at which the shape after pattern formation does not collapse and the shape of the glass powder does not remain.

[0168] If the temperature is lower than the appropriate temperature, the porosity and unevenness of the upper portion of the partition wall become large, and the discharge life is shortened and erroneous discharge is liable to occur.

If the temperature is higher than the appropriate temperature, the shape at the time of pattern formation is broken, the upper part of the partition wall becomes round, or the height becomes extremely low, so that a desired height cannot be obtained.

A heating step at 50 to 300 ° C. may be introduced during the above-mentioned coating, exposure, development and baking steps for the purpose of drying and preliminary reaction.

[0171]

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to this. The concentrations (%) in Examples and Comparative Examples are by weight unless otherwise specified. Materials used in Examples and Comparative Examples of the present invention are shown below.

Glass (1); Composition: 7% Li ₂ O, 22% SiO ₂ , 32% B ₂ O ₃ , 4% BaO, 22% Al ₂ O ₃ , 2% ZnO, 6% MgO, 4% CaO Thermophysical property: glass transition point 491 ° C., softening point 528 ° C., coefficient of thermal expansion 74 × 10 ⁻⁷ / K Particle size: D10 0.9 μm D50 2.6 μm D90 7.5 μm Maximum particle size 22.0 μm Specific surface area: 1. 92 m ² / g Refractive index: 1.59 (g line 436 nm) Specific gravity: 2.54 Glass (2); Composition: 38% Bi ₂ O ₃ , 7% SiO ₂ , 19% B ₂ O ₃ , BaO 12%, Al ₂ O ₃ 4%, ZnO 20% Thermal properties: glass transition point 475 ° C., softening point 515 ° C., thermal expansion coefficient 75 × 10 ⁻⁷ / K Particle size: D10 0.9 μm D50 2.5 μm D903 9.9 μm Maximum particle size 6.5 μm (white filler powder) Filler; TiO ₂ , specific gravity 4.61 (polymer) Polymer (1); 40% methacrylic acid (MAA), 3
0% methyl methacrylate (MMA) and 30%
0.4 equivalent of glycidyl methacrylate (G) to the carboxyl group of the copolymer of styrene (St)
MA) by addition reaction, a 40% solution of a photosensitive polymer having a weight average molecular weight of 43,000 and an acid value of 95 in γ-butyrolactone polymer (2); ethyl cellulose / terpineol = 6
/ 94 solution (weight ratio) (Monomer) Monomer _{(1); X 2 -N-} CH (CH 3) -CH 2 - (O-CH 2 -CH (CH 3)) n -NX 2 X: -CH _{2 -CH (OH) -CH 2 O} -CO-C (CH 3) = CH 2 n = 2~10 monomer (2); trimethylolpropane triacrylate modified PO (photopolymerization initiator) IC-369; Irgacure -369 (Ciba-Geigy product) 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 IC-907; Irgacure-907 (Ciba-Geigy product) 2-methyl-1- (4 -(Methylthio) phenyl-2-
Morpholinopropanone (sensitizer) DETX-S; 2,4-diethylthioxanthone (sensitizer aid) EPA; p-dimethylaminobenzoic acid ethyl ester (plasticizer) DBP; dibutyl phthalate (DBP) (thickener) SiO ₂ ; 15% solution of 2- (2-butoxyethoxy) ethyl acetate of SiO ₂ (organic dye) Sudan; azo organic dye, chemical formula C ₂₄ H ₂₀ N ₄ O, molecular weight 380.45 (solvent) γ-butyrolactone terpineol ( Dispersant) Nopcospars 092 (manufactured by San Nopco) (Stabilizer) 1,2,3-benzotriazole Example 1 First, a photosensitive paste for partition walls was prepared. 100 parts by weight of glass powder (glass (1)) and 0.0 parts of organic dye
It was weighed at a ratio of 8 parts by weight. Sudan was dissolved in acetone, a dispersant was added, and the mixture was homogeneously stirred with a homogenizer. After adding glass powder to this solution and uniformly dispersing and mixing,
Using a rotary evaporator, drying was performed at a temperature of 100 ° C., and acetone was evaporated. In this way, a powder was prepared in which the surface of the glass powder was uniformly coated with the organic dye film.

The polymer (1), the monomer (1), the photopolymerization initiator (IC-369), the sensitizer, the plasticizer, and the solvent were used in an amount of 37.5: 15:
The mixture was mixed at a weight ratio of 4.8: 4.8: 2: 7.5 and homogeneously dissolved. Thereafter, this solution was filtered using a 400-mesh filter to obtain an organic vehicle.

The above-mentioned glass powder and the above-mentioned organic vehicle were added in a weight ratio of glass powder: organic vehicle = 70: 71.6, and mixed and dispersed with three rollers to prepare a photosensitive paste for partition walls. did. The refractive index of the organic component is 1.5
9. The refractive index of the glass powder was 1.59.

Next, a paste for a dielectric layer having a weight ratio of glass (2): filler: polymer (2) = 55: 10: 35 was prepared in the same manner. This dielectric paste is pitch 1
13-inch size PD-20 manufactured by Asahi Glass Co., Ltd. in which electrodes having a size of 40 μm, a line width of 60 μm, and a thickness of 4 μm are formed in advance.
A glass substrate was uniformly applied by screen printing using a 325 mesh screen. Then 8
Dried at 0 ° C for 40 minutes and calcined at 550 ° C to a thickness of 10
A μm dielectric layer was formed.

On the dielectric layer, paste the partition wall paste
The solution was uniformly applied by screen printing using a 25-mesh screen to form a coating film. Coating and drying were repeated several times or more to prevent pinholes and the like from being generated in the coating film, and the film thickness was adjusted. The screen printing plate used was designed to be smaller than the length of the partition wall pattern in the longitudinal direction. Drying on the way is 10 at 80 ° C.
After forming the coating film for 1 minute, drying was performed at 80 ° C. for 1 hour.
The thickness of the coating film after drying was 150 μm. An inclined surface having a length of 2000 μm was formed at the end of the coating film.

Subsequently, through a 140 μm-pitch striped negative chrome mask, 50 mJ / c from the upper surface.
Ultraviolet irradiation was performed using an ultra-high pressure mercury lamp having an m ² output. The exposure amount was 1.0 J / cm ² . At this time, the chrome mask used had a partition pattern length longer than the length of the coating film in the partition longitudinal direction.

Next, a 0.2 wt% aqueous solution of monoethanolamine kept at 35 ° C. was developed by applying a shower for 170 seconds, and then washed with water using a shower spray. As a result, portions that were not photocured were removed, and a stripe-shaped partition pattern was formed on the glass substrate.

The glass substrate on which the partition pattern was formed was fired in air at 570 ° C. for 15 minutes to form a partition. The cross-sectional shape of the end of the partition pattern before and after firing was measured using a scanning electron microscope (S-240 manufactured by HITACHI).
0). The evaluation results are shown in Table 1. When there was no swelling or bouncing, "O" was given, and when there was swelling or bouncing, the contents and numerical values were described.

As a result, X was 2 mm, Y was 100 μm,
X / Y = 20, which satisfied the range of the present invention. In addition, it jumped to the end of the partition wall and was good without swelling.

Between the partition walls thus formed, red, blue,
A phosphor paste that emits green light was applied by a screen printing method, and the paste was baked (500 ° C., 30 minutes) to form a phosphor layer on the side and bottom of the partition, thereby completing the back plate.

Next, a front plate was manufactured by the following steps. First, after forming ITO by sputtering on the same glass substrate as the back plate, applying a resist, exposing and developing into a desired pattern, etching, and firing to a thickness of 0.1 μm.
m, a transparent electrode having a line width of 200 μm was formed. Further, a bus electrode having a thickness of 10 μm was formed after firing by a photolithography method using a photosensitive silver paste composed of black silver powder. Electrodes having a pitch of 140 μm and a line width of 60 μm were prepared.

Further, a transparent dielectric paste was applied to a thickness of 20 μm on the front plate on which the electrodes were formed, and baked at 430 ° C. for 20 minutes. Next, the formed transparent electrode, black electrode,
A 0.5 μm thick MgO film was formed using an electron beam evaporator so as to uniformly cover the dielectric layer, thereby completing the front plate.

After the obtained front substrate was bonded and sealed to the rear substrate, a discharge gas was sealed therein, and a driving circuit was joined to produce a plasma display. Display was performed by applying a voltage to this panel. Table 1 shows the evaluation results. When a uniform display was obtained over the entire surface, ○ was indicated, and when a problem such as erroneous discharge was observed, the content was described. Table 1
As shown in the figure, a uniform display was obtained over the entire surface.

Example 2 The dielectric layer paste was prepared by mixing glass (2), filler, polymer (2) and monomer (2) with 22.5: 2.2: 1, respectively.
A dielectric layer paste was applied on a glass substrate in the same manner as in Example 1 except that a photosensitive paste mixed at a weight ratio of 0: 10: 0.3: 1.6 was used. Thickness after drying is 1
It was 5 μm. Instead of pre-firing, 50
It was exposed to ultraviolet light with an exposure amount of 1 J / cm ^{2 using} an ultrahigh pressure mercury lamp having an output of mJ / cm ² . Thereafter, a plasma display was manufactured in the same manner as in Example 1. The dielectric layer was fired simultaneously with the firing of the partition pattern. Evaluation was performed in the same manner as in Example 1.
Table 1 shows the results.

Example 3 When the photosensitive paste for a partition was applied on a substrate by screen printing, a screen printing plate was printed with an area larger than the partition pattern length of a photomask and a thickness of 50 μm. Using a screen printing plate having a printing surface smaller than the partition wall pattern length of the
The same operation as in Example 1 was performed except that the printing was performed at 0 μm.

When the pattern was formed, a thickness of 5
The end of the lower layer of 0 μm has a right angle and a thickness of 1 μm.
The end of the upper layer of the partition wall having a thickness of 00 μm is inclined, and has the shape shown in FIG.

When sintering was performed in the same manner as in Example 1, the end of the lower layer (having a height of 33 μm after sintering) had a swell of 10 μm, but the end of the upper layer (having a height of 67 μm after sintering) had swelling It could be formed without. Upper layer is 67μ
Because of m, the swelling of the lower layer portion did not exceed the upper layer portion, and the entire partition could be formed without any problem. Thereafter, a plasma display was fabricated and evaluated in the same manner as in Example 1.
Table 1 shows the results.

Example 4 When a partition wall paste was applied on a substrate, a thickness of 250 μm before drying was applied using a slit die coater, and air was jetted using a nozzle having an inner diameter of 0.4 mm before drying. A partition pattern was formed in the same manner as in Example 1 except that an inclined surface was formed at the end of the coating film. Air pressure is 2.5
kgf / cm ² , and the spray angle is 4
Injected at an angle of 5 °. Thereafter, a plasma display was fabricated and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 5 A plasma display was produced and evaluated in the same manner as in Example 4 except that the pressure of the air jet from the nozzle was 0.5 kgf / cm ² when forming the inclined surface at the end of the coating film. . Table 1 shows the results.

Example 6 After the partition wall paste was applied on the substrate, the paste was dried at 80 ° C. for 5 minutes, and sprayed with a nozzle having an inner diameter of 1.5 mm φ at an injection pressure of 1.0 k.
g / cm ² , ethyl cellulose / terpineol = 1
A plasma display was prepared and evaluated in the same manner as in Example 4, except that a solvent of / 99 (weight ratio) was sprayed to form an inclined surface at the end of the coating film. Table 2 shows the results.

Example 7 When forming an inclined surface at the end of the coating film, the injection was performed with a gap of 0.4 m.
A plasma display was prepared and evaluated in the same manner as in Example 4, except that the measurement was performed using a slit of m. Table 2 shows the results
Shown in

Example 8 When forming an inclined surface at the end of the coating film, the coating film was
After drying for an hour, a plasma display was prepared and evaluated in the same manner as in Example 4, except that the end of the coating film was scraped off with a blade to form an inclined surface. The size of the tip of the blade is φ = 3
At 0 °, the blade was arranged at an angle Θ = 45 ° so that the blade could cover the substrate, and cutting was performed at a speed of 5 m / s by 15 μm / times. This operation was repeated five times to cut 75 μm from the upper part of the partition. Table 2 shows the results.

Example 9 First, a pitch of 200 mm was formed on an aluminum substrate by using a grinding machine.
A prototype of a partition wall having a stripe shape of μm, a line width of 30 μm, and a height of 200 μm was formed. A silicone resin is filled on the partition mold, and the pitch is 200 μm, the line width is 30 μm, and the height is 20 μm.
A silicone mold (size 300 mm square) in which 0 μm stripe-shaped grooves were formed was used as a partition wall mold. In the above, by forming an inclined portion at the end of the partition mold, the inclined portion is formed over the length of 3 mm of the end of the silicone resin partition mold.

Next, 800 g of glass powder (1), polymer
(2) 200 g, plasticizer 50 g, terpineol 250 g
And mixed and dispersed with three rollers to obtain a viscosity of 950.
A barrier paste of 0 cps was prepared.

The silicone mold was filled with the partition wall paste using a doctor blade coater.
The silicone mold was peeled off by transferring it onto a glass substrate of mm square to form a partition pattern. Next, the glass substrate on which the partition pattern was formed was fired under the same firing conditions as in Example 1 to form the partition.

Thereafter, a plasma display was manufactured and evaluated in the same manner as in Example 1. Table 2 shows the results.

Example 10 First, a copper plate having a thickness of 1 mm was etched at a pitch of 20 mm.
A stripe-shaped groove having a thickness of 0 μm, a line width of 30 μm, and a height of 200 μm was formed to obtain a partition wall matrix. The etching was performed so that an inclined portion was formed at the end of the groove during the etching.

Next, 800 g of glass powder (2), polymer
(2) 150 g, plasticizer 50 g, monomer (2) 100 g, polymerization initiator (benzoyl oxide) 10 g, solvent 250
g, and mixed and dispersed with three rollers to give a viscosity of 85.
A paste for partition walls of 00 cps was prepared.

After filling the above-mentioned partition wall matrix with the partition wall paste using a doctor blade coater, 400 mm
It pressed on the corner glass substrate and heated at 100 degreeC for 30 minutes. Next, a partition pattern was formed by peeling the partition mold, and the glass substrate on which the partition pattern was formed was fired under the same firing conditions as in Example 1 to form the partition.

Thereafter, a plasma display was manufactured and evaluated in the same manner as in Example 1. Table 2 shows the results.

Example 11 A 200 μm pitch was etched on a 1 mm thick copper plate by etching.
m, a stripe-shaped groove having a line width of 30 μm and a height of 200 μm were formed to form a partition matrix. The etching was performed such that a 10-degree inclined portion was formed at the end of the groove during the etching.

The same partition wall paste as in Example 10 was applied to the substrate in the same manner as in Example 4, and before drying, the partition wall matrix was pressed against the partition wall paste coating film on the glass substrate to be applied. Heated to 80 ° C. while pressing. Next, by separating the partition matrix, a partition pattern is formed,
The partition wall was formed by firing the glass substrate on which the partition pattern was formed under the same firing conditions as in Example 1.

Thereafter, a plasma display was manufactured and evaluated in the same manner as in Example 1. Table 3 shows the results.

Example 12 The procedure of Example 1 was repeated, except that the photosensitive paste for the partition was applied and dried, and then the edge of the photosensitive paste coating film was rubbed with a cloth containing a solvent to form an inclined surface. A plasma display was manufactured and evaluated in the same manner as in Example 1.
Table 3 shows the results.

Comparative Example 1 A partition pattern was formed in the same manner as in Example 8, except that the angle φ of the blade used was 80 degrees and the length of the inclined surface at the end of the coating layer was 35 μm.

The coating film of the present paste was 63%
Therefore, if firing is possible without swelling, X = 35 μm and Y = 100 μm after firing, and X / Y = 0.
35.

As a result of baking in the same manner as in Example 1, a jump of 80 μm occurred at the end of the partition wall. Thereafter, a plasma display was fabricated and evaluated in the same manner as in Example 1. Table 3 shows the results. Crosstalk occurred in a range of about 10 mm width around the display surface.

Comparative Example 2 A partition pattern was formed in the same manner as in Example 1 except that a chromium mask having a length smaller than the length of the coating film in the longitudinal direction of the partition was used. The ends of the partition pattern are vertical,
There were no slopes.

As a result of baking in the same manner as in Example 1, a protrusion of 20 μm was formed at the end of the partition wall. FIG. 5 shows the shape of the obtained partition end. Thereafter, a plasma display was fabricated and evaluated in the same manner as in Example 1. Table 3 shows the results. Crosstalk occurred in a range of about 10 mm width around the display surface.

[0211]

[Table 1]

[0212]

[Table 2]

[0213]

[Table 3]

[0214]

According to the partition wall end shape of the present invention, it is possible to obtain a plasma display in which the end portion does not jump up or rise. Accordingly, it is possible to provide a plasma display that can perform uniform display over the entire surface without causing erroneous discharge at the end. The plasma display of the present invention can be used for a large television or a computer monitor.

[Brief description of the drawings]

FIG. 1 is a diagram showing a structure of a plasma display.

FIG. 2 is a side view showing a shape of a partition wall according to the present invention.

FIG. 3 is a side view showing a conventional partition shape.

FIG. 4 is a side view showing a shape of a partition wall after baking.

FIG. 5 is a side view showing the shape of the raised ribs after firing.

FIG. 6 is a side view showing an example of the partition shape of the present invention.

FIG. 7 is a side view showing an example of a partition wall shape of the present invention.

FIG. 8 is a side view showing an example of the partition wall shape of the present invention.

FIG. 9 is a cross-sectional view illustrating an example of an inclined surface formed on a paste application film for a partition.

FIG. 10 is a cross-sectional view showing the relationship between the shape of a blade or a grindstone and the shape of an end portion of a coating film shaved by the shape.

FIG. 11 is an example of a method for forming an inclined surface by shaving an end portion of a coating film with a blade, which is a preferable manufacturing method of the present invention.

FIG. 12 is an example of a method for forming an inclined surface by shaving an end portion of a coating film with a blade, which is a preferable manufacturing method of the present invention.

FIG. 13 is a sectional view of a partition wall mold preferably used in the manufacturing method of the present invention.

FIG. 14 is a sectional view of a partition pattern in which an inclined surface is formed at an end of a coating film in Example 3.

Claims (11)

[Claims] 1. A plasma display having a dielectric layer and a stripe-shaped partition formed on a substrate, wherein the plasma display has an inclined portion at a longitudinal end of the partition. 2. The plasma display according to claim 1, wherein the height (Y) of the inclined portion of the partition and the length (X) of the base of the inclined portion are in the following ranges. 0.5 ≦ X / Y ≦ 100 3. The length (X) of the base of the inclined portion is 0.05 to 1
The plasma display according to claim 1, wherein the thickness is 0 mm. 4. The plasma display according to claim 1, wherein the inclination angle of the inclined portion is 0.5 to 60 degrees. 5. A method of manufacturing a plasma display comprising a substrate and a dielectric layer and stripe-shaped barrier ribs formed thereon, wherein the stripe having an inclined portion at an end using a barrier rib paste made of an inorganic material and an organic component. The partition having an inclined portion at a longitudinal end of the partition is formed through a step of forming a partition-like partition pattern on a substrate and a step of baking the partition pattern. Of manufacturing a plasma display. 6. A process of applying a paste for partition walls on a substrate so as to have an inclined surface at an end to form a coating film, wherein a stripe-shaped partition pattern is formed such that the inclined surface of the coating film is a longitudinal end. Forming stripe-shaped barrier ribs through a step of forming a barrier rib pattern and a step of firing the partition wall pattern.
The manufacturing method of the plasma display according to the above. 7. A step of applying a partition wall paste on a substrate to form a coating film, a step of processing the coating film to form an inclined surface, and making the inclined surface of the coating film a longitudinal end. 6. The method of manufacturing a plasma display according to claim 5, wherein the step of forming a stripe-shaped partition wall pattern and the step of firing the partition wall pattern form the striped partition wall. 8. The partition wall paste is a photosensitive partition wall paste, and in the step of forming the partition wall pattern, the partition wall paste coating film has a stripe pattern longer than the length of the coating film with the inclined surface as an end. 8. The method for manufacturing a plasma display according to claim 5, wherein a stripe-shaped partition pattern is formed by exposing and developing through a mask. 9. The height (Y ') of the inclined portion before firing, the length (X') of the inclined portion, and the shrinkage ratio (r) of the partition wall paste by firing have the following relationships. A method for manufacturing a plasma display according to any one of the above. 0.5 ≦ X ′ / (r × Y ′) ≦ 100 10. The method of manufacturing a plasma display according to claim 5, wherein the height (Y ′) of the inclined portion before firing is 0.2 to 1 times the height of the partition pattern before firing. 11. A dielectric paste coating film made of an inorganic material and an organic component is formed on a substrate, and a stripe-like partition pattern is formed thereon by using a partition paste. The method for manufacturing a plasma display according to claim 5, wherein the patterns are fired simultaneously.