JPH11185644A - Barrier for plasma display panel and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily manufacture with a good yield a highly accurate and high quality barrier for a plasma display panel which has no leaping of an end part by peeling and a big aspect ratio. SOLUTION: A photosensitive resin composition layer is formed on a base board and a barrier for a plasma display panel provided with a slant the height of which from a base board becomes smaller as it goes toward the furthest end in an end part, a resin pattern is formed by exposing and developing the photosensitive resin composition layer to a pattern shape, after embedding barrier material between the resin patterns, an end part of the resin pattern and an end part of the barrier material embedded between the resin patterns are removed so that their height from the base board becomes smaller as they go toward the furthest end of the both end parts, then the resin pattern is removed and remaining barrier material in a pattern shape is baked.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma display panel (hereinafter, abbreviated as PDP) used as a display device for character information or video information in a computer terminal, a wall-mounted television, a ticket vending machine, and the like. Related to manufacturing method.

[0002]

2. Description of the Related Art PDPs have, for example, a barrier and a fluorescent material inside two insulating plates (hereinafter abbreviated as a glass plate), a front plate on which a transparent electrode is formed and a rear plate on which a data electrode and an insulating film are formed. It consists of a body-formed structure. This barrier forms a cell structure that maintains a certain space between the transparent electrode group and the data electrode group that are perpendicular to each other, and is filled with a rare gas such as Ne or Xe, and the intersection of the transparent electrode and the data electrode is applied. Pixels that discharge and emit light from the phosphor by the voltage are formed to display an image.

The above barrier has a function of preventing erroneous discharge between cells and obtaining a constant discharge section by its height, width and pattern gap.

In recent years, there has been a trend toward larger displays and smaller pixels (for example, with a screen size of 40 inches or more, a barrier width of 100 μm or less and a height of 100 μm or more). A photolithographic method using a photosensitive material widely used for formation has been vigorously studied because it can form a large-sized and miniaturized panel barrier with high accuracy.

For example, in Japanese Patent Application Laid-Open No. 5-234514, a photosensitive resin composition film is laminated on a substrate, exposed through a predetermined pattern mask, and then a non-exposed portion is removed by development to form a resin pattern. A method has been proposed in which a barrier material is formed by embedding a barrier material between the resin patterns, and after drying, the resin pattern is peeled off with an alkali peeling solution to form a barrier. This method is called an additive method. In.

However, using the above-described photolithographic method, a fine barrier (aspect ratio ≧ 1.2, barrier width ≦ 1) having a particularly large aspect ratio (large ratio between height and width) is used.
(00 μm) had the following problems. Due to the shrinkage stress during the firing of the barrier, the end of the barrier is particularly peeled off at a length of about several hundred μm and jumps up. At the time of manufacturing a panel, an edge portion peels off and a jumped-up portion breaks, contaminating pixels. To solve the above problems,
828, JP-A-6-150832, etc.
A method of relaxing the shrinkage stress at the time of firing by using a barrier material having a different yield point in a multilayer structure or a stepped structure at the end has been studied.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-precision, high-definition plasma display panel having a large aspect ratio, which does not jump up due to peeling of an end portion. According to a second aspect of the present invention, there is provided a method for manufacturing a barrier of a plasma display panel having a large aspect ratio, high accuracy, and high quality, which does not cause a jump due to peeling of an end portion, and which can easily manufacture the barrier with high yield. Is provided.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a barrier for a plasma display panel having a slope at an end of which the height from the substrate decreases toward the end.

The present invention also provides a photosensitive resin composition layer formed on a substrate, exposing the photosensitive resin composition layer in a pattern, and developing the resin pattern to form a resin pattern. After the barrier material is buried between the ends of the resin pattern and the ends of the barrier material buried between the resin patterns, the height from the substrate decreases toward the extreme ends of both ends. Removing, and then removing the resin pattern, and baking the remaining patterned barrier material. A plasma having a slope at an end portion in which the height from the substrate decreases toward the end. The present invention relates to a method for manufacturing a display panel barrier.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The barrier of the plasma display panel according to the present invention has a slope at the end of the barrier and the lowest height at the end. The height is based on the substrate and is the height from the substrate. Due to the above inclination, shrinkage of the end portion at the time of firing is reduced, so that shrinkage stress is reduced, and peeling of the barrier end portion can be suppressed. The shrinkage stress is that the height of the outermost end of the barrier is smaller than the height of a portion having a certain height without inclination (a portion where a pixel made of a phosphor is formed later) by at least 10 μm. Is preferred from the viewpoint of reducing.
The height of the outermost end of the barrier is determined according to the dimension of the barrier to be formed, but is preferably 5 to 75 μm, and more preferably 10 to 50 μm from the viewpoint of dimensional accuracy and reduction of contraction stress.
m is more preferable. Figure 1 shows an example of the shape of the slope
However, the present invention is not limited to this.

When the finally obtained barrier is a stripe-shaped barrier, the length of the inclined portion at the end is preferably 50 to 300 μm, more preferably 50 μm to 300 μm.
If it is less than 3, the effect of shrinkage during firing tends to be insufficient, while if it exceeds 300 μm, the portion used as a pixel tends to be small. The shape of the barrier may be a lattice shape, a stripe shape, or the like. When the barrier shape is a stripe shape, the height (thickness) of the barrier is about 50 to 250 μm, and its width is about 20 to 150 μm. The barrier may be made of an insulating material that does not allow gas used for plasma discharge to pass therethrough, and may be made of an inorganic material, such as low-melting glass, alumina (Al ₂ O ₃ ), ordinarily oxidized. Metal oxides such as titanium, zinc oxide, barium oxide, potassium oxide, sodium oxide, calcium oxide, zirconium oxide, cadmium oxide, copper oxide, magnesium oxide, manganese oxide, bismuth oxide, and inorganic pigments. The substrate used in the present invention is not particularly limited, and examples thereof include a ceramic plate, a plastic plate, and a glass plate having a thickness of about 0.5 to 5 mm. On this substrate, an insulating layer, an electrode, a protective layer and the like may be provided.

[0012] The barrier of the plasma display panel of the present invention is formed, for example, by forming a photosensitive resin composition layer on a substrate,
Exposure of the photosensitive resin composition layer in a pattern form, development to form a resin pattern, after embedding a barrier material between the resin pattern and the resin pattern, between the end of the resin pattern and the resin pattern The end of the buried barrier material is removed so that the height from the substrate decreases toward the extreme end of both ends, then the resin pattern is removed, and the remaining patterned barrier material is fired. It can be manufactured by Hereinafter, the above-described manufacturing method will be described.

As a method of forming a photosensitive resin composition layer on a substrate, a photosensitive resin composition is applied directly on the substrate,
There are a method of drying if necessary, and a method of providing a photosensitive resin layer of a photosensitive film by transferring the photosensitive resin layer onto a substrate by using a photosensitive film with a laminator. The method using the latter photosensitive film is preferred from the viewpoint that the film thickness can be increased. The photosensitive film has a support film and a photosensitive resin layer.For example, a photosensitive resin composition is applied on a support film such as a polyethylene terephthalate film, and dried if necessary to form a photosensitive resin composition layer. It is manufactured by forming. Normally, the photosensitive resin composition layer is uncured, and is flexible and sticky, so that a protective film such as a polyethylene film is stuck on this layer to prevent external damage and foreign matter adhesion. I have. The thickness of the photosensitive resin composition layer is not particularly limited, but is preferably 15 μm or more from the viewpoint of easily increasing the thickness of the resin pattern to be formed, and the upper limit is about 250 μm.

The photosensitive resin composition is not particularly limited and known ones can be used. Examples thereof include a negative photosensitive resin composition and a positive photosensitive resin composition. As the positive photosensitive resin composition, for example, 1,2
A photo-soluble group-forming composition using a naphthoquinonediazide compound, an o-nitrobenzyl-based compound, or the like; and a photoacid generation / acid decomposition type composition using an onium salt or the like. As the negative photosensitive resin composition, for example,
It contains (a) an ethylenically unsaturated compound, (b) a carboxyl group-containing film-imparting polymer and (c) a photopolymerization initiator as essential components, and if necessary, (d) a dye or pigment; And (f) a photopolymerizable composition containing an organic solvent.

The photosensitive resin composition layer formed on the substrate using the photosensitive resin composition as described above is exposed in a pattern by, for example, irradiating active light through a negative mask having a predetermined pattern. After heating, the photosensitive resin composition layer is selectively removed by development to form a plurality of resin patterns on the substrate. The developing method is not particularly limited, and examples thereof include wet development and dry development. In the case of wet development, a developer corresponding to the photosensitive resin composition is used. Examples of the developer include a weak alkaline dilute aqueous solution such as sodium carbonate and potassium carbonate, and examples of the development method include an immersion method and a spray method. Further, the resin pattern formed on the substrate after the development may be heated and / or exposed for the purpose of improving strength, solvent resistance and the like.

A barrier material is buried between a plurality of resin patterns (gap) on the substrate thus formed using a screen, a squeegee or the like, and dried (typically 50 to 18).
(At 0 ° C. for 10 to 120 minutes), removing the edge of the resin pattern and the edge of the barrier material embedded between the resin patterns so that the height from the substrate decreases toward the extreme ends of both ends. Then, the resin pattern is removed. The barrier material is a composition comprising an inorganic material, a binder resin and an organic solvent as essential components, and, if necessary, an organic solvent, a pigment, a plasticizer, a dispersant, and an additive such as an adhesion improver. is there.

The inorganic material used for the barrier material is a low melting point glass powder, alumina (Al ₂ O ₃ ), titanium oxide,
It is made of a metal oxide such as zinc oxide, barium oxide, potassium oxide, sodium oxide, calcium oxide, zirconium oxide, cadmium oxide, copper oxide, magnesium oxide, manganese oxide, bismuth oxide, and the like. The composition of the above glass is PbO.B ₂ O ₃ .SiO ₂ , PbO.B ₂ O
₃ , ZnO.B ₂ O ₃ .SiO _{2 and the} like. The softening point of these inorganic materials is 350 to 1,000 ° C., and the particle size is
The thickness is preferably 0.1 to 5 μm from the viewpoint of workability, barrier strength, and the like.

As the binder resin used for the barrier material, a known resin can be used. Further, a resin may be used in which a curing agent is blended to impart a property of reacting and crosslinking by heat or light. Acrylic resins and the like are preferred because they have good thermal decomposability and do not have any unburnt residue after firing. The binder resin has a Tg of 0 to 50 ° C. and a weight average molecular weight of 1
It is preferably from 000 to 180,000. When the weight average molecular weight is less than 10,000, the strength of the barrier material tends to decrease, while the weight average molecular weight is less than 1
If it exceeds 80,000, it tends to be hardly soluble in a solvent.
When Tg is less than 0 ° C., the flexibility is too large,
When the Tg exceeds 50 ° C., the flexibility tends to decrease, and a part of the barrier material (especially at the corner) tends to be chipped. The weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

The content of the binder resin in the barrier material is preferably 3 to 30 parts by weight based on 100 parts by weight of the inorganic material. If the content is less than 3 parts, it does not function as a binder and the barrier material tends to collapse. On the other hand, if the amount exceeds 30 parts by weight, the flowability becomes excessive in the melting stage before the thermal decomposition and disappearance in the step of thermally decomposing and eliminating the organic matter in the barrier material by firing, and the shape of the barrier material tends to be deformed.

Examples of the organic solvent used as necessary for the barrier material include, for example, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, γ-butyl lactone, N-methylpyrrolidone, dimethylformamide, tetramethyl Methyl sulfone, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, chloroform,
Methylene chloride, methyl alcohol, ethyl alcohol,
Examples include tetralin, n-butylbenzene, P-cymene, methylnaphthalene, cyclohexylbenzene, diethylbenzene, pentylbenzene, dipentylbenzene, P-menthane, bicyclohexyl, dipentene, decalin, solvesso, and turpentine oil. These are used alone or in combination of two or more. Among these organic solvents, those having a high boiling point (170 to 280 ° C.) and being nonpolar have good leveling properties of the coating film and do not corrode the resin pattern.

The content of the organic solvent in the barrier material is not particularly limited, but the viscosity of the composition as the barrier material is 20 to 20.
It is preferable to contain an amount such that 0 poise is obtained,
It is about 10 to 100 parts by weight based on 100 parts by weight of the inorganic material. When the content of the solvent is less than 10 parts by weight, the viscosity of the composition tends to be too large and the embedding property tends to decrease,
If it exceeds 100 parts by weight, the blinking after drying tends to be too large.

It is preferable that the barrier material further contains a silane coupling agent from the viewpoint of adhesion to the substrate. Such a silane coupling agent is, for example, γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) -Ethyltrimethoxysilane, β-
Epoxysilanes such as (3,4-epoxycyclohexyl) -ethyltriethoxysilane and N-β (aminoethyl)
γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N
-Β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxycin, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. Aminosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldimethoxysilane, γ
Chloropropylsilane such as -chloropropylmethyldiethoxysilane. It is preferable that the content of the silane coupling agent in the barrier material is 0.1 to 5.0 parts by weight based on 100 parts by weight of the inorganic material. If the amount is less than 0.1 part by weight, the effect of improving the adhesiveness tends to be small, and if it exceeds 5.0 parts, unburnt residue tends to be generated during firing.

When embedding the barrier material, the barrier material is present in the upper portion of the resin pattern or the gap by using a larger amount of the barrier material than the volume between the resin patterns (gap). In this case, it is preferable to remove the barrier material existing above the resin pattern or the gap by a chemical method such as removal with a chemical solution or a physical method such as cutting or polishing. It is preferable to use a polishing method from the viewpoint of mass productivity and accuracy. For example, a machine using a sanding machine such as a hand polishing using sandpaper (# 600) while pouring water, a buff polishing machine, a belt sander polishing machine or the like. By uniformly polishing by polishing or the like until the resin pattern is visible, the barrier material existing on the upper part of the resin pattern or the gap can be removed. As a belt sander polishing machine, a polishing belt with abrasives such as a resin belt having abrasive grains such as silica or alumina adhered to the resin, a diamond belt having abrasive grains of diamond or zirconia adhered thereto (# 4)
00) is circulated and run on at least two rolls, and the belt follows the rolls and runs in an arc-shaped form. A polishing machine in which polishing is performed is preferable. As such a belt sander polisher, a belt sander polisher manufactured by Marugen Ironworks Co., Ltd. (model: wet type, MN
W type).

After the barrier material is buried and, if necessary, the above-mentioned removal is performed, the end of the resin material and the end of the barrier material buried between the resin patterns are moved from the substrate toward the extreme ends of both ends. Although the removal is performed so that the height becomes smaller, this removal can be performed by a chemical method such as removal with a chemical solution, a physical method such as cutting, polishing, or the like, but a polishing method is used in terms of mass productivity and accuracy. Is preferred. When the polishing method is used, for example, an adhesive tape (thickness: 50 μm, width: 25 mm) of a polyethylene terephthalate base material is continuously adhered to a place about 1 mm from the end of the barrier material, and sandpaper is applied while water is applied. A desired inclination can be obtained by polishing the resin material and the buried barrier material so as to reduce the height of the outermost end of the 1 mm wide portion of the barrier material using (# 600). . Here, the adhesive tape functions as a mask for partial polishing (see FIG. 2).

When embedding the barrier material, a barrier material having a volume larger than the volume between the resin patterns (gap) is used, and the barrier material is provided above the resin pattern and the gap. If present, remove the barrier material at the top of the resin pattern or the gap and remove the edge of the resin pattern and the end of the barrier material embedded between the resin patterns from the substrate toward the extreme ends of both ends. The removal to reduce the height can be performed simultaneously or almost at the same time, for example, one or more polishing belts for polishing and removing the barrier material existing on the upper part of the resin pattern or the gap, At least one polishing step for polishing and removing the edge of the resin pattern and the edge of the barrier material embedded between the resin patterns so that the height from the substrate decreases toward the extreme ends of both ends. Can be carried out by using a composed and a belt a belt sander polishing machine.

The resin pattern can be removed by various methods. For example, when the resin pattern is removed using a stripper, the stripper used is a 1 to 10% by weight aqueous solution of sodium hydroxide or potassium hydroxide. Is mentioned.
When the concentration is less than 1% by weight, the effect of peeling is small, so that the peeling time tends to take too long. When the concentration exceeds 10% by weight, the barrier material tends to be attacked. The temperature of the stripping solution is not particularly limited, and conditions for suitably stripping the resin pattern may be appropriately set. As the stripping method, any of the immersion method and the spray method is suitable, and the two methods are used in combination. You may.

After the removal of the resin pattern, organic substances such as resin are removed from the patterned barrier material remaining on the substrate, and the patterned barrier material is baked to improve the strength, gas impermeability, etc., thereby forming the barrier. obtain. The firing temperature and time are 35
0 to 580 ° C for about 1 to 20 hours.

The height (thickness) (excluding edges) of the barrier on the substrate thus manufactured is 85 to 250.
In the case of a stripe-type or lattice-type barrier, the width is about 20 to 150 μm.

[0029]

The present invention will be described below with reference to examples.

Example 1 An alkali-developable photosensitive film (thickness of the photosensitive resin composition layer: 50 μm) was stuck on a glass plate previously heated to 100 ° C. at 130 ° C. using a laminator to form a polyethylene terephthalate film. Was removed to expose the photosensitive resin composition layer. The photosensitive film was again adhered on the exposed photosensitive resin composition layer once again, and the polyethylene terephthalate film was peeled off to expose the photosensitive resin composition layer. Further, the same operation was performed once again to form a 150 μm thick photosensitive resin composition layer on the glass plate. Thereafter, a predetermined negative mask was placed on the polyethylene terephthalate film, and the photosensitive resin composition layer was exposed from above the negative mask with a parallel light exposure machine at an exposure amount of 70 mJ / cm ² . Further, the unexposed portion of the photosensitive resin composition layer is developed with a 1% by weight aqueous sodium carbonate solution,
A resin pattern was obtained on a glass plate. This resin pattern was line / space = 300 μm / 100 μm.
Next, the resin pattern was 3,000 mJ by an ultraviolet irradiation machine.
/ cm ² , and then heat-treated at 160 ° C. for 60 minutes in a dryer.

Next, a non-curable acrylic resin (composition ratio: n-butyl methacrylate / methacrylic acid = 98/2, weight average molecular weight: 100,000, solid content 35 weight) is coated on the entire surface of the heat-treated resin pattern. % Toluene / xylene (1/1 (weight ratio) solution) 51 parts by weight, low melting point glass (PbO.B ₂ O ₃ .SiO ₂ , Nippon Electric Glass Co., Ltd.)
Manufactured by GA-9) 50 parts by weight, 50 parts by weight of alumina powder and 2 parts by weight of γ-methacryloxytrimethoxysilane to which methyl naphthalene was added to form a paste-like barrier material having a viscosity adjusted to 70 poise. It was applied in a solid state by a screen printing machine having a screen of 120 mesh. Here, the glass plate after the application was put into an aluminum container equipped with a decompression device, the pressure was reduced to 10 Torr, the operation was maintained for 3 minutes, and then the operation was returned to normal pressure. By this operation, bubbles in the barrier material were removed, and the barrier material was securely embedded between the resin patterns. Then, it dried at 80 degreeC for 30 minutes with the dryer, and the solvent of the surface was volatilized.
Further, the above-described operations of applying the barrier material, reducing the pressure, and drying were performed once more, and the gap between the resin patterns was almost completely filled with the barrier material. Subsequently, after drying with a dryer at 160 ° C. for 60 minutes to evaporate the remaining solvent, the barrier material remaining on the upper part of the resin pattern and the gap is sprinkled with water while sandpaper (# 600) is applied. It was polished and removed uniformly until a resin pattern was visible.

After polishing, a commonly used adhesive tape (thickness: 50 μm, width: 25 mm) of a polyethylene terephthalate substrate is continuously adhered to a place 1 mm from the edge of the barrier, and sand is applied using water. Using a paper (# 600), the resin pattern and the embedded barrier material were polished so that the height of the barrier end was 45 μm at the barrier end portion of 1 mm width, and the wall was inclined. The adhesive tape was used as a mask during partial polishing (see FIG. 2). Thereafter, the adhesive tape used as masking was peeled off, immersed in a 5% by weight aqueous sodium hydroxide solution kept at 45 ° C. for about 10 minutes, and immediately immersed in warm water kept at 45 ° C. to peel off the resin pattern. Thereafter, the resultant was washed with water and dried at 80 ° C. for 30 minutes to obtain a patterned barrier material. The dimensions of the patterned barrier material are such that the height of the end of the barrier is 4
5 μm, the length of the slope from the end is 1 mm (1000 μm)
m). Otherwise, the width at the top of the barrier is 100
μm, the width of the bottom surface was 120 μm, and the height was 150 μm.

Finally, the barrier was obtained by firing in air using a muffle furnace. The firing conditions were as follows: the temperature was raised from room temperature to 380 ° C. at a rate of 3 ° C./min, and the temperature was maintained at 380 ° C. for 30 minutes.
Further, the temperature was raised to 550 ° C. at a rate of 5 ° C./min.
After holding at 0 ° C. for 30 minutes, the mixture was naturally cooled to room temperature. The barrier after firing was good, maintaining the above shape before firing, and the dimensions shrank due to decomposition and removal of the resin. The barrier dimensions after firing are such that the height of the barrier end is 36 μm.
And the length of the slope from the end was 1 mm (1000 μm). The other portions had a top width of 80 μm, a bottom width of 120 μm, and a height of 120 μm. The barrier after this firing was of high precision and high quality with a high aspect ratio without jumping due to peeling of the barrier edge.

[0034]

According to the first aspect of the present invention, there is provided a barrier for a plasma display panel having a large aspect ratio, high precision and high quality, which does not jump due to peeling of an end portion. According to a second aspect of the present invention, there is provided a method for manufacturing a barrier of a plasma display panel having a large aspect ratio, high accuracy, and high quality, which does not cause a jump due to peeling of an end portion, and which can easily manufacture the barrier with high yield. Is provided.

[Brief description of the drawings]

FIG. 1 is a structural view of a barrier according to the present invention.

FIG. 2 is a diagram illustrating an example of a method of forming a slope of a barrier end according to the present invention.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Ikuo Muko 4-13-1 Higashicho, Hitachi City, Ibaraki Prefecture Inside the Hitachi Chemical Co., Ltd.Yamazaki Plant No. 1 Inside the Yamazaki Plant of Hitachi Chemical Co., Ltd.

Claims (2)

[Claims] 1. A barrier of a plasma display panel, wherein an edge is provided with a slope such that a height from a substrate decreases toward an extreme end. 2. A photosensitive resin composition layer is formed on a substrate,
Exposure of the photosensitive resin composition layer in a pattern form, development to form a resin pattern, after embedding a barrier material between the resin pattern and the resin pattern, between the end of the resin pattern and the resin pattern The end of the buried barrier material is removed so that the height from the substrate decreases toward the extreme end of both ends, then the resin pattern is removed, and the remaining patterned barrier material is fired. A method for manufacturing a barrier of a plasma display panel, wherein an inclination is provided at an end portion such that a height from a substrate decreases toward an outermost end.