JP2004265867A - Method of manufacturing display member, display member, and display using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a display member, whereby a barrier can be formed with high precision and in a high yield by a simple process, and a display member using this member while having excellent display quality. <P>SOLUTION: This method of manufacturing the display member is to form a barrier pattern by going through a process to apply photosensitive paste on a substrate on which an electrode is formed, a process to expose a photosensitive paste coated film two or more times through a photo-mask, and a process to remove a portion of the already exposed coated film, which has not been exposed and has not been hardened, by a developing solution. The photo-masks on which the line width Wn of the photo-mask used for n-th exposure and the line width Wm of the photo-mask used for m-th exposure are different are used for exposure (n, m are integers of 1 to 5, and n<m is satisfied). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a display member such as a plasma display or a plasma addressed liquid crystal display used for a wall-mounted television or a large monitor, and a method of manufacturing a display, and more particularly to manufacturing of a display with improved yield in display member manufacturing and display quality. About the method.

  As a display that can be used for a thin and large-sized television, a plasma display panel (hereinafter, referred to as a PDP) has attracted attention because it can display at a higher speed than a liquid crystal panel.

  The PDP generates plasma discharge between electrodes in a discharge space provided between a front glass substrate and a rear glass substrate, and emits ultraviolet light generated from a gas sealed in the discharge space to a fluorescent light in the discharge space. The display is performed by touching the body. In this case, a partition having a width of about 20 to 80 μm and a height of about 20 to 200 μm in order to suppress the spread of discharge to a certain area and to perform display in a specified cell and to secure a uniform discharge space. Is provided.

  As a pattern forming method of this partition, a glass paste is repeatedly printed and dried by screen printing many times, a screen printing method of forming a partition pattern of a predetermined height, through a subtractive mask layer formed by a photolithography technique. A sand blast method formed by sand blast is known.

However, the screen printing method and the sand blast method involve a large number of steps and have a problem in terms of manufacturing cost. In order to solve this problem, there has been proposed a method of forming a partition by a photolithography technique using a photosensitive glass paste. (For example, see Patent Document 1). Certainly, it is possible to form a partition pattern simply by performing coating, drying, exposure, and development once each. However, this method requires mass production if the photomask used for exposure has defects such as scratches and dirt. There was a problem that the yield at the time was greatly reduced. In addition, there is a problem that it is not possible to cope with formation of a partition having a more complicated structure, particularly a partition having a step, in order to improve luminance and display quality.
JP-A-9-223462 (pages 2 to 10)

  In view of the above, it is an object of the present invention to provide a display member manufacturing method and a display capable of producing partition walls having any structure with high accuracy and high yield.

  A step of applying a photosensitive paste on the substrate on which the electrodes are formed, a step of exposing through a photomask, and a step of dissolving and removing the uncured portion with a developer to form a partition wall pattern of the display member. A method of manufacturing a display member, comprising exposing at least twice using masks having different line widths. Further, the present invention is a display member manufactured by the above manufacturing method, and a display using the display member.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the display member excellent in display quality by forming a partition with a high yield by preventing the defect generation of disconnection, chipping, etc. by a mask defect by a simple process, and a display are provided. it can.

Hereinafter, the present invention will be described in accordance with a procedure for manufacturing a PDP.
As the substrate used for the back plate as the member for the PDP of the present invention, besides soda glass, "PD200" manufactured by Asahi Glass Co., Ltd. and "PP8" manufactured by Nippon Electric Glass Co., Ltd., which are high strain point glass for PDP, are used. be able to.

  An address electrode is formed on a glass substrate using a metal such as silver, aluminum, chromium, or nickel. The formation method is a method of pattern-printing a metal paste containing these metal powder and an organic binder as main components by screen printing, or applying a photosensitive metal paste using a photosensitive organic component as an organic binder, and then passing through a photomask. The photosensitive paste method of forming a metal pattern can be used by exposing a pattern, dissolving and removing an uncured portion in a developing step, and baking at a temperature of 400 to 600 ° C. Alternatively, an etching method can be used in which a metal such as chromium, aluminum, copper, or the like is sputtered on a glass substrate, a resist is applied, and the resist is subjected to pattern exposure and development, followed by etching to remove unnecessary metal. The electrode thickness is preferably 1 to 10 μm, more preferably 2 to 5 μm. If the electrode thickness is too thin, the resistance value increases and a burden is imposed on accurate driving, and if the electrode thickness is too thick, it tends to be disadvantageous in terms of cost. The width of the address electrode is preferably 20 to 200 μm. If the width of the address electrode is too small, the resistance value tends to be high and accurate driving tends to be difficult. If the address electrode is too thick, the distance between adjacent electrodes is small, and short-circuit defects tend to occur. Further, the address electrodes are formed at a pitch corresponding to the display cell (the area where each RGB of a pixel is formed). It is preferable that the pitch is formed at a pitch of 100 to 500 μm for a normal PDP and at a pitch of 100 to 250 μm for a high definition PDP.

  Next, a dielectric layer is formed. The dielectric layer can be formed by applying a glass paste containing glass powder and an organic binder as main components on the pattern of the address electrode and baking at 400 to 600 ° C. The thickness of the dielectric layer is preferably 3 to 30 μm, more preferably 3 to 20 μm. If the thickness of the dielectric layer is too small, pinholes tend to occur frequently, and if the thickness is too large, the discharge voltage tends to increase and the power consumption tends to increase.

A partition for partitioning the discharge cells is formed on the dielectric layer.
The height of the partition wall is preferably 80 μm to 200 μm. By setting the thickness to 80 μm or more, it is possible to prevent the phosphor and the scan electrode from coming too close to each other, and to prevent the phosphor from being deteriorated due to discharge. Further, when the thickness is 200 μm or less, the distance between the discharge at the scan electrode and the phosphor can be shortened, and sufficient luminance can be obtained. The pitch (P) of the partition walls is often 100 μm ≦ P ≦ 500 μm. In the high definition plasma display, the pitch (P) of the partition walls is 100 μm ≦ P ≦ 250 μm. When the thickness is 100 μm or more, a sufficient discharge space can be obtained and sufficient luminance can be obtained. When the thickness is 500 μm or less, fine and clear images with fine pixels can be displayed. By setting the thickness to 300 μm or less, a beautiful video of HDTV (high definition) level can be displayed. The line width (L) is preferably 10 μm ≦ L ≦ 50 μm in half width. When the thickness is 10 μm or more, the strength can be maintained and breakage can be prevented when the front plate and the back plate are sealed. Further, when the thickness is 50 μm or less, the formation area of the phosphor can be increased, and high luminance can be obtained.

Such a partition is formed by forming a pattern using a photosensitive paste containing an inorganic component and an organic component containing a photosensitive component, and then firing the pattern.
As the inorganic fine particles of the photosensitive paste, glass, ceramic (alumina, cordierite, or the like) or the like can be used. In particular, glass and ceramics containing silicon oxide, boron oxide, or aluminum oxide as an essential component are preferable.

The particle size of the inorganic fine particles is selected in consideration of the shape of the pattern to be produced, but the volume average particle size (D50) is preferably from 1 to 10 μm, more preferably from 1 to 5 μm. By setting D50 to 10 μm or less, it is possible to prevent the occurrence of surface irregularities. When the thickness is 1 μm or more, the viscosity of the paste can be easily adjusted. Further, it is particularly preferable to use glass fine particles having a specific surface area of 0.2 to ³ m ² / g in pattern formation.

  Since the partition walls are preferably formed on a glass substrate having a low thermal softening point, it is preferable to use, as the inorganic fine particles, inorganic fine particles containing 60% by weight or more of glass fine particles having a heat softening temperature of 350 ° C to 600 ° C. Further, by adding glass fine particles or ceramic fine particles having a heat softening temperature of 600 ° C. or more, the shrinkage rate during firing can be suppressed, but the amount is preferably 40% by weight or less.

As a glass powder to be used, a glass having a linear expansion coefficient of 50 × 10 ^{−7 to} 90 × 10 ⁻⁷ , and further 60 × 10 ^{−7 to} 90 × 10 ⁻⁷ in order to prevent warpage of the glass substrate during firing. It is preferable to use fine particles.

  As a material for forming the partition walls, a glass material containing an oxide of silicon and / or boron is preferably used.

  Further, by containing at least one of bismuth oxide, lead oxide and zinc oxide in a total amount of 5 to 50% by weight, a glass paste having a temperature characteristic suitable for pattern processing on a glass substrate can be obtained. it can. Particularly, when glass particles containing 5 to 50% by weight of bismuth oxide are used, advantages such as a long pot life of the paste can be obtained.

Alternatively, glass fine particles containing at least one of lithium oxide, sodium oxide, and potassium oxide in an amount of 3 to 20% by weight may be used. By adding the alkali metal oxide in an amount of not more than 20% by weight, preferably not more than 15% by weight, a metal oxide such as lead oxide, bismuth oxide and zinc oxide and lithium oxide, sodium oxide, If glass fine particles containing both alkali metal oxides such as potassium oxide are used, the thermal softening temperature and the linear expansion coefficient can be easily controlled with a lower alkali content.

  It is preferable that the organic component containing a photosensitive component contains a photosensitive component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer. An initiator, a light absorber, a sensitizer, an organic solvent, a sensitization aid, and a polymerization inhibitor are added.

  The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include monofunctional and polyfunctional (meth) acrylates, vinyl compounds, allyl compounds, and the like. be able to. These can be used alone or in combination of two or more.

  As more specific examples of the photosensitive monomer, monofunctional and polyfunctional (meth) acrylates, vinyl compounds, allyl compounds, and the like can be used. These can be used alone or in combination of two or more. As the (meth) acrylate compound, an acrylic or methacrylic compound having an alkyl group represented by the chemical formulas (1), (2), (3), and (4) is preferably used.

CH ₂ = CR ³ COO-R ⁴ (1)
CH ₂ = CR ³ COO-R ⁴ -OCOCHR ¹ = CH ₂ (2)
CH ₂ = CR ³ COO-R ⁵ -OCO-R ⁶ -COO-R ⁵ -OCOCHR ³ = CH ₂ (3)
(CH ₂ = CR ³ COO- (CH ₂ CHR ⁶ O) _m ) _n -R ⁷ (4)
Here, R ³ and R ⁶ are hydrogen or a methyl or methylene group, R ⁴ is an alkyl or alkylene group having 1 to 20 carbon atoms, R ⁵ is a hydroxyalkylene group having 3 or more carbon atoms, and R ⁷ is 1 carbon atom. And m is an integer of 0 to 30; n is an integer of 3 to 6; However, the monomers used here are not limited to these.

  As the photosensitive oligomer and the photosensitive polymer, an oligomer or a polymer obtained by polymerizing at least one kind of a compound having a carbon-carbon double bond can be used. By copolymerizing the polymer or oligomer with an unsaturated acid such as an unsaturated carboxylic acid, the developability after exposure can be improved.

  Specific examples of the photopolymerization initiator include benzophenone, methyl O-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, Examples include benzoyl-4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3-diethoxyacetophenone, and 2,2-dimethoxy-2-phenyl-2-phenylacetophenone. One or more of these can be used. The photopolymerization initiator is preferably added in the range of 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the photosensitive component. If the amount of the polymerization initiator is too small, the photosensitivity tends to decrease, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion tends to be too small.

  It is also effective to add a light absorber. By adding a compound having a high ultraviolet or visible light absorption effect, a high aspect ratio, high definition, and high resolution can be obtained. As the light absorber, those composed of organic dyes are preferably used.Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes Dyes, triazine dyes, p-aminobenzoic acid dyes and the like can be used.

  A sensitizer is added to improve sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, and the like. Is mentioned. One or more of these can be used.

Examples of the organic solvent include methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether acetate, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, and γ-butyl lactone. , N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and one or more of these. An organic solvent mixture is used.
The photosensitive paste is usually prepared by mixing the above-mentioned inorganic fine particles and organic components so as to have a predetermined composition, and then uniformly mixing and dispersing the mixture using a three-roller or a kneader.

Next, a method for forming a partition in the present invention will be described. The partition wall forming method in the present invention is effective for all types of partition wall patterns. For example, a stripe-shaped and lattice-shaped partition wall pattern formation will be described.
First, in the case of forming a stripe-shaped partition, a first-layer photosensitive paste is applied on a substrate on which electrodes are formed or on a dielectric layer. As a coating method, a screen printing method, a bar coater, a roll coater, a direct coater, a blade coater, or the like can be used. The coating thickness can be adjusted by selecting the number of coatings, the mesh of the screen, and the viscosity of the paste.

After applying the photosensitive paste, the photosensitive paste is dried using a ventilation oven, a hot plate, an IR furnace, or the like to form a first photosensitive paste coating film.
Subsequently, exposure is performed using an exposure apparatus. Exposure is performed by mask exposure using a photomask as performed by a normal photolithography method. The active light source used at this time includes, for example, visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among them, ultraviolet rays are most preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, a germicidal lamp, and the like can be used. Among these, an ultra-high pressure mercury lamp is preferred. Exposure conditions vary depending on the coating thickness, but exposure is performed for 0.1 to 10 minutes using an ultra-high pressure mercury lamp having an output of 1 to 100 mW / cm ² .

  At this time, the shape of the partition pattern to be formed and the width of the partition are determined by the photomask pattern to be used and the line width of the photomask. Here, the line width of the photomask indicates a line width of a slit portion, that is, a portion through which light is transmitted. For example, in the case of forming a stripe-shaped partition, a photomask having a stripe pattern in a direction parallel to the address electrode can be used.

  A photosensitive paste is further applied on the exposed first layer of the photosensitive paste applied film and dried to form a second layer of the photosensitive paste applied film. Here, the use of the first-layer photosensitive paste for the second-layer photosensitive paste is also a preferred embodiment of the present invention. It is also a preferred embodiment of the present invention to use, as the second photosensitive paste, a material that exhibits a black color when fired. The contrast can be improved by using a second layer of the photosensitive paste which is blackened by baking. In order for the photosensitive paste to be baked to have a black color, a glass containing a metal of Ru, Mn, Ni, Cr, Fe, Co, Cu or an oxide thereof in a total of 1 to 15% by weight is used. good. Further, a black metal or a metal oxide may be attached to the glass powder or coated. Alternatively, after forming and forming a part of the partition pattern by exposing and developing the first layer of the photosensitive paste coating film, the second layer of photosensitive paste may be applied and exposed and developed to form the partition. .

  At this time, assuming that the line width of the photomask used for the n-th exposure is Wn and the line width of the photomask used for the m-th exposure is Wm, it is preferable that Wn <Wm, and it is further preferable that W1 <W2. It is preferable (n and m are integers of 1 to 5 and satisfy n <m). By satisfying this condition, it is possible to prevent formation of a partition having a shape defect due to misalignment at least during the first and second exposures. In addition, it is possible to form a good partition wall without a step on the side surface. Further, it is preferable that the photomask line width satisfies the condition of 0.01 <W1 / W2 <1. By making W1 / W2 larger than 0.01, it is possible to prevent common defects such as disconnection and chipping of the partition pattern due to mask defects such as scratches and dust adhesion on each mask. This is very effective especially in preventing the yield from decreasing during mass production. By making W1 / W2 smaller than 1, it is possible to further reduce the influence of misalignment. When the mask line width satisfies the condition of 0.1 <W1 / W2 <0.8, it is possible to more preferably prevent defects and form a partition having a good shape.

  Of course, in the case of forming a partition pattern in which the heights of the partition walls in the plane are uniform or different in height so that it is not necessary to perform coating more than once, the coating process is performed only once and only the exposure process is performed. The same effect can be obtained by performing exposure twice or more using two or more photomasks having different widths.

  After the second exposure of the photosensitive paste film, development is performed using the difference in solubility between the exposed portion and the unexposed portion in the developing solution. Development can be performed by an immersion method, a spray method, a brush method, or the like.

  As the developer, a solution in which an organic component to be dissolved in the photosensitive paste can be dissolved is used. 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, sodium hydroxide, sodium carbonate, sodium carbonate aqueous solution, calcium hydroxide aqueous solution and the like can be used, but it is preferable to use an organic alkaline aqueous solution since the alkaline component can be easily removed at the time of firing. A common amine compound can be used as the organic alkali. 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 tends not to be removed, while if the alkali concentration is too high, the pattern portion tends to peel off or corrode the non-soluble portion. The development temperature during development is preferably from 20 to 50 ° C. from the viewpoint of process control.

  In addition to development using a developer, it is also possible to form a pattern by sandblasting by utilizing the difference in the coating film hardness between the exposed and unexposed portions. In addition, by utilizing the hardness difference due to the exposure, the resist film formation, that is, the application of the resist agent, the drying, the exposure, the development, and the resist film peeling step after the sandblasting, which are used in the current sandblasting method, are omitted. Therefore, significant cost reduction is possible.

  Next, formation of a grid-like partition pattern will be described. In the case of forming the grid-like partition walls, the height of the partition wall parallel to the electrode and the height of the partition wall perpendicular to the electrode can be obtained by using a mask having a grid-like pattern for both the first and second exposures. Can form the same grid-like partition. Also in this case, the line width of the photomask is preferably Wn <Wm, more preferably W1 <W2 (n and m are integers of 1 to 5 and n <M is satisfied.). Most preferably, the condition of 0.01 <W1 / W2 <1 is satisfied. By satisfying this condition, it is possible to prevent common defects such as disconnection and chipping of the partition pattern due to mask defects such as scratches and dust attached to each mask. Even if the vertical / horizontal line width of each photomask is the same or different, the effect is not impaired.

  Furthermore, when exposing a plurality of times, it is necessary to adjust the exposure position. Specifically, it is necessary to position each exposure mask at a predetermined position with respect to the substrate to be exposed. At this time, it is preferable to satisfy 10 ≦ | W2-W1 | in order to prevent a pattern shape defect due to a shift of the exposure position between the substrate and the mask. By satisfying this condition, it is possible to suppress a pattern shape defect due to a positional shift even if the positional accuracy of the exposure machine is considered.

  In order to prevent the common defect of the partition pattern due to the mask defect by the multiple exposure according to the present invention, it is preferable that the minimum line width of the mask to be used is 5 μm or more. If it is 5 μm or more, it is possible to prevent a mask defect at a common defect portion.

The photomask used for the first layer exposure is a grid-like pattern, and the photomask used for the second layer exposure is a photomask of a stripe pattern parallel to the electrodes. In addition, it is possible to form a stepped grid-shaped partition wall having different heights of partition walls perpendicular to the electrodes. In this case, for a photomask having a lattice pattern used for the exposure of the first layer, if the line width of the pattern parallel to the electrode is Wp and the line width of the pattern perpendicular to the electrode is Wh, 0.05 < It is preferable to satisfy Wp / W2 <1.0. By satisfying this condition, it is possible to prevent common defects such as disconnection and chipping of the partition pattern due to mask defects such as scratches and dust attached to each mask. Further, by satisfying the condition of 0.1 <Wp / W2 <0.8, it is possible to more preferably prevent defects and form a partition having a good shape. On the other hand, the pattern perpendicular to the electrodes is exposed only once except for the intersections of the grids, and there is a possibility that defects such as disconnection and chipping may occur in the partition due to the influence of common defects of the mask. However, in the case of the partition wall shape having a stepped lattice pattern, the corresponding partition wall is low in height, and the influence of defects on display quality is small. Further, by applying the phosphor described later, the phosphor is buried in the partition wall defect portion, and the defect itself can be reduced, so that the display defect is less likely to occur.
In the case of forming a partition having a stepped lattice pattern shape, the use of a photomask satisfying the relationship of 0.1 <Wp / Wh <10 makes it possible to reduce the dent at the intersection of the lattice-shaped partition. More preferably, 0.1 <Wp / Wh <0.5.

  In general, a pattern forming method using a photosensitive paste goes through the above steps. Another aspect of the method of forming a partition pattern having a step according to the present invention includes, in addition to the above-described general pattern forming method, a step of exposing a coating film corresponding to a high step portion of the partition in advance. Thereby, it is possible to form the steps accurately and efficiently.

  That is, first, the dried photosensitive paste coating film is exposed through a photomask only to a portion having a higher step in the final partition pattern. The exposed portion is cured by photopolymerization of a photosensitive organic component contained in the photosensitive paste, that is, a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer. Therefore, a difference occurs in the characteristics of the film between the exposed part and the non-exposed part in the photosensitive paste applied film. In particular, there is a difference in the degree of swelling due to solvents and liquid components. For example, when heat is applied to the exposed photosensitive paste coating film, the residual solvent in the coating film and liquid components such as monomers move from the non-exposed portion to the exposed portion. As a result, the exposed portion of the coating film becomes higher than the non-exposed portion. At this time, an inorganic component in the paste may accompany.

  In this manner, the exposed photosensitive paste coating film having a step is exposed through a photomask having a partition pattern on which a final pattern is desired to be formed, and then developed, whereby a step having a step can be formed.

  On the other hand, by applying the various pastes again on the coating film that has exposed the part where the step is high, the solvent and liquid components contained in the various pastes move to the exposed part, and the step can be effectively formed It becomes. In particular, by applying a paste containing the same components as the photosensitive paste of the first layer, a step can be formed more effectively. Of course, it is also effective to use exactly the same paste for the first and second layers. In the case where the photosensitive paste is applied to the second layer, a barrier having a step can be formed by performing exposure and development through a photomask having a barrier pattern to be finally formed after drying.

  In addition, by applying the sandblasting paste to the second layer, a partition pattern having a step can be formed even by using resist formation, sandblasting, resist peeling, and ordinary sandblasting.

  In addition, the size of the step can be changed according to the temperature and time of curing after exposing the portion where the step becomes high, the type of paste applied to the second layer, and the thickness of the applied paste. Become. Further, according to the step forming method of the present invention, it is possible to form a minute step which has been difficult to form. That is, as in the past, when the step formation is controlled by the number of coatings, thin film coating is required by a method such as screen printing or a slit die coater. In the case of screen printing, traces of the screen mesh increase the roughness of the top of the partition wall, causing a problem that the partition wall is chipped or a gap is generated at the time of manufacturing a panel, thereby deteriorating the display quality. On the other hand, the slit die coater has a problem in the accuracy of thin film coating. According to the method of forming a partition having a step according to the present invention, there is no need to apply a thin film, and these problems can be solved.

  It is also a preferred embodiment of the present invention to use, as the second photosensitive paste, a material that exhibits a black color when fired. The contrast can be improved by using a second layer of the photosensitive paste which is blackened by baking. In order for the photosensitive paste to be baked to have a black color, a glass containing a metal of Ru, Mn, Ni, Cr, Fe, Co, Cu or an oxide thereof in a total of 1 to 15% by weight is used. good. Further, a black metal or a metal oxide may be attached to the glass powder or coated. Alternatively, after forming and forming a part of the partition pattern by exposing and developing the first layer of the photosensitive paste coating film, the second layer of photosensitive paste may be applied and exposed and developed to form the partition. .

  Regarding the photomask used for the exposure, the line width of the photomask used for the n-th exposure is Wn, and the line width of the photomask used for the m-th exposure is Wm for a portion of the coating film that is exposed a plurality of times. In this case, Wn <Wm is preferable, and W1 <W2 is more preferable (n and m are integers of 1 to 5 and satisfy n <m). By satisfying this condition, it is possible to prevent formation of a partition having a shape defect due to misalignment at least during the first and second exposures. Further, it is preferable that the photomask line width satisfies the condition of 0.01 <W1 / W2 <1. When a grid-like partition pattern with a step is formed using this method, the photomask used for the first layer exposure is a stripe pattern parallel to the electrodes, and the photomask used for the second layer exposure is the electrodes. By using a photomask having a grid pattern, a grid-shaped partition wall having a step difference in height of the partition wall parallel to the electrode and the height of the partition wall perpendicular to the electrode can be formed.

Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste or substrate, but firing is performed in an atmosphere such as air, nitrogen, or hydrogen. As the firing furnace, a batch-type firing furnace or a roller hearth-type continuous firing furnace can be used. The firing temperature is preferably 400 to 800 ° C. When partition walls are formed directly on a glass substrate, firing is preferably performed at a temperature of 450 to 620 ° C. for 10 to 60 minutes.
For the previous electrode, and for the formation of the dielectric, it has been described that each firing step is performed
The electrode / dielectric, the dielectric / partition, and the electrode / dielectric / partition can be fired collectively by changing each electrode paste and dielectric paste. In this case, the effect of the present invention is not impaired.

  Further, the effects of the present invention are also effective by performing two or more exposure steps. However, as the number of exposure steps increases, the cost increases, so three or less exposures are preferable. Further, two exposures are most preferable, and the effects of the present invention and the cost can be exhibited.

  Also, the formation of the stripe-shaped and lattice-shaped barrier ribs has been described in detail. In addition to the simple stripe-shaped partition, a light-shielding portion is formed in the middle of the slit portion of the stripe to form a dashed slit or a stripe line. It is also possible to use a photomask whose width is partially changed. In addition, a desired partition can be formed using a photomask having a special pattern such as a curve, an arc, and an ellipse.

  Next, a phosphor layer that emits light of each of RGB colors is formed between predetermined partition walls. The phosphor layer can be formed by applying a phosphor paste containing a phosphor powder, an organic binder and an organic solvent as main components between predetermined partitions, drying, and firing as necessary.

  As a method of applying the phosphor paste between predetermined partition walls, a screen printing method of pattern printing using a screen printing plate, a dispenser method of pattern discharging the phosphor paste from the tip of a discharge nozzle, The phosphor paste of each color can be applied to a predetermined place by the photosensitive paste method using the above-mentioned photosensitive organic component as an organic binder.

When the thickness of the R phosphor layer is Tr, the thickness of the G phosphor layer is Tg, and the thickness of the B phosphor layer is Tb, preferably,
10 μm ≦ Tr <Tb ≦ 50 μm
10 μm ≦ Tg <Tb ≦ 50 μm
By having the following relationship, the effect of the present invention can be more exhibited. In other words, by making the thickness of blue light having a low emission luminance larger than that of green or red, a plasma display having a better color balance (higher color temperature) can be manufactured. Sufficient luminance can be obtained by setting the thickness of the phosphor layer to 10 μm or more. When the thickness is 50 μm or less, a large discharge space can be obtained and high luminance can be obtained. In this case, the thickness of the phosphor layer is measured as a thickness formed at an intermediate point between adjacent partition walls. That is, it is measured as the thickness of the phosphor layer formed at the bottom of the discharge space (in the cell).

  By firing the applied phosphor layer at 400 to 550 ° C. as necessary, the member for a plasma display of the present invention can be manufactured.

  Using this plasma display member as a back plate, after sealing with the front plate, filling a discharge gas composed of helium, neon, xenon, etc. in the space formed between the front and back substrates, and then forming a drive circuit A plasma display can be manufactured by mounting. The front plate is a member in which a transparent electrode, a bus electrode, a dielectric, and a protective film (MgO) are formed in a predetermined pattern on a substrate. A color filter layer may be formed on a portion corresponding to the RGB phosphor layers formed on the back plate. Further, a black stripe may be formed to improve the contrast.

Hereinafter, the present invention will be described specifically with reference to Examples. However, the present invention is not limited to this.
A back plate of a 42-inch AC (alternating current) type plasma display panel was formed and evaluated. The forming method will be described in order.
(Examples 1 to 13, Comparative Examples 1 to 3)
As the glass substrate, a 590 × 964 × 2.8 mm 42-inch PD-200 (manufactured by Asahi Glass Co., Ltd.) was used. On this substrate, as a writing electrode, a composition of 70 parts by weight of silver powder having an average particle diameter of 2.0 μm, 69% by weight of bismuth oxide, 24% by weight of silicon oxide, 4% by weight of aluminum oxide, and 3% by weight of boron oxide was used. 2 parts by weight of glass powder having an average particle size of 2.2 μm, 8 parts by weight of a copolymer of acrylic acid, methyl methacrylate and styrene, 7 parts by weight of trimethylolpropane triacrylate, 3 parts by weight of benzophenone, 7 parts by weight of butyl carbitol acrylate Using a photosensitive silver paste consisting of 3 parts by weight of benzyl alcohol, a striped electrode having a pitch of 240 μm, a line width of 100 μm, and a thickness of 3 μm after firing was formed by photolithography.

  On this substrate, a low-melting glass powder containing 78% by weight of bismuth oxide, 14% by weight of silicon oxide, 3% by weight of aluminum oxide, 3% by weight of zinc oxide, and 2% by weight of boron oxide was 60%, and the average particle diameter was 0%. A dielectric paste having a thickness of 10 μm was applied to a dielectric paste of 10% by weight, ethyl cellulose 15%, and terpineol 15%, and fired at 580 ° C. to form a dielectric layer having a thickness of 10 μm.

The photosensitive paste for forming the partition walls used had the following composition.
Glass powder: glass composed of Bi ₂ O ₃ / SiO ₂ / Al ₂ O ₃ / ZnO / B ₂ O ₃ = 82/5/3/5/3/2 Glass powder having an average particle diameter of 2 μm 67 parts by weight Filler: average Titanium oxide having a particle size of 0.2 μm 3 parts by weight Polymer: “Cyclomer” P (ACA250, manufactured by Daicel Chemical Industries, Ltd.) 10 parts by weight Organic solvent (1): benzyl alcohol 4 parts by weight Organic solvent (2): butyl carbitol Acetate 3 parts by weight Monomer: dipentaerythritol hexaacrylate 8 parts by weight Photopolymerization initiator: benzophenone 3 parts by weight Antioxidant: 1,6-hexanediol-bis [(3,5-di-t-butyl-4-hydroxy) Phenyl) propionate] 1 part by weight Organic dye: Basic Blue 26 0.01 part by weight Thixotropic agent: N, N'-12-hydroxy Butylenediamine stearate 0.5 part by weight Surfactant: polyoxyethylene cetyl ether 0.49 part by weight After applying the above paste to a predetermined thickness using a die coater, drying at 100 ° C. for 40 minutes in a clean oven. Then, a coating film was formed. The formed coating film was exposed with a gap of 150 μm from a predetermined photomask. This coating, drying and exposure operation is repeated a predetermined number of times. Table 1 shows the coating thickness, photomask, exposure amount, and the like of each of the examples and comparative examples.

  The exposed substrate formed as described above was developed with a 0.5% aqueous solution of ethanolamine to form a partition pattern. In Example 10, a pattern was formed by a sandblast method. The substrate on which pattern formation was completed was baked at 560 ° C. for 15 minutes.

  The phosphor paste of each color was applied to the partition walls thus formed by screen printing and baked (500 ° C., 30 minutes) to form a phosphor layer on the side and bottom of the partition walls.

  Next, a front plate was produced by the following steps. First, an ITO was formed on the same glass substrate as the back plate by a sputtering method, a resist was applied, and a transparent electrode having a thickness of 0.1 μm and a line width of 200 μm was formed by exposure, development, and etching. Further, a bus electrode having a thickness of 5 μm was formed after firing by a photolithography method using a photosensitive silver paste composed of black silver powder. Electrodes having a pitch of 375 μm and a line width of 100 μm were prepared.

  Next, a glass paste obtained by kneading 70% of low-melting glass powder containing 75% by weight of lead oxide, 20% of ethylcellulose, and 10% of terpineol is screen-printed so that the bus electrode at the display portion is covered. Was applied at a thickness of 50 μm, and baked at 570 ° C. for 15 minutes to form a front dielectric.

  A 0.5 μm-thick magnesium oxide layer was formed as a protective film on the substrate on which the dielectric was formed by electron beam evaporation to produce a front plate.

  After the obtained front glass substrate was bonded and sealed to the above-mentioned rear glass substrate, a discharge gas was sealed therein, and a driving circuit was joined thereto to produce a plasma display (PDP). A display was observed by applying a voltage to the panel.

  The evaluation of the effect of suppressing the defect such as disconnection or chipping of the partition pattern due to the mask defect was performed by forming a pseudo defect in each mask and observing the shape of the partition pattern at that portion. FIG. 1 shows the shape of the pseudo mask defect.

  Table 2 shows the shape evaluation results and PDP display characteristics of the pseudo mask defects of Examples 1 to 13 and Comparative Examples 1 to 3. For the lattice pattern, the amount of depression at the intersection is also described.

  The back plate obtained in each of Examples 1 to 13 was able to form a good partition pattern without occurrence of disconnection or chipping even in a pseudo mask defect portion. The display characteristics of the PDP were also good. In the grid patterns having the steps of Examples 8 to 10, the recesses at the intersections could be formed relatively small. In Comparative Examples 1 and 2, disconnection and chipping occurred in the defective portion of the pseudo mask, and good display quality was not obtained. In Comparative Example 3, a substrate where alignment deviation occurred and good display was not possible was observed.

It is a top view showing an example of the shape of the pseudo defect of the photomask used at the time of partition formation in the present invention.

Explanation of reference numerals

1: light shielding part 2: slit part 3: pseudo disconnection defect 4: pseudo chipping defect

Claims (11)

A step of applying a photosensitive paste on the substrate on which the electrodes are formed, a step of exposing the photosensitive paste coating film a plurality of times through a photomask, and a process of developing an unexposed uncured portion of the exposed coating film with a developer. A method of manufacturing a display member for forming a partition pattern by performing a removing step, wherein a line width Wn of a photomask used for an n-th exposure and a line width Wm (n, n) of a photomask used for an m-th exposure m is an integer of 1 to 5 and satisfies n <m). A method for manufacturing a display member, wherein exposure is performed using photomasks having different values. 2. The method according to claim 1, wherein the line width of the photomask used at the time of exposure satisfies the following expression.
Wn <Wm 3. The method according to claim 1, wherein a line width of the photomask used at the time of exposure satisfies the following expression.
0.01 <W1 / W2 <1 The method for manufacturing a display member according to any one of claims 1 to 3, wherein the line width of the photomask used at the time of exposure satisfies the following expression.
10 μm ≦ | W2-W1 | The method according to claim 1, wherein a line width of the photomask used at the time of exposure satisfies the following expression.
5μm ≦ W1 The method for manufacturing a display member according to claim 1, wherein the photomask used at the time of exposure has a stripe pattern formed in a direction parallel to the electrodes. 7. The method for manufacturing a display member according to claim 1, wherein at least one of the photomasks used at the time of exposure has a lattice pattern. 8. The method according to claim 7, wherein the line width Wp of the pattern parallel to the electrode of the photomask having the lattice pattern and the line width Wh of the pattern perpendicular to the electrode satisfy the following expression.
0.1 <Wp / Wh <10 The method for manufacturing a display member according to any one of claims 1 to 8, wherein the height of the partition wall intersecting with the electrode is 1/3 to 1 of the partition height parallel to the electrode. A display member manufactured by the manufacturing method according to claim 1. A display using the display member according to claim 10.

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