WO2011001903A1

WO2011001903A1 - Glass paste for forming a photosensitive sealing layer, plasma display manufacturing method using the same, and plasma display

Info

Publication number: WO2011001903A1
Application number: PCT/JP2010/060806
Authority: WO
Inventors: 田中明彦; 井戸英夫
Original assignee: 東レ株式会社
Priority date: 2009-07-01
Filing date: 2010-06-25
Publication date: 2011-01-06
Also published as: JP5375827B2; KR20120069614A; JPWO2011001903A1; CN102471138A

Abstract

Disclosed is a photosensitive paste including (A) a glass powder with a glass transition point of 410-480℃, a yield point of 470-510℃, and a softening point of 515-550℃; (B) a photosensitive organic component; (C) a UV absorber; and (D) a solvent. The glass paste for forming a photosensitive sealing layer is characterized in that the inorganic component including the glass powder has an average refractive index (N1) fulfilling equation (1). Thus, crosstalk and noise can be prevented, and a low energy consumption plasma display can be obtained.

Description

Glass paste for forming photosensitive sealing layer, method for producing plasma display using the same, and plasma display

The present invention relates to a glass paste for forming a photosensitive sealing layer and a method for producing a plasma display.

Plasma display panels (PDPs) are capable of high-speed display compared to liquid crystal panels and are easy to increase in size, and thus have penetrated into fields such as OA equipment and public information display devices. It is also used in the field of high-definition television.

In the PDP, a slight gap formed between two glass substrates, a front plate and a back plate, is used as a discharge space, and plasma discharge is generated between the anode and the cathode electrode, and the gas enclosed in the discharge space is used. Display is performed by emitting the emitted ultraviolet light to a phosphor provided in the discharge space. In this case, the electrodes are arranged in stripes on the front plate and the back plate, respectively, a plurality of electrodes are parallel, the electrodes on the front plate and the electrodes on the back plate face each other with a slight gap and are orthogonal to each other. Formed as follows. Among the PDPs, a surface discharge type PDP having a three-electrode structure suitable for color display using a phosphor includes a plurality of electrode pairs each composed of a pair of display electrodes adjacent in parallel to each other, and a plurality of address electrodes orthogonal to each electrode pair. And have. In addition, a barrier rib for preventing crosstalk of light and securing a discharge space is formed in the space between the electrodes on the back plate. Further, a phosphor is formed in the discharge space.

The front plate and the back plate are usually sealed by applying a paste containing a sealing glass frit to the peripheral part of the panel and then performing a heat treatment at a temperature at which the sealing glass frit softens. In this case, there is variation in the size of the gap between the partition wall that partitions the discharge space of the back plate and the front plate due to substrate warpage and partition wall height variation, which may cause noise due to crosstalk and vibration. there were. As a method for forming the partition walls with high accuracy, a method using a photosensitive paste has been proposed. According to this method, a high-definition partition wall can be formed with high accuracy, but when the substrate warps, the height is high. With respect to the variation in direction, the accuracy cannot be sufficiently controlled (for example, Patent Document 1). On the other hand, in order to solve these problems, a method of providing a partition height adjustment layer between the partition formed on the back plate and the front plate has been proposed (for example, Patent Document 2). Although the partition wall height adjusting layer described in this document is effective for the above-mentioned problem, there is no method for accurately forming the top of the partition wall formed in a large and large area. In the situation where high definition has progressed such as in full hi-vision, it has been difficult to accurately form the partition height adjusting layer as in Patent Document 2 on the top of the partition.

Japanese Patent Laid-Open No. 9-310030 JP-A-8-185802

An object of the present invention is to provide a glass paste for forming a photosensitive sealing layer capable of preventing a crosstalk and noise and obtaining a low power consumption plasma display.

That is, the present invention comprises (A) a glass powder having a glass transition point of 410 to 480 ° C., a yield point of 470 to 510 ° C., and a softening point of 515 to 550 ° C., (B) a photosensitive organic component, and (C) an ultraviolet ray absorbing material. And (D) a photosensitive paste containing a solvent, wherein the average refractive index N1 of an inorganic component containing glass powder satisfies the following formula (1).
1.75 ≦ N1 ≦ 1.95 (1)
N1 preferably satisfies the following formula (2).
1.75 ≦ N1 ≦ 1.90 (2)
The average refractive index N2 of the organic component including the photosensitive organic component preferably satisfies the following formula (3).
1.45 ≦ N2 ≦ 1.65 (3)
The average refractive index N1 of the inorganic component and the average refractive index N2 of the organic component preferably satisfy the following formula (4).
0.2 ≦ N1-N2 ≦ 0.5 (4)
The ultraviolet absorber is an organic dye, and the content in the paste is preferably 0.01 to 2% by weight.

In addition, the present invention includes a step of applying a photosensitive barrier rib forming paste on a substrate, a step of applying a photosensitive sealing layer forming glass paste after a step of exposing through a photomask, and a photomasking step. A method for manufacturing a plasma display, wherein a barrier rib for partitioning a discharge space and a sealing layer are formed through a step of exposing through a mask, a developing step, and a baking step, wherein the inorganic component in the photosensitive barrier rib forming paste And the average refractive index N1 of the inorganic component in the photosensitive sealing layer-forming glass paste satisfies the following formulas (5) and (6).
1.45 <Na <1.65 (5)
0.2 ≦ N1-Na ≦ 0.5 (6)
Furthermore, the present invention includes a step of applying a first photosensitive barrier rib forming paste on a substrate, a step of exposing through a photomask, a step of applying a second photosensitive barrier rib forming paste, and a photomask. Barrier ribs for partitioning the discharge space through a step of applying the glass paste for forming a photosensitive sealing layer, a step of exposing via a photomask, a development step, and a baking step A method for manufacturing a plasma display for forming a sealing layer, comprising: an average refractive index Na of an inorganic component in the first photosensitive barrier rib forming paste; and an inorganic component in the second photosensitive barrier rib forming paste. Production of plasma display, characterized in that average refractive index Nb and average refractive index N1 of the inorganic component in said photosensitive sealing layer forming glass paste satisfy the following formulas (5) to (8): It is the law.
1.45 <Na <1.65 (5)
0.2 ≦ N1-Na ≦ 0.5 (6)
1.45 <Nb <1.65 (7)
0.2 ≦ N1-Nb ≦ 0.5 (8)
In the plasma display manufacturing method, the average refractive index Na of the inorganic component in the first photosensitive barrier rib forming paste and the average refractive index Nb of the inorganic component in the second photosensitive barrier rib forming paste are low. It is preferable to satisfy Formula (9).
−0.1 ≦ Nb—Na ≦ 0.1 (9)
Furthermore, this invention relates to the plasma display obtained by the said manufacturing method.

The glass paste for forming a photosensitive sealing layer of the present invention can form a uniform sealing layer with high accuracy at the top of the partition wall at low cost. Moreover, by using this, a high-performance plasma display can be manufactured at low cost.

The present invention relates to a glass paste for forming a photosensitive sealing layer containing glass powder, a photosensitive organic component, an ultraviolet absorber, and a solvent.

The glass paste for forming a photosensitive sealing layer of the present invention is a photosensitive glass paste used for forming a sealing layer of a display. The sealing layer refers to a layer that fuses a member constituting the display, for example, a front plate and a back plate. The glass paste for forming a photosensitive sealing layer of the present invention is preferably used for producing a patterned sealing layer, particularly a sealing layer provided on top of another pattern layer. In particular, it is preferably used when the barrier ribs are provided on the barrier ribs of the back plate of the plasma display panel, and when the barrier ribs are formed by the photosensitive glass paste method, the barrier ribs and the sealing layer are simultaneously provided.

The glass paste for forming a photosensitive sealing layer of the present invention contains a glass powder, a photosensitive organic component for forming a fine pitch pattern, an ultraviolet absorber, and a solvent for ensuring coating stability. Containing.

In the conventional glass paste for forming barrier ribs used for forming barrier ribs for plasma displays, a glass frit having a relatively high softening point is used to maintain the barrier rib shape during firing, and a high pitch and high pitch are used. In order to form an aspect ratio pattern, a glass frit having a relatively low refractive index has been used for the purpose of matching the refractive index of the glass powder with the refractive index of the organic component. However, in the method using such a photosensitive partition wall forming glass paste, there is a problem that crosstalk or noise occurs when the substrate warps or the partition wall height varies. In order to solve this problem, it is effective to bond the top of the partition wall and the front plate in a heating process at the time of sealing. For this purpose, it is necessary to form a sealing layer on the top of the partition wall. As a method for forming the sealing layer, after baking and forming the partition pattern, the paste for forming the sealing layer is applied by screen printing or a roll coater. Then, there is a method of adhering to the front plate at the time of sealing. However, in this method, the sealing layer forming step increases in addition to the conventional barrier rib forming step, so there is a problem in cost, and the accuracy of applying the sealing layer paste only on the top of the barrier rib formed with high definition There was a problem. Therefore, the photosensitive barrier rib paste is applied, the photosensitive sealing layer forming glass paste of the present invention is applied onto the coating film exposed through the photomask, exposed through the photomask, and developed in a batch. After that, the sealing layer can be accurately formed on the top of the partition wall by firing.

The glass paste for forming a photosensitive sealing layer of the present invention needs to be softened to such an extent that it adheres to the front plate at the heating temperature in the sealing process. Therefore, the glass transition point of the glass powder to be contained needs to be 410 to 480 ° C. When the temperature is lower than 410 ° C., the shape retention is poor, and when it exceeds 480 ° C., the adhesion to the front plate becomes insufficient. Similarly, the yield point of the glass powder needs to be 470 to 510 ° C. When the temperature is lower than 470 ° C., the binder removal property at the time of firing is deteriorated, voids are formed in the sealing layer after firing, and defects such as chipping may occur at the time of sealing. If it exceeds 510 ° C., the adhesion to the front plate becomes insufficient. Furthermore, the softening point of the glass powder needs to be 515 to 550 ° C. When the temperature is lower than 515 ° C., the binder removal property is insufficient, the shape retention during firing is poor, and a uniform sealing layer cannot be obtained. When it is higher than 550 ° C., the adhesion to the front plate becomes insufficient.

In the glass paste for forming a photosensitive sealing layer of the present invention, it is necessary that the average refractive index N1 of the inorganic component contained satisfies the following formula 1.
1.75 ≦ N1 ≦ 1.95 (1)
Usually, a photosensitive glass paste that forms a pattern such as a partition wall contains a photosensitive organic component for the purpose of forming a pattern with a large aspect ratio by suppressing scattering of light used for exposure (hereinafter referred to as exposure light). The average refractive index of the organic component and the average refractive index of the inorganic component are often matched. However, as described above, the glass paste for forming a photosensitive sealing layer of the present invention is formed on the top of the partition wall, and is developed and fired together with the partition wall to form a sealing layer. It is necessary to prevent exposure light from reaching the photosensitive barrier rib forming paste coating film that has been exposed. For this reason, an ultraviolet absorber is added, but if the transmittance of the exposure light is adjusted only by the ultraviolet absorber, the exposure light necessary for curing is exposed at the bottom portion of the paste coating film for forming the photosensitive sealing layer. Does not reach the point, and peels off or deforms during development.

In order to solve this problem, by setting N1 to 1.75 or more, the difference in refractive index from the organic component containing the organic component in the photosensitive sealing layer forming paste is appropriately increased, and the exposure light is reduced. It can be prevented that the photosensitive barrier rib forming paste coating film as the lower layer reaches the lower layer. Further, when a glass powder smaller than 1.75 is produced in accordance with the required glass transition point, yield point, and softening point, it is necessary to contain a large amount of an alkali metal component. The alkali metal component is not preferable because it reacts with the photosensitive organic component to gel or thicken the paste.

Further, by setting N1 to 1.95 or less, it is possible to prevent the difference in refractive index from the organic component in the photosensitive sealing layer forming paste from becoming too large, and the bottom of the sealing layer forming paste coating film is Insufficient exposure can be prevented. If it exceeds 1.95, the refractive index difference with the organic component becomes too large, and a desired pattern cannot be obtained. Preferably it is 1.90 or less.

In addition, the refractive index measurement of glass powder and a filler can be performed by glass powder and the Becke method, and it is preferable to perform a measurement by g line | wire (436 nm). The average refractive index of the inorganic powder contained in the paste is preferably determined by the volume average of the refractive index of each powder.

In the present application, the average refractive index of the inorganic component is determined by dispersing only the inorganic component contained in the paste in a solvent and applying it to soften the glass powder, or applying the paste and the glass powder softening temperature or higher. It can also be determined by measuring the refractive index of the inorganic component layer obtained by firing to remove the organic component.

Further, in order to appropriately scatter the exposure light as described above, the average refractive index N2 of the organic component including the photosensitive organic component in the photosensitive sealing layer forming paste of the present invention satisfies the following formula (3). It is preferable.
1.45 ≦ N2 ≦ 1.65 (3)
Further, N1 and N2 preferably satisfy the following formula (4).
0.2 ≦ N1-N2 ≦ 0.5 (4)
When N1 and N2 satisfy the above formulas (1), (3), and (4), it is possible to scatter the exposure light in particular, and it is sufficiently cured to the bottom of the paste coating film for forming the photosensitive sealing layer. Further, the photosensitive barrier rib forming paste coating film as the lower layer can be prevented from further curing. If N2 is smaller than 1.45 or N1-N2 is larger than 0.5, the exposure light may be scattered too much and the bottom of the photosensitive sealing layer forming paste coating film may not be sufficiently cured. If it is smaller than 0.2, the exposure light may be transmitted too much and the exposure pattern of the photosensitive barrier rib forming paste coating film may change.

In the present invention, the average refractive index of the organic component in the present invention is the average refractive index of the organic component in the paste coating film. For example, the paste is obtained by removing the inorganic component from the paste and drying to remove the solvent. It can obtain | require by measuring the refractive index of the organic component coating film obtained.

Further, as the glass powder used in the glass paste for forming a photosensitive sealing layer of the present invention, a glass material containing silicon and boron oxides is preferably used. Furthermore, in order to form a sealing layer, a glass transition suitable for forming a sealing layer is contained by containing at least one of bismuth oxide, lead oxide, and zinc oxide in a total amount of 5 to 85% by weight. A glass paste having temperature characteristics such as a point, a yield point, and a softening point can be obtained. In particular, the use of glass powder containing 5 to 85% by weight of bismuth oxide provides advantages such as a long pot life of the paste.

Further, glass powder containing 3 to 20% by weight of at least one of lithium oxide, sodium oxide, and potassium oxide may be used. By making the addition amount of the alkali metal oxide 20% by weight or less, preferably 15% by weight or less, the pot life of the paste can be kept long. In addition, if glass powder containing both metal oxides such as lead oxide, bismuth oxide and zinc oxide and alkali metal oxides such as lithium oxide, sodium oxide and potassium oxide is used, with a lower alkali content, A glass paste having temperature characteristics such as a glass transition point, a yield point, and a softening point suitable for forming a sealing layer can be obtained.

In the photosensitive sealing layer forming paste of the present invention, the volume ratio of the inorganic component containing the glass powder and the volume ratio of the organic component excluding the organic solvent are preferably controlled to 30:70 to 60:40. If the inorganic component ratio is smaller than 30:70, the organic component becomes too much, and pattern deformation may be observed during firing shrinkage. When the inorganic component ratio exceeds 60:40, the pattern forming property deteriorates, and a problem that a high-definition pattern cannot be obtained occurs. The addition amount of the glass powder in the paste is changed so as to satisfy the aforementioned volume ratio in accordance with the specific gravity of the glass powder. Moreover, in order to ensure the shape retainability of the sealing layer, it is possible to adjust the shape retainability and the adhesiveness by adding a small amount of a filler that does not soften at the firing temperature as necessary.

The volume average particle diameter of the glass powder may be appropriately selected in consideration of the line width and height of the partition to be produced, but is preferably greater than 1.5 μm and less than 5.0 μm, preferably from 1.7 μm. More preferably, it is less than 4.0 μm. When the volume average particle diameter is 1.5 μm or less, the low-melting glass powders tend to aggregate in the paste, which tends to hinder a uniform partition wall shape. When the thickness is 5.0 μm or more, there is a problem that a good shape cannot be obtained at the time of pattern formation, and disconnection or chipping is likely to occur in the partition walls.

Here, the volume average particle diameter refers to the volume average diameter of the powder measured using a laser diffraction / scattering particle size distribution meter.

Further, the maximum particle size of the glass powder is preferably 20 μm or less, and more preferably 15 μm or less. If the maximum particle size exceeds 20 μm, disconnection or chipping is likely to occur during pattern formation, and giant particles remain as abnormal protrusions, and tend to contact the front plate during panel production and easily cause disconnection or front plate failure. . The specific surface area of the glass powder is preferably 1.0 ~ 4.0cm ² / g, more preferably 1.5 ~ ^3cm 2 / g. When the specific surface area of the glass powder satisfies this range, aggregation of the glass powders in the paste can be suppressed, and the glass powder in the paste can be uniformly dispersed. This makes it possible to form a pattern with high accuracy.

The photosensitive organic component used in the glass paste for forming a photosensitive sealing layer of the present invention contains a photosensitive organic component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, and Additive components such as photopolymerization initiators, sensitizers, sensitizers, polymerization inhibitors, plasticizers, thickeners, antioxidants, dispersants, organic or inorganic precipitation inhibitors as required Additions are listed. In addition, although the glass paste for photosensitive sealing layer formation of this invention contains a solvent so that it may mention later, when using the organic solvent which does not react with a photosensitive organic component as a solvent, such an organic solvent is a photosensitive organic component. Is not included in the organic component.

Further, the glass paste for forming a photosensitive sealing layer of the present invention contains an ultraviolet absorber. As the ultraviolet absorber, an organic dye is preferable. Specifically, azo dyes, aminoketone dyes, xanthene dyes, quinoline dyes, anthraquinone dyes, benzophenone dyes, triazine dyes, p-aminobenzoic acid dyes cyanoacrylate compounds, salicylic acid compounds, benzoates Examples include triazole compounds and indole compounds. Among these, azo dyes, benzophenone compounds, cyanoacrylate compounds, and indole compounds are particularly effective. Specific examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, -Hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4 -(2-Hydroxy-3-me (Chryloxy) propoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl Acrylate, 2- (1-methyl-2-phenyl-1H-indol-3-ylmethylene) -malononitrile, etc. But it is not limited to these. The glass paste for forming a photosensitive sealing layer of the present invention is mainly used for forming a sealing layer on the top of a partition wall. As a method for forming the glass paste, for example, refraction of inorganic powder containing glass frit on a substrate is used. After applying a photosensitive paste in which the refractive index of the organic component and the refractive index of the organic component are matched and exposing through a photomask, the glass paste for forming a photosensitive sealing layer of the present invention is applied and the photomask is used. After the exposure and batch development, a partition for partitioning the discharge space and a sealing layer are formed through a baking process. Therefore, when exposing the glass paste coating film for forming a photosensitive sealing layer, it is necessary to prevent exposure light from reaching the photosensitive paste coating film for forming barrier ribs that has been previously exposed. Therefore, it is necessary to contain a relatively large amount of ultraviolet absorber that absorbs exposure light. The content depends on the thickness of the sealing layer, but is preferably 0.01 to 2% by weight in the photosensitive paste. If it is less than 0.01% by weight, the exposure light absorption is insufficient, and the desired partition wall shape may not be obtained. If it exceeds 2% by weight, curing of the coating film for forming the sealing layer becomes insufficient. There is a risk of peeling or deformation after development.

The glass paste for forming a photosensitive sealing layer of the present invention contains a solvent in order to obtain a uniform coating film. As the solvent, an organic solvent is preferable. The content of the organic solvent varies depending on the specific gravity of the glass powder, but is preferably 15 to 45% by weight in the paste. In other ranges, the paste cannot be applied well and a uniform film cannot be obtained. Examples of the organic solvent used at this time include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromo Benzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, terpineol, diethylene glycol monobutyl ether acetate and the like, and an organic solvent mixture containing one or more of these are preferably used.
Hereinafter, the photosensitive organic component of the present invention will be described.

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. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate , Butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, Serol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate , Methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate , Diethylene glycol diacre relay , 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 Acrylate, diacrylate of bisphenol A-ethylene oxide adduct, diacrylate of bisphenol A-propylene oxide adduct, acrylate such as thiophenol acrylate, benzyl mercaptan acrylate, and 1-5 of hydrogen atoms of these aromatic rings Monomer substituted with chlorine atom or bromine atom, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene Brominated α-methyl styrene, chloromethyl styrene, hydroxymethyl styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, and a part of the acrylate in the molecule of the above compound or Those changed to methacrylate all, .gamma.-methacryloxypropyltrimethoxysilane, and 1-vinyl-2-pyrrolidone. In the present invention, one or more of these can be used.

In addition to these, 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 photosensitive monomers is preferably in the range of 7 to 15% by weight in the paste. In other ranges, the pattern formability is deteriorated and the hardness after curing is not preferable.

In addition, as the photosensitive oligomer and the photosensitive polymer, an oligomer or a polymer obtained by polymerizing at least one of the compounds containing the carbon-carbon unsaturated bond can be used. The content of the compound containing a carbon-carbon unsaturated bond is preferably 10% by weight or more, and more preferably 35% by weight or more in the total amount of the photosensitive oligomer and the photosensitive polymer.

Furthermore, it is preferable to copolymerize a photosensitive oligomer or photosensitive polymer with an unsaturated acid such as an unsaturated carboxylic acid to improve developability after exposure. 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 acid value (AV) of the oligomer or polymer having an acidic group such as a carboxyl group in the side chain thus obtained is preferably 30 to 150, more preferably 70 to 120. If the acid value is less than 30, the solubility of the unexposed area in the developing solution is lowered. Therefore, when the developing solution concentration is increased, the exposed area is peeled off, and a high-definition pattern tends to be difficult to obtain. Further, when the acid value exceeds 150, the development allowable width tends to be narrowed.

These photo-sensitive oligomers and photo-polymers can be used as photo-sensitive photo-polymers and photo-oligomers by adding a photoreactive group to the side chain or molecular end. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.

Such a side chain can be added to an oligomer or polymer by using an ethylenically unsaturated compound having a glycidyl group or an isocyanate group relative to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method of addition reaction of acid chloride or allyl chloride.

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 crotonic acid, and glycidyl ether of isocrotonic acid.

Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate.

In addition, the ethylenically unsaturated compound having glycidyl group or isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is 0.05 to 1 molar equivalent to the mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to add.

The content of the photosensitive oligomer and / or the photosensitive polymer in the glass paste for forming a photosensitive sealing layer of the present invention is 7 to 15% by weight in the paste from the viewpoint of pattern formability and shrinkage after baking. It is preferable to be within the range. Outside this range, it is not preferable because pattern formation is impossible or the pattern becomes thick.

Specific examples of photopolymerization initiators include benzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- t-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketanol, benzylmethoxyethyl acetal, benzoin, benzoin Ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p -Azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-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, Mihi Lerketone, 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, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide and Examples include photoreductive dyes such as eosin and methylene blue, and reducing agents such as ascorbic acid and triethanolamine. In the present invention, one or more of these can be used.

The photopolymerization initiator is preferably added in an amount of 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, based on the photosensitive organic component. When the photopolymerization initiator is less than 0.05% by weight, the photosensitivity tends to be poor, and when the photopolymerization initiator exceeds 20% by weight, the residual ratio of the exposed portion tends to be too small.

Sensitizers are added as necessary 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, 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-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isononafthiazole, 1,3-bis (4-dimethylaminoben) Colander) acetone, 1,3-carbonyl-bis (4-diethyl) Aminobenzal) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, dimethylaminobenzoic acid Examples thereof include isoamyl, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, and 1-phenyl-5-ethoxycarbonylthiotetrazole. 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 glass paste of the present invention, the addition amount is usually preferably 0.05 to 30% by weight, more preferably 0.1 to 20% by weight, based on the photosensitive organic component. It is. If it is less than 0.05% by weight, the effect of improving the photosensitivity tends to be hardly exhibited, and if it exceeds 30% by weight, the residual ratio of the exposed portion tends to be too small.

Polymerization inhibitor is added as necessary to improve the thermal stability during storage. Specific examples of the polymerization inhibitor include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples thereof include methylphenol, chloranil, pyrogallol and p-methoxyphenol. Further, by adding, the threshold value of the photocuring reaction is increased, the pattern line width is reduced, and the pattern upper portion with respect to the gap is eliminated.

The addition amount of the polymerization inhibitor is preferably 0.01 to 1% by weight in the glass paste for forming the photosensitive sealing layer. If it is less than 0.01% by weight, the effect of addition tends to be difficult, and if it exceeds 1% by weight, the sensitivity tends to decrease, so that a large amount of exposure tends to be required for pattern formation.

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

An antioxidant is added as necessary to prevent oxidation of the acrylic copolymer during storage. Specific examples of the antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-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-4-hydroxy-6-tert-butylphenyl) butane, bis [3,3-bis- (4-hydroxy-3-tert-butylphenyl) butyric Acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like. When an antioxidant is added, the addition amount is preferably 0.01 to 1% by weight in the glass paste.

The glass paste for forming a photosensitive sealing layer of the present invention is usually at least one of the above-mentioned photosensitive monomer, photosensitive oligomer, and photosensitive polymer, and further, if necessary, a photopolymerization initiator, an ultraviolet absorber, an increase agent. Additive components such as sensitizers, sensitization aids, polymerization inhibitors, plasticizers, thickeners, organic solvents, antioxidants, dispersants, organic or inorganic precipitation inhibitors are formulated to have a predetermined composition After that, it is prepared by uniformly mixing and dispersing with an inorganic component containing glass powder using a three roller or kneader.

The viscosity of the glass paste for forming a photosensitive sealing layer is appropriately adjusted, but the range is preferably 0.2 to 200 Pa · s. For example, in order to obtain a film thickness of 10 to 20 μm by applying it once by a screen printing method, 10 to 100 Pa · s is more preferable. Further, in order to obtain a similar film thickness by coating once with a slit die coater, 10 to 50 Pa · s is more preferable.

The present invention also includes a step of applying and drying the above-mentioned glass paste for forming a photosensitive sealing layer to form a paste coating film, a step of exposing the paste coating film through a photomask, and an exposed paste coating film. The present invention relates to a method for manufacturing a plasma display including a developing step and a step of forming a pattern by baking.

As a method of forming the sealing layer on the top of the partition wall that partitions the discharge space of the plasma display using the glass paste for forming the photosensitive sealing layer of the present invention, an application in which the photosensitive partition wall forming paste is applied on the substrate After the film is exposed through a photomask having a final partition wall pattern, the coating film coated with the photosensitive sealing layer forming glass paste of the present invention is applied through a photomask having a sealing layer pattern. After exposure and development in a lump, baking is performed, whereby barrier ribs and a sealing layer for partitioning the discharge space can be formed. At this time, since the partition height of the plasma display needs to be about 70 to 150 μm after firing, the average refractive index Na of the inorganic component contained in the paste for forming the photosensitive partition is the refractive index difference of the organic component excluding the solvent. It is necessary to make it small, and it is preferable to satisfy the following formula (5).
1.45 <Na <1.65 (5)
On the other hand, the sealing layer is 2 to 10 μm after firing, which is relatively thin compared to the barrier ribs. The exposure of the glass paste coating film for forming the photosensitive sealing layer is first performed so as not to affect the barrier rib pattern of the lower layer. It is necessary to adjust so that the exposure light does not reach the barrier rib forming paste coating film. On the other hand, it is necessary to transmit the exposure light to the bottom of the glass paste coating film for forming the photosensitive sealing layer and to cure it firmly. Therefore, the average refractive index N1 of the inorganic component in the glass paste for forming a photosensitive sealing layer of the present invention needs to control the refractive index difference from the organic component excluding the solvent. The average refractive index Na of the inorganic component of the conductive partition wall forming paste needs to be controlled so as to satisfy the following formula (6).
0.2 ≦ N1-Na ≦ 0.5 (6)
As for the sealing layer pattern formed on the top of the partition wall, if the partition pattern is a simple stripe structure, there is no problem even if the sealing layer is formed on the entire top surface of the partition wall. In such a case, if the sealing layer is formed in exactly the same manner as the barrier rib pattern, the cell surrounded by the barrier ribs and the sealing layer is completely sealed after sealing with the front plate. For this reason, gas cannot be exhausted sufficiently. For this reason, in the case of a partition pattern such as a cross-beam structure or a waffle structure, the problem of exhaust can be solved by forming a sealing layer only on the top of the partition formed parallel to the address electrodes.

Further, as described above, since the sealing layer is formed as thin as 2 to 10 μm after firing, the thickness of the sealing layer alone may result in insufficient exhaust after sealing. For this reason, the barrier rib pattern formed parallel to the address electrode is formed higher than the height of the barrier rib pattern formed to be perpendicular to or intersecting with the address electrode, and the sealing layer is formed only on the high barrier rib pattern, Can solve the problem of exhaust. In this case, a step of applying a first photosensitive barrier rib forming paste on the substrate, a step of exposing through a photomask having a pattern perpendicular to or intersecting with the address electrodes, the first photosensitive barrier rib forming paste A step of applying a second photosensitive barrier rib forming paste on the coating film, a step of exposing through a photomask having a pattern parallel to the address electrodes, and then applying a photosensitive sealing layer forming glass paste of the present invention Then, exposure is performed through a photomask having a sealing layer pattern, and then a development process and a baking process are performed, so that a partition wall pattern formed in parallel to the address electrode is formed to be perpendicular to or intersecting with the address electrode. It can be formed higher than the height of the partition wall pattern, and the sealing layer can be formed only on the high partition wall pattern. At this time, the first and second photosensitive partition forming photosensitive pastes need to be adjusted to reduce the average refractive index of the inorganic material contained and the refractive index of the organic component excluding the solvent. The average refractive index Na of the inorganic component in the photosensitive barrier rib forming paste and the average refractive index Nb of the inorganic component in the second photosensitive barrier rib forming paste satisfy the following expressions (5) and (7). Important. In addition, as described above, the exposure light does not reach the barrier rib forming paste coating film that has been previously exposed so that the exposure of the photosensitive sealing layer forming glass paste coating film does not affect the barrier rib pattern of the lower layer. On the other hand, since it is necessary to transmit the exposure light to the bottom of the glass paste coating film for forming the photosensitive sealing layer, it is necessary to cure firmly, so that the photosensitive sealing layer of the present invention is formed. The average refractive index N1 of the inorganic component in the glass paste must be controlled for the difference in refractive index with the organic component excluding the solvent, and it is important that the following formulas (6), (8), and (9) are satisfied. is there.
1.45 <Na <1.65 (5)
0.2 ≦ N1-Na ≦ 0.5 (6)
1.45 <Nb <1.65 (7)
0.2 ≦ N1-Nb ≦ 0.5 (8)
-0.1 ≤ Nb-Na ≤ 0.1 (9)
After the photosensitive glass paste for forming the barrier ribs is applied, exposure is performed using an exposure apparatus, and the exposure is generally performed by a mask exposure using a photomask, as in a normal photolithography method. is there.

As the exposure apparatus, a stepper exposure machine, a proximity exposure machine, or the like can be used. Examples of the active light source used include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet rays are most preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, or a germicidal lamp can be used. Among these, an ultrahigh pressure mercury lamp is suitable. Although exposure conditions vary depending on the coating thickness, exposure is usually performed for 0.1 to 10 minutes using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² .

Thereafter, the glass paste for forming a photosensitive sealing layer of the present invention is applied on the exposed coating film of the photosensitive glass paste for forming a partition wall. As a coating method, a general method such as a screen printing method, a bar coater, a roll coater, a die coater, or a blade coater can be used. The coating thickness is adjusted according to the sealing layer to be formed after firing. Thereafter, mask exposure is performed using a photomask that matches the sealing layer pattern formed on the top of the partition wall. As the exposure apparatus and the light source, the same ones as used for forming the partition walls can be used.

The exposure method is determined by the structure of the partition wall to be formed and the structure of the sealing layer. When the sealing layer is simply formed on the entire top surface of the partition wall, a sealing layer forming photomask having the same pattern as the partition wall pattern forming photomask is used. The opening width of the photomask is adjusted as appropriate, but in order to form the sealing layer only on the top of the partition wall with high accuracy, the opening width of the photomask for partition wall formation is W1, and the opening width W2 of the photomask for sealing layer formation is In this case, it is preferable to satisfy the following formula.
W2 <W1
In addition, when the barrier rib pattern is not a simple stripe structure but a cross beam structure or a waffle structure, if the sealing layer is formed in exactly the same manner as the barrier rib pattern, the barrier rib pattern is surrounded by the barrier rib and the sealing layer. After the inside of the cell is sealed with the front plate, the gas is not completely exhausted because the cell is completely sealed. For this reason, in the case of a barrier rib pattern such as a cross-beam structure or a waffle structure, the height of the barrier rib pattern formed perpendicular to the barrier rib pattern formed parallel to the address electrodes is changed, and the sealing layer is formed only on the high barrier rib pattern. The problem of exhaust can be solved by forming.

Usually, since the partition wall parallel to the address electrode is the main partition wall, the partition wall is formed to have a high height.

Developing methods can be performed by dipping, showering, spraying, or brushing.

As the developer, a solution that can dissolve the organic component to be dissolved in the photosensitive glass paste is used. When a compound having an acidic group such as a carboxyl group is present in the photosensitive glass paste, development can be performed with an alkaline aqueous solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, sodium carbonate aqueous solution, calcium hydroxide aqueous solution or the like can be used. However, it is preferable to use an organic alkaline aqueous solution because an alkaline component can be easily removed during firing. As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine. The concentration of the alkaline aqueous solution is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight. If the concentration of the aqueous alkali solution is less than 0.01% by weight, the soluble part tends to be removed, and if it exceeds 10% by weight, the pattern part tends to be peeled off and the insoluble part tends to corrode. Further, the development temperature at the time of development is preferably 20 to 50 ° C. for process control.

Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste and substrate. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. The firing temperature is usually 500 to 600 ° C. The firing temperature is determined by the glass powder to be used, but it is preferable to fire at an appropriate temperature that does not break the shape after pattern formation and does not leave the shape of the glass powder. When the temperature is lower than the appropriate temperature, the porosity and the unevenness at the upper part of the partition wall are increased, so that the discharge life is shortened and erroneous discharge is easily caused. On the other hand, if the temperature is higher than the appropriate temperature, the shape at the time of pattern formation collapses, the height becomes extremely low, or a desired height cannot be obtained, which is not preferable.

Further, a heating step at 50 to 300 ° C. may be introduced for the purpose of drying and preliminary reaction during each of the above coating, exposure and development steps and between any of the coating, exposure, development and baking steps. .

After forming the barrier ribs and the adhesion layer, phosphor layers that emit light in RGB colors are formed. A phosphor layer can be formed by forming a phosphor paste containing phosphor powder, an organic binder and an organic solvent as main components between predetermined partitions. As a method of forming the phosphor paste between the predetermined partition walls, a screen printing method for pattern printing using a screen printing plate, a dispenser method for pattern ejection of the phosphor paste from the tip of the ejection nozzle, and the organic binder described above By using an organic component having photosensitivity, a photosensitive phosphor paste can be prepared, and each color phosphor layer can be formed in a predetermined place by a photosensitive paste method.

The substrate for plasma display of the present invention can be produced by firing the substrate on which the phosphor layer is formed, if necessary, at 400 to 550 ° C.

Using the plasma display substrate as a back plate, sealing with the front plate is performed. By applying a paste containing glass powder for sealing around the panel and heat-treating it, the impure gas is exhausted simultaneously with sealing. Usually, the sealing paste is applied to the periphery of the back plate, and the heat treatment temperature is in the range of 450 to 520 ° C. because it is performed at a temperature at which the phosphor does not deteriorate. Under the present circumstances, the sealing layer of the partition top part formed previously can also be adhere | attached with a front plate. After a discharge gas composed of helium, neon, xenon, or the like is sealed in the space formed between the front and rear substrates, a plasma display can be manufactured by mounting a drive circuit. The front plate is a substrate in which a transparent electrode, bus electrode, dielectric, and protective film (MgO) are formed in a predetermined pattern on the substrate, and the color corresponding to the RGB color phosphor layers formed on the back substrate is colored. A filter layer may be formed. Further, a black stripe may be formed in order to improve contrast.

Since the display of the present invention obtained by the above manufacturing method has various patterns with reduced surface roughness and waviness, generation of erroneous discharge (crosstalk) due to leakage of plasma discharge and vibration due to vibration, which are conventional problems, are present. Since generation | occurrence | production can be eliminated, the stable display can be obtained.

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to such examples.

(Examples 1 to 14, Comparative Examples 1 to 4)
Table 1 shows the glass powder used in the examples.

In addition, the following glass powder and the average particle diameter (D50) and maximum particle diameter (Dmax) of a filler are the values measured using the Nikkiso Co., Ltd microtrac particle size distribution measuring apparatus (MT3000). The glass transition point and softening point of the glass powder are heated in air at a heating rate of 10 ° C./min using differential thermal analysis, and the temperature is plotted on the horizontal axis and the amount of heat is plotted on the vertical axis to draw a DTA curve. The read value. The yield point of the glass powder is a value measured by heating in air at a heating rate of 5 ° C./min using a thermal expansion measuring device.

Moreover, the refractive index measurement of the glass powder and the filler was performed by the Becke method, and the measurement was performed with g-line (436 nm). The average refractive index of the inorganic powder was determined by the volume average of the powder refractive index contained.

The refractive index of the organic component was measured by applying a material obtained by removing the inorganic component from the paste composition and drying the resultant at 100 ° C. for 30 minutes to remove the solvent and measuring the refractive index of the organic component coating film. The measurement was performed with g-line (436 nm).

The glass powder of Table 1 and the raw material containing the filler are weighed in the compositions and ratios shown in Tables 2 and 3, mixed, kneaded with three rollers to produce a photosensitive sealing layer forming glass paste, and after firing Exposure was performed after applying the partition wall forming paste and the sealing layer forming paste so as to have respective heights.

Filler J: 40 parts by weight of silicon oxide, 10 parts by weight of boron oxide, 5 parts by weight of zinc oxide, 30 parts by weight of aluminum oxide, 5 parts by weight of magnesium oxide, 5 parts by weight of barium oxide, 5 parts by weight of calcium oxide. High melting point glass filler K having a glass transition point of 650 ° C., a softening point of 740 ° C. and a refractive index of 1.58: a silicon oxide polymer having an average particle diameter of 0.2 μm: an acid value = 85, and a photosensitivity having a weight average molecular weight (Mw) of 32,000 Acrylic polymer (APX-716 manufactured by Toray Industries, Inc.)
Monomer: Propylene oxide modified trimethylolpropane triacrylate (Daiichi Kogyo Seiyaku Co., Ltd.)
Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Ciba Specialty Chemicals Co., Ltd., IC-369)
Sensitizer: 4,4-bis (diethylamino) benzophenone Dispersant: Polymer activator of polycarboxylic acid compound (“Kuroei” G-700DMEA, manufactured by Kyoeisha Chemical Co., Ltd.)
Aliphatic amide compound: N, N′-12-hydroxystearic acid butylenediamine UV absorber: Basic Blue 26
Polymerization inhibitor: p-methoxyphenol Organic solvent: diethylene glycol monobutyl ether acetate A 42-inch PD-200 (manufactured by Asahi Glass Co., Ltd.) of 590 × 964 × 1.8 mm was used as a glass substrate. On this substrate, as an address electrode, 70 parts by weight of silver powder having an average particle diameter of 2.0 μm, Bi ₂ O ₃ / SiO ₂ / Al ₂ O ₃ / B ₂ O ₃ / BaO = 69/20/4/7 2 parts by weight of glass powder (average particle size 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, Using a photosensitive silver paste composed of 7 parts by weight of butyl carbitol acrylate and 3 parts by weight of benzyl alcohol, a striped electrode having a pitch of 160 μm, a line width of 60 μm, and a thickness of 3 μm after firing was formed by photolithography.

On this substrate, glass powder composed of Bi ₂ O ₃ / SiO ₂ / Al ₂ O ₃ / ZnO / B ₂ O ₃ / BaO = 60/20/5/10/2/3 (weight%) (average particle diameter 2 μm) ) 60 parts by weight, 10 parts by weight of titanium oxide powder having a volume average particle diameter of 0.2 μm, 5% by weight of ethyl cellulose, and 20% by weight of terpineol, and then baked at 580 ° C. to form a dielectric having a thickness of 10 μm. A layer was formed.

As the partition wall forming paste, glass powder (average grain) made of Li ₂ O / SiO ₂ / Al ₂ O ₃ / ZnO / B ₂ O ₃ / BaO = 8/21/15/7/39/10 (weight%) 40 parts by weight of diameter 2 μm, refractive index 1.59), 10 parts by weight of filler J, polymer (photosensitive acrylic polymer having an acid value of 85 and a weight average molecular weight of 32,000 (APX-716 manufactured by Toray Industries, Inc.)) 10 parts by weight, 7 parts by weight of monomer (trimethylolpropane triacrylate), 3 parts by weight of IC-369 manufactured by Ciba Specialty Chemicals Co., Ltd., 0.005 parts by weight of Basic Blue 26 as an ultraviolet absorber, benzyl alcohol 4 A partition wall forming paste 1 was prepared by adding parts by weight and 20 parts by weight of butyl carbitol acetate and kneading with three rollers. The average refractive index Na of the inorganic component was 1.59. Further, glass powder (average particle diameter 2 μm, refractive index) made of Li ₂ O / SiO ₂ / Al ₂ O ₃ / ZnO / B ₂ O ₃ / BaO = 10/20/15/7/38/10 (wt%) 1.57) 30 parts by weight, filler J 20 parts by weight, polymer (acid value = 85, weight average molecular weight 32,000 photosensitive acrylic polymer (APX-716, Toray Industries, Inc.)) 12 parts by weight, monomer (Trimethylolpropane triacrylate) 7 parts by weight, 2 parts by weight of IC-369 manufactured by Ciba Specialty Chemicals Co., Ltd., 0.001 part by weight of basic blue 26 as a UV absorber, 4 parts by weight of benzyl alcohol, butylcarb A partition wall forming paste 2 was prepared by adding 20 parts by weight of tall acetate and kneading with three rollers. The average refractive index Nb of the inorganic component was 1.57.

In Examples 1 to 12 and Comparative Examples 1 to 4, the partition wall forming paste 1 was applied with a die coater so as to have a thickness of 100 μm after firing, and then dried in a clean oven at 100 ° C. for 40 minutes. Thus, a coating film was formed. Thereafter, exposure is performed through the photomasks shown in Tables 2 and 3. Further, the partition wall forming paste 2 was applied with a die coater so as to have a predetermined thickness, and then dried in a clean oven at 100 ° C. for 30 minutes to form a coating film. Exposure is performed through the photomask shown. Each photomask pattern is shown below.

Photomask A: stripe pattern perpendicular to address electrodes, pitch 480 μm, opening 40 μm
Photomask B: stripe pattern parallel to address electrodes, pitch 160 μm, opening 40 μm
Photomask C: lattice pattern, pattern pitch 480 μm perpendicular to the address electrodes, pattern pitch parallel to the address electrodes 160 μm, and openings 40 μm in all.
Photomask D: stripe pattern parallel to address electrodes, pitch 160 μm, opening 20 μm
The photosensitive sealing layer forming glass pastes of Examples and Comparative Examples were applied on the exposed partition wall forming paste coating film by a die coater so that the dry film thickness was 10 μm. Thereafter, exposure was performed through the photomask pattern D. Thereafter, development was performed collectively with a 0.5 wt% sodium carbonate aqueous solution, followed by baking at 590 ° C. for 15 minutes to form a partition wall pattern and a sealing layer pattern.

On the other hand, in Examples 13 and 14, the partition wall forming paste 1 was applied by a die coater so as to have a thickness of 115 μm after firing, and then dried in a clean oven at 100 ° C. for 40 minutes, whereby a coating film And exposure is performed through the photomask C. Then, the glass paste for photosensitive sealing layer formation of each Example was apply | coated with the die-coater so that the dry film thickness might be set to 10 micrometers. Thereafter, exposure was performed through a photomask D. Thereafter, development was performed collectively with a 0.5 wt% sodium carbonate aqueous solution, followed by baking at 590 ° C. for 15 minutes to form a partition wall pattern and a sealing layer pattern.

Each phosphor phosphor paste was applied to the barrier ribs thus formed by screen printing and baked (500 ° C., 30 minutes) to form a phosphor layer on the side and bottom of the barrier ribs.

For forming the front plate, a 42-inch PD-200 (Asahi Glass Co., Ltd.) measuring 980 × 554 × 1.8 mm was used as a glass substrate. After forming ITO by sputtering, 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 processing and etching processing.

Subsequently, a photosensitive glass paste containing a black pigment was applied onto the substrate by screen printing, dried, and exposed through a photomask.

The photosensitive silver paste was applied and dried by screen printing on the exposed black paste coating film, exposed through a predetermined photomask, and developed to form an unfired pattern. After pattern formation, baking was performed at 570 ° C. for 15 minutes, or IR drying was performed at 190 ° C. for 10 minutes.

Next, 70 parts by weight of glass powder containing 70% by weight of bismuth oxide, 10% by weight of silicon oxide, 5% by weight of aluminum oxide, 5% by weight of zinc oxide, and 10% by weight of boron oxide, 10 parts by weight of ethyl cellulose, and 20% of terpineol A glass paste obtained by kneading the parts by weight was applied by screen printing to a thickness of 50 μm so as to cover the bus electrode of the display part, and then baked at 570 ° C. for 15 minutes to form a transparent dielectric.

A magnesium oxide layer having a thickness of 0.5 μm was formed as a protective film by electron beam evaporation on the substrate on which the dielectric was formed, and a front plate was produced.

The obtained front substrate was bonded to the above-mentioned rear substrate, kept at 490 ° C. for 20 minutes, and then kept at 400 ° C. for 3 hours, thereby sealing and exhausting. Thereafter, a discharge gas was sealed and a drive circuit was joined to produce a full high-definition plasma display panel with a resolution of 1920 × 1080.

The plasma display panels obtained in Examples 1 to 14 and Comparative Examples 1 to 4 were evaluated by the following methods.
<Pattern formability (partition / sealing layer)>
The state of occurrence of defective partition wall shape, pattern thickening and pattern chipping, and defective sealing layer shape of the 42-inch back plate was confirmed. This evaluation was carried out on 10 panel samples, and the defective partition walls in 10 sheets were counted and evaluated according to the following evaluation criteria.
AA: 0 partition wall defect that causes display failure and 1 defect or less that does not cause display failure A: 0 partition wall defect that causes display failure and 2 to 5 defects that do not cause display failure B: 0 partition wall defect that causes display failure 6 to 10 defects that do not cause display defects C: 1 or more partition wall defects that cause display defects or 11 or more defects that do not cause display defects <Sealing layer adhesion>
After applying the temperature under the sealing conditions with the front substrate and the rear substrate overlapped (without applying the peripheral frit on the periphery), a force of 2 kg is applied in the direction to peel off the front plate and the back plate. The panel 10 sample was checked for the peeled state of the sealing layer. Evaluation was performed according to the following evaluation criteria.
A: Peeling part 0 part B: Peeling part 1 part C: Peeling part 2 or more <partition wall strength>
The produced plasma display was placed horizontally with the front plate side facing up, and an alumina ceramic ball having a weight of 300 g was dropped from a height of 1 m to confirm the occurrence of partition wall chipping and micro chipping. This was repeated 10 times, and the occurrence of partition wall chipping and micro chipping was confirmed. This evaluation was performed on 10 samples of each level of the panel, and when the panel in which chipping occurred was 1 sample, it was expressed as 1/10. The minute chipping is a chipping of 5 μm or less that does not cause a problem when the PDP is turned on. Evaluation was performed according to the following evaluation criteria.
AA: partition wall chip 0/10 and minute chip 0/10
A: partition wall chip 0/10 and minute chip 1/10
B: Separation of the partition wall 0/10 and minute chipping 2/10 to 4/10
C: 1/10 or more of partition wall chipping or 5/10 or more of micro chipping <Crosstalk evaluation>
The produced front substrate and back substrate were sealed, and Ne gas containing Xe 15% was sealed so as to have an internal gas pressure of 66500 Pa. Further, a driving circuit was mounted to produce a PDP. A voltage was applied to the scan electrode of the PDP to emit light. Crosstalk evaluation raises the voltage from the applied voltages V ₁ to full lighting were measured voltage difference between the applied voltage V ₂ crosstalk occurs _V ₂ -V 1 _(V). Evaluation was performed according to the following evaluation criteria.
AA: 90 ≦ V ₂ −V ₁
A: 70 ≦ V ₂ −V ₁ <90
B: 50 ≦ V ₂ −V ₁ <70
C: V ₂ −V ₁ <50
<Residual gas amount evaluation>
After sealing the produced front substrate and back substrate, the whole panel was heated to 400 ° C., and the moisture and CH gas content discharged from the panel were measured. Evaluation was made with reference to the gas amount of the panel on which the sealing layer was not formed.
<Noise evaluation>
The produced front substrate and back substrate were sealed, and Ne gas containing Xe 15% was sealed so as to have an internal gas pressure of 66500 Pa. Further, a driving circuit was mounted to produce a PDP. The external pressure was changed from atmospheric pressure to 600 hPa sequentially, and the presence or absence of noise generation was confirmed when voltage was applied to the PDP scan electrode to emit light, and the following evaluation criteria were used.
AA: No noise is generated at an external pressure of 600 hPa A: Noise is not generated at an external pressure of 700 hPa, but noise is generated at 600 hPa B: Noise is not generated at an external pressure of 800 hPa, but noise is generated at 700 hPa C: Noise is generated at an external pressure of 800 hPa Evaluation result Is shown in Table 4.

The plasma display panels obtained in Examples 1 to 14 were able to form good partition walls and sealing layer patterns. In addition, good results were obtained with respect to partition wall strength and panel characteristics. In Comparative Examples 1 to 4, satisfactory results were not obtained in terms of partition wall and sealing layer pattern formation, partition wall strength, panel characteristics, and the like.

Claims

(A) Glass powder having a glass transition point of 410 to 480 ° C., a yield point of 470 to 510 ° C., and a softening point of 515 to 550 ° C., (B) a photosensitive organic component, (C) an ultraviolet absorber, and (D) A photosensitive paste containing a solvent, wherein an average refractive index N1 of an inorganic component containing glass powder satisfies the following formula (1).
1.75 ≦ N1 ≦ 1.95 (1)
The average refractive index N1 of the inorganic component containing the said glass powder satisfy | fills the following Formula (2), The glass paste for photosensitive sealing layer formation of Claim 1 characterized by the above-mentioned.
1.75 ≦ N1 ≦ 1.90 (2)
The glass paste for forming a photosensitive sealing layer according to claim 1 or 2, wherein an average refractive index N2 of the organic component containing the photosensitive organic component satisfies the following formula (3).
1.45 ≦ N2 ≦ 1.65 (3)
4. The glass paste for forming a photosensitive sealing layer according to claim 1, wherein an average refractive index N <b> 1 of the inorganic component and an average refractive index N <b> 2 of the organic component satisfy the following formula (4).
0.2 ≦ N1-N2 ≦ 0.5 (4)
5. The glass paste for forming a photosensitive sealing layer according to claim 1, wherein the ultraviolet absorber is an organic dye, and the content in the paste is 0.01 to 2% by weight. .
The glass paste for forming a photosensitive sealing layer according to claim 1, 2, 3, 4, or 5, after a step of applying a photosensitive partition wall forming paste on a substrate and a step of exposing through a photomask. A method for manufacturing a plasma display, wherein a barrier rib for partitioning a discharge space and a sealing layer are formed through a coating step, an exposure step through a photomask, a development step, and a baking step. An average refractive index Na of an inorganic component in the paste and an average refractive index N1 of the inorganic component in the photosensitive sealing layer forming glass paste satisfy the following expressions (5) and (6): Production method.
1.45 <Na <1.65 (5)
0.2 ≦ N1-Na ≦ 0.5 (6)
A step of applying a first photosensitive barrier rib forming paste on a substrate, a step of exposing via a photomask, a step of applying a second photosensitive barrier rib forming paste, and a step of exposing via a photomask After passing, the discharge space is formed through a step of applying the glass paste for forming a photosensitive sealing layer according to claim 1, a step of exposing through a photomask, a developing step, and a baking step. A plasma display manufacturing method for forming partition walls and a sealing layer for partitioning, wherein the average refractive index Na of the inorganic component in the first photosensitive partition wall forming paste, the second photosensitive partition wall forming paste An average refractive index Nb of the inorganic component therein and an average refractive index N1 of the inorganic component in the photosensitive sealing layer forming glass paste satisfy the following formulas (5) to (8): Manufacturing method of the stomach.
1.45 <Na <1.65 (5)
0.2 ≦ N1-Na ≦ 0.5 (6)
1.45 <Nb <1.65 (7)
0.2 ≦ N1-Nb ≦ 0.5 (8)
8. The method of manufacturing a plasma display according to claim 7, wherein the average refractive index Na of the inorganic component in the first photosensitive barrier rib forming paste and the average of the inorganic component in the second photosensitive barrier rib forming paste. A method of manufacturing a plasma display, wherein the refractive index Nb satisfies the following formula (9).
-0.1 ≤ Nb-Na ≤ 0.1 (9)
The plasma display obtained by the manufacturing method of the plasma display of Claim 6, 7 or 8.