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

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

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Publication number
WO2011001903A1
WO2011001903A1 PCT/JP2010/060806 JP2010060806W WO2011001903A1 WO 2011001903 A1 WO2011001903 A1 WO 2011001903A1 JP 2010060806 W JP2010060806 W JP 2010060806W WO 2011001903 A1 WO2011001903 A1 WO 2011001903A1
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WO
WIPO (PCT)
Prior art keywords
photosensitive
paste
forming
sealing layer
refractive index
Prior art date
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PCT/JP2010/060806
Other languages
French (fr)
Japanese (ja)
Inventor
田中明彦
井戸英夫
Original Assignee
東レ株式会社
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Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to CN2010800258935A priority Critical patent/CN102471138A/en
Priority to JP2010526083A priority patent/JP5375827B2/en
Publication of WO2011001903A1 publication Critical patent/WO2011001903A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/48—Sealing, e.g. seals specially adapted for leading-in conductors
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H01J9/26—Sealing together parts of vessels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H01J9/26—Sealing together parts of vessels
    • H01J9/261—Sealing together parts of vessels the vessel being for a flat panel display

Definitions

  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • Patent Document 2 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).
  • Patent Document 2 a method of providing a partition height adjustment layer between the partition formed on the back plate and the front plate.
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the average refractive index N1 of the inorganic component contained satisfies the following formula 1. 1.75 ⁇ N1 ⁇ 1.95 (1)
  • 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).
  • exposure light The average refractive index of the organic component and the average refractive index of the inorganic component are often matched.
  • 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.
  • 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.
  • 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.
  • N1 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the paste is obtained by removing the inorganic component from the paste and drying to remove the solvent. It can obtain
  • a glass material containing silicon and boron oxides is preferably used.
  • 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.
  • 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.
  • glass powder containing 3 to 20% by weight of at least one of lithium oxide, sodium oxide, and potassium oxide may be used.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m and less than 5.0 ⁇ m, preferably from 1.7 ⁇ m. More preferably, it is less than 4.0 ⁇ m.
  • the volume average particle diameter is 1.5 ⁇ m or less, the low-melting glass powders tend to aggregate in the paste, which tends to hinder a uniform partition wall shape.
  • the thickness is 5.0 ⁇ m 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.
  • volume average particle diameter refers to the volume average diameter of the powder measured using a laser diffraction / scattering particle size distribution meter.
  • the maximum particle size of the glass powder is preferably 20 ⁇ m or less, and more preferably 15 ⁇ m or less. If the maximum particle size exceeds 20 ⁇ m, 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.
  • 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.
  • the glass paste for forming a photosensitive sealing layer of the present invention contains an ultraviolet absorber.
  • an organic dye is preferable.
  • 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.
  • 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.
  • a method for forming the glass paste for example, refraction of inorganic powder containing glass frit on a substrate is used.
  • the glass paste for forming a photosensitive sealing layer of the present invention is applied and the photomask is used.
  • a partition for partitioning the discharge space and a sealing layer are formed through a baking process.
  • 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.
  • a 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, ⁇ -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.
  • 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.
  • monofunctional and polyfunctional (meth) acrylates 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, heptade
  • the developability after exposure can be improved by adding an unsaturated acid such as an unsaturated carboxylic acid.
  • 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.
  • 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.
  • a photosensitive oligomer or photosensitive polymer with an unsaturated acid such as an unsaturated carboxylic acid to improve developability after exposure.
  • 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.
  • 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.
  • 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.
  • 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.
  • photopolymerization initiators include benzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-dichloro.
  • 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.
  • 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
  • sensitizers can also be used as photopolymerization initiators.
  • 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.
  • plasticizer examples 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.
  • 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.
  • the range is preferably 0.2 to 200 Pa ⁇ s.
  • 10 to 100 Pa ⁇ s is more preferable.
  • 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.
  • 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)
  • the sealing layer is 2 to 10 ⁇ m 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.
  • 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)
  • 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.
  • 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.
  • 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.
  • the sealing layer is formed as thin as 2 to 10 ⁇ m after firing, the thickness of the sealing layer alone may result in insufficient exhaust after sealing.
  • 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.
  • 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.
  • 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.
  • the sealing layer can be formed only on the high partition wall pattern.
  • 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.
  • 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.
  • the photosensitive sealing layer of the present invention 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.
  • a stepper exposure machine, a proximity exposure machine, or the like can be used.
  • the active light source used include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light.
  • 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.
  • an ultrahigh pressure mercury lamp is suitable.
  • 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 .
  • 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.
  • 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.
  • mask exposure is performed using a photomask that matches the sealing layer pattern formed on the top of the partition wall.
  • 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.
  • 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.
  • the barrier rib pattern is not a simple stripe structure but a cross beam structure or a waffle structure
  • 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.
  • 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.
  • a solution that can dissolve the organic component to be dissolved in the photosensitive glass paste is used.
  • 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.
  • an alkaline aqueous solution sodium hydroxide, sodium carbonate, sodium carbonate aqueous solution, calcium hydroxide aqueous solution or the like can be used.
  • an organic alkaline aqueous solution because an alkaline component can be easily removed during firing.
  • a general amine compound can be used.
  • 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.
  • the firing atmosphere and temperature vary depending on the type of paste and substrate.
  • 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.
  • 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.
  • 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.
  • 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. .
  • 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.
  • 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
  • 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.
  • the plasma display substrate as a back plate, sealing with the front plate is performed.
  • a paste containing glass powder for sealing around the panel and heat-treating it the impure gas is exhausted simultaneously with sealing.
  • 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.
  • the sealing layer of the partition top part formed previously can also be adhere
  • 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.
  • a black stripe may be formed in order to improve contrast.
  • 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
  • Table 1 shows the glass powder used in the examples.
  • 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 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.
  • 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.
  • 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 ⁇ m) ) 60 parts by weight, 10 parts by weight of titanium oxide powder having a volume average particle diameter of 0.2 ⁇ m, 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 ⁇ m. A layer was formed.
  • 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.
  • a partition wall forming paste 2 was prepared by adding 20 parts by weight of tall acetate and kneading with three rollers.
  • the partition wall forming paste 1 was applied with a die coater so as to have a thickness of 100 ⁇ m 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 ⁇ m, opening 40 ⁇ m
  • Photomask B stripe pattern parallel to address electrodes, pitch 160 ⁇ m
  • Photomask C lattice pattern, pattern pitch 480 ⁇ m perpendicular to the address electrodes, pattern pitch parallel to the address electrodes 160 ⁇ m, and openings 40 ⁇ m in all.
  • Photomask D stripe pattern parallel to address electrodes, pitch 160 ⁇ m, opening 20 ⁇ m
  • 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 ⁇ m. 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.
  • the partition wall forming paste 1 was applied by a die coater so as to have a thickness of 115 ⁇ m 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
  • 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.
  • a 42-inch PD-200 (Asahi Glass Co., Ltd.) measuring 980 ⁇ 554 ⁇ 1.8 mm was used as a glass substrate.
  • a resist was applied, and a transparent electrode having a thickness of 0.1 ⁇ m and a line width of 200 ⁇ m was formed by exposure / development processing and etching processing.
  • 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.
  • 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 ⁇ m 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 ⁇ m 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.
  • 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 ⁇ m 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
  • 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.
  • 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.

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

感光性封着層形成用ガラスペーストおよびそれを用いたプラズマディスプレイの製造方法、ならびにプラズマディスプレイGlass paste for forming photosensitive sealing layer, method for producing plasma display using the same, and plasma display
　本発明は、感光性封着層形成用ガラスペーストおよびプラズマディスプレイの製造方法に関する。 The present invention relates to a glass paste for forming a photosensitive sealing layer and a method for producing a plasma display.
　プラズマディスプレイパネル（ＰＤＰ）は液晶パネルに比べて高速の表示が可能であり、かつ大型化が容易であることから、ＯＡ機器および広報表示装置等の分野に浸透している。また、高品位テレビジョンの分野等で活用されている。 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.
　ＰＤＰは、前面板と背面板の２枚のガラス基板の間に作られた僅かな隙間を放電空間とし、アノードおよびカソード電極間にプラズマ放電を生じさせ、放電空間内に封入されているガスから発生した紫外線を、放電空間内に設けた蛍光体にあてて発光させることにより表示を行うものである。この場合、電極は前面板と背面板にそれぞれストライプ状に配置され、複数本の電極が平行にあり、前面板の電極と背面板の電極は僅かの間隙を介して対向し、かつ互いに直交するように形成される。ＰＤＰの中で、蛍光体によるカラー表示に適した３電極構造の面放電型ＰＤＰは、互いに平行に隣接した一対の表示電極からなる複数の電極対と、各電極対と直交する複数のアドレス電極とを有する。また、背面板には光のクロストークを防ぎ、放電空間を確保するための隔壁が、電極間のスペースに形成される。さらに、その放電空間内に蛍光体が形成されている。 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.
　前面板と背面板との封着は、パネルの周辺部分に封着用ガラスフリットを含むペーストを塗布後、封着ガラスフリットが軟化する温度での熱処理によって行うのが通常の方法であるが、この場合、基板の反りや隔壁高さのバラツキにより、背面板の放電空間を仕切る隔壁と前面板との間にできる隙間の大きさにバラツキがあり、クロストークや振動によるノイズの原因となる場合があった。隔壁を精度良く形成する方法としては、感光性ペーストを用いる方法が提案されているが、この方法によれば高精細な隔壁を精度良く形成できるが、基板の反りが発生する場合など、高さ方向のバラツキに関しては、精度が十分に制御できない（例えば、特許文献１）。一方、こういった課題を解決するために、背面板に形成された隔壁と前面板の間に隔壁高さ調整層を設けるなどの方法が提案されている（例えば、特許文献２）。この文献の中で記載されている隔壁高さ調整層は、前記の課題には有効であるものの、大型・大面積に形成された隔壁頂部に精度良く形成する方法がなく、特に、昨今のハイビジョンやフルハイビジョンのように高精細化が進んだ状況では、特許文献２のような隔壁高さ調整層を隔壁頂部に精度よく形成することが困難となっていた。 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.
特開平９－３１００３０Japanese Patent Laid-Open No. 9-310030 特開平８－１８５８０２JP-A-8-185802
　本発明は、クロストークやノイズを防止し、低消費電力のプラズマディスプレイを得ることができる感光性封着層形成用ガラスペーストを提供することを目的とする。 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.
　すなわち、本発明は、（Ａ）ガラス転移点が４１０～４８０℃、屈伏点が４７０～５１０℃、軟化点が５１５～５５０℃のガラス粉末、（Ｂ）感光性有機成分、（Ｃ）紫外線吸収剤、および（Ｄ）溶剤を含む感光性ペーストであって、ガラス粉末を含む無機成分の平均屈折率Ｎ１が下式（１）を満たす感光性封着層形成用ガラスペーストに関する。
１．７５≦Ｎ１≦１．９５　　（１）
Ｎ１は、下式（２）を満たすことが好ましい。
１．７５≦Ｎ１≦１．９０　　（２）
　前記感光性有機成分を含む有機成分の平均屈折率Ｎ２は下式（３）を満たすことが好ましい。
１．４５≦Ｎ２≦１．６５　　（３）
　前記無機成分の平均屈折率Ｎ１と前記有機成分の平均屈折率Ｎ２は下式（４）を満たすことが好ましい。
０．２≦Ｎ１－Ｎ２≦０．５　　（４）
　前記紫外線吸収剤は有機染料であり、ペースト中の含有量が０．０１～２重量％であることが好ましい。 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.
　また、本発明は、基板上に、感光性隔壁形成用ペーストを塗布する工程、フォトマスクを介して露光する工程を経た後に、上述の感光性封着層形成用ガラスペーストを塗布する工程、フォトマスクを介して露光する工程、現像工程、焼成工程を経て、放電空間を仕切るための隔壁および封着層を形成するプラズマディスプレイの製造方法であって、前記感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎａおよび前記感光性封着層形成用ガラスペースト中の無機成分の平均屈折率Ｎ１が下式（５）および（６）を満たすことを特徴とするプラズマディスプレイの製造方法に関する。
１．４５＜Ｎａ＜１．６５　　（５）
０．２≦Ｎ１－Ｎａ≦０．５　　（６）
　さらに、本発明は、基板上に、第１の感光性隔壁形成用ペーストを塗布する工程、フォトマスクを介して露光する工程、第２の感光性隔壁形成用ペーストを塗布する工程、フォトマスクを介して露光する工程を経た後に、上述の感光性封着層形成用ガラスペーストを塗布する工程、フォトマスクを介して露光する工程、現像工程、焼成工程を経て、放電空間を仕切るための隔壁および封着層を形成するプラズマディスプレイの製造方法であって、前記第１の感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎａ、前記第２の感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎｂおよび前記感光性封着層形成用ガラスペースト中の無機成分の平均屈折率Ｎ１が下式（５）～（８）を満たすことを特徴とするプラズマディスプレイの製造方法である。
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）
　前記プラズマディスプレイの製造方法においては、前記第１の感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎａおよび前記第２の感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎｂが下式（９）を満たすことが好ましい。
－０．１≦Ｎｂ－Ｎａ≦０．１　　（９）
　さらに、本発明は、前記製造方法により得られたプラズマディスプレイに関する。 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.
　本発明の感光性封着層形成用ガラスペーストは、低コストで隔壁頂部に均一な封着層を精度よく形成することができる。また、これを用いることによって、高性能なプラズマディスプレイを低コストで製造できる。 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.
　本発明は、ガラス粉末、感光性有機成分、紫外線吸収剤、および溶剤を含む感光性封着層形成用ガラスペーストに関する。 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.
　本発明の感光性封着層形成用ガラスペーストは、ディスプレイの封着層を形成するために用いる感光性ガラスペーストである。封着層とは、ディスプレイを構成する部材、例えば前面板と背面板を融着する層を指す。本発明の感光性封着層形成用ガラスペーストはパターン化した封着層、特に他のパターン層の上部に設ける封着層の製造に好ましく用いられる。とりわけ、プラズマディスプレイパネルの背面板の隔壁上に設ける場合であって、隔壁を感光性ガラスペースト法により形成する場合に、隔壁と封着層を同時に設ける場合に好適に用いられる。 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.
　本発明の感光性封着層形成用ガラスペーストは、ガラス粉末を含有する他、ファインピッチのパターンを形成するための感光性有機成分、紫外線吸収剤、および、塗布安定性を確保するための溶剤を含有する。 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.
　従来のプラズマディスプレイ用隔壁を形成するために用いる感光性隔壁形成用ガラスペーストにおいては、焼成時の隔壁形状保持のために、比較的軟化点が高いガラスフリットを使用し、また、ファインピッチで高アスペクト比のパターンを形成するために、ガラス粉末の屈折率を有機成分の屈折率と合わせる目的で、比較的屈折率の小さいガラスフリットを用いてきた。しかしながら、このような感光性隔壁形成用ガラスペーストを用いた方法では、基板の反りや隔壁の高さバラツキが発生した場合に、クロストークやノイズが発生するといった問題があった。これを解消するためには、隔壁頂部と前面板とを封着時の加熱工程で接着させることが有効である。そのためには、隔壁頂部に封着層を形成する必要があるが、その形成方法としては、隔壁パターンを焼成して形成した後、封着層形成用ペーストをスクリーン印刷やロールコーターを用いて塗布し、封着時に前面板と接着させる方法がある。しかしながら、この方法では、従来の隔壁形成工程に加え封着層形成工程が増えるため、コスト的に問題があり、さらに高精細に形成された隔壁頂部のみに封着層用ペーストを塗布する精度面で課題があった。そこで、感光性隔壁用ペーストを塗布し、フォトマスクを介して露光した塗布膜上に本発明の感光性封着層形成用ガラスペーストを塗布し、フォトマスクを介して露光し、一括して現像した後に、焼成することにより、封着層を隔壁頂部に精度良く形成することが可能となる。 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.
　本発明の感光性封着層形成用ガラスペーストは、封着工程での加熱温度で前面板と接着する程度に軟化する必要がある。そのため、含有するガラス粉末のガラス転移点は４１０～４８０℃であることが必要である。４１０℃より低いと形状保持性が悪く、４８０℃を超えると前面板との接着性が不十分となる。同様に、ガラス粉末の屈伏点は、４７０～５１０℃であることが必要である。４７０℃より低いと焼成時の脱バインダー性が悪くなり、焼成後の封着層に空隙ができ、封着時に欠けなどの欠陥が生じる恐れがある。５１０℃を超えると前面板との接着性が不十分となる。さらに、ガラス粉末の軟化点は５１５～５５０℃である必要がある。５１５℃より低いと脱バインダー性が不十分になり、また焼成時の形状保持性が悪く、均一な封着層が得られない。５５０℃よりも高いと前面板との接着性が不十分となる。 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.
　また、本発明の感光性封着層形成用ガラスペーストは、含有する無機成分の平均屈折率Ｎ１が下式１を満足することが必要である。
１．７５≦Ｎ１≦１．９５　　（１）
　通常、隔壁などのパターン形成を行う感光性ガラスペーストにおいては、露光に用いる光（以下、露光光という）の散乱を抑えることによってアスペクト比の大きなパターンを形成する目的で、感光性有機成分を含む有機成分の平均屈折率と無機成分の平均屈折率を整合させることが多い。しかし、本発明の感光性封着層形成用ガラスペーストは、先にも述べたとおり、隔壁頂部に形成し、隔壁と一括して現像、焼成を行い封着層を形成するために、先に露光を施した感光性隔壁形成用ペースト塗布膜に露光光を届かせないようにする必要がある。このため、紫外線吸収剤を添加するが、紫外線吸収剤のみで露光光の透過率を調整しようとすると、硬化のために必要な露光光が感光性封着層形成用ペースト塗布膜の底の部分にまで到達せず、現像時に剥がれたり、変形したりする。 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.
　この問題を解決するために、Ｎ１を１．７５以上とすることによって、感光性封着層形成用ペースト中の有機成分を含む有機成分との屈折率の差が適度に大きくなり、露光光が下層である感光性隔壁形成用ペースト塗布膜まで届くのを防ぐことができる。また、１．７５より小さいガラス粉末を必要なガラス転移点、屈伏点、軟化点の熱特性に合わせて作製する場合、アルカリ金属成分を多く含有させる必要がある。アルカリ金属成分は感光性有機成分と反応し、ペーストをゲル化させたり、増粘させたりするため、好ましくない。 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.
　また、Ｎ１を１．９５以下とすることによって感光性封着層形成用ペースト中の有機成分との屈折率差が大きくなりすぎるのを防ぐことができ、封着層形成用ペースト塗布膜底部が露光不足となるのを防ぐことができる。１．９５を超える場合には、有機成分との屈折率差が大きくなりすぎ、所望のパターンを得られなくなる。好ましくは１．９０以下である。 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.
　なお、ガラス粉末、およびフィラーの屈折率測定は、ガラス粉末、ベッケ法により行うことができ、測定はｇ線（４３６ｎｍ）で行うことが好ましい。ペースト中に含有する無機粉末の平均屈折率は、各粉末の屈折率の体積平均により求めることが好ましい。 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.
　また、本願において、無機成分の平均屈折率は、ペースト中に含まれる無機成分のみを溶剤に分散し、塗布してガラス粉末を軟化させたり、あるいはペーストを塗布し、ガラス粉末の軟化温度以上で焼成することにより、有機成分を除去して形成して得られた無機成分層の屈折率を測定することによって求めることも可能である。 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.
　また、上述のように露光光を適度に散乱させるために、本発明の感光性封着層形成用ペースト中の感光性有機成分を含む有機成分の平均屈折率Ｎ２は下式（３）を満たすことが好ましい。
１．４５≦Ｎ２≦１．６５　　（３）
　さらに、Ｎ１およびＮ２は下式（４）を満たすことが好ましい。
０．２≦Ｎ１－Ｎ２≦０．５　　（４）
　Ｎ１、Ｎ２が上式（１）、（３）、（４）を満たすことによって、特に露光光を適度に散乱させることができ、感光性封着層形成用ペースト塗布膜の底部まで十分硬化し、下層である感光性隔壁形成用ペースト塗布膜をさらに硬化させないようにすることができる。Ｎ２が１．４５より小さいか、Ｎ１－Ｎ２が０．５よりも大きいと露光光が散乱しすぎて感光性封着層形成用ペースト塗布膜の底部まで十分硬化しない場合があり、Ｎ１－Ｎ２が０．２よりも小さいと露光光が透過しすぎて感光性隔壁形成用ペースト塗布膜の露光パターンが変化してしまう場合がある。 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.
　なお、本発明において有機成分の平均屈折率とは、ペースト塗布膜中の有機成分の平均屈折率であり、例えばペーストから無機成分を除いたものを塗布し、乾燥して溶媒を除去して得られる有機成分塗布膜の屈折率を測定することによって求めることができる。 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.
　また、本発明の感光性封着層形成用ガラスペーストに使用するガラス粉末としては、ケイ素およびホウ素の酸化物を含有したガラス材料が好ましく用いられる。さらに、封着層を形成するために、酸化ビスマス、酸化鉛、酸化亜鉛のうちの少なくとも１種類を合計で５～８５重量％含有させることによって、封着層を形成するのに適したガラス転移点、屈伏点、軟化点などの温度特性を有するガラスペーストを得ることができる。特に、酸化ビスマスを５～８５重量％含有するガラス粉末を用いることにより、ペーストのポットライフが長いなどの利点が得られる。 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.
　また、酸化リチウム、酸化ナトリウム、酸化カリウムのうち、少なくとも１種類を３～２０重量％含むガラス粉末を用いてもよい。アルカリ金属酸化物の添加量は、２０重量％以下、好ましくは、１５重量％以下にすることによって、ペーストのポットライフを長く保つことができる。また、酸化鉛、酸化ビスマス、酸化亜鉛のような金属酸化物と酸化リチウム，酸化ナトリウム、酸化カリウムのようなアルカリ金属酸化物の両方を含有するガラス粉末を用いれば、より低いアルカリ含有量で、封着層を形成するのに適したガラス転移点、屈伏点、軟化点などの温度特性を有するガラスペーストを得ることができる。 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.
　また、本発明の感光性封着層形成用ペーストは上述のガラス粉末を含む無機成分の体積比率と有機溶剤を除く有機成分の体積比率を３０：７０～６０：４０に制御することが好ましい。無機成分比率が３０：７０より小さくなると有機成分が多くなりすぎ、焼成収縮の際にパターンの変形が見られる場合がある。無機成分比率が６０：４０を超えると、パターン形成性が悪化し、高精細のパターンが得られないという問題が発生する。ペースト中のガラス粉末は、ガラス粉末の比重にあわせて前述の体積比率を満たすように添加量を変更する。また、封着層の形状保持性を確保するために、必要に応じて焼成温度で軟化しないフィラーを少量添加することにより、形状保持性と接着性を調整することも可能である。 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.
　ガラス粉末の体積平均粒子径は、作製しようとする隔壁の線幅や高さを考慮して適宜選択すればよいが、１．５μｍより大きく５．０μｍ未満であることが好ましく、１．７μｍより大きく４．０μｍ未満であることがより好ましい。体積平均粒子径が１．５μｍ以下であるとペースト内で低融点ガラス粉末同士が凝集しやすく、均一な隔壁形状を妨げる傾向がある。５．０μｍ以上だとパターン形成時に良好な形状が得られない、また、隔壁に断線や欠けを発生させやすい問題を生じる。 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.
　ここで、体積平均粒子径とは、レーザー回折散乱式の粒度分布計を用いて測定した粉末の体積平均径を指す。 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.
　また、ガラス粉末の最大粒子サイズは、２０μｍ以下であることが好ましく、１５μｍ以下であることがより好ましい。最大粒子サイズが２０μｍを超えるとパターン形成時に断線や欠けを発生させやすく、また、巨大粒子が異常突起として残り、パネル作製時に前面板と接触して断線や前面板不良を発生させ易い傾向がある。ガラス粉末の比表面積は、１．０～４．０ｃｍ２／ｇであることが好ましく、１．５～３ｃｍ２／ｇであることがより好ましい。ガラス粉末の比表面積がこの範囲を満たすことにより、ペースト内でガラス粉末同士が凝集することを抑制でき、ペースト中のガラス粉末を均一に分散することができる。このことにより、精度良いパターン形成が可能となる。 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.
　本発明の感光性封着層形成用ガラスペーストに用いられる感光性有機成分としては、感光性モノマー、感光性オリゴマー、感光性ポリマーのうち少なくとも１種類から選ばれる感光性有機成分を含有し、さらに必要に応じて、光重合開始剤、増感剤、増感助剤、重合禁止剤、可塑剤、増粘剤、酸化防止剤、分散剤、有機あるいは無機の沈殿防止剤などの添加剤成分を加えたものがあげられる。なお、本発明の感光性封着層形成用ガラスペーストは後述するように溶剤を含むが、溶剤として感光性有機成分と反応しない有機溶媒を用いる場合、このような有機溶媒は感光性有機成分にも、有機成分にも含めない。 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.
　また、本発明の感光性封着層形成用ガラスペーストは、紫外線吸収剤を含有する。紫外線吸収剤としては有機染料が好ましい。具体的には、アゾ系染料、アミノケトン系染料、キサンテン系染料、キノリン系染料、アントラキノン系染料、ベンゾフェノン系染料、トリアジン系染料、ｐ－アミノ安息香酸系染料シアノアクリレート系化合物、サリチル酸系化合物、ベンゾトリアゾール系化合物、インドール系化合物が挙げられる。これらの中でもアゾ系染料、ベンゾフェノン系化合物、シアノアクリレート系化合物、インドール系化合物が特に有効である。これらの具体例としては、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２，２’－ジヒドロキシ－４－メトキシベンゾフェノン、２，２’－ジヒドロキシ－４，４’－ジメトキシベンゾフェノン、２，２’－ジヒドロキシ－４，４’－ジメトキシ－５－スルホベンゾフェノン、２－ヒドロキシ－４－メトキシ－２’－カルボキシベンゾフェノン、２－ヒドロキシ－４－メトキシ－５－スルホベンゾフェノントリヒドレート、２－ヒドロキシ－４－ｎ－オクトキシベンゾフェノン、２－ヒドロキシ－４－オクタデシロキシベンゾフェノン、２，２’，４，４’－テトラヒドロキシベンゾフェノン、４－ドデシロキシ－２－ヒドロキシベンゾフェノン、２－ヒドロキシ－４－（２－ヒドロキシ－３－メタクリロキシ）プロポキシベンゾフェノン、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’－ｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－４’－ｎ－オクトキシフェニル）ベンゾトリアゾール、２－エチルヘキシル－２－シアノ－３，３－ジフェニルアクリレート、２－エチル－２－シアノ－３，３－ジフェニルアクリレート、２－（１－メチル－２－フェニル－１Ｈ－インドール－３－イルメチレン）－マロノニトリル等が挙げられるがこれらに限定されない。本発明の感光性封着層形成用ガラスペーストは主に隔壁の頂部に封着層を形成するために用いられ、その形成方法としては、例えば、基板上に、ガラスフリットを含む無機粉末の屈折率と有機成分の屈折率を整合させた感光性ペーストを塗布し、フォトマスクを介して露光する工程を経た後に、本発明の感光性封着層形成用ガラスペーストを塗布し、フォトマスクを介して露光し、一括して現像した後に、焼成工程を経て、放電空間を仕切るための隔壁、および、封着層を形成する。そのため、感光性封着層形成用ガラスペースト塗布膜を露光する際に、先に露光を施した隔壁形成のための感光性ペースト塗布膜に露光光を届かせないようにする必要がある。そのため、露光光を吸収する紫外線吸収剤を比較的多く含有する必要がある。その含有量は、封着層の厚みにもよるが、感光性ペースト中に０．０１～２重量％含有することが好ましい。０．０１重量％未満では、露光光の吸収が不十分で、所望の隔壁形状が得られない場合があり、２重量％を超えると、封着層形成用塗布膜の硬化が不十分となり、現像後に剥がれたり、変形してしまったりする恐れがある。 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.
　本発明の感光性封着層形成用ガラスペーストは、均一な塗布膜を得るために、溶剤を含む。溶剤としては有機溶媒が好ましい。この有機溶媒の含有量は、ガラス粉末の比重によって変化するが、ペースト中に１５～４５重量％であることが好ましい。これ以外の範囲では、ペーストの塗布が上手くできず、均一な膜が得られない。また、このとき使用される有機溶媒としては、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルエチルケトン、ジオキサン、アセトン、シクロヘキサノン、シクロペンタノン、イソブチルアルコール、イソプロピルアルコール、テトラヒドロフラン、ジメチルスルフォキシド、γ－ブチロラクトン、ブロモベンゼン、クロロベンゼン、ジブロモベンゼン、ジクロロベンゼン、ブロモ安息香酸、クロロ安息香酸、テルピネオール、ジエチレングリコールモノブチルエーテルアセテートなどやこれらのうちの１種以上を含有する有機溶媒混合物が好ましく用いられる。
以下、本発明の感光性有機成分について記載する。 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.
　感光性モノマーとしては、炭素－炭素不飽和結合を含有する化合物で、その具体的な例としては、単官能および多官能の（メタ）アクリレート類、ビニル系化合物類、アリル系化合物類などを用いることができ、例えば、メチルアクリレート、エチルアクリレート、ｎ－プロピルアクリレート、イソプロピルアクリレート、ｎ－ブチルアクリレート、ｓｅｃ－ブチルアクリレート、イソ－ブチルアクリレート、ｔｅｒｔ－ブチルアクリレート、ｎ－ペンチルアクリレート、アリルアクリレート、ベンジルアクリレート、ブトキシエチルアクリレート、ブトキシトリエチレングリコールアクリレート、シクロヘキシルアクリレート、ジシクロペンタニルアクリレート、ジシクロペンテニルアクリレート、２－エチルヘキシルアクリレート、グリセロールアクリレート、グリシジルアクリレート、ヘプタデカフロロデシルアクリレート、２－ヒドロキシエチルアクリレート、イソボニルアクリレート、２－ヒドロキシプロピルアクリレート、イソデシルアクリレート、イソオクチルアクリレート、ラウリルアクリレート、２－メトキシエチルアクリレート、メトキシエチレングリコールアクリレート、メトキシジエチレングリコールアクリレート、オクタフロロペンチルアクリレート、フェノキシエチルアクリレート、ステアリルアクリレート、トリフロロエチルアクリレート、アリル化シクロヘキシルジアクリレート、１，４－ブタンジオールジアクリレート、１，３－ブチレングリコールジアクリレート、エチレングリコールジアクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールモノヒドロキシペンタアクリレート、ジトリメチロールプロパンテトラアクリレート、グリセロールジアクリレート、メトキシ化シクロヘキシルジアクリレート、ネオペンチルグリコールジアクリレート、プロピレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、トリグリセロールジアクリレート、トリメチロールプロパントリアクリレート、アクリルアミド、アミノエチルアクリレート、フェニルアクリレート、フェノキシエチルアクリレート、ベンジルアクリレート、１－ナフチルアクリレート、２－ナフチルアクリレート、ビスフェノールＡジアクリレート、ビスフェノールＡ－エチレンオキサイド付加物のジアクリレート、ビスフェノールＡ－プロピレンオキサイド付加物のジアクリレート、チオフェノールアクリレート、ベンジルメルカプタンアクリレート等のアクリレート、また、これらの芳香環の水素原子のうち、１～５個を塩素原子または臭素原子に置換したモノマー、もしくは、スチレン、ｐ－メチルスチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、塩素化スチレン、臭素化スチレン、α－メチルスチレン、塩素化α－メチルスチレン、臭素化α－メチルスチレン、クロロメチルスチレン、ヒドロキシメチルスチレン、カルボキシメチルスチレン、ビニルナフタレン、ビニルアントラセン、ビニルカルバゾール、および、上記化合物の分子内のアクリレートを一部もしくはすべてをメタクリレートに変えたもの、γ－メタクリロキシプロピルトリメトキシシラン、１－ビニル－２－ピロリドンなどがあげられる。本発明ではこれらを１種または２種以上使用することができる。 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.
　これら以外に、不飽和カルボン酸等の不飽和酸を加えることによって、感光後の現像性を向上させることができる。不飽和カルボン酸の具体的な例としては、アクリル酸、メタアクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、ビニル酢酸、またはこれらの酸無水物などがあげられる。 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.
　これら感光性モノマーの含有率は、ペースト中の７～１５重量％の範囲内であることが好ましい。これ以外の範囲では、パターンの形成性の悪化、硬化後の硬度不足が発生するため好ましくない。 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.
　また、感光性オリゴマー、感光性ポリマーとしては、前記炭素－炭素不飽和結合を含有する化合物のうちの少なくとも１種類を重合して得られるオリゴマーやポリマーを用いることができる。前記炭素－炭素不飽和結合を含有する化合物の含有率は、感光性オリゴマーおよび感光性ポリマーの合計量中、１０重量％以上であることが好ましく、３５重量％以上であることがより好ましい。 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.
　さらに、感光性オリゴマー、感光性ポリマーに不飽和カルボン酸などの不飽和酸を共重合することによって、感光後の現像性を向上することができるため好ましい。不飽和カルボン酸の具体的な例として、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、ビニル酢酸またはこれらの酸無水物などがあげられる。こうして得られた側鎖にカルボキシル基等の酸性基を有するオリゴマーまたはポリマーの酸価（ＡＶ）は３０～１５０であることが好ましく、７０～１２０であることがより好ましい。酸価が３０未満であると、未露光部の現像液に対する溶解性が低下するため現像液濃度を濃くすると露光部まで剥がれが発生し、高精細なパターンが得られにくい傾向がある。また、酸価が１５０を超えると現像許容幅が狭くなる傾向がある。 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.
　これらの感光性オリゴマー、感光性ポリマーに対して、光反応性基を側鎖または分子末端に付加させることによって、感光性を持つ感光性ポリマーや感光性オリゴマーとして用いることができる。好ましい光反応性基は、エチレン性不飽和基を有するものである。エチレン性不飽和基としては、ビニル基、アリル基、アクリル基、メタクリル基などがあげられる。 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.
　このような側鎖をオリゴマーやポリマーに付加させる方法は、ポリマー中のメルカプト基、アミノ基、水酸基やカルボキシル基に対して、グリシジル基やイソシアネート基を有するエチレン性不飽和化合物やアクリル酸クロライド、メタクリル酸クロライドまたはアリルクロライドを付加反応させる方法がある。 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.
　グリシジル基を有するエチレン性不飽和化合物としては、アクリル酸グリシジル、メタクリル酸グリシジル、アリルグリシジルエーテル、エチルアクリル酸グリシジル、クロトニルグリシジルエーテル、クロトン酸グリシジルエーテル、イソクロトン酸グリシジルエーテルなどがあげられる。 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.
　イソシアネート基を有するエチレン性不飽和化合物としては、（メタ）アクリロイルイソシアネート、（メタ）アクリロイルエチルイソシアネート等がある。 Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate.
　また、グリシジル基やイソシアネート基を有するエチレン性不飽和化合物やアクリル酸クロライド、メタクリル酸クロライドまたはアリルクロライドは、ポリマー中のメルカプト基、アミノ基、水酸基やカルボキシル基に対して０．０５～１モル当量付加させることが好ましい。 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.
　本発明の感光性封着層形成用ガラスペースト中の感光性オリゴマーおよび／または感光性ポリマーの含有量は、パターン形成性、焼成後の収縮率の点から、ペースト中の７～１５重量％の範囲内であることが好ましい。この範囲外では、パターン形成が不可能もしくは、パターンの太りがでるため好ましくない。 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.
　光重合開始剤としての具体的な例として、ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、４，４’－ジクロロベンゾフェノン、４－ベンゾイル－４－メチルジフェニルケトン、ジベンジルケトン、フルオレノン、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２－ヒドロキシ－２－メチルプロピオフェノン、ｐ－ｔ－ブチルジクロロアセトフェノン、チオキサントン、２－メチルチオキサントン、２－クロロチオキサントン、２－イソプロピルチオキサントン、ジエチルチオキサントン、ベンジルジメチルケタノール、ベンジルメトキシエチルアセタール、ベンゾイン、ベンゾインメチルエーテル、ベンゾインブチルエーテル、アントラキノン、２－ｔ－ブチルアントラキノン、２－アミルアントラキノン、β－クロルアントラキノン、アントロン、ベンズアントロン、ジベンゾスベロン、メチレンアントロン、４－アジドベンザルアセトフェノン、２，６－ビス（ｐ－アジドベンジリデン）シクロヘキサノン、２，６－ビス（ｐ－アジドベンジリデン）－４－メチルシクロヘキサノン、２－フェニル－１，２－ブタジオン－２－（ｏ－メトキシカルボニル）オキシム、１－フェニル－プロパンジオン－２－（ｏ－エトキシカルボニル）オキシム、１，３－ジフェニル－プロパントリオン－２－（ｏ－エトキシカルボニル）オキシム、１－フェニル－３－エトキシ－プロパントリオン－２－（ｏ－ベンゾイル）オキシム、ミヒラーケトン、２－メチル－［４－（メチルチオ）フェニル］－２－モルフォリノ－１－プロパノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン－１、ナフタレンスルホニルクロライド、キノリンスルホニルクロライド、Ｎ－フェニルチオアクリドン、４，４’－アゾビスイソブチロニトリル、ジフェニルジスルフィド、ベンズチアゾールジスルフィド、トリフェニルホスフィン、カンファーキノン、四臭素化炭素、トリブロモフェニルスルホン、過酸化ベンゾインおよびエオシン、メチレンブルーなどの光還元性の色素とアスコルビン酸、トリエタノールアミンなどの還元剤などがあげられる。本発明ではこれらを１種または２種以上使用することができる。 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.
　光重合開始剤は、感光性有機成分に対し、０．０５～２０重量％の範囲で添加されることが好ましく、より好ましくは０．１～１５重量％である。光重合開始剤が０．０５重量％未満であると、光感度が不良となる傾向があり、光重合開始剤が２０重量％を超えると、露光部の残存率が小さくなりすぎる傾向がある。 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.
　増感剤は、感度を向上させるために必要に応じ添加される。増感剤の具体例としては、２，４－ジエチルチオキサントン、イソプロピルチオキサントン、２，３－ビス（４－ジエチルアミノベンザル）シクロペンタノン、２，６－ビス（４－ジメチルアミノベンザル）シクロヘキサノン、２，６－ビス（４－ジメチルアミノベンザル）－４－メチルシクロヘキサノン、ミヒラーケトン、４，４’－ビス（ジエチルアミノ）－ベンゾフェノン、４，４’－ビス（ジメチルアミノ）カルコン、４，４’－ビス（ジエチルアミノ）カルコン、ｐ－ジメチルアミノシンナミリデンインダノン、ｐ－ジメチルアミノベンジリデンインダノン、２－（ｐ－ジメチルアミノフェニルビニレン）－イソナフトチアゾール、１，３－ビス（４－ジメチルアミノベンザル）アセトン、１，３－カルボニル－ビス（４－ジエチルアミノベンザル）アセトン、３，３’－カルボニル－ビス（７－ジエチルアミノクマリン）、Ｎ－フェニル－Ｎ－エチルエタノールアミン、Ｎ－フェニルエタノールアミン、Ｎ－トリルジエタノールアミン、Ｎ－フェニルエタノールアミン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、３－フェニル－５－ベンゾイルチオテトラゾール、１－フェニル－５－エトキシカルボニルチオテトラゾールなどがあげられる。本発明ではこれらを１種または２種以上使用することができる。なお、増感剤の中には光重合開始剤としても使用できるものがある。増感剤を本発明のガラスペーストに添加する場合、その添加量は、感光性有機成分に対して通常０．０５～３０重量％であることが好ましく、より好ましくは０．１～２０重量％である。０．０５重量％未満では光感度を向上させる効果が発揮されにくい傾向があり、３０重量％を超えると露光部の残存率が小さくなりすぎる傾向がある。 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.
　重合禁止剤は、必要に応じ保存時の熱安定性を向上させるために添加される。重合禁止剤の具体的な例としては、ヒドロキノン、ヒドロキノンのモノエステル化物、Ｎ－ニトロソジフェニルアミン、フェノチアジン、ｐ－ｔ－ブチルカテコール、Ｎ－フェニルナフチルアミン、２，６－ジ－ｔ－ブチル－ｐ－メチルフェノール、クロラニール、ピロガロール、ｐ－メトキシフェノールなどがあげられる。また添加することにより、光硬化反応のしきい値が大きくなり、パターン線幅の縮小化、ギャップに対するパターン上部の太りがなくなる。 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.
　重合禁止剤の添加量は、感光性封着層形成用ガラスペースト中に、０．０１～１重量％であることが好ましい。０．０１重量％未満であると添加効果がでにくい傾向があり、１重量％を超えると感度が低下するため、パターン形成するための露光量が多く必要になる傾向がある。 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.
　可塑剤の具体的な例としては、ジブチルフタレート、ジオクチルフタレート、ポリエチレングリコール、グリセリンなどがあげられる。 Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.
　酸化防止剤は、保存時におけるアクリル系共重合体の酸化を防ぐために、必要に応じ添加される。酸化防止剤の具体的な例としては、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、ブチル化ヒドロキシアニソール、２，６－ジ－ｔ－ブチル－４－エチルフェノール、２，２’－メチレン－ビス（４－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレン－ビス（４－エチル－６－ｔ－ブチルフェノール）、４，４’－ビス（３－メチル－６－ｔ－ブチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－６－ｔ－ブチルフェニル）ブタン、ビス［３，３－ビス－（４－ヒドロキシ－３－ｔ－ブチルフェニル）ブチリックアシッド］グリコールエステル、ジラウリルチオジプロピオナート、トリフェニルホスファイトなどがあげられる。酸化防止剤を添加する場合、その添加量は、ガラスペースト中に、０．０１～１重量％であることが好ましい。 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.
　本発明の感光性封着層形成用ガラスペーストは、通常、前記感光性モノマー、感光性オリゴマー、感光性ポリマーのうち少なくとも１種類、さらに必要に応じて、光重合開始剤、紫外線吸収剤、増感剤、増感助剤、重合禁止剤、可塑剤、増粘剤、有機溶媒、酸化防止剤、分散剤、有機あるいは無機の沈殿防止剤などの添加剤成分を所定の組成となるように調合した後、３本ローラーや混練機を用いてガラス粉末を含む無機成分と均質に混合分散して作製する。 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.
　感光性封着層形成用ガラスペーストの粘度は、適宜調整されるが、その範囲は０．２～２００Ｐａ・ｓであることが好ましい。たとえば、スクリーン印刷法で１回塗布して膜厚１０～２０μｍを得るには、１０～１００Ｐａ・ｓがより好ましい。また、スリットダイコーターで１回塗布して同様の膜厚を得るには、１０～５０Ｐａ・ｓがより好ましい。 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.
　また、本発明は、上記した感光性封着層形成用ガラスペーストを塗布・乾燥してペースト塗布膜を形成する工程、ペースト塗布膜にフォトマスクを介して露光する工程、露光したペースト塗布膜を現像する工程、および焼成によりパターンを形成する工程からなるプラズマディスプレイの製造方法に関する。 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.
　本発明の感光性封着層形成用ガラスペーストを用いて、プラズマディスプレイの放電空間を仕切る隔壁頂部に封着層を形成する方法としては、基板上に、感光性隔壁形成用ペーストを塗布した塗布膜を、最終的な隔壁パターンを有するフォトマスクを介して露光した後に、本発明の感光性封着層形成用ガラスペーストを塗布した塗布膜を、封着層のパターンを有するフォトマスクを介して露光し、一括して現像した後で、焼成することにより、放電空間を仕切るための隔壁および封着層を形成することができる。この際、プラズマディスプレイの隔壁高さは焼成後で７０～１５０μｍ程度必要なため、感光性隔壁形成用ペーストは、含有する無機成分の平均屈折率Ｎａは、溶剤を除く有機成分の屈折率差を小さくする必要があり、下式（５）を満たすことが好ましい。
１．４５＜Ｎａ＜１．６５　　（５）
　一方、封着層は焼成後２～１０μｍと隔壁と比べて比較的薄く、感光性封着層形成用ガラスペースト塗布膜の露光は、下層の隔壁パターンに影響しないように、先に露光を施している隔壁形成用ペースト塗布膜へ露光光が届かないように調整する必要がある。一方で、感光性封着層形成用ガラスペースト塗布膜底部まで露光光を透過させて、しっかりと硬化させる必要がある。このことから、本発明の感光性封着層形成用ガラスペースト中の無機成分の平均屈折率Ｎ１は、溶剤を除く有機成分との屈折率差を制御する必要があり、結果として、先の感光性隔壁形成用ペーストの無機成分の平均屈折率Ｎａとは、下式（６）を満たす用制御する必要がある。
０．２≦Ｎ１－Ｎａ≦０．５　　（６）
　また、隔壁頂部に形成する封着層パターンについては、隔壁パターンが単純なストライプ構造であれば、隔壁頂部全面に封着層を形成しても問題はないが、隔壁構造が井桁構造やワッフル構造などの場合には、封着層を隔壁パターンと全く同じように形成してしまうと、隔壁および封着層に囲まれたセル内が前面板との封着後には、完全に密閉されてしまうため、ガスの排気が十分に行われなくなってしまう。このため、井桁構造やワッフル構造などの隔壁パターンの場合には、アドレス電極に平行に形成される隔壁頂部にのみ封着層を形成することで、排気の問題を解決できる。 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.
　また、封着層は先述の通り、焼成後の厚みで２～１０μｍと比較的薄く形成されるため、封着層の厚みだけでは、封着後の排気が不十分となることがある。このため、アドレス電極に平行に形成される隔壁パターンをアドレス電極と垂直または交わるように形成される隔壁パターンの高さよりも高く形成し、高い隔壁パターン上にのみ封着層を形成することで、排気の問題を解決できる。この場合、基板上に、第１の感光性隔壁形成用ペーストを塗布する工程、アドレス電極と垂直または交差するパターンを有するフォトマスクを介して露光する工程、前記第１の感光性隔壁形成用ペースト塗布膜上に第２の感光性隔壁形成用ペーストを塗布する工程、アドレス電極と平行なパターンを有するフォトマスクを介して露光する工程、次いで本発明の感光性封着層形成用ガラスペーストを塗布し、封着層パターンを有するフォトマスクを介して露光し、その後、現像工程、焼成工程を経ることにより、アドレス電極に平行に形成される隔壁パターンをアドレス電極と垂直または交わるように形成される隔壁パターンの高さよりも高く形成し、高い隔壁パターン上にのみ封着層を形成することができる。この際、前記、第１および第２の感光性隔壁形成用感光性ペーストは、含有する無機物の平均屈折率と溶剤を除く有機成分との屈折率を小さく調整する必要があるため、第１の感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎａ、前記第２の感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎｂは、下式（５）、（７）を満たすことが重要がある。また、先述の通り、感光性封着層形成用ガラスペースト塗布膜の露光は、下層の隔壁パターンに影響しないように、先に露光を施している隔壁形成用ペースト塗布膜へ露光光が届かないように調整する必要があり、一方で、感光性封着層形成用ガラスペースト塗布膜底部まで露光光を透過させて、しっかりと硬化させる必要があることから、本発明の感光性封着層形成用ガラスペースト中の無機成分の平均屈折率Ｎ１は、溶剤を除く有機成分との屈折率差を制御する必要があり、下式（６）、（８）、（９）を満たすことが重要である。
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）
　隔壁形成用の感光性ガラスペーストを塗布した後、露光装置を用いて露光を行うが、露光は、通常のフォトリソグラフィー法で行われるように、フォトマスクを用いてマスク露光する方法が一般的である。 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.
　露光装置としては、ステッパー露光機、プロキシミティ露光機などを用いることができる。使用される活性光源としては、例えば、可視光線、近紫外線、紫外線、電子線、Ｘ線、レーザー光などが挙げられる。これらの中で紫外線が最も好ましく、その光源として、例えば、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ハロゲンランプ、殺菌灯などが使用できる。これらのなかでも超高圧水銀灯が好適である。露光条件は、塗布厚みによって異なるが、通常、１～１００ｍＷ／ｃｍ２の出力の超高圧水銀灯を用いて０．１～１０分間露光を行う。 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 .
　その後、露光を施した隔壁形成用感光性ガラスペーストの塗布膜上に、本発明の感光性封着層形成用ガラスペーストを塗布する。塗布方法としては、スクリーン印刷法、バーコーター、ロールコーター、ダイコーター、ブレードコーターなど一般的な方法を用いることができる。塗布膜厚は、焼成後に形成したい封着層に合わせて調整する。その後、隔壁頂部に形成する封着層パターンに合わせたフォトマスクを用いてマスク露光する。露光装置や光源は、隔壁形成時と同様のものを使用することができる。 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.
　露光方法に関しては、形成する隔壁の構造と封着層の構造により決定される。単純に隔壁の頂部全面に封着層を形成する場合には、隔壁パターン形成用フォトマスクと同じパターンの封着層形成用フォトマスクを使用する。フォトマスクの開口幅は適宜調整するが、隔壁頂部にのみ封着層を精度良く形成するためには、隔壁形成用フォトマスクの開口幅をＷ１、封着層形成用フォトマスクの開口幅Ｗ２とした場合には、以下の式を満たすことが好ましい。
Ｗ２＜Ｗ１
　また、隔壁パターンが、単純なストライプ構造ではなく、井桁構造やワッフル構造などの場合には、封着層を隔壁パターンと全く同じように形成してしまうと、隔壁および封着層に囲まれたセル内が前面板との封着後には、完全に密閉されてしまうため、ガスの排気が十分に行われなくなってしまう。このため、井桁構造やワッフル構造などの隔壁パターンの場合には、アドレス電極に平行に形成される隔壁パターンと垂直に形成される隔壁パターンの高さを変え、高い隔壁パターン上にのみ封着層を形成することで、排気の問題を解決できる。 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.
　通常、アドレス電極と平行な隔壁が主隔壁となるため、隔壁の高さが高くなるように形成する。 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.
　現像方法としては、浸漬法、シャワー法、スプレー法、ブラシ法で行うことができる。 Developing methods can be performed by dipping, showering, spraying, or brushing.
　現像液は、感光性ガラスペースト中の溶解させたい有機成分が溶解可能である溶液を用いる。感光性ガラスペースト中にカルボキシル基などの酸性基をもつ化合物が存在する場合、アルカリ水溶液で現像できる。アルカリ水溶液としては、水酸化ナトリウムや炭酸ナトリウム、炭酸ナトリウム水溶液、水酸化カルシウム水溶液などが使用できるが、有機アルカリ水溶液を用いた方が焼成時にアルカリ成分を除去しやすいので好ましい。有機アルカリとしては、一般的なアミン化合物を用いることができる。具体的には、テトラメチルアンモニウムヒドロキサイド、トリメチルベンジルアンモニウムヒドロキサイド、モノエタノールアミン、ジエタノールアミンなどが挙げられる。アルカリ水溶液の濃度は、０．０１～１０重量％であることが好ましく、０．１～５重量％であることがより好ましい。アルカリ水溶液の濃度が０．０１重量％未満であると可溶部が除去されない傾向があり、１０重量％を超えるとパターン部を剥離させ、また、非可溶部を腐食させる傾向がある。また、現像時の現像温度は、２０～５０℃で行うことが工程管理上好ましい。 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.
　次に、焼成炉にて焼成を行う。焼成雰囲気や温度は、ペーストや基板の種類によって異なる。焼成炉としては、バッチ式の焼成炉やベルト式の連続型焼成炉を用いることができる。焼成温度は、通常５００～６００℃で行う。なお焼成温度は用いるガラス粉末によって決まるが、パターン形成後の形が崩れず、かつガラス粉末の形状が残らない適正な温度で焼成するのが好ましい。適正温度より低いと、気孔率、隔壁上部の凹凸が大きくなり、放電寿命が短くなったり、誤放電を起こしやすくなったりするため好ましくない。また適正温度より高いとパターン形成時の形状が崩れたり、極端に高さが低くなったり、所望の高さが得られないため、好ましくない。 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.
　また、以上の塗布や露光、現像の各工程中や、塗布、露光、現像、焼成のいずれかの工程間に、乾燥、予備反応の目的で、５０～３００℃加熱工程を導入しても良い。 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. .
　隔壁および付着層を形成した後に、ＲＧＢ各色に発光する蛍光体層を形成する。蛍光体粉末、有機バインダーおよび有機溶媒を主成分とする蛍光体ペーストを所定の隔壁間に形成することにより、蛍光体層を形成することができる。蛍光体ペーストを所定の隔壁間に形成する方法としては、スクリーン印刷版を用いてパターン印刷するスクリーン印刷法、吐出ノズルの先端から蛍光体ペーストをパターン吐出するディスペンサー法、また、有機バインダーとして、前述の感光性を有する有機成分を用いることにより、感光性蛍光体ペーストを作製して、感光性ペースト法により各色蛍光体層を所定の場所に形成することができる。 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.
　蛍光体層を形成した該基板を必要に応じて、４００～５５０℃で焼成する事により、本発明のプラズマディスプレイ用基板を作製することができる。 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.
　該プラズマディスプレイ用基板を背面板として用いて、前面板との封着を行う。パネル周囲部に封着用ガラス粉末を含むペーストを塗布し、熱処理することにより、封着と同時に不純ガスの排気を行う。通常、封着用ペーストは背面板周囲部分に塗布し、熱処理温度は、蛍光体の劣化しない温度で実施するため、４５０～５２０℃の範囲で行う。この際、先に形成した隔壁頂部の封着層も前面板と接着させることができる。前背面の基板間隔に形成された空間に、ヘリウム、ネオン、キセノンなどから構成される放電ガスを封入後、駆動回路を装着してプラズマディスプレイを作製できる。前面板は、基板上に所定のパターンで透明電極、バス電極、誘電体、保護膜（ＭｇＯ）を形成した基板であり、背面基板上に形成されたＲＧＢ各色蛍光体層に一致する部分にカラーフィルター層を形成しても良い。また、コントラストを向上するために、ブラックストライプを形成しても良い。 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.
　前記製造方法により得られる本発明のディスプレイは、表面粗さやうねりを低減した各種パターンを有するため、従来の問題点であったプラズマ放電のリークによる誤放電（クロストーク）の発生や振動によるノイズの発生を解消することができるため、安定した表示を得ることできるものである。 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.
　つぎに本発明を実施例により具体的に説明するが、本発明はかかる実施例のみに限定されるものではない。 Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to such examples.
　（実施例１～１４、比較例１～４）
表１に実施例に用いたガラス粉末を示す。 (Examples 1 to 14, Comparative Examples 1 to 4)
Table 1 shows the glass powder used in the examples.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　なお、以下のガラス粉末、フィラーの平均粒子径（Ｄ５０）および最大粒子径（Ｄｍａｘ）は日機装株式会社製マイクロトラック粒度分布測定装置（ＭＴ３０００）を用いて測定した値である。また、ガラス粉末のガラス転移点、軟化点は示差熱分析法を用いて、昇温速度１０℃／分空気中で加熱し、横軸に温度、縦軸に熱量をプロットしてＤＴＡ曲線を描き、読み取った値である。ガラス粉末の屈伏点は、熱膨張測定装置を用いて、昇温速度５℃／分空気中で加熱し、測定した値である。 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.
　また、ガラス粉末、およびフィラーの屈折率測定は、ベッケ法により行い、測定はｇ線（４３６ｎｍ）で実施した。無機粉末の平均屈折率は、含有する粉末屈折率の体積平均により、求めた。 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.
　有機成分の屈折率の測定は、ペースト組成から無機成分を除いたものを塗布し、１００℃で３０分乾燥により、溶媒を除去して得られる有機成分塗布膜の屈折率を測定した。測定はｇ線（４３６ｎｍ）で実施した。 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).
　表１のガラス粉末、およびフィラーを含む原材料を表２、３に示す組成、比率で計量後、混合し、３本ローラーで混練して感光性封着層形成用ガラスペーストを作製し、焼成後それぞれの高さになるように、隔壁形成用ペースト、封着層形成用ペーストを塗布後、露光を行った。 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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
フィラーＪ：酸化ケイ素４０重量部、酸化ホウ素１０重量部、酸化亜鉛５重量部、酸化アルミニウム３０重量部、酸化マグネシウム５重量部、酸化バリウム５重量部、酸化カルシウム５重量部。ガラス転移点６５０℃、軟化点７４０℃、屈折率１．５８の高融点ガラス
フィラーＫ：平均粒子径０．２μｍの酸化ケイ素
ポリマー：酸価＝８５、重量平均分子量（Ｍｗ）３２，０００の感光性アクリルポリマー（東レ（株）製ＡＰＸ－７１６）
モノマー：プロピレンオキシド変性トリメチロールプロパントリアクリレート（第一工業製薬（株）製）
光重合開始剤：２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１（チバ・スペシャルティ・ケミカルズ（株）製、ＩＣ－３６９）
増感剤：４，４－ビス（ジエチルアミノ）ベンゾフェノン
分散剤：ポリカルボン酸化合物の高分子活性剤（共栄社化学（株）製、“フローノン”Ｇ－７００ＤＭＥＡ）
脂肪族アミド化合物：Ｎ，Ｎ’－１２－ヒドロキシステアリン酸ブチレンジアミン
紫外線吸収剤：ベーシックブルー２６
重合禁止剤：ｐ－メトキシフェノール
有機溶剤：ジエチレングリコールモノブチルエーテルアセテート
　ガラス基板として、５９０×９６４×１．８ｍｍの４２インチサイズのＰＤ－２００（旭硝子（株）製）を使用した。この基板上に、アドレス電極として、平均粒径２．０μｍの銀粉末を７０重量部、Ｂｉ２Ｏ３／ＳｉＯ２／Ａｌ２Ｏ３／Ｂ２Ｏ３／ＢａＯ＝６９／２０／４／７（重量％）からなるガラス粉末（平均粒径２．２μｍ）を２重量部、アクリル酸、メチルメタクリレート、スチレンの共重合ポリマー８重量部、トリメチロールプロパントリアクリレート７重量部、ベンゾフェノン３重量部、ブチルカルビトールアクリレート７重量部、ベンジルアルコール３重量部からなる感光性銀ペーストを用いて、フォトリソグラフィー法により、ピッチ１６０μｍ、線幅６０μｍ、焼成後厚み３μｍのストライプ状電極を形成した。 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.
　この基板に、Ｂｉ２Ｏ３／ＳｉＯ２／Ａｌ２Ｏ３／ＺｎＯ／Ｂ２Ｏ３／ＢａＯ＝６０／２０／５／１０／２／３（重量％）からなるガラス粉末（平均粒径２μｍ）を６０重量部、体積平均粒子径０．２μｍの酸化チタン粉末を１０重量部、エチルセルロース５重量％、テルピネオール２０重量％誘電体ペースト塗布した後、５８０℃で焼成して、厚み１０μｍの誘電体層を形成した。 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.
　隔壁形成用ペーストとしては、Ｌｉ２Ｏ／ＳｉＯ２／Ａｌ２Ｏ３／ＺｎＯ／Ｂ２Ｏ３／ＢａＯ＝８／２１／１５／７／３９／１０（重量％）からなるガラス粉末（平均粒径２μｍ、屈折率１．５９）を４０重量部、フィラーＪを１０重量部、ポリマー（酸価＝８５、重量平均分子量３２，０００の感光性アクリルポリマー（東レ（株）製ＡＰＸ－７１６））１０重量部、モノマー（トリメチロールプロパントリアクリレート）７重量部、チバ・スペシャルティ・ケミカルズ（株）製ＩＣ－３６９を３重量部、紫外線吸収剤としてベーシックブルー２６を０．００５重量部、ベンジルアルコール４重量部、ブチルカルビトールアセテート２０重量部を加え、３本ローラーで混練することにより、隔壁形成用ペースト１を作製した。無機成分の平均屈折率Ｎａは１．５９であった。また、Ｌｉ２Ｏ／ＳｉＯ２／Ａｌ２Ｏ３／ＺｎＯ／Ｂ２Ｏ３／ＢａＯ＝１０／２０／１５／７／３８／１０（重量％）からなるガラス粉末（平均粒径２μｍ、屈折率１．５７）を３０重量部、フィラーＪを２０重量部、ポリマー（酸価＝８５、重量平均分子量３２，０００の感光性アクリルポリマー（東レ（株）製ＡＰＸ－７１６））１２重量部、モノマー（トリメチロールプロパントリアクリレート）７重量部、チバ・スペシャルティ・ケミカルズ（株）製ＩＣ－３６９を２重量部、紫外線吸収剤としてベーシックブルー２６を０．００１重量部、ベンジルアルコール４重量部、ブチルカルビトールアセテート２０重量部を加え、３本ローラーで混練することにより、隔壁形成用ペースト２を作製した。無機成分の平均屈折率Ｎｂは１．５７であった。 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.
　実施例１～１２、および、比較例１～４は、それぞれ焼成後１００μｍの厚みになるように隔壁形成用ペースト１をダイコーターにより塗布した後、クリーンオーブンにて１００℃、４０分の乾燥することにより、塗布膜を形成した。その後、表２および表３に示すフォトマスクを介して露光を行う。さらに所定の厚みになるように隔壁形成用ペースト２をダイコーターにより塗布した後、クリーンオーブンにて１００℃、３０分の乾燥することにより、塗布膜を形成し、同様に表２および表３に示すフォトマスクを介して露光を行う。それぞれのフォトマスクパターンを以下に示す。 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.
　フォトマスクＡ：アドレス電極と垂直なストライプパターン、ピッチ４８０μｍ、開口４０μｍ
　フォトマスクＢ：アドレス電極と平行なストライプパターン、ピッチ１６０μｍ、開口４０μｍ
　フォトマスクＣ：格子状パターン、アドレス電極と垂直なパターンピッチ４８０μｍ、アドレス電極と平行なパターンピッチ１６０μｍ、開口はいずれも４０μｍ
　フォトマスクＤ：アドレス電極と平行なストライプパターン、ピッチ１６０μｍ、開口２０μｍ
　露光を施した隔壁形成用ペースト塗布膜上に、乾燥膜厚が１０μｍとなるように、各実施例、および比較例の感光性封着層形成用ガラスペーストをダイコーターにより塗布した。その後、フォトマスクパターンＤを介して露光を実施した。その後０．５重量％の炭酸ナトリウム水溶液で一括して現像し、さらに、５９０℃で１５分間焼成することにより、隔壁パターンおよび、封着層パターンを形成した。 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.
　一方、実施例１３，および１４は、それぞれ焼成後１１５μｍの厚みになるように隔壁形成用ペースト１をダイコーターにより塗布した後、クリーンオーブンにて１００℃、４０分の乾燥することにより、塗布膜を形成し、上記フォトマスクＣを介して露光を行う。その後、乾燥膜厚が１０μｍとなるように、各実施例の感光性封着層形成用ガラスペーストをダイコーターにより塗布した。その後、フォトマスクＤを介して露光を実施した。その後０．５重量％の炭酸ナトリウム水溶液で一括して現像し、さらに、５９０℃で１５分間焼成することにより、隔壁パターンおよび、封着層パターンを形成した。 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.
　このようにして形成された隔壁に各色蛍光体ペーストをスクリーン印刷法により塗布、焼成（５００℃、３０分）して隔壁の側面および底部に蛍光体層を形成した。 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.
　前面板形成は、ガラス基板として、９８０×５５４×１．８ｍｍの４２インチサイズのＰＤ－２００（旭硝子（株）製）を使用した。ＩＴＯをスパッタ法で形成後、レジスト塗布し、露光・現像処理、エッチング処理によって厚み０．１μｍ、線幅２００μｍの透明電極を形成した。 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.
　続いて、黒色顔料を含む感光性ガラスペーストを基板上にスクリーン印刷により塗布後、乾燥し、フォトマスクを介して露光を行った。 Subsequently, a photosensitive glass paste containing a black pigment was applied onto the substrate by screen printing, dried, and exposed through a photomask.
　この露光済み黒色ペースト塗布膜の上から、感光性銀ペーストをスクリーン印刷により塗布・乾燥し、所定のフォトマスクを介して、露光した後、現像を行って未焼成パターンを形成した。パターン形成後、５７０℃で１５分間の焼成、または、１９０℃で１０分間ＩＲ乾燥を行った。 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.
　次に、酸化ビスマスを７０重量％、酸化珪素１０重量％、酸化アルミニウム５重量％、酸化亜鉛５重量％、酸化硼素１０重量％を含有するガラス粉末を７０重量部、エチルセルロース１０重量部、テルピネオール２０重量部を混練して得られたガラスペーストをスクリーン印刷により、表示部分のバス電極が覆われるように５０μｍの厚みで塗布した後に、５７０℃１５分間の焼成を行って透明誘電体を形成した。 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.
　誘電体を形成した基板上に電子ビーム蒸着により保護膜として、厚み０．５μｍの酸化マグネシウム層を形成して前面板を作製した。 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.
　得られた前面基板を、前記の背面基板と貼り合わせ、４９０℃２０分間キープした後、４００℃で３時間キープすることにより、封着、排気を行った。その後、放電用ガスを封入し、駆動回路を接合して解像度１９２０×１０８０のフルハイビジョンプラズマディスプレイパネルを作製した。 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.
　上記実施例１～１４、比較例１～４で得られたプラズマディスプレイパネルを下記の方法で評価した。
＜パターン形成性（隔壁・封着層）＞
　作製した４２インチ背面板の隔壁形状不良箇所、パターン太りやパターン欠け、封着層の形状不良の発生状況を確認した。この評価をパネル１０サンプルについて実施し、１０枚中の隔壁不良箇所をカウントし、以下の評価基準により評価した。
ＡＡ：表示不良となる隔壁欠陥０箇所、かつ表示不良とならない欠陥１箇所以下
Ａ：表示不良となる隔壁欠陥０箇所、かつ表示不良とならない欠陥２～５箇所
Ｂ：表示不良となる隔壁欠陥０箇所、かつ表示不良とならない欠陥６～１０箇所
Ｃ：表示不良となる隔壁欠陥１箇所以上、または表示不良とならない欠陥１１箇所以上
＜封着層密着性＞
　作製した前面基板と背面基板を重ねた状態で（周辺部の封着フリット塗布せずに）封着条件にて温度をかけた後、前面板と背面板を剥がす方向に２ｋｇ重の力を加えた際の封着層の剥がれ状態をパネル１０サンプルについて確認した。以下の評価基準により評価した。
Ａ：剥がれ箇所０箇所
Ｂ：剥がれ箇所１箇所
Ｃ：剥がれ箇所２箇所以上
＜隔壁強度＞
　作製したプラズマディスプレイを前面板側を上にして水平に床置きし、１ｍの高さから重さ３００ｇのアルミナ製セラミックボールを落下させ、隔壁欠け、および微小欠けの発生状況を確認した。これを１０回繰り返し、隔壁欠け、および微小欠けの発生状況を確認した。この評価を各水準のパネル１０サンプルについて行い、欠けが発生したパネルが１サンプルであった場合１／１０として表記した。微小欠けはＰＤＰを点灯した際に問題とならない５μｍ以下の欠けとする。以下の評価基準により評価した。
ＡＡ：隔壁欠け０／１０、かつ微小欠け０／１０
Ａ：隔壁欠け０／１０、かつ微小欠け１／１０
Ｂ：隔壁欠け０／１０、かつ微小欠け２／１０～４／１０
Ｃ：隔壁欠け１／１０以上、または微小欠け５／１０以上
＜クロストーク評価＞
　作製した前面基板と背面基板を封着して、Ｘｅ１５％含有のＮｅガスを内部ガス圧６６５００Ｐａになるように封入した。さらに、駆動回路を実装してＰＤＰを作製した。ＰＤＰのスキャン電極に電圧を印加して発光させた。クロストーク評価は、全面点灯する印可電圧Ｖ１から電圧を上昇させ、クロストークが発生する印可電圧Ｖ２間の電圧差Ｖ２－Ｖ１（Ｖ）を測定した。以下の評価基準により評価した。
ＡＡ：９０≦Ｖ２－Ｖ１
Ａ：７０≦Ｖ２－Ｖ１＜９０
Ｂ：５０≦Ｖ２－Ｖ１＜７０
Ｃ：Ｖ２－Ｖ１＜５０
＜残留ガス量評価＞
　作製した前面基板と背面基板を封着した後、パネル全体を４００℃に加熱し、パネル内から排出される水分、ＣＨ系ガス量を測定した。封着層を形成していないパネルのガス量を規準として、評価した。
＜ノイズ評価＞
　作製した前面基板と背面基板を封着して、Ｘｅ１５％含有のＮｅガスを内部ガス圧６６５００Ｐａになるように封入した。さらに、駆動回路を実装してＰＤＰを作製した。外気圧を大気圧から６００ｈＰａまで順次変化させ、ＰＤＰのスキャン電極に電圧を印加して発光させた際のノイズ発生の有無を確認し、以下の評価基準により評価した。
ＡＡ：外気圧６００ｈＰａでノイズ発生しない
Ａ：外気圧７００ｈＰａではノイズ発生しないが６００ｈＰａでノイズ発生する
Ｂ：外気圧８００ｈＰａではノイズ発生しないが７００ｈＰａでノイズ発生する
Ｃ：外気圧８００ｈＰａでノイズ発生する
　評価結果を表４に示す。 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.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　実施例１～１４で得られたプラズマディスプレイパネルは、良好な隔壁および封着層パターンを形成できた。また、隔壁強度やパネル特性についても良好な結果が得られた。比較例１～４については、隔壁および封着層のパターン形成、隔壁強度、およびパネル特性などの点で満足を得られるものが得られなかった。 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 (9)

  1. （Ａ）ガラス転移点が４１０～４８０℃、屈伏点が４７０～５１０℃、軟化点が５１５～５５０℃のガラス粉末、（Ｂ）感光性有機成分、（Ｃ）紫外線吸収剤、および（Ｄ）溶剤を含む感光性ペーストであって、ガラス粉末を含む無機成分の平均屈折率Ｎ１が下式（１）を満たすことを特徴とする感光性封着層形成用ガラスペースト。
    １．７５≦Ｎ１≦１．９５　　（１）     (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)
  2. 前記ガラス粉末を含む無機成分の平均屈折率Ｎ１が下式（２）を満たすことを特徴とする請求項１に記載の感光性封着層形成用ガラスペースト。
    １．７５≦Ｎ１≦１．９０　　（２）     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)
  3. 前記感光性有機成分を含む有機成分の平均屈折率Ｎ２が下式（３）を満たすことを特徴とする請求項１または２記載の感光性封着層形成用ガラスペースト。
    １．４５≦Ｎ２≦１．６５　　（３）     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. 前記無機成分の平均屈折率Ｎ１と前記有機成分の平均屈折率Ｎ２が下式（４）を満たすことを特徴とする請求項１、２または３に記載の感光性封着層形成用ガラスペースト。
    ０．２≦Ｎ１－Ｎ２≦０．５　　（４）     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. 前記紫外線吸収剤が有機染料であり、ペースト中の含有量が０．０１～２重量％であることを特徴とする請求項１、２、３または４記載の感光性封着層形成用ガラスペースト。 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. .
  6. 基板上に、感光性隔壁形成用ペーストを塗布する工程、フォトマスクを介して露光する工程を経た後に、請求項１、２、３、４または５記載の感光性封着層形成用ガラスペーストを塗布する工程、フォトマスクを介して露光する工程、現像工程、焼成工程を経て、放電空間を仕切るための隔壁および封着層を形成するプラズマディスプレイの製造方法であって、前記感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎａおよび前記感光性封着層形成用ガラスペースト中の無機成分の平均屈折率Ｎ１が下式（５）および（６）を満たすことを特徴とするプラズマディスプレイの製造方法。
    １．４５＜Ｎａ＜１．６５　　（５）
    ０．２≦Ｎ１－Ｎａ≦０．５　　（６）     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)
  7. 基板上に、第１の感光性隔壁形成用ペーストを塗布する工程、フォトマスクを介して露光する工程、第２の感光性隔壁形成用ペーストを塗布する工程、フォトマスクを介して露光する工程を経た後に、請求項１、２、３、４または５記載の感光性封着層形成用ガラスペーストを塗布する工程、フォトマスクを介して露光する工程、現像工程、焼成工程を経て、放電空間を仕切るための隔壁および封着層を形成するプラズマディスプレイの製造方法であって、前記第１の感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎａ、前記第２の感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎｂおよび前記感光性封着層形成用ガラスペースト中の無機成分の平均屈折率Ｎ１が下式（５）～（８）を満たすことを特徴とするプラズマディスプレイの製造方法。
    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）     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. 請求項７記載のプラズマディスプレイの製造方法であって、前記第１の感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎａおよび前記第２の感光性隔壁形成用ペースト中の無機成分の平均屈折率Ｎｂが下式（９）を満たすことを特徴とするプラズマディスプレイの製造方法。
    －０．１　≦　Ｎｂ－Ｎａ　≦　０．１　　（９）     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)
  9. 請求項６、７または８記載のプラズマディスプレイの製造方法によって得られるプラズマディスプレイ。 The plasma display obtained by the manufacturing method of the plasma display of Claim 6, 7 or 8.
PCT/JP2010/060806 2009-07-01 2010-06-25 Glass paste for forming a photosensitive sealing layer, plasma display manufacturing method using the same, and plasma display WO2011001903A1 (en)

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