JP2011075612A - Photosensitive paste, method of forming insulating pattern, and method of producing panel for flat display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive paste capable of forming a good barrier rib pattern and forming barrier ribs having a high reflectance and high in-plane uniformity after firing, and to provide a flat display in which the barrier ribs having the high reflectance are formed and which is superior in display characteristics such as luminance and color purity. <P>SOLUTION: The photosensitive paste includes at least an inorganic component and a photosensitive organic component, wherein the photosensitive paste includes, as the inorganic component, aggregated particles consisting of oxide particles whose refractive index is in the range of 1.40-1.80 and having an average secondary particle size in the range of 0.1-5 μm and low-softening glass powder. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive paste suitable for forming an insulating pattern used in a flat display such as a plasma display panel, a field emission display, and a fluorescent display tube, a method for forming an insulating pattern using the same, and a flat display The present invention relates to a panel manufacturing method.

  In recent years, development of flat displays such as plasma display panels, field emission displays, fluorescent display tubes, liquid crystal display devices, electroluminescence displays, and light emitting diodes has been rapidly advanced. Among these, the plasma display generates plasma discharge between the anode electrode and the cathode electrode facing each other in the discharge space provided between the front glass substrate and the rear glass substrate, and is enclosed in the discharge space. Display is performed by irradiating phosphors provided in the discharge space with ultraviolet rays generated from gas. A gas discharge type display such as a plasma display or a fluorescent display tube requires an insulating partition for partitioning a discharge space. A field emission display such as a field emission display requires an insulating partition for isolating the gate electrode from the cathode.

  As a method of forming these barrier ribs, barrier rib paste was repeatedly applied in a pattern by a screen printing plate, followed by a screen printing method of firing, masking with a resist on the dried barrier rib material layer, and shaving by sandblasting After firing the sand blasting method for firing, baking the dried partition wall material, masking with a resist on the layer, etching method for etching, pressing a mold having a pattern against the coating film of the partition wall paste to form the pattern After forming, a mold transfer method (imprint method) in which baking is performed, a partition material made of a photosensitive paste material is applied, dried, exposed and developed, and then subjected to a photosensitive paste method (photolithography method) in which baking is performed. ) Etc. are known. Among these pattern forming methods, the photosensitive paste method is a method that can cope with an increase in area with high definition and a high cost merit.

  On the other hand, the partition wall not only divides the light emitting area, but also affects the display characteristics of the display such as light emission luminance and color purity. In particular, in the plasma display panel, there is a demand to increase the reflectance of the partition wall in order to improve the light emission efficiency from the phosphor layer. In other words, if the light transmittance of the barrier rib is high and the reflectance is low, the display light emitted from the phosphor layer applied to the side surfaces of the barrier ribs and the bottom surface between the barrier ribs is not sufficiently reflected, and the fluorescence between the adjacent barrier ribs is further reduced. The display light of the body layer leaks, and a display with high brightness and good color purity cannot be obtained.

  Therefore, in order to improve the light emission efficiency from the phosphor layer and increase the color purity, a method of forming a partition with a high reflectance by a photosensitive paste method has been proposed (see Patent Documents 1 and 2). In Patent Documents 1 and 2, after forming a pattern with a photosensitive paste in which inorganic fine particles (nanoparticles) having a high refractive index are uniformly dispersed, a partition wall having high reflectivity is formed by aggregating the nanoparticles during firing. Yes. However, in this method, the nanoparticles dispersed in the paste are agglomerated again in the baking step, so it is difficult to control the particle size of the agglomerated particles, and the reflectance varies within the panel surface. Met.

JP 2001-229838 A JP 2001-27802 A

  Accordingly, the present invention focuses on the problems of the prior art described above, and an object of the present invention is to provide a photosensitive paste that can form partition walls having high reflectivity and high in-panel uniformity. It is another object of the present invention to provide a flat display having excellent display characteristics such as luminance and color purity by forming a partition wall having high reflectivity.

In order to solve the above problems, the present invention has the following configuration.
(1) A photosensitive paste containing at least an inorganic component and a photosensitive organic component, and an average secondary particle composed of oxide particles having a refractive index in the range of 1.40 to 1.80 as an inorganic component A photosensitive paste comprising aggregated particles having a diameter in the range of 0.1 to 5 μm and a low softening point glass powder.
(2) The photosensitive paste according to (1), wherein the oxide is transition alumina.
(3) The photosensitive paste according to (1) or (2), wherein the proportion of oxide particles in the inorganic component is 2 to 8% by volume.
(4) Insulation characterized by applying the photosensitive paste according to any one of (1) to (3) so that the film thickness after drying becomes 100 μm or more, and then drying, exposing, developing, and baking at least. Of forming a sex pattern.
(5) After applying the photosensitive paste according to any one of (1) to (3) on the substrate so that the film thickness after drying becomes 100 μm or more, at least drying, exposing, developing, and baking to insulate A method of manufacturing a flat display panel, wherein a pattern is formed.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive paste which can form the partition with a high reflectance and the panel in-plane uniformity high can be provided. In addition, it is possible to stably provide a plasma display which is formed with a partition wall having high reflectivity and is excellent in display characteristics such as luminance and color purity.

  The photosensitive paste as used in the present invention refers to a film that has been coated and dried, and is irradiated with actinic rays, so that the irradiated portion undergoes reactions such as photocrosslinking, photopolymerization, photodepolymerization, and photomodification. A paste whose chemical structure changes to enable development with a developer. In particular, the present invention provides a negative photosensitive paste that can be patterned by making the irradiated part insoluble in the developer by irradiation with actinic light and then removing only the non-irradiated part with the developer. Good characteristics can be obtained. The actinic light here means light in the wavelength region of 250 to 1100 nm causing such a chemical reaction. Specifically, ultraviolet light such as an ultrahigh pressure mercury lamp and a metal halide lamp, visible light such as a halogen lamp, helium- Specific examples include laser beams having specific wavelengths such as a cadmium laser, a helium-neon laser, an argon ion laser, a semiconductor laser, a YAG laser, and a carbon dioxide gas laser.

  As a result of intensive studies on a method for forming a partition wall having high reflectivity and high in-plane uniformity of the panel, the inventors have found that an inorganic component in a photosensitive paste containing at least an inorganic component and a photosensitive organic component. It is necessary to contain aggregate particles having an average secondary particle diameter of 0.1 to 5 μm and low softening point glass powder composed of oxide particles having a refractive index in the range of 1.40 to 1.80. It revealed that.

  The photosensitive paste of the present invention contains a low softening point glass powder described later as an essential component. By containing the low softening point glass powder, it can be baked at a temperature equal to or higher than the softening temperature of the low softening point glass powder to remove organic components such as a photosensitive organic component described later to obtain a pattern made of an inorganic component. .

  The photosensitive paste of the present invention is characterized by containing at least oxide particles as a filler component. The filler component in the present invention refers to inorganic particles that are added to improve pattern strength, firing shrinkage rate, or increase reflectivity, and hardly melt and flow even at firing temperatures. Specifically, it refers to an inorganic particle that does not have a softening temperature, a melting point, or a decomposition temperature at 600 ° C. or lower and exists as a solid at 600 ° C. By adding a filler component, shrinkage due to firing of the pattern can be suppressed, the strength of the pattern can be improved, and the reflectance can be increased.

  The refractive index of the oxide particles used in the paste of the present invention needs to be 1.40 to 1.80. Pattern processing is facilitated by matching the refractive indexes of the inorganic component and the organic component and suppressing light scattering. Examples of the oxide having a refractive index in this range include silica, alumina, magnesia, silica-based composite oxide, and alumina-based composite oxide. As the metal oxide component constituting the silica-based composite oxide and the alumina-based composite oxide, in addition to silica and alumina, lithium, sodium, potassium, magnesium, calcium, strontium, barium, titanium, zirconium, germanium, hafnium, tin or Examples thereof include oxides of metals such as lead. These oxide particles are low in cost and can be used stably. Optimum oxide particles can be selected from the functions of the oxide particles and the reactivity with the organic components used. Other than the above oxides, it is not preferable because it is expensive and difficult to use stably. The refractive index is more preferably 1.40 to 1.75.

  The refractive index of the oxide particles and the low softening point glass powder in the present invention can be measured by the Becke line detection method. The refractive index at a wavelength of 436 nm (g-line of a mercury lamp) at 25 ° C. is the refractive index in the present invention. It was. When the average secondary particle size is small and cannot be measured by the Becke line detection method, the oxide and its crystal structure are identified by elemental analysis and X-ray diffraction measurement, and the average secondary particle size with the same composition and the same crystal structure is identified. Large agglomerated particles were measured by the Becke line detection method and used as the refractive index in the present invention.

  As the oxide particles in the present invention, it is preferable to use transition alumina particles. Transition alumina, also called intermediate alumina, is a general term for ρ alumina, γ alumina, η alumina, δ alumina, θ alumina, χ alumina, κ alumina, etc. that are usually generated during the dehydration and pyrolysis process of alumina hydrate. Finally, it is an intermediate that produces α-alumina that is a high-temperature stable phase by heating. This transition alumina is usually an ultrafine particle having a primary particle size of about several tens of nanometers and a refractive index in the range of 1.58 to 1.76 between aluminum hydroxide and α-alumina. .

  The photosensitive paste of the present invention needs to contain agglomerated particles having an average secondary particle size of 0.1 to 5 μm constituted by oxide particles. When the average secondary particle diameter of the aggregated particles is less than 0.1 μm, the aggregated growth of the particles occurs during firing, as in the case where the fine oxide particles are uniformly dispersed in the paste, and the particle aggregation cannot be controlled. Further, the uniformity of the reflectance within the panel surface is lowered. When the average secondary particle diameter is larger than 5 μm, when the dried film is exposed, the aggregates inhibit the transmission of the exposure light to the paste film, thereby suppressing the photocuring reaction. Dimensional variations in height are likely to occur or abnormal protrusions may be caused. The average particle diameter of the agglomerated particles can be determined, for example, by observing a dry paste film obtained by applying and drying a photosensitive paste under a transmission electron microscope. The cross section perpendicular to the film surface of the dry paste film is observed with a transmission electron microscope (for example, “JEM-4000EX” manufactured by JEOL Ltd.), and the observation photograph of the aggregated particles is image-processed, and the apparent area of the aggregated particles The diameter when converted into a circle having the same area as the above is obtained, observation and image processing are performed on 50 aggregated particles, and the average value thereof is defined as the average secondary particle diameter of the aggregated particles. The average secondary particle diameter is more preferably 1 to 5 μm.

  Aggregated particles having an average secondary particle size of 0.1 to 5 μm in the present invention are preferably composed of oxide particles having an average primary particle size of 0.05 μm or less.

  In the present invention, by containing aggregated particles having an average secondary particle diameter of 0.1 to 5 μm constituted by oxide particles, the partition wall has a high reflectance and a high in-panel uniformity. The reason for the remarkable effect that can be formed is not clear, but the following mechanism is conceivable.

  In general, when aggregated particles are included in a photosensitive paste, the particles themselves or voids present in the aggregated particles become a light scattering source during exposure, making it difficult to obtain a pattern with high resolution and a high aspect ratio. However, when the photosensitive paste contains aggregated particles composed of oxide particles whose refractive index matches the refractive index of the photosensitive organic component contained in the photosensitive paste, the oxide particles and the photosensitive organic component Is close to the refractive index, so that scattering by the oxide particles themselves is suppressed. The voids present in the agglomerated particles disappear when the photosensitive organic component, which is the paste constituent, soaks in, and does not become a scattering source. A pattern that exhibits transparency, high resolution, and high aspect ratio can be obtained. Note that when baking is performed after exposure and development, the photosensitive organic components and the solvent soaked in the gaps between the aggregated particles are burned out, and the gaps between the aggregated particles become voids. This gap serves as a light scattering source due to the difference in refractive index between air and the inorganic component, and a partition wall having high reflectivity can be formed. In addition, the reason for the high uniformity in the panel surface of the reflectivity is that it exists in the paste as agglomerated particles. Presumably higher.

  In the photosensitive paste of the present invention, the proportion of oxide particles in the inorganic component is preferably 2 to 8% by volume. If the ratio of the oxide particles is less than 2% by volume, the effect of improving the reflectance due to the addition may not be obtained sufficiently, which is not preferable. On the other hand, if it exceeds 8% by volume, pattern formation is hindered, sintering of the low-melting glass is hindered at the time of firing, the porosity is increased, and the partition wall strength may be lowered, which is not preferable. More preferably, it is 2 to 5% by volume. The ratio of the oxide particles in the inorganic component can be calculated from the blending amount of each component at the time of creating the paste, but by baking the paste dry film or dry film obtained by applying and drying the photosensitive paste It can also be determined by observing the cross section of the obtained paste fired film with a scanning electron microscope. A cross section perpendicular to the film surface of the paste dry film or paste fired film is observed with a transmission electron microscope (for example, “JEM-4000EX” manufactured by JEOL Ltd.), and the type of inorganic component is distinguished by the density of the image, Image analysis may be performed. The relationship between the density of the image and the inorganic component can be specified by using elemental analysis by X-ray. As an evaluation area of the transmission electron microscope, for example, an area of about 20 μm × 100 μm is targeted, and observation may be performed at about 1000 to 3000 times.

  As an inorganic component in this invention, low softening point glass powder is made into an essential component other than said oxide particle. In the present invention, the low softening point glass powder refers to a glass powder having a load softening temperature in the range of 400 to 600 ° C. This is because when the load softening temperature is within this range, there is no deformation of the pattern during sintering, and the meltability becomes appropriate. A more preferable range of the load softening temperature is 450 to 550 ° C. The proportion of the low softening temperature glass powder in the inorganic component is preferably 60% by volume to 98% by volume. When the content ratio is less than 60% by volume, sintering during firing becomes difficult and the porosity of the pattern after firing becomes large, which is not preferable. If it exceeds 98% by volume, the fluidity of the entire inorganic component at the time of firing becomes large, so it becomes difficult to control the pattern shape after firing, the mechanical strength of the pattern after firing is small, and the pattern is missing due to impact. This is not preferable because problems such as occurrence may occur.

The refractive index of the low softening point glass powder is preferably 1.50 to 1.65. By matching the refractive indexes of the inorganic component and the organic component and suppressing light scattering, highly accurate pattern processing becomes easy. The particle size of the low softening point glass powder is selected in consideration of the shape of the pattern to be produced, but the 50% particle size (average particle size) d ₅₀ in the weight distribution curve is 0.1 to 3.0 μm. The maximum particle diameter d _max is preferably 10 μm or less.

The low softening point glass powder that can be preferably used has, for example, the following composition in oxide notation.
Lithium oxide, sodium oxide or potassium oxide 3-15% by mass
Silicon oxide 5-30% by mass
Boron oxide 20-45 mass%
Barium oxide or strontium oxide 2-15% by mass
Aluminum oxide 10-25% by mass
Magnesium oxide or calcium oxide 2-15% by mass
As described above, at least one kind of alkali metal oxides of lithium oxide, sodium oxide, or potassium oxide is used, and the total amount is preferably 3 to 15% by mass, and more preferably 3 to 10% by mass.

  Alkali metal oxides not only facilitate the control of the glass transition temperature and thermal expansion coefficient of glass, but also can lower the refractive index of glass, thus reducing the difference in refractive index from the photosensitive organic component. Becomes easier. By making the total amount of alkali metal oxides 3% by mass or more, the effect of lowering the softening point of the glass can be obtained, and by making it 15% by mass or less, the chemical stability of the glass is maintained and thermal expansion is achieved. The coefficient can be kept small. As the alkali metal, lithium is preferably selected because it can lower the refractive index of the glass and prevent ion migration.

  The blending amount of silicon oxide is preferably 5 to 30% by mass, more preferably 10 to 30% by mass. Silicon oxide is effective in improving the denseness, strength and stability of glass, and is effective in lowering the refractive index of glass. In addition, when a glass substrate is used as the base material, the thermal expansion coefficient can be controlled to prevent problems such as peeling due to mismatch with the glass substrate. By setting it as 5 mass% or more, a thermal expansion coefficient can be suppressed small and it can be made hard to produce a crack, when baking to a glass substrate. Further, the refractive index can be kept low. By setting it as 30 mass% or less, a glass transition point can be restrained low and the baking temperature to a glass substrate can be made low.

  Boron oxide is effective for lowering the refractive index, and is preferably blended in the range of 20 to 45 mass%, more preferably 20 to 40 mass%. By setting it as 20 mass% or more, the glass transition point is kept low and baking onto the glass substrate is facilitated. Moreover, the chemical stability of glass can be maintained by setting it as 45 mass% or less.

  Of these, at least one of barium oxide and strontium oxide is used, and the total amount is preferably 2 to 15% by mass, more preferably 2 to 10% by mass. These components are effective in adjusting the thermal expansion coefficient, and are also preferable in terms of ensuring electrical insulation and stability and denseness of a pattern to be formed. The devitrification by crystallization can also be prevented by setting it as 2 mass% or more. Moreover, by setting it as 15 mass% or less, a thermal expansion coefficient and a refractive index can be restrained low, and the chemical stability of glass can also be maintained.

  Aluminum oxide has the effect of expanding the vitrification range and stabilizing the glass, and is effective in extending the pot life of the paste. It is preferable to mix | blend in 10-25 mass%, By making it in this range, a glass transition temperature can be kept low and baking on a glass substrate can be made easy.

  Further, at least one of magnesium oxide and calcium oxide is used, and the total amount is preferably 2 to 15% by mass. These components are effective in controlling the coefficient of thermal expansion while facilitating melting of the glass. By making the total amount 2% by mass or more, devitrification of the glass due to crystallization is prevented, and 15% by mass or less. Thus, the chemical stability of the glass can be maintained.

  Further, although not described in the above composition, it is also preferable to contain zinc oxide, titanium oxide, zirconium oxide or the like.

  As a method for producing a low softening point glass powder, for example, raw materials such as lithium oxide, silicon oxide, boron oxide, barium oxide, aluminum oxide, and magnesium oxide are mixed so as to have a predetermined composition, and 900 to 1200 ° C. After melting, it is cooled and made into a glass frit and then pulverized to a fine powder of 1 to 5 μm. High purity carbonates, oxides, hydroxides and the like can be used as raw materials. Depending on the type and composition of the glass powder, it is possible to use ultra-pure alkoxides of 99.99% or more and organic metal raw materials, and use powders that are homogeneously produced by the sol-gel method. This is preferable because a small and high-purity fired film can be obtained.

  Moreover, the oxide particle which is an essential component of this invention exhibits the function as a filler component. In the present invention, as the filler component, at least one selected from a high softening point glass powder having a load softening temperature of 600 to 1200 ° C. and a ceramic powder such as cordierite and zirconia is oxidized in addition to the oxide particles. Although it can be used simultaneously with physical particles, it is preferable to use a high softening point glass powder from the viewpoint of easy adjustment of the average particle diameter and the average refractive index.

Filler component other than the oxide particles dispersibility and packing property to the photosensitive paste, considering suppression of light scattering during exposure, the average particle diameter d ₅₀ of 0.1 to 3.0 m, an average refractive index of 1 What is .50 to 1.65 can be preferably used.

  The photosensitive paste in the present invention needs to contain a photosensitive organic component. If necessary, non-photosensitive polymer components, antioxidants, organic dyes, photopolymerization initiators, sensitizers, sensitizers, plasticizers, thickeners, dispersants, organic solvents, precipitation inhibitors Organic components such as can be added as needed. The photosensitive organic component is selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer.

  An alkali-soluble polymer can be preferably used as the photosensitive polymer. This is because the polymer is alkali-soluble, so that an aqueous alkaline solution can be used as a developer instead of an organic solvent having a problem with the environment. As the alkali-soluble polymer, an acrylic copolymer can be preferably used. The acrylic copolymer is a copolymer containing at least an acrylic monomer as a copolymerization component. Specific examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n -Butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, di Cyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxy Acrylic monomers such as ethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate, benzyl mercaptan acrylate, and these acrylates into methacrylates Listed are alternatives It is. As the copolymer component other than the acrylic monomer, a compound having a carbon-carbon double bond can be used, but preferably styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene. Styrenes such as chloromethyl styrene and hydroxymethyl styrene, 1-vinyl-2-pyrrolidone and the like.

  In order to impart alkali solubility to the acrylic copolymer, it is achieved by adding an unsaturated acid such as an unsaturated carboxylic acid as a monomer. Specific examples of the unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, or acid anhydrides thereof. The acid value of the polymer after adding these is preferably in the range of 50-150.

  When using an acrylic copolymer, in order to increase the reaction rate of the curing reaction by exposure of the photosensitive paste, an acrylic copolymer having a carbon-carbon double bond at the side chain or molecular end may be used. preferable. Examples of the group having a carbon-carbon double bond include a vinyl group, an allyl group, an acrylic group, and a methacryl group. In order to add such a functional group to an acrylic copolymer, a glycidyl group or an isocyanate group and a carbon-carbon double bond with respect to the mercapto group, amino group, hydroxyl group, or carboxyl group in the acrylic copolymer. And a method of making an addition reaction of a compound having acrylic acid chloride, methacrylic acid chloride or allyl chloride.

  Examples of the compound having a glycidyl group and a carbon-carbon double bond include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonate, and glycidyl isocrotonate. Examples of the compound having an isocyanate group and a carbon-carbon double bond include acryloyl isocyanate, methacryloyl isocyanate, acryloylethyl isocyanate, and methacryloylethyl isocyanate.

  Furthermore, the photosensitive paste of the present invention may contain a non-photosensitive polymer component as an organic component, for example, a cellulose compound such as methylcellulose and ethylcellulose, a high molecular weight polyether, and the like.

  The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond. Specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate. , Isobutyl 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, glycerol Acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate , Isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl 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 diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, di Pentaerythritol hexaac Rate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane Triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, bisphenol A-propylene oxide Adjunct Diacrylate, thiophenol acrylate, benzyl mercaptan acrylate, a monomer in which 1 to 5 hydrogen atoms of these aromatic rings are substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methyl Styrene, m-methyl styrene, chlorinated styrene, brominated styrene, α-methyl styrene, chlorinated α-methyl styrene, brominated α-methyl styrene, chloromethyl styrene, hydroxymethyl styrene, carboxymethyl styrene, vinyl naphthalene, Examples include vinyl anthracene, vinyl carbazole, and those obtained by substituting some or all of the acrylates in the molecule with methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, and the like. In the polyfunctional monomer, the group having an unsaturated bond may be a mixture of an acryl group, a methacryl group, a vinyl group, and an allyl group. In the present invention, one or more of these can be used.

  The photosensitive paste used in the present invention preferably further contains a urethane compound. By including a urethane compound, the flexibility of the paste dry film is improved, the stress during firing can be reduced, and defects such as cracks and disconnections can be effectively suppressed. Moreover, by containing a urethane compound, thermal decomposability improves and it becomes difficult to generate | occur | produce a baking residue in a baking process. Examples of the urethane compound preferably used in the present invention include compounds represented by the following general formula (1).

Here, R ¹ and R ² are selected from the group consisting of a substituent containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyaralkyl group. Yes, they may be the same or different. R3 is an alkylene oxide group or alkylene oxide oligomer, and R4 is an organic group containing a urethane bond. n is an integer of 1-10.

As such a urethane compound, a compound containing an ethylene oxide unit is preferable. More preferably, in the general formula (1), R ⁴ is an oligomer containing an ethylene oxide unit (hereinafter referred to as EO) and a propylene oxide unit (hereinafter referred to as PO), and the EO content in the oligomer Is a compound in the range of 8 to 70% by mass. When the EO content is 70% by mass or less, the flexibility is further improved and the firing stress can be reduced, so that defects can be effectively suppressed. Furthermore, the thermal decomposability is improved, and the firing residue is less likely to occur in the subsequent firing step. Moreover, compatibility with other organic components improves because EO content is 8% or more.

  It is also preferred that the urethane compound has a carbon-carbon double bond. When the carbon-carbon double bond of the urethane compound reacts with the carbon-carbon double bond of another crosslinking agent and is contained in the crosslinked product, polymerization shrinkage can be further suppressed.

  Specific examples of urethane compounds preferably used in the present invention include UA-2235PE (molecular weight 18000, EO content 20%), UA-3238PE (molecular weight 19000, EO content 10%), UA-3348PE (molecular weight 22000, EO). Content rate 15%), UA-5348PE (molecular weight 39000, EO content rate 23%) (the above-mentioned, Shin-Nakamura Chemical Co., Ltd. product) etc. are mentioned, However, It is not limited to these. Moreover, you may use these compounds in mixture.

  It is preferable that content of a urethane compound is 0.1-20 mass% of the organic component except a solvent. By setting the content to 0.1% by mass or more, the flexibility of the paste dry film can be improved, and the firing shrinkage stress when the paste dry film is fired can be reduced. When the content exceeds 20% by mass, the dispersibility of the organic component and the inorganic component is lowered, and the concentrations of the monomer and the photopolymerization initiator are relatively lowered, so that defects are likely to occur.

  As the photopolymerization initiator, a photoradical initiator that generates radicals upon irradiation with an active light source can be preferably used. Specific examples thereof include benzophenone, methyl o-benzoylbenzoate, and 4,4-bis (dimethylamine). Benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2 -Phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone Benzyl, benzyldimethylketanol, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methylene Anthrone, 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, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride Quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, peroxidation Examples thereof include a combination of a photoreductive dye such as benzoin, eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. In the present invention, one or more of these can be used. A photoinitiator is 0.05-20 mass% with respect to the total amount of a photosensitive monomer and a photosensitive polymer, More preferably, it adds in 0.1-15 mass%. If the amount of the polymerization initiator is too small, the photosensitivity may be deteriorated. If the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion may be too small.

  Moreover, a sensitizer can be used with a photoinitiator, a sensitivity can be improved or the wavelength range effective for reaction can be expanded. Specific examples of the sensitizer include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis ( 4-dimethylaminobenzal) -4-methylcyclohexanone, mihira-ketone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p- Dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis- (7-diethylamino) Coumarin), triethanolamine, methyldiethanol Amine, triisopropanolamine, N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate , Isoamyl diethylaminobenzoate, ethyl (2-dimethylamino) benzoate, 4-dimethylaminobenzoate (n-butoxy) ethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, 3-phenyl-5-benzoylthio Examples include tetrazole 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 adding a sensitizer to the photosensitive paste of this invention, the addition amount becomes like this. Preferably it is 0.05-10 mass% with respect to the organic component except a solvent, More preferably, it is 0.1-10 mass%. By setting the addition amount of the sensitizer within this range, good photosensitivity can be obtained while maintaining the remaining ratio of the exposed portion.

  In the present invention, an antioxidant is preferably added. The antioxidant has a radical chain inhibiting action, a triplet elimination action, and a hydroperoxide decomposition action. When an antioxidant is added to the photosensitive paste, the antioxidant captures radicals and returns the energy state of the excited photopolymerization initiator and sensitizer to the ground state, thereby causing excess light due to scattered light. Since the reaction is suppressed and a photoreaction occurs abruptly at an exposure amount that cannot be suppressed by the antioxidant, it is possible to increase the contrast of dissolution and insolubility in the developer. Specifically, p-benzoquinone, naphthoquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, hydroquinone, p-t -Butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butyl-p-cresol, hydroquinone monomethyl ether, α-naphthol, hydrazine hydrochloride , Trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene, picric acid, quinonedioxime, Lohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, cuperone, 2,2′-thiobis (4-tert-octylphenolate) -2-ethylhexylaminonickel- (II), 4, 4′-thiobis- (3-methyl-6-tert-butylphenol), 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,2,3-trihydroxybenzene, etc. Although it is mentioned, it is not limited to these. In the present invention, one or more of these can be used. The addition amount of the antioxidant is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass in the photosensitive paste. By making the addition amount of the antioxidant within this range, it is possible to maintain the photosensitivity of the photosensitive paste, and maintain the degree of polymerization and maintain the pattern shape, while increasing the contrast between the exposed portion and the non-exposed portion. it can.

  By containing an ultraviolet absorber in the photosensitive paste of the present invention, scattered light inside the paste due to exposure light can be absorbed and scattered light can be weakened. The ultraviolet absorber is particularly effective as long as it has excellent absorbance at wavelengths near the g-line, h-line, and i-line. Specific examples include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, and benzotriazole compounds. Examples thereof include compounds, indole compounds, and inorganic fine-particle metal oxides. Among these, benzophenone compounds, cyanoacrylate compounds, benzotriazole compounds, and indole compounds are particularly effective. Specific examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-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, 2-hydroxy-4-n-octoxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2'-G Roxy-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-chlorobenzotriazole, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, 2-ethylhexyl- 2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl acrylate, BONASORB UA-3901 (manufactured by Orient Chemical Co., Ltd.), BONASORB UA-3902 (indole UV absorber) Orient Chemical Co., Ltd.), BONASORB UA-3911 (Orient Chemical Co., Ltd.), SOM-2-0008 (Orient Chemical Co., Ltd.), Basic Blue, Sudan Blue, Sudan R, Sudan I, Sudan II, Sudan III, Sudan IV, Oil Orange SS, Oil Violet, Oil Yellow OB (above, Aldrich), etc. Not. Furthermore, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

  As the ultraviolet absorber in the present invention, a photobleaching compound can also be used. The photobleaching compound absorbs light in the wavelength region of active light and emits light when irradiated with light in the wavelength region of active light. It means that the absorbance in the wavelength region of the active light source becomes smaller than that before irradiation through chemical structural changes such as decomposition and photodenaturation. Usually, the exposure used in the photolithography technique is performed using g-line (436 nm), h-line (405 nm), and i-line (365 nm) of an ultra-high pressure mercury lamp. It is preferable that the compound also has absorption in the g-line, h-line, and i-line regions. By adding the photo-fading compound to the photosensitive paste, it is possible to prevent exposure light from entering the non-exposed part, which is a part not exposed to exposure light in pattern design, and to suppress the pattern bottom thickness. . Further, in the exposed portion, the photochromic compound absorbs the energy of the exposure light and does not gradually absorb through photodecomposition or photomodification, so that sufficient exposure light easily reaches the lower layer. Therefore, the photocuring contrast between the non-exposed portion and the exposed portion becomes clear, and the exposure amount margin can be reliably improved. Specific examples include photodegradable dyes, photoacid generators, photobase generators, photodegradable compounds such as nitrone compounds, and photomodifying compounds such as azo dyes and photochromic compounds. Specific examples of the photoacid generator include onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, diazoketone compounds, and the like.

  As for content of a ultraviolet absorber, 0.001-1 mass% is preferable in a photosensitive paste, More preferably, it is 0.001-0.5 mass%. By making the addition amount of the ultraviolet absorber within this range, it is possible to absorb the scattered light, suppress the pattern bottom thickness, and maintain the sensitivity to the exposure light.

  In the present invention, an organic dye can be added as a mark for exposure and development. By adding a dye and coloring it, the visibility is improved, and it becomes easy to distinguish the portion where the paste remains during development and the portion where it has been removed. Although it does not specifically limit as organic dye, The thing which does not remain in the insulating film after baking is preferable. Specifically, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, phthalimide dyes Dyes and perinone dyes can be used. In particular, it is preferable to select one that absorbs light having a wavelength in the vicinity of h-line and i-line, for example, a carbonium dye such as basic blue. The addition amount of the organic dye is preferably 0.001 to 1% by mass with respect to the organic components excluding the solvent.

  An organic solvent is used to adjust the viscosity at the time of applying the photosensitive paste to the substrate according to the application method. As the organic solvent used at this time, methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl carbitol, ethyl carbitol, butyl carbitol acetate, ethyl carbitol acetate, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, Isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and organic solvent mixtures containing one or more of these are used.

  The photosensitive paste of the present invention comprises an organic component comprising at least an inorganic component containing a low softening point glass powder and oxide particles, a photosensitive organic component, an ultraviolet absorber, an antioxidant, an organic dye, a dispersant, and a solvent. After preparing each of these components so as to have a predetermined composition, main kneading is performed using a kneading apparatus such as a three-roller to produce a photosensitive paste. In addition, it is also preferable to appropriately filter and degas the photosensitive paste after the main kneading.

  The present invention relates to a method for forming an insulating pattern obtained by coating the photosensitive paste of the present invention thus obtained so that the film thickness after drying becomes 100 μm or more, and then drying, exposing, developing and baking. By using the insulating pattern forming method of the present invention, it is possible to form a good partition pattern, and it is possible to form a partition wall having high reflectivity and high in-plane reflectance uniformity after baking. As described above, the photosensitive paste of the present invention has high sensitivity because it scatters little exposure light, and can be patterned by one exposure even when the thickness after drying is 100 μm or more.

  Furthermore, this invention relates to the manufacturing method of the panel for flat displays including the process of forming a partition pattern using the above-mentioned pattern formation method. According to the method for manufacturing a flat display panel of the present invention, it is possible to form a flat panel panel having high reflectivity and excellent display characteristics such as luminance with high accuracy and stability.

  The plasma display member and the manufacturing procedure of the plasma display are described below. Here, the basic structure and the like will be described using the most common alternating current (AC) plasma display as an example of the plasma display, but the plasma display is not necessarily limited thereto.

  The plasma display is a member formed by sealing the front plate and the rear plate so that the phosphor layer formed on the front plate and / or the rear plate faces the inner space. The discharge gas is sealed in the tube. That is, on the front plate, a transparent electrode (sustain electrode, scan electrode) for display discharge is formed on the substrate on the display surface side. A bus electrode may be formed on the back side of the transparent electrode for the purpose of forming a lower resistance electrode. However, the bus electrode is made of Ag, Cr / Cu / Cr or the like and is often opaque. Therefore, unlike the transparent electrode, it interferes with the display of the cell, and is preferably provided at the outer edge of the display surface. In the case of an AC type plasma display, a transparent dielectric layer and an MgO thin film as a protective film are often formed on the upper layer of the electrode. On the back plate, electrodes (address electrodes) for selecting cells to be displayed are formed. The partition walls and phosphor layers for partitioning the cells may be formed on either or both of the front plate and the back plate, but are often formed only on the back plate. In the plasma display, the front plate and the back plate are sealed, and an internal space between the two is filled with a discharge gas such as Xe-Ne or Xe-Ne-He.

  First, regarding the member manufacturing process, a method for manufacturing the front plate will be described. As the substrate, “PP8” (manufactured by Nippon Electric Glass Co., Ltd.) and “PD200” (manufactured by Asahi Glass Co., Ltd.), which are heat-resistant glass for soda glass and plasma display, can be used. The size of the glass substrate is not particularly limited, and a glass substrate having a thickness of 1 to 5 mm can be used.

  First, indium-tin oxide (ITO) is sputtered on a glass substrate, and a pattern is formed by a photoetching method. Subsequently, the black electrode paste for black electrodes is printed. The black electrode paste is composed mainly of an organic binder, a black pigment, conductive powder, and a photosensitive component when used in a photolithography method. As the black pigment, a metal oxide is preferably used. Examples of metal oxides include titanium black, copper, iron, manganese oxides and their composite oxides, and cobalt oxides. Cobalt oxides are less susceptible to fading when mixed with glass and fired. Is excellent. Examples of the conductive powder include metal powder and metal oxide powder. As the metal powder, gold, silver, copper, nickel or the like that is usually used as an electrode material can be used without any particular limitation. Since this black electrode has a high resistivity, an electrode paste having a high conductivity (for example, a material containing silver as a main component) is printed on the black electrode paste in order to produce a bus electrode by producing an electrode with a low resistivity. Print on the side. As this conductive paste, an electrode paste used for an address electrode can also be suitably used. Then, batch exposure / development is performed to produce a bus electrode pattern. In order to ensure the conductivity, a highly conductive electrode paste may be printed again before development, and may be collectively developed after re-exposure. After the bus electrode pattern is formed, baking is performed. Thereafter, it is preferable to form a black stripe or a black matrix in order to improve contrast. The film thicknesses of the black electrode paste after firing and the conductive paste after firing are each preferably in the range of 1 to 5 μm. Moreover, it is preferable that the line | wire width after baking is 20-100 micrometers.

  Next, a transparent dielectric layer is formed using a transparent dielectric paste. The transparent dielectric paste is mainly composed of an organic binder, an organic solvent, and glass, but an additive such as a plasticizer may be appropriately added. The method for forming the transparent dielectric layer is not particularly limited. For example, the transparent dielectric paste is applied on the entire surface of the electrode forming substrate by screen printing, bar coater, roll coater, die coater, blade coater, spin coater, or the like. After application, the thick film can be formed by drying using an optional oven such as a ventilating oven, a hot plate, an infrared drying oven, or vacuum drying. It is also possible to make the transparent dielectric paste into a green sheet and laminate it on the electrode forming substrate. The thickness is preferably 0.01 to 0.03 mm.

  Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in air, in an atmosphere of nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a roller conveyance type continuous firing furnace can be used. The baking temperature is preferably a temperature at which the resin to be used sufficiently debinds. Usually, when an acrylic resin is used, baking is performed at 430 to 650 ° C. If the firing temperature is too low, the resin component tends to remain, and if it is too high, the glass substrate may be distorted and cracked.

Further, a protective film is formed. As the protective film, MgO, MgGd ₂ O ₄ , BaGd ₂ O ₄ , Sr _0.6 Ca _0.4 Gd ₂ O ₄ , Ba _0.6 Sr _0.4 Gd ₂ O ₄ , SiO ₂ , TiO ₂ , Al ₂ O ₃ and at least one kind from the above-mentioned group of low softening point glasses are preferably used, and MgO is particularly preferable. A known technique such as electron beam evaporation or ion plating can be used as a method for forming the protective film.

  Next, a method for manufacturing the back plate will be described. As the glass substrate, soda glass, “PD200”, “PP8” or the like can be used as in the case of the front plate. An address stripe electrode pattern is formed on a glass substrate with a metal such as silver, aluminum, chromium, or nickel. As a forming method, these metal powders and a metal paste mainly composed of an organic binder are pattern-printed by screen printing, or after applying a photosensitive metal paste using a photosensitive organic component as an organic binder, It is possible to use a photosensitive paste method in which pattern exposure is performed using a mask, unnecessary portions are dissolved and removed in a development step, and further heated and baked at 350 to 600 ° C. to form an electrode pattern. Further, an etching method can be used in which after chromium or aluminum is vapor-deposited on a glass substrate, a resist is applied, and after the resist is subjected to pattern exposure and development, unnecessary portions are removed by etching. Furthermore, it is preferable to provide a dielectric layer on the address electrode. By providing the dielectric layer, it is possible to improve the stability of discharge and to prevent the partition wall formed on the upper layer of the dielectric layer from falling or peeling off. In addition, as a method of forming the dielectric layer, a dielectric paste mainly composed of an inorganic component such as glass powder or a high melting point glass powder and an organic binder is printed or applied by screen printing, a slit die coater, or the like. There is.

  Next, a method for forming partition walls by photolithography will be described. The partition pattern is not particularly limited, but a lattice shape, a waffle shape, or the like is preferable. First, a barrier rib paste made of the photosensitive paste of the present invention is applied on a substrate on which a dielectric is formed. As a coating method, methods such as a bar coater, a roll coater, a slit die coater, a blade coater, and screen printing can be used. The coating thickness can be determined in consideration of the desired partition wall height and the shrinkage rate due to baking of the paste. The coating thickness can be adjusted by the number of coatings, screen mesh, paste viscosity, and the like. In this invention, it is preferable to apply | coat so that the application thickness after drying may be 100 micrometers or more. By setting the thickness to 100 μm or more, a sufficient discharge space is obtained, and the brightness of the plasma display can be improved by expanding the application range of the phosphor.

  The applied partition paste is dried and then exposed. In general, the exposure is performed through a photomask, as in normal photolithography. Alternatively, a method of directly drawing with a laser beam or the like without using a photomask may be used. 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 at this time include near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. 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 0.01 to 30 minutes using an ultrahigh pressure mercury lamp having an output of 1 to 100 mW / cm 2.

  After the exposure, development is performed by utilizing the difference in solubility between the exposed portion and the non-exposed portion in the developer. Usually, the immersion method, the spray method, the brush method, and the like are performed. As the developer, an organic solvent in which an organic component in the photosensitive paste can be dissolved can be used. However, when a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an alkaline aqueous solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, potassium 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 density | concentration of aqueous alkali solution is 0.05-5 mass% normally, More preferably, it is 0.1-1 mass%. If the alkali concentration is too low, it is difficult to remove the soluble part, and if the alkali concentration is too high, the pattern may be peeled off or corroded, which is not preferable. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  Moreover, the partition may be composed of two or more layers. By using a structure of two or more layers, the configuration range of the partition wall shape can be expanded three-dimensionally. For example, in the case of a two-layer structure, the first layer is applied and exposed in a stripe shape, then the second layer is applied, the first layer is exposed to a stripe shape in the vertical direction, and development is performed, thereby causing unevenness. It is possible to form a partition wall having a cross-beam structure. Next, baking is performed by holding at a temperature of 520 to 620 ° C. for 10 to 60 minutes in a baking furnace to form partition walls.

  The photosensitive paste of the present invention is suitable for the formation of the above-described partition wall, and the photosensitive paste of the present invention can form a partition wall having high reflectivity and high in-plane uniformity with high accuracy, and is excellent. A plasma display having the above characteristics can be manufactured.

Next, a phosphor is formed using the phosphor paste. It can be formed by a photolithography method using a photosensitive phosphor paste, a dispenser method, a screen printing method, or the like. Although the thickness of a fluorescent substance is not specifically limited, It is 10-30 micrometers, More preferably, it is 15-25 micrometers. The phosphor powder is not particularly limited, but the following phosphors are preferable from the viewpoint of light emission intensity, chromaticity, color balance, lifetime, and the like. Blue is an aluminate phosphor (for example, BaMgAl ₁₀ O ₁₇ : Eu) or CaMgSi ₂ O ₆ activated with divalent europium. In green, Zn ₂ SiO ₄ : Mn, YBO ₃ : Tb, BaMg ₂ Al ₁₄ O ₂₄ : Eu, Mn, BaAl ₁₂ O ₁₉ : Mn, and BaMgAl ₁₄ O23: Mn are preferable from the viewpoint of panel luminance. More preferably _Zn 2 _SiO 4: is Mn. In red, (Y, Gd) BO ₃ : Eu, Y ₂ O ₃ : Eu, YPVO: Eu, and YVO ₄ : Eu are also preferable. More preferred is (Y, Gd) BO ₃ : Eu. When the phosphor is formed through the firing step, it may be performed simultaneously with the above-described firing of the dielectric layer and the partition wall.

  Next, a method for manufacturing a plasma display panel will be described. After sealing the back plate and the front plate, after evacuating while heating the space formed between the two substrates, a discharge gas composed of He, Ne, Xe, etc. is sealed and sealed . From both sides of discharge voltage and brightness. Xe-Ne mixed gas having 5 to 15% by volume of Xe is preferable. In order to increase the generation efficiency of ultraviolet rays, Xe may be further increased to about 30% by volume.

  Finally, a plasma display panel can be manufactured by mounting and aging the drive circuit.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to this.
(Examples 1-6, Comparative Examples 1-3)
A. Evaluation of Particle Size Distribution of Glass Powder Using a particle size distribution measuring device (“MT3300” manufactured by Nikkiso), the average particle size d ₅₀ and the maximum particle size d _max of the glass powder were evaluated. Glass powder was put into a sample chamber filled with water, and measurement was performed after ultrasonic treatment for 300 seconds.
B. Refractive Index Evaluation of Oxide Particles For oxide particles O-1 to O-5, a light source part of an optical microscope is attached with a halogen lamp and observed using an interference filter for g-line. The refractive index was evaluated. The catalog value was used about the oxide particle O-6.
C. Production of photosensitive paste The raw materials used for the photosensitive paste for barrier ribs are as follows.
Photosensitive monomer M-1: trimethylolpropane triacrylate photosensitive monomer M-2: tetrapropylene glycol dimethacrylate photosensitive polymer: carboxyl group of copolymer consisting of methacrylic acid / methyl methacrylate / styrene = 40/40/30 To which 0.4 equivalent of glycidyl methacrylate was added and reacted (weight average molecular weight 43,000, acid value 100)
Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (IC369 manufactured by Ciba Specialty Chemicals).
Sensitizer: 2,4-diethylthioxanthone antioxidant: 1,6-hexanediol-bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate])
Ultraviolet absorber: Sudan IV (Tokyo Ohka Kogyo Co., Ltd., absorption wavelength: 350 nm and 520 nm)
Low softening point glass powder: lithium oxide 7% by mass, silicon oxide 22% by mass, boron oxide 33% by mass, zinc oxide 3% by mass, aluminum oxide 19% by mass, magnesium oxide 6% by mass, barium oxide 5% by mass, calcium oxide 5% by mass (glass transition temperature 491 ° C., d ₅₀ : 2 μm, d _max : 10 μm)
High softening point glass powder: sodium oxide / 1% by mass, silicon oxide / 40% by mass, boron oxide / 10% by mass, aluminum oxide / 33% by mass, zinc oxide / 4% by mass, calcium oxide / 9% by mass, titanium oxide / 3 mass% (glass transition temperature; 652 ° C., d ₅₀ : 2 μm, d _max : 10 μm)
Oxide particles O-1: transition alumina (θ alumina, AKP-G008, manufactured by Sumitomo Chemical Co., Ltd., refractive index: 1.67, average primary particle size <0.05 μm)
Oxide particle O-2: Transition alumina (γ alumina, AKP-G015 manufactured by Sumitomo Chemical Co., Ltd., refractive index: 1.67, average primary particle diameter <0.05 μm)
Oxide particles O-3: transition alumina (θ alumina, TM-100 manufactured by Daimei Chemical Co., Ltd., refractive index: 1.67, average primary particle size: 0.014 μm)
Oxide particle O-4: Transition alumina (γ-alumina, TM-300 manufactured by Daimei Chemical Co., Ltd., refractive index: 1.67, average primary particle size: 0.007 μm)
Oxide particles O-5: transition alumina (θ alumina, manufactured by Daimei Chemical Co., Ltd. TM-100D, refractive index: 1.67, average primary particle size: 0.014 μm)
Oxide particle O-6: Titanium oxide (rutile type, manufactured by Ishihara Sangyo Co., Ltd., TTO-51 (A), refractive index: 2.71, average primary particle size: 0.02 μm)
The photosensitive paste was produced as follows.

  Photosensitive monomers, photosensitive polymers, photopolymerization initiators, sensitizers, antioxidants and ultraviolet absorbers were weighed in the amounts shown in Table 1, and then γ-BL was added as a solvent as appropriate to adjust the viscosity. Next, inorganic components were adjusted and added at the ratios shown in Table 2, and then kneaded with a three-roller kneader to obtain a photosensitive paste.

D. Production of Evaluation Sample An evaluation sample was produced by the following procedure. Address electrode patterns were formed on a “PD-200” glass substrate (42 inches) manufactured by Asahi Glass Co., Ltd. by a photolithography method using a photosensitive silver paste. Next, a dielectric layer having a thickness of 20 μm was formed on the glass substrate on which the address electrodes were formed by screen printing. Thereafter, the photosensitive paste was uniformly applied on the back plate glass substrate on which the address electrode pattern and the dielectric layer were formed by screen printing until a desired thickness was obtained. In order to avoid the occurrence of pinholes and the like in the coating film, coating and drying were repeated several times or more so that the thickness after drying was 150 μm. Intermediate drying was performed at 100 ° C. for 10 minutes. Next, exposure was performed through an exposure mask. The exposure mask is a chromium mask designed to enable the formation of a stripe-shaped barrier rib pattern in a plasma display with a pitch of 300 μm and a line width of 50 μm. For the exposure, 300 mJ / cm ² ultraviolet exposure was performed with an ultrahigh pressure mercury lamp having an output of 50 mW / cm ² . Thereafter, a 0.3 mass% aqueous solution of monoethanolamine was developed by applying it for 150 seconds in a shower, and was washed with water using a shower spray to remove the uncured space portion. Furthermore, it was held at 590 ° C. for 30 minutes and fired to obtain a sample.
E. Evaluation of reflectance The reflectance in the SCI mode at a wavelength of 550 nm was measured for a sample for evaluation using a spectrocolorimeter “CM-2002” manufactured by Konica Minolta. 50 points in the sample surface were measured, the standard deviation of the reflectance was obtained, and used as an index of the in-plane uniformity of the reflectance. The case where the reflectance was 45% or more was allowed, and the case where the reflectance was less than 45% was made impossible. When the reflectance standard deviation is less than 1.5, the variation is small and good, and when the reflectance standard deviation is 1.5 or more, the variation is large and impossible.
F. Evaluation of partition wall shape D. The cross section of the partition was observed with the scanning electron microscope (Hitachi Ltd. make, S-2400), and the evaluation board | substrate produced by (1) was evaluated. The magnification was 800 times, 50 cross-sections of the partition walls were observed, the partition wall shape was a rectangle or a trapezoidal shape with a thin top portion, and there were no protruding foreign objects of 10 μm or more.
F. D. Evaluation of average secondary particle diameter of aggregated particles After obtaining a paste dry film in the process up to application and drying before exposure by the method described in 1), it was cleaved in a cross section perpendicular to the film surface, and a transmission electron microscope (manufactured by JEOL Ltd., JEM-4000EX). ), Image processing of the observation photograph of the aggregated particles, obtaining a diameter when converted into a circle having the same area as the apparent area of the aggregated particles, performing observation and image processing on 50 aggregated particles, The average value was defined as the average secondary particle size of the aggregated particles.

  Table 3 shows the evaluation results of the photosensitive pastes and partition walls obtained in Examples 1 to 6 and Comparative Examples 1 to 3.

  In Examples 1 to 4, the average secondary particle diameter of the aggregated particles composed of oxide particles is in the range of 0.1 to 5 μm, and in any case, the reflectance is high and the reflectance is in-plane uniform. A partition wall with high properties could be formed.

  In Example 5, since the addition ratio of the oxide particles was small, the reflectance was slightly reduced as compared with Examples 1 to 4, but it was an acceptable level. The in-plane uniformity of reflectivity was also good.

  In Example 6, since the addition ratio of the oxide particles was large, the porosity of the partition wall was high, so that the reflectance was higher than that of Examples 1 to 4, and the reflectance standard deviation was larger, but the acceptable level. Met.

  Comparative Example 1 in which no oxide particles were added was not possible because of low reflectance.

  In Comparative Example 2 in which the average secondary particle diameter of the aggregated particles composed of the oxide particles is larger than 5 μm, there is a protruding foreign material of 10 μm or more on the partition wall, which is impossible.

  In Comparative Example 3 in which titanium oxide having a refractive index greater than 1.8 was added as oxide particles, the refractive index became inconsistent, so that light scattering during exposure was remarkably increased, and a rectangular or narrow trapezoidal partition wall pattern. Was not possible.

  (Comparative Example 4) The oxide particles O-1 were subjected to a dispersion treatment before preparing the paste. Oxide particles O-1, dispersant (polycarboxylic acid ammonium salt), and γ-BL were mixed, stirred, and then supersonic under ice cooling using an ultrasonic crusher (Sonics & Materials, VCX-500, output 500 W). By irradiating with sound waves, a 20 wt% slurry was obtained. It carried out like Example 1 except having used this slurry as oxide particles. Although the oxide particle O-1 added to Example 1 is used, since the average secondary particle diameter of the aggregated particles was smaller than 0.1 μm after the dispersion treatment was performed before the paste was produced, the in-plane reflectivity The uniformity was low and was not possible.

  INDUSTRIAL APPLICABILITY The present invention can be usefully used as a photosensitive paste for forming a partition wall having high reflectance and high in-plane uniformity. Moreover, it can be usefully used as a plasma display in which partition walls having high reflectivity are formed and which has excellent display characteristics such as luminance.

Claims (5)

A photosensitive paste containing at least an inorganic component and a photosensitive organic component, and having an average secondary particle diameter of 0 as an inorganic component composed of oxide particles having a refractive index of 1.40 to 1.80. A photosensitive paste comprising aggregated particles and a low softening point glass powder in the range of 1 to 5 μm. The photosensitive paste according to claim 1, wherein the oxide is transition alumina. The photosensitive paste according to claim 1 or 2, wherein the proportion of oxide particles in the inorganic component is 2 to 8% by volume. A method for forming an insulating pattern, comprising: applying the photosensitive paste according to any one of claims 1 to 3 so that a film thickness after drying becomes 100 μm or more, and at least drying, exposing, developing, and baking. . After applying the photosensitive paste according to any one of claims 1 to 3 on a substrate so that the film thickness after drying becomes 100 μm or more, at least drying, exposing, developing, and baking to form an insulating pattern. A method for producing a flat display panel, characterized by comprising: