WO2012132652A1 - Paste and method for manufacturing panel for flat display - Google Patents
Paste and method for manufacturing panel for flat display Download PDFInfo
- Publication number
- WO2012132652A1 WO2012132652A1 PCT/JP2012/054225 JP2012054225W WO2012132652A1 WO 2012132652 A1 WO2012132652 A1 WO 2012132652A1 JP 2012054225 W JP2012054225 W JP 2012054225W WO 2012132652 A1 WO2012132652 A1 WO 2012132652A1
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- WIPO (PCT)
- Prior art keywords
- softening point
- paste
- mol
- glass powder
- point glass
- Prior art date
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Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- 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
- H01J11/10—AC-PDPs with at least one main electrode being out of contact with the plasma
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- 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
- H01J11/34—Vessels, containers or parts thereof, e.g. substrates
- H01J11/36—Spacers, barriers, ribs, partitions or the like
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J31/00—Cathode ray tubes; Electron beam tubes
- H01J31/08—Cathode ray tubes; Electron beam tubes having a screen on or from which an image or pattern is formed, picked up, converted, or stored
- H01J31/10—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes
- H01J31/12—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes with luminescent screen
- H01J31/15—Image or pattern display tubes, i.e. having electrical input and optical output; Flying-spot tubes for scanning purposes with luminescent screen with ray or beam selectively directed to luminescent anode segments
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- 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
- H01J9/241—Manufacture or joining of vessels, leading-in conductors or bases the vessel being for a flat panel display
- H01J9/242—Spacers between faceplate and backplate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
- H01J2211/20—Constructional details
- H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
- H01J2211/36—Spacers, barriers, ribs, partitions or the like
- H01J2211/366—Spacers, barriers, ribs, partitions or the like characterized by the material
Definitions
- the present invention relates to a paste used for forming an insulating pattern and a method for manufacturing a flat display panel using the paste.
- 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.
- barrier rib paste is repeatedly applied in a pattern by a screen printing plate, dried and then screen printed by baking, masked with a resist on the dried barrier rib material layer, and sandblasted. After shaving, sand blasting method for firing, baking the dried partition material, masking with a resist on the layer, etching method for etching, pressing a mold having a pattern on the coating film of partition paste After the pattern is formed, 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 (photo) Lithography method) is known.
- 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 (photo) Lithography method
- Each of these pattern formation methods is provided with a paste coating film patterned using a paste containing a low softening point glass and an organic component, and the organic component is removed by baking to form an insulating pattern containing a low softening point glass.
- This is a method of forming a partition wall.
- the photosensitive paste method is a method that can cope with an increase in area with high definition and a high cost merit.
- a pattern is formed using a paste containing a low softening point glass and an organic component, and then fired to form partition walls, so that the organic component remains slightly after firing.
- the partition walls are colored, and there is a problem that the display characteristics of the display such as the light emission efficiency and color purity of the panel are affected.
- the organic component remaining in the barrier ribs is generated as a gas in the sealing process in which the front plate and the rear plate are bonded to form a panel, which affects the front plate protective layer and increases the discharge voltage. There is a problem that the reliability of the panel cannot be improved due to the deterioration of the characteristics of the panel and the impurity gas remaining in the panel.
- Patent Document 1 is characterized in that a resin containing a hydroxyl group and a polymerizable unsaturated group is used as an organic component in the paste, for example, a polyol having excellent thermal decomposability at high temperatures.
- Patent Document 2 is characterized in that an acrylic copolymer having a polyalkylene oxide segment having a high oxygen atom content is used as the organic component in order to increase the thermal decomposability of the organic component.
- Patent Document 3 is characterized by the use of a low softening point glass having a glass transition point that is 10 ° C.
- the present invention pays attention to the above-mentioned problems of the prior art, and provides a paste capable of forming a partition wall that has good thermal decomposability of organic components during firing, suppresses adsorption of pyrolyzed products to glass, and has few remaining organic components.
- the purpose is to do.
- Another object of the present invention is to provide a flat display panel that is formed with a partition wall having a small amount of residual organic components, has excellent display characteristics such as luminance and color purity, and has high reliability.
- the present invention has the following configuration. (1) It contains a glass powder having a softening point of 570 to 620 ° C. and an organic component, and the glass powder having a low softening point contains silicon oxide, boron oxide, alkali metal oxide, alkaline earth metal oxide and zinc oxide. And the silicon oxide content in the low softening point glass powder is X (SiO 2 ) (mol%), and the boron oxide content in the low softening point glass powder is X (B 2 O 3 ) (mol%).
- the alkali metal oxide content in the low softening point glass powder is X (M 2 O) (mol%), and the alkaline earth metal oxide content in the low softening point glass powder is X (MO) (mol). %),
- X (ZnO) (mol%) When the zinc oxide content in the low softening point glass powder is X (ZnO) (mol%), the value of A represented by the following formula (1) is in the range of 35 to 46, In addition, the value of B represented by the following formula (2) is 1.5 to 5. Of in the range, and paste the values of C represented by the following formula (3) is being in the range of 24-30.
- A X (SiO 2 ) + X (B 2 O 3 ) ⁇ X (M 2 O) (1)
- B X (ZnO) (2)
- C X (M 2 O) + X (MO) + X (ZnO) (3)
- a method for manufacturing a flat display panel comprising applying a paste according to any one of (1) to (2) above on a substrate and baking to form an insulating pattern.
- a method for producing a flat display panel comprising applying a paste according to (2) above on a substrate, exposing, developing, and baking to form an insulating pattern.
- A X (SiO 2 ) + X (B 2 O 3 ) ⁇ X (M 2 O) (1)
- B X (ZnO) (2)
- C X (M 2 O) + X (MO) + X (ZnO) (3)
- the present invention it is possible to provide a paste capable of forming an insulating pattern with little residual organic components.
- an insulating pattern with a small amount of residual organic components can be formed, and a display panel having excellent display characteristics such as luminance and color purity and high reliability can be stably provided.
- the paste referred to in the present invention includes an inorganic component capable of pattern formation by a method such as a screen printing method, a sand blast method, an etching method, a mold transfer method (imprint method), and a photosensitive paste method (photolithography method). It is a mixture of organic components.
- a photosensitive paste containing a photosensitive organic component as an organic component is preferable.
- the paste of the present invention contains a low softening point glass powder having a softening point of 570 to 620 ° C. as an essential component as an inorganic component.
- the low softening point glass powder having a softening point of 570 to 620 ° C. is the main component of the partition wall, and is fired at a temperature near the softening point of the low softening point glass powder to remove the organic components described later, thereby reducing the low softening point glass.
- a pattern comprising an inorganic component can be obtained.
- the low softening point glass powder in the present invention refers to a glass powder having a softening point in the range of 570 to 620 ° C.
- the softening point is in this range, there is no deformation of the pattern during sintering, and the meltability is also appropriate.
- an insulating pattern is formed on a glass substrate, it is sufficiently softened even when sintered at a relatively low temperature so that problems such as distortion of the substrate do not occur. A pattern can be obtained.
- the softening point is preferably in the range of 575 to 597 ° C, more preferably in the range of 580 to 595 ° C.
- the softening point as used in the present invention can usually be measured using a differential thermal analyzer (DTA).
- DTA differential thermal analyzer
- the endothermic end temperature at the endothermic peak is determined by the tangent method. It can be obtained by extrapolation.
- the refractive index of the low softening point glass powder is preferably 1.45 to 1.65.
- the refractive index in the present invention can be measured by the Becke line detection method, and the refractive index at a wavelength of 436 nm (g-ray of a mercury lamp) at 25 ° C. is defined as the refractive index in the present invention.
- the particle size of the low softening point glass powder used in the paste of the present invention 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. It is preferable that the particle diameter is ⁇ 3.0 ⁇ m and the maximum particle diameter d max is 20 ⁇ m or less.
- the low softening point glass powder used in the paste of the present invention must contain silicon oxide, boron oxide, and alkali metal oxide in terms of oxides as constituent components. Furthermore, the silicon oxide content in the low softening point glass powder is X (SiO 2 ) (mol%), the boron oxide content in the low softening point glass powder is X (B 2 O 3 ) (mol%), and the softening is low.
- the alkali metal oxide content in the point glass powder is X (M 2 O) (mol%), it is essential that the value of A represented by the following formula (1) is in the range of 35 to 46. It is.
- the alkali metal refers to lithium, sodium, potassium, rubidium, and cesium.
- the alkali metal oxide contained as a constituent of the low softening point glass powder of the present invention includes lithium oxide, sodium oxide, and potassium oxide. It is necessary to include one or more of these as essential components, and the total content of lithium oxide, sodium oxide, and potassium oxide to be X (M 2 O) and satisfy the above formula (1).
- the residual organic component can be reduced by setting A to 46 or less.
- A when A is small, the content of the alkali metal oxide is increased, and the partition wall is yellowed after firing.
- it is in the range of 36 to 45, more preferably in the range of 38 to 44.
- Silicon oxide and boron oxide are acidic components
- alkali metal oxides are basic components
- a in the above formula (1) is an index indicating the balance between acidic components and basic components in the glass powder.
- Silicon oxide is a material that forms a glass skeleton. It is effective in improving the denseness, strength and stability of glass, and is effective in reducing the refractive index of glass.
- the thermal expansion coefficient can be controlled to prevent problems such as peeling due to mismatch with the glass substrate.
- the compounding ratio of silicon oxide is preferably 10 to 40 mol%, more preferably 20 to 40 mol%. By setting it to 10 mol% or more, it is possible to suppress the thermal expansion coefficient to be small, to make it difficult for cracks to occur when baked on a glass substrate, and to keep the refractive index low. Moreover, by setting it as 40 mol% or less, a softening point can be restrained low and the baking temperature to a glass substrate can be made low.
- Boron oxide is a material that forms a glass skeleton. It has the effect of lowering the softening point and is effective for lowering the refractive index.
- the compounding ratio of boron oxide is preferably 20 to 45 mol%, more preferably 20 to 40 mol%. By setting it as 20 mol% or more, the softening point can be kept low, baking onto the glass substrate can be facilitated, and the refractive index can be kept low. Moreover, the chemical stability of glass can be maintained by setting it as 45 mol% or less.
- Alkali metal oxides such as lithium oxide, sodium oxide and potassium oxide have an effect of not only facilitating control of the thermal expansion coefficient of the glass but also lowering the softening point.
- the total blending ratio of alkali metal oxides is preferably 10 to 30 mol%, more preferably 10 to 20 mol%. By making it 10 mol% or more, the effect of lowering the softening point of the glass can be obtained. Moreover, chemical stability can be maintained by setting it as 30 mol% or less, a thermal expansion coefficient can be restrained small, and a refractive index can be restrained low.
- the alkali metal it is preferable to select lithium because yellowing due to migration of silver ions can be reduced.
- the low softening point glass powder in the present invention it is essential to further contain 1.5 to 5.5 mol% of zinc oxide in terms of oxide as a constituent component. Since zinc oxide has the effect of lowering the softening point without greatly changing the thermal expansion coefficient of the glass, it is necessary to contain 1.5 mol% or more. Further, when the content is increased, the stability of the glass is lowered, the refractive index is increased, the reactivity with the organic component in the paste is increased, and the paste viscosity is likely to increase with time, so that 5.5 mol. It is necessary to mix
- the low softening point glass powder in the present invention further contains an alkaline earth metal oxide in terms of oxide as a constituent component, and the total of alkali metal oxide, alkaline earth metal oxide and zinc oxide is 24 to It is essential to be 30 mol%.
- alkaline earth metal oxides refer to calcium oxide, strontium oxide, barium oxide, and radium oxide.
- alkaline earth metal oxides include magnesium oxide, calcium oxide, strontium oxide, and barium oxide. Yes, including an alkaline earth metal oxide means containing one or more of these, and the total of these contents is used as the content of the alkaline earth metal oxide.
- Alkali metal oxides, alkaline earth metal oxides, and zinc oxides all have an effect of lowering the softening point, and therefore the total amount thereof must be 24 mol% or more. Moreover, since a refractive index will become high if content rate becomes high, it is necessary to mix
- Alkaline earth metal oxides are effective in adjusting the thermal expansion coefficient and have the effect of lowering the softening point.
- the blending ratio of the alkaline earth metal oxide is preferably 2 to 20 mol%, more preferably 3 to 18 mol%. By making it 2 mol% or more, the effect of lowering the softening point of the glass can be obtained. Moreover, the chemical stability of glass can be maintained and refractive index can be restrained low by setting it as 20 mol% or less.
- it may contain aluminum oxide, titanium oxide, zirconium oxide or the like which has an effect of improving the chemical stability of glass, or bismuth oxide or lead oxide which has an effect of lowering the softening point. good.
- raw materials such as lithium oxide, silicon oxide, boron oxide, barium oxide, magnesium oxide and aluminum oxide as constituent components are mixed so as to have a predetermined composition, and 900 to After melting at 1200 ° C., it is cooled, made into a glass frit, pulverized and classified to a fine powder of 20 ⁇ m or less.
- High purity carbonates, oxides, hydroxides and the like can be used as raw materials.
- 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.
- the constituent components of the low softening point glass powder and the content thereof can be calculated from the raw materials and the blending ratio at the time of glass powder production, but can also be calculated from the glass powder, paste, or partition.
- glass powder it can be quantitatively determined by performing atomic absorption analysis and inductively coupled plasma (ICP) emission spectroscopic analysis.
- ICP inductively coupled plasma
- partition wall it can be quantitatively determined by Auger electron spectroscopy.
- the low softening point glass is distinguished by the difference in density of the SEM image of the partition wall cross section, and elemental analysis is performed by Auger electron spectroscopy.
- ICP emission spectroscopic analysis can be used supplementarily.
- a paste it can be analyzed by the same technique as that for glass powder by isolating the glass powder by operations such as filtration and washing. Or it can analyze by the method similar to a partition by apply
- the calculation method of the content rate of a component from an elemental analysis result is as follows.
- elemental analysis information on the mass ratio of the elements contained in the glass powder is obtained, so based on the atomic weight, the formula weight of the oxide, the number of cations in the oxide composition formula, the mass ratio in terms of oxide, That is, the mass ratio of the constituent components can be calculated.
- Conversion to the molar ratio of the mass ratio of the obtained structural component can be performed by the following formula when Ri: mass% of structural component i, Fi: formula weight of structural component i, and ⁇ : sum of all components. (Ri / Fi) / ⁇ (Ri / Fi) ⁇ 100 (mol%)
- a filler as an inorganic component.
- the filler in the present invention is added to improve the strength of the partition wall, and refers to an inorganic powder that hardly melts and flows even at the firing temperature. Specifically, it refers to an inorganic powder that does not have a softening point, a melting point, or a decomposition temperature at 650 ° C. or lower and exists as a solid at 650 ° C.
- the filler at least one selected from high softening point glass powder having a softening point of 650 to 1200 ° C. and ceramic powder such as cordierite, alumina, silica, magnesia, zirconia, and the like can be used.
- a 50% particle size (average particle diameter) d 50 and the average high softening point glass powder in terms of ease of adjustment of the refractive index in the weight distribution curve is preferable.
- a filler having an average particle size of 0.1 to 3.0 ⁇ m and a maximum particle size of 20 ⁇ m or less can be preferably used.
- the proportion of the low softening point glass powder in the inorganic component is preferably 50% by volume to 98% by volume. It is preferable for the content ratio to be 50% by volume or more because sintering during firing becomes easy and the porosity of the pattern after firing can be kept small. Further, if it is 98% by volume or less, it is possible to control the fluidity of the entire inorganic component at the time of firing, to prevent the deformation of the pattern shape, to improve the mechanical strength of the pattern after firing, This is preferable because there is an advantage that a difficult pattern can be formed.
- the ratio of the low softening point glass powder and filler in the inorganic component can be calculated from the blending ratio of each component at the time of preparing the paste, but 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 fired paste film obtained by firing with a scanning electron microscope.
- the cross section perpendicular to the film surface of the paste dry film or paste fired film may be observed with a scanning electron microscope, and the image analysis may be performed by distinguishing the types of inorganic components according to the density of the image.
- the relationship between the contrast of the image and the inorganic component can be specified by elemental analysis using X-rays.
- an evaluation area of the scanning electron microscope for example, an area of about 20 ⁇ m ⁇ 100 ⁇ m is targeted, and observation may be performed at about 1000 to 3000 times.
- the high softening point glass powder that can be preferably used has, for example, the following composition in oxide notation.
- the refractive index of the filler is preferably 1.45 to 1.65.
- the inorganic component is preferably contained in the solid content of the paste in a total content of 35 to 80% by volume, more preferably 40 to 70% by volume.
- solid content means the organic component except the inorganic component contained in a paste, and a solvent. If the content of the inorganic component is less than 35% by volume, the pattern shrinkage due to firing increases, and the shape tends to be unfavorable. Moreover, since it will become difficult to apply
- the content ratio (volume%) of the inorganic component in the solid content can be controlled by the addition amount (mass%) in consideration of the density of the inorganic component and the organic component when preparing the paste.
- a method of analyzing the content ratio of the inorganic component there are a method of obtaining by thermogravimetry (TGA) and density measurement of the fired film of the inorganic component, or transmission electron of a paste dry film obtained by applying and drying the paste.
- TGA thermogravimetry
- density measurement of the fired film of the inorganic component or transmission electron of a paste dry film obtained by applying and drying the paste.
- image analysis of a microscope observation image There is a method of obtaining by image analysis of a microscope observation image.
- TGA for example, “TGA-50” manufactured by Shimadzu Corporation.
- TGA-50 manufactured by Shimadzu Corporation.
- the ratio of the weight after heating up to 600 ° C. with respect to the weight after evaporation of the solvent (corresponding to the weight of the inorganic component because the organic component is removed)
- the mass ratio of the inorganic component and the organic component is obtained.
- the content ratio can be evaluated by evaluating the density of the inorganic component based on the film thickness, area and mass of the fired film.
- a cross section perpendicular to the film surface of the paste dry film is observed with a transmission electron microscope (for example, “JEM-4000EX” manufactured by JEOL Ltd.).
- the image analysis may be performed by distinguishing the inorganic component and the organic component according to the density of the image.
- an evaluation area of the transmission electron microscope for example, an area of about 20 ⁇ m ⁇ 100 ⁇ m is targeted, and observation may be performed at about 1000 to 3000 times.
- the paste in the present invention needs to contain an organic component.
- the organic component only needs to have an appropriate viscosity when applying the paste, and maintain the pattern shape when the paste is applied and dried as necessary.
- the organic component used in the paste of the present invention is selected by the partition forming process and is not particularly limited.
- a cellulose compound typified by ethyl cellulose, an acrylic polymer typified by polyisobutyl methacrylate, or the like can be used.
- resins such as polyvinyl alcohol, polyvinyl butyral, methacrylic acid ester polymer, acrylic acid ester polymer, acrylic acid ester-methacrylic acid ester copolymer, ⁇ -methylstyrene polymer, butyl methacrylate and the like can be mentioned.
- the paste of the present invention is a photosensitive paste, it is characterized by containing a photosensitive organic component.
- the photosensitive organic component is selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer. 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 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.
- 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 ray here means a ray in a wavelength region of 250 to 1100 nm causing such a chemical reaction.
- an ultraviolet ray such as an ultrahigh pressure mercury lamp or a metal halide lamp, a visible ray such as a halogen lamp, helium—
- a laser beam having a specific wavelength 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.
- 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.
- an acrylic copolymer can be preferably used as the alkali-soluble polymer.
- the acrylic copolymer is a copolymer containing at least an acrylic monomer as a copolymerization component.
- acrylic monomer examples 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,
- a compound having a carbon-carbon double bond can be used, and preferably styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene.
- Styrenes such as chloromethylstyrene and hydroxymethylstyrene, 1-vinyl-2-pyrrolidone and the like.
- an unsaturated acid such as an unsaturated carboxylic acid
- an 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 to 150.
- an acrylic copolymer having a carbon-carbon double bond in the side chain or molecular end may be used in order to increase the reaction rate of the curing reaction by exposure of the photosensitive paste.
- the group having a carbon-carbon double bond include a vinyl group, an allyl group, an acrylic group, and a methacryl group.
- a glycidyl group or an isocyanate group and a carbon-carbon double bond with respect to the mercapto group, amino group, hydroxyl group, and carboxyl group in the acrylic copolymer is 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.
- 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 methyl cellulose or ethyl cellulose, a high molecular weight polyether, or the like.
- a non-photosensitive polymer component as an organic component, for example, a cellulose compound such as methyl cellulose or ethyl cellulose, a high molecular weight polyether, or 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.
- the photosensitive paste used in the present invention preferably further contains a urethane compound.
- 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 an organic component becomes difficult to remain
- Examples of the urethane compound preferably used in the present invention include compounds represented by the following general formula (1).
- 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 to 10.
- 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. Since EO content rate is 70 mass% or less, a softness
- the urethane compound has a carbon-carbon double bond.
- the carbon-carbon double bond of the urethane compound reacts with the carbon-carbon double bond of the other crosslinking agent and is contained in the crosslinked product, the polymerization shrinkage can be further suppressed.
- urethane compound preferably used in the present invention examples 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%) (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like, but are not limited thereto. Moreover, you may use these compounds in mixture.
- the content of the urethane compound is preferably 0.1 to 20% by mass of the organic component excluding the solvent.
- the content is preferably 0.1 to 20% by mass of the organic component excluding the solvent.
- a photoradical initiator that generates radicals upon irradiation with an active light source can be preferably used.
- Specific examples include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4- Methyl diphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloro Acetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyld
- the photopolymerization initiator is added in the range of 0.05 to 20% by mass, more preferably 0.1 to 18% by mass, based on the total amount of the photosensitive monomer and the photosensitive polymer. 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.
- sensitizer examples include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis ( 4-dimethylaminobenzal) -4-methylcyclohexanone, Michler-ketone, 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p- Dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal
- the addition amount is preferably 0.05 to 10% by mass, more preferably 0.1 to 10% by mass with respect to the organic component excluding the solvent. 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.
- an antioxidant has a radical chain inhibiting action, a triplet elimination action, and a hydroperoxide decomposition action.
- 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.
- p-benzoquinone p-benzoquinone, naphthoquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, hydroquinone, pt -Butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butyl-p-cresol, hydroquinone monomethyl ether, ⁇ -naphthol, hydrazine hydrochloride , Trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl- ⁇ -naphthylamine, parabenzylaminophenol, di- ⁇ -naphthylparaphen
- 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.
- an ultraviolet absorber for the photosensitive paste of the present invention.
- an ultraviolet absorber By adding an ultraviolet absorber, 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.
- a photo-fading compound can also be used as an ultraviolet absorber.
- a photochromic compound absorbs light in the wavelength region of actinic rays when irradiated with light in the wavelength region of actinic rays and passes through changes in the chemical structure such as photodegradation and photodenaturation, and then the wavelength region of the active light source The absorbance at is lower than that before irradiation.
- the photo-fading compound used in the present invention is also g.
- Absorption is preferably in the line, h-line, and i-line regions.
- the photo-fading compound 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.
- 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.
- photodegradable dyes include photodegradable dyes, photoacid generators, photobase generators, photodegradable compounds such as nitrone compounds, and photomodifying compounds such as azo dyes and photochromic compounds.
- photoacid generator include onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, diazoketone compounds, and the like.
- the content of the ultraviolet absorber is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass in the photosensitive paste. 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.
- an organic dye as a mark for exposure and development.
- 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.
- the organic dye is preferably 0.001 to 1% by mass with respect to the organic components excluding the solvent.
- an organic solvent in order to adjust the viscosity when applying the paste to the substrate according to the application method.
- 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, ⁇ -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 paste of the present invention is prepared by mixing each component of the inorganic component and each component of the organic component so as to have a predetermined composition, and then performing main kneading using a kneading apparatus such as a three roller. Further, it is also preferable to appropriately filter and degas the paste after the main kneading.
- the method for manufacturing a flat display panel according to the present invention is characterized in that the above-mentioned paste is applied on a substrate and baked to form an insulating pattern. This makes it possible to form an insulating pattern with little residual organic components after firing and no coloration, so that a flat display panel having excellent display characteristics such as luminance and color purity and high reliability can be obtained. it can.
- the method for producing a flat display panel of the present invention is characterized in that the above-mentioned photosensitive paste is applied on a substrate, exposed, developed, and baked to form an insulating pattern.
- the above-mentioned photosensitive paste is applied on a substrate, exposed, developed, and baked to form an insulating pattern.
- the flat display panel of the present invention is a flat display panel having a partition mainly composed of a low softening point glass having a softening point of 570 to 620 ° C., and the low softening point glass includes silicon oxide, boron oxide and alkali metal. It contains an oxide, the silicon oxide content in the low softening point glass is X (SiO 2 ) (mol%), and the boron oxide content in the low softening point glass is X (B 2 O 3 ) (mol%). ), When the alkali metal oxide content in the low softening point glass is X (M 2 O) (mol%), the value of A represented by the following formula (1) is within the range of 35 to 46. It is characterized by being.
- A X (SiO 2 ) + X (B 2 O 3 ) ⁇ X (M 2 O) (1)
- the value of A is preferably in the range of 36 to 45, more preferably in the range of 38 to 44.
- the main component here means a component having the largest volume fraction among all solid components.
- the content ratio of the low softening point glass can be obtained by observing the cross section of the partition wall with an electron microscope and analyzing the cross sectional area of the low softening point glass in the total cross sectional area of the solid component.
- the low softening point glass and other solid components can be distinguished by the difference in light and shade of the image. Further, components can be strictly distinguished by mapping atoms by a technique such as a scanning analysis microscope (SEM-EDX) equipped with an energy dispersive X-ray spectrometer.
- SEM-EDX scanning analysis microscope
- the constituent components and the content of the low softening point glass which is the main component of the partition walls, can be quantitatively determined by Auger electron spectroscopy.
- the low softening point glass is distinguished by the difference in density of the SEM image of the partition wall cross section, and elemental analysis is performed by Auger electron spectroscopy.
- other known analysis means such as selectively cutting out the low softening point glass from the partition wall and performing atomic absorption analysis or inductively coupled plasma (ICP) emission spectroscopic analysis can be used supplementarily.
- the softening point of the low softening point glass which is the main component of the partition walls, can be measured using a differential thermal analyzer (DTA) after selectively cutting the low softening point glass from the partition walls. From the DTA curve obtained by measuring the glass powder, the endothermic end temperature at the endothermic peak can be extrapolated by the tangent method.
- DTA differential thermal analyzer
- the low softening point glass powder which is the main component of the partition wall, contains zinc oxide, and its content is in the range of 1.5 to 5.5 mol%.
- Zinc oxide is characterized by containing 1.5 mol% or more because it has the effect of lowering the softening point without greatly changing the thermal expansion coefficient of the glass. Further, when the content is increased, the stability of the glass is lowered, the refractive index is increased, the reactivity with the organic component in the paste is increased, and the paste viscosity is likely to increase with time, so that 5.5 mol. It is the characteristic to mix
- the low softening point glass powder as the main component of the partition contains an alkali metal oxide, an alkaline earth metal oxide and zinc oxide, and the total content thereof is 24 to 30 mol%. It is in the range of. Alkali metal oxides, alkaline earth metal oxides, and zinc oxide are all effective in lowering the softening point, and are therefore characterized by a total content of 24 mol% or more. When the content rate increases, the refractive index increases. Since it becomes high, it is the characteristic that the total is mix
- the plasma display panel 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 inside. 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.
- 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.
- a transparent dielectric layer and an MgO thin film as a protective film are often formed on the upper layer of the electrode.
- electrodes address electrodes
- 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.
- 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.
- the method for producing the front plate will be described regarding the panel manufacturing process.
- the substrate “PP8” (manufactured by Nippon Electric Glass Co., Ltd.) or “PD200” (manufactured by Asahi Glass Co., Ltd.), which is a heat resistant glass for soda glass or plasma display panel, 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.
- 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.
- 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.
- the conductive powder include metal powder and metal oxide powder.
- 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.
- an electrode paste having a high conductivity for example, a material containing silver as a main component
- the film thicknesses of the fired black electrode paste and the fired conductive paste are each preferably in the range of 1 to 5 ⁇ m.
- the line width after firing is preferably 20 to 100 ⁇ m.
- 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.
- 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.
- 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.
- 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.
- 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.
- a protective film is formed.
- 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.
- 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.
- 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.
- 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.
- a method of forming the dielectric layer there is a method in which a dielectric paste mainly composed of an inorganic component such as glass powder or high softening point glass powder and an organic binder is printed or applied on the whole surface by screen printing, a slit die coater, or the like. is there.
- the partition pattern is not particularly limited, but a lattice shape, a waffle shape, or the like is preferable.
- the photosensitive paste of this invention is apply
- 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.
- the application thickness after drying may be 100 micrometers or more.
- the application thickness after drying may be 100 micrometers or more.
- the coated barrier rib paste is dried and then exposed.
- the exposure is performed through a photomask, as in normal photolithography.
- a method of directly drawing with a laser beam or the like without using a photomask may be used.
- the exposure apparatus a stepper exposure machine, a proximity exposure machine, or the like can be used.
- the active light source used at this time include near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams.
- 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 0.01 to 30 minutes using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm 2.
- development is performed using the difference in solubility in the developer between the exposed and unexposed areas, but usually by dipping, spraying, brushing, or the like.
- an organic solvent in which an organic component in the photosensitive paste can be dissolved can be used.
- development can be performed with an alkaline aqueous solution.
- the alkaline aqueous solution sodium hydroxide, sodium carbonate, potassium hydroxide aqueous solution or the like can be used.
- a general amine compound can be used as the organic alkali.
- Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine.
- the concentration of the alkaline aqueous solution is usually 0.05 to 5% by mass, more preferably 0.1 to 1% by 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. Further, the development temperature during development is preferably 20 to 50 ° C. in terms of process control.
- the partition may be composed of two or more layers.
- the configuration range of the partition wall shape can be expanded three-dimensionally.
- the first layer is applied and exposed in a stripe shape
- 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.
- firing is performed by holding in a firing furnace at a temperature of 520 to 620 ° C. for 10 to 60 minutes to form partition walls.
- the photosensitive paste of the present invention is suitable for the formation of the above-described barrier ribs, and the photosensitive paste of the present invention can form barrier ribs with a small amount of residual organic components, and has excellent display characteristics such as luminance and color purity. A reliable flat display can be manufactured.
- a phosphor is formed using the phosphor paste. It can be formed by a photolithography method using a phosphor paste, a dispenser method, a screen printing method, or the like.
- the thickness of the phosphor is not particularly limited, but is 10 to 30 ⁇ m, more preferably 15 to 25 ⁇ m.
- 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.
- 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 in terms of panel luminance. More preferably Zn 2 SiO 4: is Mn.
- (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.
- a method for manufacturing a plasma display panel 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.
- a plasma display panel can be fabricated by attaching a drive circuit and aging.
- Examples 1 to 16, Comparative Examples 1 to 10 Comparative Examples 1 to 10.
- Photosensitive monomer M-1 trimethylolpropane triacrylate
- Photosensitive monomer M-2 tetrapropylene glycol dimethacrylate
- Low softening point glass powder Glass powder having the composition, softening point, and particle size distribution shown in Tables 2 and 3 (Note that the symbols in the table have the following meanings: SiO 2 : silicon oxide, B 2 O 3 : boron oxide.
- 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% by mass, softening point Ts: 740 ° C., d 50 : 2 ⁇ m, d max : 10 ⁇ m) c.
- the firing conditions were 10 ° C./min to 500 ° C. in air and 15 minutes at 500 ° C. 15 mg of the powder after firing was measured using a pyrolysis gas chromatograph mass spectrometer (GCMS-QP2010Plus, manufactured by Shimadzu Corporation) at 550 ° C. in a He atmosphere, and the residual organic component was determined as the total value of all peak areas derived from the organic component. evaluated. When the total value of the peak areas was 5 ⁇ 10 6 or more, many residual organic components were considered inappropriate.
- GCMS-QP2010Plus pyrolysis gas chromatograph mass spectrometer
- a dielectric layer having a thickness of 20 ⁇ m 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 ⁇ m. 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 so that a vertical pitch of 150 ⁇ m, a vertical line width of 25 ⁇ m, a horizontal pitch of 450 ⁇ m, a horizontal line width of 25 ⁇ m, and a grid-like insulating pattern can be formed in a plasma display.
- Exposure was carried out eight points exposure at 25 mJ / cm 2 intervals in the range of 250 ⁇ 375mJ / cm 2 by varying the exposure time by using a ultra-high pressure mercury lamp with an output of 50 mW / cm 2. Thereafter, a 0.3% by mass aqueous solution of monoethanolamine was developed by showering for 150 seconds and washed with water to remove the uncured space.
- the partition was formed by hold
- F. Yellowing Evaluation A portion of the substrate prepared in E having a partition wall bottom width of 55 ⁇ m was measured with a spectrocolorimeter (“CM-2002” manufactured by Konica Minolta) SCE mode, and a b * value was evaluated. When the b * value is 10 or more, yellowing of the partition walls is extremely inappropriate.
- the viscosity of the paste was measured twice after the first day of production and after storage for 7 days at 23 ° C., and the rate of increase in viscosity after 7 days of storage was calculated based on the viscosity of the first day of production to evaluate the viscosity stability. When the viscosity increase rate after 7 days is 10% or more, the viscosity stability is poor and is not suitable.
- H The partition wall of the substrate manufactured with the minimum bottom partition wall width E was observed, the partition bottom width where peeling did not occur was measured, and the minimum value was defined as the minimum partition wall bottom width.
- the partition top width is about 38 ⁇ m under the production conditions of E, the smaller the minimum partition bottom width is in the range of 38 ⁇ m or more, the more preferable the rectangular partition is formed.
- the minimum partition wall bottom width is 50 ⁇ m or more, a thin partition pattern cannot be formed, which is inappropriate.
- the paste prepared in C was applied on a glass substrate (PD-200, 5 inches manufactured by Asahi Glass Co., Ltd.) with a film thickness of 50 ⁇ m using a blade coater, and then dried at 100 ° C. for 30 minutes. Then, it hold
- arithmetic average roughness (Ra) measured by Surfcom was measured.
- the measurement conditions were ISO-'97 standard “surface roughness measurement”, measurement length: 1 mm, measurement speed: 0.30 mm / s.
- a paste having a surface roughness Ra of 2.0 ⁇ m or more is not suitable because the display characteristics of a panel manufactured using this paste deteriorate.
- Tables 2 and 3 show the evaluation results of the pastes obtained in Examples 1 to 16 and Comparative Examples 1 to 10.
- A is in the range of 35 to 46
- B is in the range of 1.5 to 5.5
- C is in the range of 24 to 30, In some cases, the remaining organic components were small and good.
- the glass has a high content of silicon oxide and boron oxide, and the acid-base balance of the glass is poor.
- the present invention can be usefully used as a paste for forming a partition with a small amount of residual organic components. Further, a partition wall having a small amount of remaining organic components is formed, and it can be effectively used as a flat panel display with excellent display characteristics such as luminance and color purity and high panel reliability.
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Abstract
Description
(1)軟化点570~620℃の低軟化点ガラス粉末および有機成分を含有し、前記低軟化点ガラス粉末が酸化ケイ素、酸化ホウ素、アルカリ金属酸化物、アルカリ土類金属酸化物および酸化亜鉛を含有し、前記低軟化点ガラス粉末中の酸化ケイ素含有率をX(SiO2)(モル%)、前記低軟化点ガラス粉末中の酸化ホウ素含有率をX(B2O3)(モル%)、前記低軟化点ガラス粉末中のアルカリ金属酸化物含有率をX(M2O)(モル%)、前記低軟化点ガラス粉末中のアルカリ土類金属酸化物含有率をX(MO)(モル%)、前記低軟化点ガラス粉末中の酸化亜鉛含有率をX(ZnO)(モル%)とした時に、下記式(1)で表されるAの値が35~46の範囲内であり、かつ、下記式(2)で表されるBの値が1.5~5.5の範囲内であり、かつ、下記式(3)で表されるCの値が24~30の範囲内であることを特徴とするペースト。 In order to solve the above problems, the present invention has the following configuration.
(1) It contains a glass powder having a softening point of 570 to 620 ° C. and an organic component, and the glass powder having a low softening point contains silicon oxide, boron oxide, alkali metal oxide, alkaline earth metal oxide and zinc oxide. And the silicon oxide content in the low softening point glass powder is X (SiO 2 ) (mol%), and the boron oxide content in the low softening point glass powder is X (B 2 O 3 ) (mol%). The alkali metal oxide content in the low softening point glass powder is X (M 2 O) (mol%), and the alkaline earth metal oxide content in the low softening point glass powder is X (MO) (mol). %), When the zinc oxide content in the low softening point glass powder is X (ZnO) (mol%), the value of A represented by the following formula (1) is in the range of 35 to 46, In addition, the value of B represented by the following formula (2) is 1.5 to 5. Of in the range, and paste the values of C represented by the following formula (3) is being in the range of 24-30.
B=X(ZnO) (2)
C=X(M2O)+X(MO)+X(ZnO) (3)
(2)前記有機成分が感光性有機成分を含むことを特徴とする上記(1)に記載のペースト。
(3)基板上に上記(1)~(2)のいずれかに記載のペーストを塗布し、焼成して絶縁性パターンを形成することを特徴とする平面ディスプレイ用パネルの製造方法。
(4)基板上に上記(2)に記載のペーストを塗布し、露光し、現像し、焼成して絶縁性パターンを形成することを特徴とする平面ディスプレイ用パネルの製造方法。
(5)軟化点570~620℃の低軟化点ガラスを主成分とする隔壁を有する平面ディスプレイ用パネルであって、前記低軟化点ガラス粉末が酸化ケイ素、酸化ホウ素、アルカリ金属酸化物、アルカリ土類金属酸化物および酸化亜鉛を含有し、前記低軟化点ガラス粉末中の酸化ケイ素含有率をX(SiO2)(モル%)、前記低軟化点ガラス粉末中の酸化ホウ素含有率をX(B2O3)(モル%)、前記低軟化点ガラス粉末中のアルカリ金属酸化物含有率をX(M2O)(モル%)、前記低軟化点ガラス粉末中のアルカリ土類金属酸化物含有率をX(MO)(モル%)、前記低軟化点ガラス粉末中の酸化亜鉛含有率をX(ZnO)(モル%)とした時に、下記式(1)で表されるAの値が35~46の範囲内であり、かつ、下記式(2)で表されるBの値が1.5~5.5の範囲内であり、かつ、下記式(3)で表されるCの値が24~30の範囲内であることを特徴とする平面ディスプレイ用パネル。 A = X (SiO 2 ) + X (B 2 O 3 ) −X (M 2 O) (1)
B = X (ZnO) (2)
C = X (M 2 O) + X (MO) + X (ZnO) (3)
(2) The paste as described in (1) above, wherein the organic component contains a photosensitive organic component.
(3) A method for manufacturing a flat display panel, comprising applying a paste according to any one of (1) to (2) above on a substrate and baking to form an insulating pattern.
(4) A method for producing a flat display panel, comprising applying a paste according to (2) above on a substrate, exposing, developing, and baking to form an insulating pattern.
(5) A flat display panel having a partition mainly composed of a low softening point glass having a softening point of 570 to 620 ° C., wherein the low softening point glass powder is silicon oxide, boron oxide, alkali metal oxide, alkaline earth A metal oxide and zinc oxide, the silicon oxide content in the low softening point glass powder is X (SiO 2 ) (mol%), and the boron oxide content in the low softening point glass powder is X (B 2 O 3 ) (mol%), the alkali metal oxide content in the low softening point glass powder is X (M 2 O) (mol%), the alkaline earth metal oxide content in the low softening point glass powder When the rate is X (MO) (mol%) and the zinc oxide content in the low softening point glass powder is X (ZnO) (mol%), the value of A represented by the following formula (1) is 35. In the range of -46 and the following formula (2 A plane having a B value represented by the following formula in the range of 1.5 to 5.5 and a C value represented by the following formula (3) in the range of 24 to 30: Display panel.
B=X(ZnO) (2)
C=X(M2O)+X(MO)+X(ZnO) (3) A = X (SiO 2 ) + X (B 2 O 3 ) −X (M 2 O) (1)
B = X (ZnO) (2)
C = X (M 2 O) + X (MO) + X (ZnO) (3)
なお、一般にはアルカリ金属はリチウム、ナトリウム、カリウム、ルビジウム、セシウムを指すが、本発明の低軟化点ガラス粉末の構成成分として含まれるアルカリ金属酸化物とは、酸化リチウム、酸化ナトリウムおよび酸化カリウムを指し、これらのうち1つ以上を必須成分として含み、酸化リチウム、酸化ナトリウムおよび酸化カリウムの合計の含有率をX(M2O)とし、上記式(1)を満たすことが必要である。 A = X (SiO 2 ) + X (B 2 O 3 ) −X (M 2 O) (1)
In general, the alkali metal refers to lithium, sodium, potassium, rubidium, and cesium. The alkali metal oxide contained as a constituent of the low softening point glass powder of the present invention includes lithium oxide, sodium oxide, and potassium oxide. It is necessary to include one or more of these as essential components, and the total content of lithium oxide, sodium oxide, and potassium oxide to be X (M 2 O) and satisfy the above formula (1).
(Ri/Fi)/Σ(Ri/Fi)×100 (モル%)
本発明では、無機成分としてフィラーを添加しても好ましい。本発明におけるフィラーとは、隔壁の強度を改善するために添加されるものであり、焼成温度でも溶融流動しにくい無機粉末を指す。具体的には、650℃以下で軟化点や融点、分解温度を有さず、650℃において固体として存在するような無機粉末をいう。フィラーとして、軟化点が650~1200℃である高軟化点ガラス粉末や、コーディエライト、アルミナ、シリカ、マグネシア、ジルコニアなどのセラミックス粉末から選ばれた少なくとも1種を用いることができる。重量分布曲線における50%粒子径(平均粒子径)d50や平均屈折率の調節のしやすさの点から高軟化点ガラス粉末の使用が好ましい。フィラーはペースト中への分散性や充填性、露光時の光散乱の抑制を考慮し、平均粒子径0.1~3.0μm、最大粒子径20μm以下であるものを好ましく使用することができる。 The calculation method of the content rate of a component from an elemental analysis result is as follows. In elemental analysis, information on the mass ratio of the elements contained in the glass powder is obtained, so based on the atomic weight, the formula weight of the oxide, the number of cations in the oxide composition formula, the mass ratio in terms of oxide, That is, the mass ratio of the constituent components can be calculated. Conversion to the molar ratio of the mass ratio of the obtained structural component can be performed by the following formula when Ri: mass% of structural component i, Fi: formula weight of structural component i, and Σ: sum of all components.
(Ri / Fi) / Σ (Ri / Fi) × 100 (mol%)
In the present invention, it is preferable to add a filler as an inorganic component. The filler in the present invention is added to improve the strength of the partition wall, and refers to an inorganic powder that hardly melts and flows even at the firing temperature. Specifically, it refers to an inorganic powder that does not have a softening point, a melting point, or a decomposition temperature at 650 ° C. or lower and exists as a solid at 650 ° C. As the filler, at least one selected from high softening point glass powder having a softening point of 650 to 1200 ° C. and ceramic powder such as cordierite, alumina, silica, magnesia, zirconia, and the like can be used. Using a 50% particle size (average particle diameter) d 50 and the average high softening point glass powder in terms of ease of adjustment of the refractive index in the weight distribution curve is preferable. In consideration of dispersibility and filling properties in the paste and suppression of light scattering during exposure, a filler having an average particle size of 0.1 to 3.0 μm and a maximum particle size of 20 μm or less can be preferably used.
酸化リチウム、酸化ナトリウムまたは酸化カリウム 0~5質量%
酸化ケイ素 15~50質量%
酸化ホウ素 5~25質量%
酸化亜鉛 0~20質量%
酸化アルミニウム 10~50質量%
酸化マグネシウムまたは酸化カルシウム 1~15質量%
酸化バリウムまたは酸化ストロンチウム 0~10質量%
本発明のペーストを感光性ペーストとする場合、フィラーの屈折率は1.45~1.65であることが好ましい。無機成分と有機成分の屈折率を整合させ、光散乱を抑制することにより高精度のパターン加工が容易になる。 The high 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 0-5% by mass
Silicon oxide 15-50% by mass
Boron oxide 5-25% by mass
Zinc oxide 0-20% by mass
Aluminum oxide 10-50% by mass
Magnesium oxide or calcium oxide 1-15% by mass
Barium oxide or strontium oxide 0-10% by mass
When the paste of the present invention is a photosensitive paste, the refractive index of the filler is preferably 1.45 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.
好ましくない。 The inorganic component is preferably contained in the solid content of the paste in a total content of 35 to 80% by volume, more preferably 40 to 70% by volume. Here, solid content means the organic component except the inorganic component contained in a paste, and a solvent. If the content of the inorganic component is less than 35% by volume, the pattern shrinkage due to firing increases, and the shape tends to be unfavorable. Moreover, since it will become difficult to apply | coat uniformly when it exceeds 80 volume%, it is unpreferable.
Aの値を35~46の範囲内とすることによって、輝度や色純度等の表示特性に優れ、信頼性が高い平面ディスプレイ用パネルとすることができる。Aの値は、好ましくは36~45の範囲内であり、より好ましくは38~44の範囲内である。ここでいう主成分とは、固体成分全体のうち体積分率が最大の成分を意味する。低軟化点ガラスの含有割合は、隔壁の断面を電子顕微鏡で観察し、固体成分の総断面積に占める低軟化点ガラスの断面積を画像解析することにより求めることができる。低軟化点ガラスとその他の固体成分は画像の濃淡の差により区別できる。また、エネルギー分散型X線分光分析装置を備えた走査型分析顕微鏡(SEM-EDX)等の手法により原子をマッピングすることにより、成分を厳密に区別することもできる。 A = X (SiO 2 ) + X (B 2 O 3 ) −X (M 2 O) (1)
By setting the value of A within the range of 35 to 46, a flat display panel having excellent display characteristics such as luminance and color purity and high reliability can be obtained. The value of A is preferably in the range of 36 to 45, more preferably in the range of 38 to 44. The main component here means a component having the largest volume fraction among all solid components. The content ratio of the low softening point glass can be obtained by observing the cross section of the partition wall with an electron microscope and analyzing the cross sectional area of the low softening point glass in the total cross sectional area of the solid component. The low softening point glass and other solid components can be distinguished by the difference in light and shade of the image. Further, components can be strictly distinguished by mapping atoms by a technique such as a scanning analysis microscope (SEM-EDX) equipped with an energy dispersive X-ray spectrometer.
(実施例1~16、比較例1~10)
A.ガラス粉末の粒度分布評価
粒度分布測定装置(日機装株式会社製「MT3300」)を用いて、ガラス粉末の平均粒子径d50と、最大粒子径dmaxを評価した。水を満たした試料室にガラス粉末を投入し、300秒間、超音波処理を行った後に測定を行った。
B.ガラス粉末の軟化点評価
示差熱分析装置(株式会社リガク製「差動型示差熱天秤TG8120」)を用いて、アルミナ粉末を標準試料として室温から20℃/分で昇温して得られたDTA曲線より、吸熱ピークにおける吸熱終了温度を接線法により外挿して軟化点Tsを求めた。
C.ペーストの作製
以下の手順でペーストを作製した。
a.有機成分
以下の原料からなる有機固形分を表1に示す重量比で秤量、混合し、有機固形分40.1重量部に対して有機溶媒(γ-ブチロラクタム)42重量部を加え、混合、撹拌して有機ビヒクルを作製した。
有機固形分の組成:
感光性モノマM-1(トリメチロールプロパントリアクリレート):6重量部
感光性モノマM-2(テトラプロピレングリコールジメタクリレート):6重量部
感光性ポリマ(メタクリル酸/メタクリル酸メチル/スチレン=40/40/30からなる共重合体のカルボキシル基に対して0.4当量のグリシジルメタクリレートを付加反応させたもの、重量平均分子量43000、酸価100):18重量部
光重合開始剤(2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-1-ブタノン、BASF社製 IC369(商品名)):5重量部
増感剤(2,4-ジエチルチオキサントン):1重量部
酸化防止剤(1,6-ヘキサンジオール-ビス[(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]):4重量部
紫外線吸収剤(スダンIV(東京応化工業株式会社製、吸収波長;350nmおよび520nm):0.1重量部 Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to this.
(Examples 1 to 16, Comparative Examples 1 to 10)
A. Evaluation of Particle Size Distribution of Glass Powder Using a particle size distribution measuring device (“MT3300” manufactured by Nikkiso Co., Ltd.), 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. Evaluation of softening point of glass powder DTA obtained by heating from room temperature to 20 ° C / min using alumina powder as a standard sample using a differential thermal analyzer (“Differential Differential Thermal Balance TG8120” manufactured by Rigaku Corporation) From the curve, the endothermic end temperature at the endothermic peak was extrapolated by the tangent method to obtain the softening point Ts.
C. Preparation of paste A paste was prepared according to the following procedure.
a. Organic solids composed of raw materials below the organic component are weighed and mixed in the weight ratio shown in Table 1, and 42 parts by weight of organic solvent (γ-butyrolactam) is added to 40.1 parts by weight of organic solids, and mixed and stirred. Thus, an organic vehicle was produced.
Composition of organic solids:
Photosensitive monomer M-1 (trimethylolpropane triacrylate): 6 parts by weight Photosensitive monomer M-2 (tetrapropylene glycol dimethacrylate): 6 parts by weight Photopolymer (methacrylic acid / methyl methacrylate / styrene = 40/40) / 30, a copolymer obtained by addition reaction of 0.4 equivalent of glycidyl methacrylate with respect to the carboxyl group, weight average molecular weight 43000, acid value 100): 18 parts by weight photopolymerization initiator (2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -1-butanone, manufactured by BASF IC369 (trade name)): 5 parts by weight sensitizer (2,4-diethylthioxanthone): 1 part by weight antioxidant (1 , 6-Hexanediol-bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) : 4 parts by weight UV absorber (Sudan IV (manufactured by Tokyo Ohka Kogyo Co., Ltd., absorption wavelength: 350 nm and 520 nm)): 0.1 parts by weight
以下の組成の低軟化点ガラス粉末80体積%と高軟化点ガラス粉末20体積%を混合し、無機成分として用いた。
低軟化点ガラス粉末:表2、表3記載の組成、軟化点、粒度分布のガラス粉末(なお、表中の記号は以下の意味を有する。SiO2:酸化ケイ素、B2O3:酸化ホウ素、ZnO:酸化亜鉛、Li2O:酸化リチウム、Na2O:酸化ナトリウム、K2O:酸化カリウム、MgO:酸化マグネシウム、CaO:酸化カルシウム、BaO:酸化バリウム、Al2O3:酸化アルミニウム)
高軟化点ガラス粉末(酸化ナトリウム:1質量%、酸化ケイ素:40質量%、酸化ホウ素:10質量%、酸化アルミニウム:33質量%、酸化亜鉛:4質量%、酸化カルシウム:9質量%、酸化チタン:3質量%、軟化点Ts:740℃、d50:2μm、dmax:10μm)
c.ペーストの調整
上のようにして得た有機ビヒクルと無機粉末を混合し、有機溶媒を除いた全固形分中の有機固形分の割合が42体積%、無機成分の割合が58体積%となるよう調整、添加した後3本ローラー混練機にて混練し、感光性ペーストとした。
D.残存有機成分量の評価
表2、表3記載のガラス粉末20gとエチルセルロース溶液(エチルセルロース:25質量%、γ-BL:75質量%)40gを混合したものを250mLアルミ容器に0.75g入れ、アルミ蓋をかぶせ密閉し、焼成した。焼成条件は、空気中で500℃まで10℃/分で昇温、500℃で15分キープとした。焼成後の粉末15mgを熱分解ガスクロマトグラフ質量分析計(島津製作所製GCMS-QP2010Plus)を用いて550℃、He雰囲気下で測定し、有機成分由来のすべてのピーク面積の合計値で残存有機成分を評価した。ピーク面積の合計値が5×106以上である場合は、残存有機成分が多く不適とした。
E.評価用基板の作製
評価用基板は以下の手順にて作製した。旭硝子株式会社製“PD-200”ガラス基板(42インチ)上に、感光性銀ペーストを用いたフォトリソグラフィ法によりアドレス電極パターンを形成した。次いで、アドレス電極が形成されたガラス基板上に誘電体層をスクリーン印刷法により20μmの厚みで形成した。しかる後、感光性ペーストをスクリーン印刷法によりアドレス電極パターンおよび誘電体層が形成された背面板ガラス基板上に所望の厚みになるまで均一に塗布した。塗布膜にピンホールなどの発生を回避するために塗布・乾燥を数回以上繰り返し行い、乾燥後の厚みが150μmとなるようにした。途中の乾燥は100℃で10分行った。次に露光マスクを介して露光を行った。露光マスクは、縦ピッチ150μm、縦線幅25μm、横ピッチ450μm、横線幅25μm、プラズマディスプレイにおける格子状の絶縁性パターン形成が可能になるように設計したクロムマスクである。露光は、50mW/cm2の出力の超高圧水銀灯を用いて露光時間を変更することによって250~375mJ/cm2の範囲内で25mJ/cm2間隔で8点露光を行った。その後、モノエタノールアミンの0.3質量%水溶液を150秒間シャワーすることにより現像し、水洗浄して光硬化していないスペース部分を除去した。さらに、590℃で30分保持して焼成することにより隔壁を形成し、評価用基板を得た。
F.黄変評価
Eで作製した基板のうち、隔壁底部幅が55μmとなる箇所を分光測色計(コニカミノルタ社製「CM-2002」)SCEモードで測定し、b*値を評価した。b*値が10以上である場合は、隔壁の黄変が著しく不適である。
G.粘度安定性
デジタル演算機能付きB型粘度計(米国ブルックフィールド製、DV-II)を用いて、Cで作製したペーストの温度25℃、回転数3rpmにおける粘度を測定した。ペーストの粘度を作製初日と23℃下7日間保管後の2回測定し、作製初日の粘度を基準に、7日間保管後の粘度の上昇率を計算し、粘度安定性を評価した。7日後粘度上昇率が10%以上である場合は、粘度安定性が悪く不適である。
H.最小底部隔壁幅
Eで作製した基板の隔壁を観察し、はがれが発生しなかった隔壁底部幅を測定し、その最小値を最小隔壁底部幅とした。Eの作製条件では隔壁頂部幅は約38μmとなるので、最小隔壁底部幅が38μm以上の範囲で小さいほど矩形の隔壁が形成されることになるため好ましい。最小隔壁底部幅が50μm以上である場合は、細い隔壁パターンを形成できず不適である。
I.表面粗さ評価
Cで作製したペーストをブレードコーターによりガラス基板(旭硝子株式会社製PD-200、5インチ)上に膜厚50μmで塗布後、100℃30分間乾燥した。その後、590℃で30分保持して焼成し、表面粗さ評価用サンプルを作製した。表面粗さは、サーフコム(東京精密製「1400D」)による算術平均粗さ(Ra)を測定した。測定条件は、ISO-‘97規格「表面粗さ測定」で測定長:1mm、測定速度:0.30mm/sとした。表面粗さRaが2.0μm以上となるペーストは、このペーストを用いて製造したパネルの表示特性が悪化するため不適である。 b. 80% by volume of a low softening point glass powder having a composition below the inorganic component and 20% by volume of a high softening point glass powder were mixed and used as an inorganic component.
Low softening point glass powder: Glass powder having the composition, softening point, and particle size distribution shown in Tables 2 and 3 (Note that the symbols in the table have the following meanings: SiO 2 : silicon oxide, B 2 O 3 : boron oxide. , ZnO: zinc oxide, Li 2 O: lithium oxide, Na 2 O: sodium oxide, K 2 O: potassium oxide, MgO: magnesium oxide, CaO: calcium oxide, BaO: barium oxide, Al 2 O 3: aluminum oxide)
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% by mass, softening point Ts: 740 ° C., d 50 : 2 μm, d max : 10 μm)
c. Preparation of Paste The organic vehicle and inorganic powder obtained as described above are mixed so that the organic solid content in the total solid content excluding the organic solvent is 42% by volume, and the inorganic component content is 58% by volume. After adjustment and addition, the mixture was kneaded with a three-roller kneader to obtain a photosensitive paste.
D. Evaluation of residual organic component amount 0.75 g of a mixture of 20 g of the glass powder listed in Tables 2 and 3 and 40 g of an ethylcellulose solution (ethylcellulose: 25% by mass, γ-BL: 75% by mass) was placed in a 250 mL aluminum container, and aluminum Covered with lid, sealed and baked. The firing conditions were 10 ° C./min to 500 ° C. in air and 15 minutes at 500 ° C. 15 mg of the powder after firing was measured using a pyrolysis gas chromatograph mass spectrometer (GCMS-QP2010Plus, manufactured by Shimadzu Corporation) at 550 ° C. in a He atmosphere, and the residual organic component was determined as the total value of all peak areas derived from the organic component. evaluated. When the total value of the peak areas was 5 × 10 6 or more, many residual organic components were considered inappropriate.
E. Production of Evaluation Substrate An evaluation substrate 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 photolithography 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 so that a vertical pitch of 150 μm, a vertical line width of 25 μm, a horizontal pitch of 450 μm, a horizontal line width of 25 μm, and a grid-like insulating pattern can be formed in a plasma display. Exposure was carried out eight points exposure at 25 mJ / cm 2 intervals in the range of 250 ~ 375mJ / cm 2 by varying the exposure time by using a ultra-high pressure mercury lamp with an output of 50 mW / cm 2. Thereafter, a 0.3% by mass aqueous solution of monoethanolamine was developed by showering for 150 seconds and washed with water to remove the uncured space. Furthermore, the partition was formed by hold | maintaining and baking at 590 degreeC for 30 minutes, and the board | substrate for evaluation was obtained.
F. Yellowing Evaluation A portion of the substrate prepared in E having a partition wall bottom width of 55 μm was measured with a spectrocolorimeter (“CM-2002” manufactured by Konica Minolta) SCE mode, and a b * value was evaluated. When the b * value is 10 or more, yellowing of the partition walls is extremely inappropriate.
G. Viscosity stability Using a B-type viscometer with digital arithmetic function (Brookfield, USA, DV-II), the viscosity of the paste prepared in C at a temperature of 25 ° C. and a rotation speed of 3 rpm was measured. The viscosity of the paste was measured twice after the first day of production and after storage for 7 days at 23 ° C., and the rate of increase in viscosity after 7 days of storage was calculated based on the viscosity of the first day of production to evaluate the viscosity stability. When the viscosity increase rate after 7 days is 10% or more, the viscosity stability is poor and is not suitable.
H. The partition wall of the substrate manufactured with the minimum bottom partition wall width E was observed, the partition bottom width where peeling did not occur was measured, and the minimum value was defined as the minimum partition wall bottom width. Since the partition top width is about 38 μm under the production conditions of E, the smaller the minimum partition bottom width is in the range of 38 μm or more, the more preferable the rectangular partition is formed. When the minimum partition wall bottom width is 50 μm or more, a thin partition pattern cannot be formed, which is inappropriate.
I. Surface Roughness Evaluation The paste prepared in C was applied on a glass substrate (PD-200, 5 inches manufactured by Asahi Glass Co., Ltd.) with a film thickness of 50 μm using a blade coater, and then dried at 100 ° C. for 30 minutes. Then, it hold | maintained at 590 degreeC for 30 minutes and baked, and the sample for surface roughness evaluation was produced. For the surface roughness, arithmetic average roughness (Ra) measured by Surfcom (Tokyo Seimitsu "1400D") was measured. The measurement conditions were ISO-'97 standard “surface roughness measurement”, measurement length: 1 mm, measurement speed: 0.30 mm / s. A paste having a surface roughness Ra of 2.0 μm or more is not suitable because the display characteristics of a panel manufactured using this paste deteriorate.
Claims (5)
- 軟化点570~620℃の低軟化点ガラス粉末および有機成分を含有し、前記低軟化点ガラス粉末が酸化ケイ素、酸化ホウ素、アルカリ金属酸化物、アルカリ土類金属酸化物および酸化亜鉛を含有し、前記低軟化点ガラス粉末中の酸化ケイ素含有率をX(SiO2)(モル%)、前記低軟化点ガラス粉末中の酸化ホウ素含有率をX(B2O3)(モル%)、前記低軟化点ガラス粉末中のアルカリ金属酸化物含有率をX(M2O)(モル%)、前記低軟化点ガラス粉末中のアルカリ土類金属酸化物含有率をX(MO)(モル%)、前記低軟化点ガラス粉末中の酸化亜鉛含有率をX(ZnO)(モル%)とした時に、下記式(1)で表されるAの値が35~46の範囲内であり、かつ、下記式(2)で表されるBの値が1.5~5.5の範囲内であり、かつ、下記式(3)で表されるCの値が24~30の範囲内であることを特徴とするペースト。
A=X(SiO2)+X(B2O3)-X(M2O) (1)
B=X(ZnO) (2)
C=X(M2O)+X(MO)+X(ZnO) (3) A low softening point glass powder having a softening point of 570 to 620 ° C. and an organic component, wherein the low softening point glass powder contains silicon oxide, boron oxide, alkali metal oxide, alkaline earth metal oxide and zinc oxide; The silicon oxide content in the low softening point glass powder is X (SiO 2 ) (mol%), the boron oxide content in the low softening point glass powder is X (B 2 O 3 ) (mol%), the low The alkali metal oxide content in the softening point glass powder is X (M 2 O) (mol%), the alkaline earth metal oxide content in the low softening point glass powder is X (MO) (mol%), When the zinc oxide content in the low softening point glass powder is X (ZnO) (mol%), the value of A represented by the following formula (1) is in the range of 35 to 46, and The value of B represented by the formula (2) is in the range of 1.5 to 5.5. An inner and paste the values of C represented by the following formula (3) is being in the range of 24-30.
A = X (SiO 2 ) + X (B 2 O 3 ) −X (M 2 O) (1)
B = X (ZnO) (2)
C = X (M 2 O) + X (MO) + X (ZnO) (3) - 前記有機成分が感光性有機成分を含むことを特徴とする請求項1に記載のペースト。 The paste according to claim 1, wherein the organic component includes a photosensitive organic component.
- 基板上に請求項1~2のいずれかに記載のペーストを塗布し、焼成して絶縁性パターンを形成することを特徴とする平面ディスプレイ用パネルの製造方法。 A method for producing a flat display panel, wherein the paste according to any one of claims 1 and 2 is applied onto a substrate and baked to form an insulating pattern.
- 基板上に請求項2に記載のペーストを塗布し、露光し、現像し、焼成して絶縁性パターンを形成することを特徴とする平面ディスプレイ用パネルの製造方法。 A method for producing a flat display panel, comprising applying a paste according to claim 2 on a substrate, exposing, developing, and baking to form an insulating pattern.
- 軟化点570~620℃の低軟化点ガラスを主成分とする隔壁を有する平面ディスプレイ用パネルであって、前記低軟化点ガラス粉末が酸化ケイ素、酸化ホウ素、アルカリ金属酸化物、アルカリ土類金属酸化物および酸化亜鉛を含有し、前記低軟化点ガラス粉末中の酸化ケイ素含有率をX(SiO2)(モル%)、前記低軟化点ガラス粉末中の酸化ホウ素含有率をX(B2O3)(モル%)、前記低軟化点ガラス粉末中のアルカリ金属酸化物含有率をX(M2O)(モル%)、前記低軟化点ガラス粉末中のアルカリ土類金属酸化物含有率をX(MO)(モル%)、前記低軟化点ガラス粉末中の酸化亜鉛含有率をX(ZnO)(モル%)とした時に、下記式(1)で表されるAの値が35~46の範囲内であり、かつ、下記式(2)で表されるBの値が1.5~5.5の範囲内であり、かつ、下記式(3)で表されるCの値が24~30の範囲内であることを特徴とする平面ディスプレイ用パネル。
A=X(SiO2)+X(B2O3)-X(M2O) (1)
B=X(ZnO) (2)
C=X(M2O)+X(MO)+X(ZnO) (3) A flat display panel having a partition mainly composed of a low softening point glass having a softening point of 570 to 620 ° C., wherein the low softening point glass powder comprises silicon oxide, boron oxide, alkali metal oxide, alkaline earth metal oxidation And the zinc oxide content in the low softening point glass powder is X (SiO 2 ) (mol%), and the boron oxide content in the low softening point glass powder is X (B 2 O 3 ) (Mol%), the alkali metal oxide content in the low softening point glass powder is X (M 2 O) (mol%), the alkaline earth metal oxide content in the low softening point glass powder is X (MO) (mol%), when the zinc oxide content in the low softening point glass powder is X (ZnO) (mol%), the value of A represented by the following formula (1) is 35 to 46 Within the range and represented by the following formula (2) A flat display panel, wherein the value of B is in the range of 1.5 to 5.5 and the value of C represented by the following formula (3) is in the range of 24 to 30: .
A = X (SiO 2 ) + X (B 2 O 3 ) −X (M 2 O) (1)
B = X (ZnO) (2)
C = X (M 2 O) + X (MO) + X (ZnO) (3)
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CN2012800118144A CN103415480A (en) | 2011-03-28 | 2012-02-22 | Paste and method for manufacturing panel for flat display |
KR1020137017642A KR101883192B1 (en) | 2011-03-28 | 2012-02-22 | Paste and method for manufacturing panel for flat display |
JP2012513107A JP5158289B2 (en) | 2011-03-28 | 2012-02-22 | Paste and flat panel display manufacturing method |
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EP2857368A4 (en) * | 2012-05-25 | 2016-02-17 | Toray Industries | Partition paste, method for manufacturing member having partitions, and members having partition |
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CN108886847B (en) | 2016-03-28 | 2021-02-12 | 东洋制罐集团控股株式会社 | Substrate for flexible device and method for producing the same |
CN107117819B (en) * | 2017-06-06 | 2020-06-09 | 长春理工大学 | Lead-free high-volume resistivity low-temperature sealing glass |
CN108766664A (en) * | 2018-05-15 | 2018-11-06 | 王召惠 | A kind of preparation method of Modified Activated Carbon element base electrode paste |
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JP2006117440A (en) * | 2004-10-19 | 2006-05-11 | Central Glass Co Ltd | Lead-free glass having low melting point |
JP2011225439A (en) * | 2010-03-31 | 2011-11-10 | Nihon Yamamura Glass Co Ltd | Lead-free glass composition |
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JPH1152561A (en) | 1997-08-08 | 1999-02-26 | Toray Ind Inc | Photosensitive paste |
JP2000016835A (en) * | 1998-06-30 | 2000-01-18 | Toray Ind Inc | Insulation paste for display |
JP2001305729A (en) | 2000-04-18 | 2001-11-02 | Daicel Chem Ind Ltd | Water or dilute alkali developable photo-curable resin composition |
KR100772653B1 (en) * | 2005-10-14 | 2007-11-02 | 주식회사 휘닉스피디이 | Photosensitivity lead free glass composition for barrier rib of plasma display panel and plasma display panel comprising barrier rib comprising same |
JP2008050594A (en) | 2006-07-26 | 2008-03-06 | Sekisui Chem Co Ltd | Binder resin composition |
JP2008195572A (en) * | 2007-02-14 | 2008-08-28 | Sumitomo Chemical Co Ltd | Glass paste for partition in plasma display |
EP2416341B1 (en) * | 2009-03-31 | 2014-12-31 | Toray Industries, Inc. | Flat-panel display member, and paste for the uppermost layer of partition wall of flat-panel display member |
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JP2006117440A (en) * | 2004-10-19 | 2006-05-11 | Central Glass Co Ltd | Lead-free glass having low melting point |
JP2011225439A (en) * | 2010-03-31 | 2011-11-10 | Nihon Yamamura Glass Co Ltd | Lead-free glass composition |
Cited By (2)
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EP2857368A4 (en) * | 2012-05-25 | 2016-02-17 | Toray Industries | Partition paste, method for manufacturing member having partitions, and members having partition |
US9481601B2 (en) | 2012-05-25 | 2016-11-01 | Toray Industries, Inc. | Barrier rib paste, method of manufacturing member including barrier rib, and member including barrier rib |
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JP5158289B2 (en) | 2013-03-06 |
KR101883192B1 (en) | 2018-07-30 |
CN103415480A (en) | 2013-11-27 |
TW201245090A (en) | 2012-11-16 |
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