TWI549921B - Paste and method for manufacturing panel of flat-panel display - Google Patents

Description

Method for manufacturing paste and panel for flat panel display

The present invention relates to a paste used in forming an insulating pattern and a method of manufacturing a panel for a flat panel display using the paste.

In recent years, development of flat panel displays such as plasma display panels, field emission displays, fluorescent display tubes, liquid crystal display devices, electroluminescence displays, and light-emitting diodes has been rapidly advanced. In the flat display, the plasma display is displayed by generating a plasma discharge between the anode electrode and the cathode electrode in a discharge space provided between the front glass substrate and the back glass substrate. Ultraviolet rays generated by the gas enclosed in the discharge space are irradiated onto the phosphor provided in the discharge space. A gas discharge type display such as a plasma display or a fluorescent display tube must have an insulating spacer that is useful to separate the discharge space. Moreover, a field emission type display such as a field emission display necessarily requires an insulating spacer for isolating the gate electrode from the cathode.

A method of forming the separators is known in which a separator paste is applied in a pattern by a screen printing plate and dried, and then subjected to a screen printing method of calcination; a blasting method in which a layered material is removed by sandblasting and then calcined; after the dried separator material is calcined, the layer is covered by a resist and an etching method is performed; After the pattern of the mold is pressed against the coating film of the separator paste to form a pattern, the mold transfer method (imprint method) for baking is performed, and the separator material containing the photosensitive paste material is applied and dried. Secondly, exposure and development A photosensitive paste method (photolithography method) or the like which is subjected to calcination after the treatment. In the pattern forming method, a patterned paste coating film is provided by using a paste containing a low softening point glass and an organic component, and the organic component is removed by calcination to form an insulating pattern containing a low softening point glass. The method of the partition. Among them, the photosensitive paste method is a method capable of coping with a large area with high precision, and is a method with high cost advantage.

In the prior formation method, a pattern is formed by using a paste containing a low-softening point glass and an organic component, and then calcined to form a separator, so that a trace amount of an organic component remains after calcination. If there are many remaining organic components, there is a problem in that the spacer is colored, which affects the display characteristics of the display such as the luminous efficiency and the color purity of the panel. In addition, in the plasma display, there is a problem that in the step of sealing the front panel and the back panel, the organic component remaining on the separator is generated as a gas, which affects the protective layer of the front panel. The characteristics such as the rise in the discharge voltage are deteriorated, or the reliability of the panel cannot be improved due to the residual impurity gas remaining in the panel.

Therefore, in order to produce a display having excellent display characteristics such as brightness and color purity and high panel reliability, various methods for reducing residual organic components after firing have been proposed (see Patent Document 1 to Patent Document 3). Patent Document 1 is characterized in that a resin containing a hydroxyl group and a polymerizable unsaturated group, for example, a polyol having excellent thermal decomposition property at a high temperature is used as an organic component in the paste. Patent Document 2 is characterized in that an acrylic copolymer having a polyoxyalkylene segment having a high oxygen atom content is used as an organic component in order to improve the thermal decomposition property of the organic component. Patent Document 3 is characterized in that, in order to The machine component decomposition product does not remain in the glass, and a low softening point glass having a glass transition point higher than the temperature at which the organic component reduction rate reaches 80% is used at 10 ° C or higher. However, these components can reduce the component which causes thermal decomposition defects in the residual organic component, and since the thermal decomposition product cannot be inhibited from adsorbing on the glass, there is a problem that the residual organic component of the separator is insufficient. .

Prior technical literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2001-305729

Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-50594

Patent Document 3: Japanese Patent Laid-Open No. Hei 11-52561

Accordingly, the present invention has been made in view of the above problems of the prior art, and an object thereof is to provide a paste which is excellent in thermal decomposition property of an organic component during calcination, which inhibits adsorption of a thermally decomposed substance on glass, and can form a residual organic component. Less partition. Further, a panel for a flat panel display is provided which has a separator having a small amount of residual organic components, and is excellent in display characteristics such as brightness and color purity, and has high reliability.

The present invention has the following configuration in order to solve the above problems.

(1) A paste comprising: a low-softening point glass powder having a softening point of 570 ° C to 620 ° C and an organic component, the low-softening point glass powder containing cerium oxide, boron oxide, an alkali metal oxide, an alkaline earth The metal oxide and the zinc oxide have a cerium oxide content in the low-softening point glass powder as X (SiO ₂ ) (mol%), and a boron oxide content in the low-softening point glass powder. X(B ₂ O ₃ ) (mol%), the alkali metal oxide content in the low-softening point glass powder is set to X (M ₂ O) (mol%), and the low-softening point glass powder is used When the alkaline earth metal oxide content is X (MO) (mol%) and the zinc oxide content in the low softening point glass powder is X (ZnO) (mol%), the following formula (1) The value of A is in the range of 35 to 46, and the value of B represented by the following formula (2) is in the range of 1.5 to 5.5, and the value of C represented by the following formula (3) is 24 Within the range of ~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).

(2) The paste according to the above (1), wherein the organic component contains a photosensitive organic component.

(3) A method of producing a panel for a flat panel display, characterized in that the paste according to the above (1) or (2) is applied onto a substrate and fired to form an insulating pattern.

(4) A method for producing a panel for a flat panel display, comprising applying the paste according to the above (2) to a substrate, exposing, developing, and firing to form an insulating pattern.

(5) A panel for a flat panel display, which is a panel for a flat panel display having a separator having a low softening point glass having a softening point of 570 ° C to 620 ° C as a main component, wherein the low softening point glass powder contains The cerium oxide, the boron oxide, the alkali metal oxide, the alkaline earth metal oxide, and the zinc oxide, wherein the cerium oxide content in the low-softening point glass powder is X (SiO ₂ ) (mol%), which is low The content of boron oxide in the softening point glass powder is X (B ₂ O ₃ ) (mol%), and 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%), 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 in the range of 35 to 46, and the value of B represented by the following formula (2) is in the range of 1.5 to 5.5, and the following The value of C represented by the 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).

According to the present invention, it is possible to provide a paste capable of forming an insulating pattern in which a small amount of organic components remain. Further, it is possible to stably provide a panel for a display which is formed with an insulating pattern having a small amount of residual organic components, and is excellent in display characteristics such as brightness and color purity, and has high reliability.

The paste in the present invention is a screen printing method, a sandblasting method, an etching method, a mold transfer method (imprint method), a photosensitive paste method (photolithography method). A mixture of an inorganic component and an organic component which are patterned by a method. When a high-definition insulating pattern such as a separator for forming a plasma display is used, 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 ° C to 620 ° C as an inorganic component as an essential component. The low softening point glass powder having a softening point of 570 ° C to 620 ° C is a main component of the separator, and is calcined at a temperature near the softening point of the glass powder of the low softening point to remove the organic component described later, thereby obtaining a low content including Softening the pattern of the inorganic components of the glass.

The low softening point glass powder in the present invention means a glass powder having a softening point in the range of 570 ° C to 620 ° C. By setting the softening point within this range, there is no pattern deformation at the time of sintering, and the meltability is also suitable. Further, particularly in the case where an insulating pattern is formed on a glass substrate, even when sintering is performed at a relatively low temperature so as not to cause deformation of the substrate or the like, sufficient softening can be performed, and thus it is possible to obtain An insulating pattern with a small surface roughness. The softening point is preferably in the range of 575 ° C to 597 ° C, more preferably in the range of 580 ° C to 595 ° C.

The softening point in the present invention can be generally measured by using a differential thermal analyzer (DTA). For example, the DTA curve obtained by measuring the glass powder can be obtained by extrapolating the endothermic end temperature in the endothermic peak by a tangent method.

In the case where the paste of the present invention is used as a photosensitive paste, it is preferred that the low softening point glass powder has a refractive index of 1.45 to 1.65. By making inorganic The composition has the same refractive index as the organic component, and suppresses light scattering to facilitate high-precision pattern processing. The refractive index in the present invention can be measured by the Becker line detection method, and the refractive index at a wavelength of 436 nm (g line of a mercury lamp) at 25 ° C is taken as the refractive index of the present invention.

The particle diameter of the low-softening point glass powder used in the paste of the present invention can be selected in consideration of the shape of the pattern to be produced, and it is preferred that the 50% particle diameter (average particle diameter) d ₅₀ in the weight distribution curve is 0.1 μm to 3.0 μm, and the maximum particle diameter d _max is 20 μm or less.

The low-softening point glass powder used in the paste of the present invention must contain, as an oxide, cerium oxide, boron oxide, or an alkali metal oxide as a constituent component. Further, the content of cerium oxide 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) When the alkali metal oxide content in the low-softening point glass powder is X (M ₂ O) (mol%), the value of A represented by the following formula (1) must be 35 to 46. Within the scope.

A=X(SiO ₂ )+X(B ₂ O ₃ )-X(M ₂ O) (1)

In addition, in general, an alkali metal means lithium, sodium, potassium, rubidium, or cesium, and the alkali metal oxide contained as a constituent component of the low-softening point glass powder of the present invention means lithium oxide, sodium oxide, and potassium oxide, and must be In addition, one or more of these are essential components, and the total content of lithium oxide, sodium oxide, and potassium oxide is X (M ₂ O), and the above formula (1) is satisfied.

By setting A to 46 or less, the residual organic component can be reduced. The other side When A is small, the content of the alkali metal oxide increases, and the separator is yellowed after calcination, so it is necessary to be 35 or more. Preferably, it is in the range of 36 to 45, and more preferably in the range of 38 to 44.

In the present invention, the reason why the A of the above formula (1) is 46 or less and the remarkable effect of forming a separator having a small residual organic component is not clear, but it is considered to be the following mechanism.

The cerium oxide and the boron oxide are acidic components, and the alkali metal oxide is an alkali component, and A in the above formula (1) is an index indicating the balance between the acidic component and the alkaline component in the glass powder. When the content of the alkali metal oxide is small and A is greater than 46, the acid-base balance of the glass shifts, and thus becomes chemically unstable, thereby causing reaction with the organic component in the paste, or adsorption of the thermal decomposition product. There are more organic components remaining. It is presumed that by increasing the alkali metal oxide as an alkaline component and making A 46 or less, the acid-base balance of the glass can be improved, and as a result, it becomes chemically stable and reacts with the organic component in the paste. The suppression is suppressed, or the adsorption of the thermal decomposition product is suppressed, so that the residual organic component can be reduced.

Hereinafter, each component constituting the low-softening point glass powder will be described.

Cerium oxide is a material that forms a glass skeleton. It can effectively improve the compactness, strength or stability of the glass, and is also effective for the low refractive index of the glass. Further, when a glass substrate is used as the substrate, the thermal expansion coefficient can be controlled to prevent problems such as peeling due to mismatch with the glass substrate. The blending ratio of cerium oxide is preferably from 10 mol% to 40 mol%, more preferably from 20 mol% to 40 mol%. By setting the cerium oxide ratio to 10 mol% or more, the thermal expansion coefficient can be suppressed to be small and burned on a glass substrate. When it is difficult to generate cracks, the refractive index can be suppressed low. Further, by setting the cerium oxide ratio to 40 mol% or less, the softening point can be suppressed to be low, and the baking temperature on the glass substrate can be lowered.

Boron oxide is a material that forms a glass skeleton. It has an effect of lowering the softening point and is effective for lowering the refractive index. The blending ratio of boron oxide is preferably from 20 mol% to 45 mol%, more preferably from 20 mol% to 40 mol%. When the blending ratio of boron oxide is 20 mol% or more, the softening point can be suppressed to be low, and the printing on the glass substrate can be easily performed, and the refractive index can be suppressed low. Further, by setting the boron oxide compounding ratio to 45 mol% or less, the chemical stability of the glass can be maintained.

Lithium oxide, sodium oxide and potassium oxide which are alkali metal oxides not only facilitate the control of the thermal expansion coefficient of the glass, but also have an effect of lowering the softening point. The total blending ratio of the alkali metal oxide is preferably from 10 mol% to 30 mol%, more preferably from 10 mol% to 20 mol%. When the total blending ratio of the alkali metal oxide is 10 mol% or more, the effect of lowering the softening point of the glass can be obtained. In addition, when the total blending ratio of the alkali metal oxide is 30 mol% or less, chemical stability can be maintained, the thermal expansion coefficient can be kept small, and the refractive index can be suppressed low. As the alkali metal, lithium is preferably selected from the viewpoint of reducing the yellowing caused by the migration of silver ions.

The low-softening point glass powder in the present invention must further contain 1.5 mol% to 5.5 mol% of a zinc oxide as a constituent component in terms of oxide. The self-oxidizing zinc has an effect of not lowering the thermal expansion coefficient of the glass and lowering the softening point, and it is necessary to contain 1.5 mol% or more. and In addition, when the content rate is high, the stability of the glass is lowered, the refractive index is increased, and the reactivity with the organic component in the paste is increased, and the viscosity of the paste is likely to rise with time, so it must be 5.5 mol% or less. Provisioning within the scope. It is preferably 2.5 mol% to 3.3 mol%.

In the low-softening point glass powder of the present invention, it is necessary to further contain, as a constituent component, an alkaline earth metal oxide represented by an oxide, and the total of the alkali metal oxide, the alkaline earth metal oxide, and the zinc oxide is 24 mol% to 30 mol. %.

In addition, in general, an alkaline earth metal oxide refers to calcium oxide, cerium oxide, cerium oxide, and oxidized radium. The alkaline earth metal oxides in the present invention are magnesium oxide, calcium oxide, cerium oxide, and cerium oxide, and so-called alkaline earth metal oxides. It is one or more types of these compounds, and the total content rate is used as the content rate of an alkaline earth metal oxide.

Since the alkali metal oxide, the alkaline earth metal oxide, and the zinc oxide all have an effect of lowering the softening point, the total content thereof must be 24 mol% or more. In addition, when the content ratio is high, the refractive index is high, and therefore it is necessary to carry out the formulation in a range of 30 mol% or less in total. It is preferably 25 mol% to 29 mol%, more preferably 26 mol% to 28 mol%.

The alkaline earth metal oxide can effectively adjust the coefficient of thermal expansion and has an effect of lowering the softening point. The blending ratio of the alkaline earth metal oxide is preferably from 2 mol% to 20 mol%, more preferably from 3 mol% to 18 mol%. When the blending ratio of the alkaline earth metal oxide is 2 mol% or more, the effect of lowering the softening point of the glass can be obtained. Moreover, by setting the alkaline earth metal oxide to a compounding ratio of 20 mol% or less, the chemical stability of the glass can be maintained, and the refraction can be performed. The rate is suppressed low.

The other component may contain alumina, titanium oxide, zirconium oxide, or the like, which has an effect of improving the chemical stability of the glass, and may contain cerium oxide or lead oxide having an effect of lowering the softening point.

As a method for producing a low-softening point glass powder, for example, a raw material such as lithium oxide, cerium oxide, boron oxide, cerium oxide, magnesium oxide, or aluminum oxide as a constituent component is mixed so as to have a predetermined blending composition, and is 900 ° C. After melting at ~1200 ° C, it is quenched to obtain a glass frit, and then pulverized and classified to obtain a fine powder of 20 μm or less. High-purity carbonates, oxides, hydroxides, and the like can be used as the raw materials. Further, it is preferable to use a powder having a high electric resistance and a high density, and having a small number of pores and a high purity, and the powder is used in an ultrahigh purity alkane of 99.99% or more depending on the kind or composition of the glass powder. A raw material of alkoxide or organometallic, which is homogeneously prepared by a sol-gel method.

In the present invention, 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 producing the glass powder, and can be calculated from the glass powder, the paste or the separator. In the case of glass powder, it can be quantitatively determined by performing atomic absorption analysis and inductively coupled plasma (ICP) emission spectrometry. In the case of a separator, it can be quantitatively determined by Auger electron spectroscopy. Specifically, the low-softening point glass is distinguished according to the difference in SEM image of the cross-section of the separator, and elemental analysis is performed by the Auger electron spectrum. It is also possible to use other well-known analytical means, such as selectively cutting low-softening point glass from the separator, performing atomic absorption analysis, and inductively coupled plasma (ICP) emission spectroscopy. In paste In this case, the glass powder can be separated by an operation of filtering the paste, washing, or the like, and thereby analyzing by the same method as the glass powder. Alternatively, the separator may be formed by applying a paste and calcining, and then analyzing by the same method as the separator.

The method of calculating the content ratio of the constituent components based on the result of the elemental analysis is as follows. Since information on the mass ratio of the elements contained in the glass powder is obtained by elemental analysis, the mass ratio of the oxide conversion can be calculated based on the atomic weight, the amount of the oxide, and the number of cations in the composition formula of the oxide, that is, The mass ratio of the constituents. In the conversion of the mass ratio of the obtained constituent components into the molar ratio, Ri is assumed to be the mass % of the constituent component i, Fi is the formula of the component i, and Σ is the sum of all the components. In time, conversion can be performed by the following formula.

(Ri/Fi)/Σ(Ri/Fi)×100 (mol%)

In the present invention, a filler may also be added as an inorganic component. The filler in the present invention is added to improve the strength of the separator, and is an inorganic powder which is difficult to melt even at a calcination temperature. Specifically, it means an inorganic powder which does not have a softening point or a melting point and a decomposition temperature below 650 ° C and is present as a solid at 650 ° C. As the filler, at least one selected from the group consisting of a high softening point glass powder having a softening point of 650 ° C to 1200 ° C or a ceramic powder such as cordierite, alumina, ceria, magnesia or zirconia may be used. From the viewpoint of the easiness of adjustment of the 50% particle diameter (average particle diameter) d ₅₀ or the average refractive index in the weight distribution curve, it is preferred to use a high softening point glass powder. The filler can be preferably used in consideration of dispersibility or filling property in the paste and light scattering during exposure, and an average particle diameter of 0.1 μm to 3.0 μm and a maximum particle diameter of 20 μm or less are preferably used.

In the case where a low-softening point glass and a filler are added as an inorganic component, the proportion of the low-softening point glass powder in the inorganic component is preferably from 50 vol% to 98 vol%. When the content ratio is 50 vol% or more, sintering at the time of firing becomes easy, and it is preferable to maintain a small pattern void ratio after firing. Further, when the content ratio is 98 vol% or less, it is preferable to control the fluidity of the inorganic component as a whole during calcination, prevent deformation of the pattern shape, and improve mechanical strength of the pattern after calcination, which may be difficult to form due to A pattern that is broken by impact and the like.

The ratio of the low-softening point glass powder and the filler in the inorganic component can be calculated according to the blending ratio of each component in the preparation of the paste, and the film can be dried by a scanning electron microscope (coating the photosensitive paste and The section obtained by drying or obtained by baking a paste-fired film (obtained by calcination of a dry film) was computed. The cross section perpendicular to the film surface of the paste-dried film or the paste-fired film is observed by a scanning electron microscope, and the type of the inorganic component is distinguished according to the shade of the image, and image analysis can be performed. The relationship between the shade of the image and the inorganic component can be determined by elemental analysis using X-rays. The evaluation area of the scanning electron microscope may be, for example, an area of about 20 μm × 100 μm, and may be observed by about 1000 to 3000 times.

The high softening point glass powder which can be preferably used has, for example, an oxide composition having the following composition.

In the case where the paste of the present invention is used as a photosensitive paste, it is preferred that the filler has a refractive index of 1.45 to 1.65. By matching the refractive indices of the inorganic component and the organic component, light scattering is suppressed, and high-precision pattern processing is facilitated.

It is preferable that the inorganic component is contained in the solid content of the paste in a total content of 35 vol% to 80 vol%, more preferably 40 vol% to 70 vol%. Here, the solid matter is an inorganic component contained in the paste and an organic component other than the solvent. When the content ratio of the inorganic component becomes less than 35 vol%, the pattern shrinkage due to firing becomes large, and the shape is liable to be deteriorated and is not preferable. Moreover, when it becomes more than 80 vol%, it becomes difficult to apply uniformly and it is unpreferable.

The content ratio (vol%) of the inorganic component in the solid matter can be controlled by the addition ratio (% by mass) in consideration of the density of the inorganic component and the organic component in the preparation of the paste. Further, as a method of analyzing the content ratio of the inorganic component, a method of determining the density of the calcined film of the inorganic component by thermogravimetry (TGA) or a method of drying the film by a paste (coating paste and A method of obtaining an image analysis of a video by a transmission electron microscope obtained by drying. Density of calcined film by thermal gravimetric determination with inorganic components In the case of the measurement, for example, a paste of about 10 mg is used as a sample, and a weight change of room temperature to 600 ° C is evaluated by TGA (for example, "TGA-50" manufactured by Shimadzu Corporation). Usually, the solvent in the paste evaporates at 100 ° C to 150 ° C, so the weight after the temperature is raised to 600 ° C (the organic component is removed, so the weight of the inorganic component is equivalent to the weight of the solvent after evaporation) The weight ratio of the inorganic component to the organic component is determined. On the other hand, when the density of the inorganic component is evaluated based on the film thickness, the area, and the mass of the calcined film, the content ratio can be evaluated. In addition, when the content is determined by a transmission electron microscope, a dry film perpendicular to the paste is observed by a transmission electron microscope (for example, "JEM-4000EX" manufactured by JEOL Ltd.). The cross section of the film surface can be distinguished from the inorganic component and the organic component according to the shade of the image, and the image analysis can be performed. The evaluation area of the transmission electron microscope may be observed at an area of about 20 μm × 100 μm, for example, at about 1000 to 3000 times.

The paste in the present invention must contain an organic component. Here, the organic component may have a moderate viscosity when the paste is applied, and the pattern may be maintained when the paste is applied and dried as needed. The organic component used in the paste of the present invention can be selected according to the separator forming process, and is not particularly limited. For example, a cellulose compound typified by ethyl cellulose, an acrylic polymer typified by polybutyl methacrylate, or the like can be used. Further, examples thereof include resins such as polyvinyl alcohol, polyvinyl butyral, methacrylate polymers, acrylate polymers, acrylate-methacrylate copolymers, and α-methylstyrene polymers.

In the case where the paste of the present invention is used as a photosensitive paste, it is characterized by containing a photosensitive organic component. The photosensitive organic component is at least one selected from the group consisting of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer. Further, a non-photosensitive polymer component, an antioxidant, an organic dye, a photopolymerization initiator, a sensitizer, a sensitizer, a plasticizer, a thickener, a dispersant, an organic solvent, a suspending agent may be added as needed. And other organic ingredients.

In the present invention, the photosensitive paste is obtained by irradiating active light rays to a coating film which has been applied and dried, and the irradiation portion is subjected to a reaction such as photocrosslinking, photopolymerization, photopolymerization, or photo-modification to generate a chemical. The structure is changed, so that it becomes possible to perform the development using the development of the developer. In particular, the present invention obtains good characteristics by making a negative photosensitive paste which can make the irradiated portion insoluble in the developing solution by irradiating the active light, and then utilizes development. The liquid is removed, and only the unirradiated portion is removed, whereby patterning is performed. The active light referred to herein is light having a wavelength range of 250 nm to 1100 nm which generates such a chemical reaction, and specific examples thereof include ultraviolet light such as an ultrahigh pressure mercury lamp or a metal halide lamp, visible light rays such as a halogen lamp, and cesium-cadmium. Laser light of a specific wavelength such as laser, 氦-氖 laser, argon ion laser, semiconductor laser, YAG laser, carbon dioxide laser, and the like.

As the photosensitive polymer, an alkali-soluble polymer can be preferably used. The reason for this is that by making the polymer alkali-soluble, it is possible to use an alkaline aqueous solution as a developing solution without using an organic solvent which is problematic for the environment. As the alkali-soluble polymer, an acrylic copolymer can be preferably used. The acrylic copolymer is a copolymer comprising at least an acrylic monomer Specific examples of the polymer and the acrylic monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, second butyl acrylate, isobutyl acrylate, and acrylic acid. Butyl ester, n-amyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxy triethylene glycol acrylate, cyclohexyl acrylate, dicyclopentyl acrylate, dicyclopentyl acrylate Alkenyl ester, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, acrylic acid-2- Hydroxypropyl ester, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxy ethylene glycol acrylate, methoxy diethylene glycol acrylate, acrylic acid Octafluoropentyl ester, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, 1-naphthyl acrylate, acrylic acid - 2-naphthyl ester, thiophenol Acrylic monomers acrylate, benzyl acrylate, thiol and replacing the more acrylate methacrylate and the like are formed. As the copolymerization component other than the acrylic monomer, a compound having a carbon-carbon double bond can be used, and preferably, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, and α-methyl styrene are exemplified. And styrene such as chloromethylstyrene or hydroxymethylstyrene or 1-vinyl-2-pyrrolidone.

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

In the case of using an acrylic copolymer, in order to increase the reaction rate of the hardening reaction by exposure of the photosensitive paste, it is preferred to prepare an acrylic resin having a carbon-carbon double bond at a side chain or a molecular end. Copolymer. Examples of the group having a carbon-carbon double bond include a vinyl group, an allyl group, a propenyl group, a methacryl group, and the like. In order to add such a functional group to an acrylic copolymer, there is a method of: a compound having a glycidyl group or an isocyanate group and a carbon-carbon double bond, or a propylene chloride, a methacrylium chloride or an allyl group. Chlorine is produced by addition reaction of a mercapto group, an amine group, a hydroxyl group, and a carboxyl group in an acrylic copolymer.

Examples of the compound having a glycidyl group and a carbon-carbon double bond include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl acrylate, butenyl glycidyl ether, and butene. Glycidyl methacrylate, glycidyl methacrylate, and the like. Examples of the compound having an isocyanate group and a carbon-carbon double bond include propylene decyl isocyanate, methacryl oxime isocyanate, propylene decyl ethyl isocyanate, and methacryl oxiranyl ethyl isocyanate.

Further, 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, or a high molecular weight polyether. Wait.

Further, the photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and acrylic acid second. Ester, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxy triethylene glycol Ester, cyclohexyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxy Ethylene glycol acrylate, methoxy diethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylic acid Ester, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene Alcohol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy pentaacrylate, di-trimethylolpropane tetraacrylate, glycerol diacrylate, methoxycyclohexyl diacrylate, neopentyl Alcohol diacrylate, propylene glycol diacrylate, Propylene glycol diacrylate, tripropylene triol diacrylate, trimethylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, acrylic acid - 1-naphthyl ester, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, diacrylic acid of bisphenol A-propylene oxide adduct Ester, thiophenol acrylate, benzyl thiol acrylate, and one to five of the hydrogen atoms of the aromatic ring of the compounds are substituted with a monomer of a chlorine or bromine atom, or styrene or p-methylbenzene Ethylene, o-methyl styrene, m-methyl styrene, chlorinated styrene, brominated styrene, α-methyl styrene, α-methyl styrene chloride, α-methyl styrene bromide, chlorine Methylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinyl Naphthalene, vinyl anthracene, vinyl carbazole, and some or all of the acrylates in the molecule of the above compound are substituted with methacrylate, γ-methacryloxypropyltrimethoxydecane, 1-vinyl-2-pyrrolidone and the like. Further, in the polyfunctional monomer, the group having an unsaturated bond may be a mixture of a propenyl group, a methacryl group, a vinyl group, and an allyl group. In the present invention, one type or two or more types of these compounds can be used.

The photosensitive paste used in the present invention preferably further contains a urethane compound. The reason for this is that by containing a urethane compound, the flexibility of the dried film of the paste can be improved, the stress at the time of firing can be reduced, and defects such as cracks or breakage can be effectively suppressed. Further, by containing a urethane compound, thermal decomposition property can be improved, and it becomes difficult to retain an organic component in the calcination step. The urethane compound which is preferably used in the present invention is, for example, a compound represented by the following formula (1).

Here, R ₁ and R ₂ are a group 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. , can be the same or different. R ₃ is an alkylene oxide or alkylene oxide oligomer, and R ₄ is an organic group containing a urethane bond. n is an integer from 1 to 10.

Such a urethane compound is preferably a compound containing an ethylene oxide unit. More preferably, in the formula (1), R ₄ is an oligomer comprising an ethylene oxide unit (hereinafter referred to as EO) and a propylene oxide unit (hereinafter referred to as PO), and the oligomer The compound having an EO content of from 8% by mass to 70% by mass. When the EO content is 70% by mass or less, the flexibility can be further improved and the calcination stress can be reduced, so that defects can be effectively suppressed. Further, the thermal decomposition property is improved, and in the subsequent calcination step, the organic component becomes difficult to remain. Further, by making the EO content rate 8% or more, the compatibility with other organic components can be improved.

Moreover, it is also preferred that the urethane compound has a carbon-carbon double bond. The carbon-carbon double bond of the urethane compound is contained in the crosslinked body by reacting with the carbon-carbon double bond of the other crosslinking agent, whereby the polymerization shrinkage can be further suppressed.

Specific examples of the urethane compound preferably used in the present invention include UA-2235PE (molecular weight: 18,000, EO content: 20%), UA-3238PE (molecular weight: 19,000, EO content: 10%), UA-3348PE (molecular weight: 22,000, EO content: 15%), UA-5348PE (molecular weight: 39,000, EO content: 23%) (the above is manufactured by Shin-Nakamura Chemical Co., Ltd.), etc., but is not limited thereto. Some compounds. Moreover, these compounds may also be used in combination.

The content of the urethane compound is preferably from 0.1% by mass to 20% by mass based on the organic component other than the solvent. By setting the content to be 0.1% by mass or more, the flexibility of the paste-dried film can be improved, and the calcination shrinkage stress at the time of baking the paste-dried film can be alleviated. When the content is more than 20% by mass, the dispersibility of the organic component and the inorganic component is lowered, and the concentration of the monomer and the photopolymerization initiator is relatively lowered, so that defects are likely to occur.

As the photopolymerization initiator, a photoradical initiator which generates a radical by irradiation with an active light source can be preferably used. Specific examples thereof include benzophenone, Methyl benzalkonium benzoate, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 4,4-dichloro Benzene, 4-benzylidene-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2 -Phenyl-2-acetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone , 2-isopropyl thioxanthone, diethyl thioxanthone, benzoin, methyl benzyl benzoate, benzyl methoxy ethyl acetal, benzoin, benzoin methyl ether, benzoin,蒽醌, 2-tert-butyl fluorene, 2-pentyl hydrazine, β-chloropurine, fluorenone, benzofluorenone, dibenzocycloheptanone, methylene fluorenone, 4-azide Phenylstyryl ketone, 2,6-bis(p-azidobenzylidene)cyclohexanone, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone , 2-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)anthracene, 1-phenyl-propanedione-2-(o-ethoxycarbonyl)anthracene, 1,3-two Phenyl-propanetrione-2-(o-ethoxycarbonyl)anthracene, 1-phenyl-3-ethoxy-propanetrione-2-(o-benzylidene) , Michlerone, 2-methyl-[4-(methylthio)phenyl]-2-N-morpholinyl-1-propanone, naphthalenesulfonium chloride, 2-benzyl-2-dimethyl Amino-1-(4-N-morpholinylphenyl)-1-butanone, quinoline sulfonium chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl Disulfide, benzothiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylphosphonium, peroxidized benzoin and eosin, methylene blue and other photoreducible pigments and reduction of ascorbic acid, triethanolamine, etc. Combination of agents, etc. One or two or more kinds of these compounds can be used in the present invention. The photopolymerization initiator is added in an amount of 0.05% by mass to 20% by mass, and more preferably 0.1% by mass 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, there is a problem that the photosensitivity becomes poor; When the amount of the starting agent is too large, the residual ratio of the exposed portion becomes too small.

Further, the use of a sensitizer together with a photopolymerization initiator improves the sensitivity and expands the wavelength range effective for the reaction. Specific examples of the sensitizer include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2,3-bis(4-diethyl). Aminobenzylidene)cyclopentanone, 2,6-bis(4-dimethylaminobenzylidene)-4-methylcyclohexanone, mischrone, 4,4-bis(diethyl Amino) chalcone, p-dimethylamino cinnamicin, p-dimethylaminobenzylidene ketone, 2-(p-dimethylaminophenyl vinyl) Iso-naphthylthiazole, 1,3-bis(4-dimethylaminobenzylidene)acetone, 1,3-carbonylbis(4-diethylaminobenzylidene)acetone, 3,3-carbonyl double -(7-diethylaminocoumarin), triethanolamine, methyldiethanolamine, triisopropanolamine, N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-methylphenyl Ethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, benzoic acid 2-dimethylamino)ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 3-phenyl -5-benzimidylthiotetrazole, 1-phenyl-5-ethoxy Carbonylthiotetrazole and the like. In the present invention, one type or two or more types of these compounds can be used. In addition, there are also those which can be used as a photopolymerization initiator in the sensitizer. When a sensitizer is added to the photosensitive paste of the present invention, the amount thereof is preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass based on the organic component other than the solvent. %~10% by mass. By setting the amount of the sensitizer to be within this range, the residual ratio of the exposed portion can be maintained and a good photosensitivity can be obtained.

It is also preferred to use an antioxidant in the present invention. Antioxidant It is a one that has a free radical chain inhibition effect, a triplet elimination effect, and a decomposition of a hydroperoxide. When an antioxidant is added to the photosensitive paste, the antioxidant traps the radical, or restores the energy state of the excited photopolymerization initiator or sensitizer to the ground state, thereby suppressing the excess caused by the scattered light. The photoreaction produces an abrupt photoreaction with an amount of exposure that cannot be suppressed by the antioxidant, thereby improving the contrast of dissolution and insolubility in the developer. Specific examples thereof include p-benzoquinone, naphthoquinone, p-dimethylphenylhydrazine, p-methylbenzoquinone, 2,6-dichloropurine, 2,5-diethyloxy-p-benzoquinone, 2, 5-dicarboxylic acid (dicaproxy)-p-benzoquinone, hydroquinone, p-tert-butylcatechol, 2,5-dibutyl hydroquinone, mono-tert-butyl hydroquinone, 2, 5-di-p-pentyl hydroquinone, di-tert-butyl-p-cresol, hydroquinone monomethyl ether, α-naphthol, hydrazine hydrochloride, trimethylbenzylammonium chloride , trimethylbenzyl ammonium oxalate, phenyl-β-naphthylamine, p-benzylaminophenol, bis-β-naphthyl p-phenylenediamine, dinitrobenzene, trinitrobenzene, picric acid, hydrazine Diterpenoid, cyclohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, copper iron, 2,2'-thiobis (4-third Octyl phenolate)-2-ethylhexylamino nickel (II), 4,4'-thiobis-(3-methyl-6-tert-butylphenol), 2,2'-methylene Bis-(4-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(t-butyl-5-methyl-4-hydroxyphenyl)propionic acid], 1, 6-hexanediol-bis[(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid], 1,2,3-trihydroxybenzene, etc. However, it is not limited to these compounds. One or more of these compounds can be used in the present invention. The amount of the antioxidant added is preferably from 0.01% by mass to 30% by mass, more preferably from 0.05% by mass to 20% by mass, based on the photosensitive paste. By making the amount of the antioxidant added within this range, the light of the photosensitive paste can be maintained The sensitivity is maintained, and the degree of polymerization is maintained to maintain the pattern shape, so that the contrast between the exposed portion and the unexposed portion can be largely obtained.

It is also preferred to use an ultraviolet absorber in the photosensitive paste of the present invention. By adding an ultraviolet absorber, the scattered light inside the paste caused by the exposure light can be absorbed, and the scattered light is weakened. The ultraviolet absorber is particularly effective when it absorbs light at a wavelength near the g line, the h line, and the i line, and specific examples thereof include a benzophenone compound, a cyanoacrylate compound, a salicylic acid compound, and benzo. A triazole compound, an anthraquinone compound, an inorganic fine particle metal oxide or the like. Among these compounds, a benzophenone-based compound, a cyanoacrylate compound, a benzotriazole-based compound, and an anthraquinone-based compound are particularly effective. Specific examples of such compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxy group. Benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone , 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-octadecyloxy Benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-(2-hydroxy-3- Methyl propylene oxime) propoxy benzophenone, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy- 3'-Tertibutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5 -Chlorobenzotriazole, 2-(2'-hydroxy-4'-n-octyloxyphenyl)benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate , 2-ethyl-2-cyano-3,3-diphenyl acrylate, BONASORB UA-3901, BONASORB UA-3902, BONASORB UA-3911 as a lanthanide UV absorber SOM-2-0008 (manufactured by Orient Chemical Industries Co., Ltd.), Basic Blue, Sudan Blue, Sudan R, Sudan I, Sudan II, Sudan III, Sudan IV, oil-soluble orange SS, oil-soluble purple, Oil-soluble yellow OB (manufactured by Aldrich Co., Ltd.) or the like, but is not limited to these compounds. Further, a methacryl group or the like may be introduced into the skeleton of the ultraviolet absorber to be used as a reaction type. In the present invention, one type or two or more types of these compounds can be used.

In the present invention, a photo-fading compound can also be used as the ultraviolet absorber. The photofading compound refers to a compound having a property of absorbing a light in a wavelength region of the active light, and absorbing a light in a wavelength region of the active light, and changing the chemical structure such as photolysis or photo-modification to the active light source. The absorbance in the wavelength region becomes smaller than before the irradiation. In general, in the photosensitive paste method, the light is used in the g-line (436 nm), the h-line (405 nm), and the i-line (365 nm) of the ultrahigh pressure mercury lamp, and therefore the light used in the present invention is preferred. The fading compound is also absorptive in the g-line, h-line, and i-line regions. By adding a photo-fading compound to the photosensitive paste, it is possible to prevent the exposure light from entering the unexposed portion which is a portion which is not exposed to the exposure light, and to suppress the coarseness of the bottom portion of the pattern. Further, in the exposed portion, the photofadable compound absorbs the energy of the exposure light, and gradually becomes non-absorbed by photodecomposition or photo-modification, so that it is easy to allow sufficient exposure light to reach the lower layer. Therefore, the contrast of the light hardening of the unexposed portion and the exposed portion becomes clear, and the exposure amount margin can be surely improved. Specific examples thereof include photodegradable dyes such as photofading dyes, photoacid generators, photobase generators, and nitrone compounds, or azo dyes. Photo-modified compounds such as materials and photochromic compounds. Specific examples of the photoacid generator include an onium salt, a halogen-containing compound, a diazomethane compound, an anthraquinone compound, a sulfonate compound, a sulfonimide compound, a diazomethanone compound, and the like.

The content of the ultraviolet absorber is preferably 0.001% by mass to 1% by mass, and more preferably 0.001% by mass to 0.5% by mass, based on the photosensitive paste. By setting the amount of the ultraviolet absorber to be in this range, the scattered light can be absorbed, the bottom of the pattern can be suppressed from being coarse, and the sensitivity to the exposure light can be maintained.

Further, in the present invention, it is also preferred to use an organic dye as a mark for exposure and development. By adding a dye to colorize, the visibility is improved, and it becomes easy to distinguish the part of the residual paste at the time of development and the part which removes the paste. The organic dye is not particularly limited, and it is preferred that it does not remain in the insulating film after firing. Specifically, an anthraquinone dye, an indigo dye, a phthalocyanine dye, a carbonium ion dye, a quinone imine dye, a methine dye, a quinoline dye, a nitro dye, a nitroso can be used. A dye, a benzoquinone dye, a naphthoquinone dye, a phthalimide dye, a purple ketone dye, or the like. Particularly preferred is a dye which absorbs light of a wavelength near the h-line and the i-line, such as a carbon ray ion dye such as basic blue. The amount of the organic dye added is preferably 0.001% by mass to 1% by mass based on the organic component other than the solvent.

In order to adjust the viscosity when the paste is applied onto the substrate according to the coating method, it is also preferred to use an organic solvent. At this time, the organic solvent used may be methyl acesulfame, ethyl acesulfame, butyl siroli, butyl carbene. Alcohol, ethyl carbitol, butyl carbitol acetate, ethyl carbitol acetate, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutanol, isopropanol , tetrahydrofuran, dimethyl hydrazine, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, etc. or one or more organic solvents containing these solvents mixture.

In the paste of the present invention, each component of the inorganic component and each component of the organic component are adjusted to a predetermined composition, and then kneaded by a kneading machine such as a three-roll mill to form a paste. Further, the paste after the completion of the final kneading may be appropriately filtered and defoamed in advance.

The method for producing a panel for a flat panel display according to the present invention is characterized in that the paste is applied onto a substrate and fired to form an insulating pattern. As a result, an insulating pattern having little residual organic component after firing and having no coloration can be formed. Therefore, a flat panel display panel having excellent display characteristics such as brightness and color purity and high reliability can be obtained.

Further, the method for producing a panel for a flat panel display according to the present invention is characterized in that the photosensitive paste is applied onto a substrate, exposed, developed, and fired to form an insulating pattern. In this way, not only an insulating pattern having less residual organic components after firing but also a coloring-free insulating pattern can be formed, and a high-definition insulating pattern can be formed with high precision, so that excellent display properties such as brightness and color purity can be obtained stably and at low cost. Highly reliable panel for flat panel displays.

The panel for a flat panel display of the present invention is a panel for a flat panel display having a separator having a low softening point glass having a softening point of 570 ° C to 620 ° C as a main component, wherein the low softening point glass contains cerium oxide and oxidizes. Boron and an alkali metal oxide, wherein the cerium 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%), A of the following formula (1) The value is in the range of 35~46.

A=X(SiO ₂ )+X(B ₂ O ₃ )-X(M ₂ O) (1)

By setting the value of A to the range of 35 to 46, it is possible to produce a panel for a flat panel display having excellent display characteristics such as brightness or color purity and high reliability. The value of A is preferably in the range of 36 to 45, and more preferably in the range of 38 to 44. Here, the main component is a component which indicates the largest volume fraction of the solid component. The ratio of the content of the low-softening point glass can be obtained by observing the cross section of the separator by an electron microscope, and performing image analysis on the cross-sectional area occupied by the low-softening point glass in the total cross-sectional area of the solid component. Low softening point glass and other solid components can be distinguished by the contrast of the image. Further, the atom can be mapped by a mechanism such as a scanning analysis microscope (SEM-EDX) having an energy dispersive X-ray spectrum analyzer, and the components can be closely distinguished.

The constituent components of the low-softening point glass which is a main component of the separator and the content thereof can be quantitatively determined by Auger electron spectroscopy. Specifically, it means that the low-softening point glass is distinguished by the difference in SEM image of the cross-section of the separator, and elemental analysis is performed by the Auger electron spectrum. Moreover, other well-known analytical means may be additionally used, such as selective cutting of low-softening point glass from the separator, atomic absorption analysis, inductively coupled plasma (ICP) Emission spectrum analysis.

The softening point of the low-softening point glass which is a main component of the separator can be selectively cut from the separator to a low-softening point glass, and is measured using a differential thermal analyzer (DTA). The DTA curve obtained by measuring the glass powder can be obtained by extrapolating the endothermic end temperature in the endothermic peak by a tangent method.

In the panel for a flat panel display of the present invention, the low-softening point glass powder which is a main component of the separator contains zinc oxide, and the content thereof is in the range of 1.5 mol% to 5.5 mol%. Zinc oxide has an effect of lowering the softening point without significantly changing the thermal expansion coefficient of the glass, and is characterized by containing 1.5 mol% or more. Further, when the content ratio is high, 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 viscosity of the paste is easily increased with the passage of time. The formulation is carried out within a range of 5.5 mol% or less. It is preferably 2.5 mol% to 3.3 mol%.

In the panel for a flat panel display of the present invention, the low-softening point glass powder which is a main component of the separator contains an alkali metal oxide, an alkaline earth metal oxide and zinc oxide, and the total content thereof is 24 mol% to 30 mol. Within the range of %. Each of the alkali metal oxide, the alkaline earth metal oxide, and the zinc oxide has an effect of lowering the softening point, and is characterized in that the total content thereof is 24 mol% or more, and if the content ratio is high, the refractive index is high, and thus the characteristics thereof are The compounding is carried out in a range of 30 mol% or less in total. It is preferably 25 mol% to 29 mol%, more preferably 26 mol% to 28 mol%.

Hereinafter, a plasma display device and a battery using a photosensitive paste method will be described. The order in which the pulp display panels are produced is used as the order of the panels for the flat panel display, but is not necessarily limited thereto. Further, here, the basic structure and the like of the plasma display will be described by taking the most general alternating current (AC) type plasma display as an example.

The plasma display panel is formed by sealing the front panel and the back panel in such a manner that the phosphor layer formed on the front panel and/or the back panel faces the inner space, and the discharge is sealed in the inner space. The gas is the one. That is, in the front panel, a transparent electrode (sustaining electrode, scanning electrode) for performing discharge for display is formed on the substrate on the display surface side. In order to form an electrode having a lower resistance, a bus electrode may be formed on the back side of the transparent electrode. Among them, the bus electrode includes a material of Ag, Cr/Cu/Cr, etc., and is opaque in many cases. Therefore, unlike the transparent electrode, it interferes with the display of the cell, and therefore it is preferably provided at the outer edge portion of the display surface. In the case of an AC type plasma display, in many cases, a transparent dielectric layer and a MgO film as a protective film are formed on the upper layer of the electrode. An electrode (addressing electrode) for performing address selection on the unit for display is formed on the back panel. A separator or a phosphor layer for separating the cells may be formed on either or both of the front panel and the back panel, but in most cases, it is formed only on the back panel. The plasma display panel is formed by sealing the front panel and the back panel, and a discharge gas such as Xe-Ne or Xe-Ne-He is sealed in the internal space between the two.

First, the method of manufacturing the front panel will be described with respect to the panel manufacturing steps. As the substrate, soda glass or "PP8" (manufactured by Nippon Electric Glass Co., Ltd.) and "PD200" (manufactured by Asahi Glass Co., Ltd.) for heat-resistant glass for a plasma display panel can be used. The size of the glass substrate is not limited For the thickness, the thickness can be 1mm~5mm.

First, indium tin oxide (ITO) was sputtered on a glass substrate, and a pattern was formed by photolithography. Next, a black electrode paste for black electrodes was printed. The main component of the black electrode paste is an organic binder, a black pigment, a conductive powder, and a photosensitive component in the case of use in a photolithography method. A metal oxide can be preferably used as the black pigment. The metal oxide is titanium oxide or an oxide of copper, iron or manganese, or a composite oxide thereof, cobalt oxide or the like, and is preferably cobalt oxide since it is mixed with glass and has little fading when calcined. The conductive powder may be a metal powder or a metal oxide powder. As the metal powder, gold, silver, copper, nickel, or the like which is generally used as an electrode material can be used without particular limitation. Since the black electrode has a large specific resistance, a bus electrode is formed to form an electrode having a small specific resistance, and a highly conductive electrode paste (for example, a component containing silver as a main component) is printed on the printing surface of the black electrode paste. As the conductive paste, an electrode paste used in the address electrode can also be suitably used. Then, collective light exposure/development is performed to produce a bus electrode pattern. In order to surely ensure conductivity, it is also possible to reprint an electrode paste having high conductivity before development, and perform total development after exposure again. Calcination is performed after forming the bus electrode pattern. Thereafter, in order to increase the contrast, it is preferred to form a black stripe or a black matrix. It is preferable that the film thickness of the black electrode paste after calcination and the conductive paste after calcination is in the range of 1 μm to 5 μm, respectively. Further, it is preferred that the line width after calcination is from 20 μm to 100 μm.

Next, a transparent dielectric paste is formed using a transparent dielectric paste. The main component of the transparent dielectric paste is an organic binder, an organic solvent, or a glass, and an additive such as a suitable plasticizer may be added. The formation of a transparent dielectric layer The method is not particularly limited. For example, the transparent dielectric paste may be coated or partially coated on the entire surface by screen printing, bar coating, roll coating, die coating, knife coating, spin coating or the like. The electrode is formed on a substrate, and then dried using a ventilating oven, a hot plate, an infrared drying oven, vacuum drying, or the like to form a thick film. Further, the transparent dielectric paste may be formed into a sheet and laminated on the electrode-formed substrate. The thickness is preferably from 0.01 mm to 0.03 mm.

Next, calcination is carried out in a calciner. The calcination environment or temperature varies depending on the type of the paste or the substrate, and can be calcined in the air or in an environment such as nitrogen or hydrogen. The calciner may use a batch type calciner or a roll transfer type continuous calciner. As the calcination temperature, the resin to be used can be sufficiently subjected to the temperature of the debonding agent. Usually, in the case of using an acrylic resin, calcination is carried out at 430 ° C to 650 ° C. When the baking temperature is too low, the resin component tends to remain; if it is too high, it is deformed by the glass substrate and is broken.

A protective film is further formed. The protective film may be selected from the group consisting of 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 , the aforementioned low At least one of the groups of softening point glass, particularly preferably MgO. A known technique such as electron beam evaporation or ion plating can be used as the method for producing the protective film.

Next, a method of manufacturing the back panel will be described. As for the glass substrate, soda glass, "PD200", "PP8", or the like can be used similarly to the case of the front panel. A stripe electrode pattern for addressing is formed on the glass substrate by silver or a metal such as aluminum, chromium or nickel. The formation method may be a method of using a metal paste containing a powder of the metal and an organic binder as a main component by screen printing. a method of pattern printing; or a photosensitive paste method, after applying a photosensitive metal paste using a photosensitive organic component as an organic binder, pattern exposure using a photomask, which is unnecessary by a development step Partially dissolved and removed, and further heated to 350 ° C to 600 ° C to be calcined to form an electrode pattern. Further, after etching or depositing chromium or aluminum on the glass substrate by an etching method, a resist is applied, and the resist is subjected to pattern exposure and development, and then unnecessary portions are removed by etching. Additionally, it is preferred to provide a dielectric layer on the addressed electrode. By providing a dielectric layer, it is possible to improve discharge stability or to suppress collapse or peeling of the spacer formed on the layer of the dielectric layer. The method of forming a dielectric layer includes a method of using a dielectric paste containing an inorganic component such as a glass powder or a high-softening point glass powder and an organic binder as a main component by screen printing, slit die coating, or the like. The agent is printed or coated on the entire surface.

Next, a method of forming a separator using a photosensitive paste method will be described. The pattern of the separator is not particularly limited, and is preferably a lattice shape, a muffin shape or the like. First, the photosensitive paste of the present invention is applied onto a substrate on which a dielectric is formed. The coating method may be a method such as bar coating, roll coating, slit die coating, blade coating, screen printing or the like. The coating thickness can be determined in consideration of the height of the desired separator and the shrinkage rate produced by the calcination of the paste. The coating thickness can be adjusted by the number of coatings, the mesh of the screen, and the viscosity of the paste. In the present invention, it is preferred to apply the coating thickness after drying to 100 μm or more. By making the coating thickness 100 μm or more, a sufficient discharge space can be obtained, and the coating range of the phosphor can be enlarged to increase the brightness of the plasma display panel.

The applied separator paste was exposed after drying. Exposure is generally a method of exposing through a mask as is conventional in photolithography. Further, a method of directly drawing by laser light or the like without using a photomask may be used. The exposure apparatus can use a stepper, a proximity exposure machine, or the like. Examples of the active light source used at this time include near ultraviolet rays, ultraviolet rays, electron beams, X rays, and laser light. The most preferable ones are ultraviolet rays, and for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, a germicidal lamp, or the like can be used. Suitable for these are ultra high pressure mercury lamps. The exposure conditions vary depending on the thickness of the coating, and an ultrahigh pressure mercury lamp having an output of 1 mW/cm ² to 100 mW/cm ² is usually used for exposure for 0.01 minutes to 30 minutes.

After the exposure, development is performed by the difference in solubility between the exposed portion and the unexposed portion with respect to the developer, and is usually carried out by a dipping method, a jet method, a brush method, or the like. As the developer, an organic solvent capable of dissolving the organic component in the photosensitive paste can be used. However, when a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be carried out by an aqueous alkaline solution. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, potassium hydroxide aqueous solution or the like can be used, and when an organic alkaline aqueous solution is used, it is easy to remove an alkaline component during calcination, which is preferable.

As the organic base, a general amine compound can be used. Specific examples thereof include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine.

The concentration of the alkaline aqueous solution is usually 0.05% by mass to 5% by mass, and more preferably 0.1% by mass to 1% by mass. If the alkali concentration is too low, it is difficult to remove When the concentration of the alkali is too high, there is a problem that the pattern is peeled off or corrosion is generated, which is unsatisfactory. Further, in terms of step management, it is preferred to carry out the development at a developing temperature of 20 ° C to 50 ° C.

Further, the separator may also contain two or more layers. By making it a structure of two or more layers, the structural range of a separator shape can be expanded three-dimensionally. For example, in the case of a two-layer structure, after applying the first layer and exposing it to a stripe shape, the second layer is applied and exposed to a stripe shape perpendicular to the first layer, and development is carried out to form a patch having a pattern. A partition of a well-shaped structure. Next, calcination is carried out in a calciner at a temperature of 520 ° C to 620 ° C for 10 minutes to 60 minutes to form a separator.

The photosensitive paste of the present invention is suitable for the formation of the above-mentioned separator, and the photosensitive paste of the present invention can form a separator having a small amount of residual organic components, and can have excellent display characteristics such as brightness and color purity, and high panel reliability. Flat panel display.

Next, a phosphor is formed using a phosphor paste. It can be formed by a photolithography method using a phosphor paste, a dispensing method, a screen printing method, or the like. The thickness of the phosphor is not particularly limited, but is preferably 10 μm to 30 μm, more preferably 15 μm to 25 μm. The phosphor powder is not particularly limited, and the following phosphors are suitable from the viewpoints of self-luminous intensity, chromaticity, color balance, and lifetime. Blue is an aluminate phosphor (for example, BaMgAl ₁₀ O ₁₇ :Eu) or CaMgSi ₂ O ₆ which is activated by the activation of divalent europium. In green, from the viewpoint of panel brightness, Zn ₂ SiO ₄ : Mn, YBO ₃ : Tb, BaMg ₂ Al ₁₄ O ₂₄ : Eu, Mn, BaAl ₁₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn are suitable. . More preferably, it is Zn ₂ SiO ₄ : Mn. Also preferable in red is (Y, Gd) BO ₃ :Eu, Y ₂ O ₃ :Eu, YPVO:Eu, YVO ₄ :Eu. More preferably (Y, Gd) BO ₃ :Eu. In the case where a phosphor is formed by the calcination step, the calcination of the dielectric layer or the separator may be simultaneously performed.

Next, a method of manufacturing the plasma display panel will be described. After the back panel and the front panel are melted, the space formed between the two substrates is heated and evacuated, and then a discharge gas containing He, Ne, Xe or the like is sealed and sealed. From the standpoint of self-discharge voltage and brightness, it is preferred that Xe is a mixed gas of Xe-Ne of 5 vol% to 15 vol%. In order to increase the efficiency of ultraviolet light generation, Xe can be further increased to about 30 vol%.

Finally, the drive circuit is mounted and aged, whereby a plasma display panel can be fabricated.

Instance

Hereinafter, the present invention will be more specifically described by way of examples. However, the invention is not limited thereto.

(Example 1 to Example 16, Comparative Example 1 to Comparative Example 10)

A. Evaluation of particle size distribution of glass powder

The average particle diameter d ₅₀ and the maximum particle diameter d _{max of the} glass powder were evaluated using a particle size distribution measuring apparatus ("MT3300" manufactured by Nikkiso Co., Ltd.). The glass powder was placed in a sample chamber filled with water, and subjected to ultrasonic treatment for 300 seconds, and then measured.

B. Softening evaluation price of glass powder

Using a differential thermal analysis device (manufactured by RIGAKU Co., Ltd.) "Differential type differential thermostat TG8120"), using alumina powder as a standard sample, and raising the temperature at room temperature from 20 ° C / min. According to the obtained DTA curve, the endothermic end temperature in the endothermic peak is performed by a tangent method. Extrapolation to determine the softening point Ts.

C. Making of paste

The paste was prepared by the following procedure.

a. organic ingredients

The organic solid matter containing the following raw materials was weighed and mixed by the weight ratio shown in Table 1, and 42 parts by weight of an organic solvent (γ-butyrolactone) was added to 40.1 parts by weight of the organic solid matter, and mixed. The organic vehicle was prepared by stirring.

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

Photosensitive polymer (polymer and weight formed by adding 0.4 equivalent of glycidyl methacrylate to a carboxyl group containing a copolymer of methacrylic acid/methyl methacrylate/styrene=40/40/30) The average molecular weight is 43,000 and the acid value is 100): 18 parts by weight

Photopolymerization initiator (2-benzyl-2-dimethylamino-1-(4-N-morpholinylphenyl)-1-butanone, IC369 (trade name) manufactured by BASF Corporation): 5 Parts by weight

Sensitizer (2,4-diethylthioxanthone): 1 part by weight

Antioxidant (1,6-hexanediol-bis[(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid] ester): 4 parts by weight

UV absorber (Sudan IV (manufactured by Tokyo Ohka Kogyo Co., Ltd., absorption wavelengths of 350 nm and 520 nm): 0.1 parts by weight

b. Inorganic components

80 vol% of the low-softening point glass powder of the following composition and 20 vol% of the high-softening point glass powder were mixed and used as an inorganic component.

Low-softening point glass powder: glass powder of the composition, softening point, and particle size distribution described in Table 2 and Table 3 (in addition, the symbols in the table have the following meanings. SiO ₂ : yttrium 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: yttrium oxide, Al ₂ O ₃ : alumina)

High softening point glass powder (sodium oxide: 1% by mass, cerium oxide: 40% by mass, boron oxide: 10% by mass, alumina: 33% by mass, zinc oxide: 4% by mass, calcium oxide: 9% by mass, titanium oxide) : 3 mass%, softening point Ts: 740 ° C, d ₅₀ : 2 μm, d _max : 10 μm)

c. Modulation of paste

The organic vehicle obtained above and the inorganic powder are mixed, prepared and added so that the ratio of the organic solids in all the solid components except the organic solvent is 42 vol%, and the ratio of the inorganic components is 58 vol%, The roller kneading machine was kneaded to prepare a photosensitive paste.

D. Evaluation of the amount of residual organic components

60 g of the glass powder described in Table 2 and Table 3 and 40 g of ethyl cellulose solution (ethylcellulose: 25 mass%, γ-BL: 75 mass%) were mixed and placed in 250 mL of aluminum. The container was covered with an aluminum lid and sealed to be calcined. The calcination conditions were such that the temperature was raised to 500 ° C at 10 ° C / min in air and held at 500 ° C for 15 minutes. The calcined powder 15 mg was measured at 550 ° C in a He environment using a thermal decomposition gas chromatography mass spectrometer (GCMS-QP2010 Plus manufactured by Shimadzu Corporation), and the total value of all peak areas derived from the organic component was measured. The residual organic components were evaluated. When the total value of the peak area is 5 × 10 ⁶ or more, there are many organic components remaining and it is not preferable.

E. Production of evaluation substrate

The evaluation substrate can be produced by the following procedure. The address electrode pattern was formed by a photolithography method using a photosensitive silver paste on a "PD-200" glass substrate (42 inch) manufactured by Asahi Glass Co., Ltd. Next, a dielectric layer was formed on the glass substrate on which the address electrodes were formed by a screen printing method to a thickness of 20 μm. Thereafter, the photosensitive paste is uniformly applied to the back glass substrate on which the address electrode pattern and the dielectric layer are formed by a screen printing method until the desired thickness is obtained. In order to avoid occurrence of pinholes or the like on the coating film, coating and drying were repeated several times or more, and the thickness after drying was 150 μm. Drying on the way was carried out at 100 ° C for 10 minutes. Next, exposure is performed by exposure of the mask. The exposure mask is a chrome mask designed to form a lattice-like insulating pattern in a plasma display having a vertical pitch of 150 μm, a vertical line width of 25 μm, a lateral pitch of 450 μm, and a horizontal line width of 25 μm. Exposure may be by using 50mW / cm ² power output of the superhigh pressure mercury lamp in the exposure time is changed within a range of 250mJ / cm ² ~ 375mJ / cm ² at an interval of 25mJ / cm ² for 8-point of exposure. Thereafter, development was carried out by spraying a 0.3% by mass aqueous solution of monoethanolamine for 150 seconds, and washing with water to remove the uncured space portion. Moreover, the separator was formed by baking at 590 ° C for 30 minutes, and the substrate for evaluation was obtained.

F. Yellowing evaluation

The position of the bottom of the separator in the substrate prepared in E was 55 μm by the SCE mode of a spectroscopic spectrometer ("CM-2002" manufactured by Konica Minolta Co., Ltd.). , evaluate the b* value. When the b* value is 10 or more, the yellowing of the separator is remarkable and unsatisfactory.

G. Viscosity stability

The viscosity of the paste prepared in C at a temperature of 25 ° C and a rotation speed of 3 rpm was measured using a B-type viscometer (manufactured by Brookfield, USA, DV-II) equipped with a digital calculation function. The viscosity of the paste after storage on the first day and the storage at 23 ° C for 7 days was measured twice, and the viscosity of the first day was calculated as the standard for the viscosity of the first day, and the viscosity was evaluated. When the viscosity increase rate after 7 days is 10% or more, the viscosity stability is poor and is not good.

H. Minimum bottom partition width

The separator of the substrate prepared in E was observed, and the width of the bottom of the separator which did not peel off was measured, and the minimum value was taken as the minimum width of the bottom of the separator. In the production condition of E, the width of the top of the separator is about 38 μm, so that the smaller the width of the bottom of the separator is smaller than 38 μm or more, the more the separator becomes a rectangular separator, which is preferable. When the width of the bottom of the minimum separator is 50 μm or more, the fine separator pattern cannot be formed and is not preferable.

I. Surface roughness evaluation

The paste prepared in C was applied onto a glass substrate (PD-200, 5: manufactured by Asahi Glass Co., Ltd.) at a film thickness of 50 μm by doctor blade coating, and then dried at 100 ° C for 30 minutes. Thereafter, the mixture was fired at 590 ° C for 30 minutes to prepare a sample for surface roughness evaluation. The surface roughness was measured by the arithmetic mean deviation (Ra) of the contour by Surfcom ("1400D" manufactured by Tokyo Precision Co., Ltd.). The measurement conditions were such that the measurement length was 1 mm in the ISO-'97 measurement "surface roughness measurement", and the measurement speed was set to 0.30 mm/s. As the paste having a surface roughness Ra of 2.0 μm or more, the display characteristics of the panel produced by using the paste are deteriorated, which is not preferable.

The evaluation results of the pastes obtained in Examples 1 to 16 and Comparative Examples 1 to 10 are shown in Table 2 and Table 3.

In Table 3, A = X (SiO ₂ ) + X (B ₂ O ₃ ) - X (M ₂ O)

In Examples 1 to 16, A is in the range of 35 to 46, and B (zinc oxide content) is in the range of 1.5 to 5.5, and C (alkali metal oxide, alkaline earth metal oxide, zinc oxide content) In total, it is in the range of 24 to 30, and in any case, the residual organic component is small and good.

In Comparative Example 1 in which A is less than 35, the alkali metal oxide in the glass The content rate is large, the b* value becomes large, and the separator is yellowed, so it is not good.

In Comparative Example 2 to Comparative Example 4 in which A is larger than 46, the content of cerium oxide and boron oxide in the glass is large, and the acid-base balance of the glass is poor, so that there are many organic components remaining and it is not preferable.

In Comparative Example 5 in which B (zinc oxide content) was less than 1.5, since zinc oxide was small, the surface roughness Ra was large and unsatisfactory.

In Comparative Example 6 in which B (zinc oxide content) was more than 5.5, since there was a large amount of zinc oxide, the viscosity increase rate of the paste was large and unsatisfactory.

In Comparative Example 7 in which C (the total content of alkali metal oxides, alkaline earth metal oxides, and zinc oxides) was less than 24, the total amount of zinc oxide, alkali metal oxide, and alkaline earth metal oxide was small, and thus the surface roughness Ra was Big and poor.

In Comparative Examples 8 to 10 in which C (the total content of alkali metal oxides, alkaline earth metal oxides, and zinc oxides) is more than 30, the total amount of zinc oxide, alkali metal oxide, and alkaline earth metal oxide is large. The low softening point glass powder has a high refractive index and a large difference in refractive index from the organic component. As a result, the width of the bottom of the smallest separator becomes large, and it becomes impossible to form a fine pattern and is not preferable.

(industrial availability)

The present invention can be used usefully as a paste for forming a separator having a small residual organic component. Further, it can be used as a flat panel display which forms a separator having a small amount of residual organic components, and is excellent in display characteristics such as brightness and color purity, and has high panel reliability.

Claims (5)

A paste comprising: a low softening point glass powder having a softening point of 570 ° C to 620 ° C; and an organic component, the low softening point glass powder containing cerium oxide, boron oxide, an alkali metal oxide, an alkaline earth metal oxide And zinc oxide, wherein the cerium 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 set to X (M ₂ O) (mol%), and the alkaline earth in the low-softening point glass powder When the metal oxide content is X (MO) (mol%) and the zinc oxide content in the low softening point glass powder is X (ZnO) (mol%), it is represented by the following formula (1) The value of A is in the range of 35 to 46, and the value of B represented by the following formula (2) is in the range of 1.5 to 5.5, and the value of C represented by the following formula (3) is 24 to 30. Within the range: 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 paste of claim 1, wherein the organic component comprises a photosensitive organic component. A method for manufacturing a panel for a flat panel display, characterized in that a paste as described in claim 1 or 2 is applied to a substrate. The agent is calcined to form an insulating pattern. A method for producing a panel for a flat panel display, comprising: applying a paste as described in claim 2 to a substrate, exposing, developing, and calcining to form an insulating pattern. A flat panel display panel having a separator having a low softening point glass having a softening point of 570 ° C to 620 ° C as a main component, wherein the low softening point glass powder contains cerium oxide, a boron oxide, an alkali metal oxide, an alkaline earth metal oxide, and a zinc oxide, wherein the low-softening point glass powder has a cerium oxide content of X (SiO ₂ ) (mol%), and the low softening point glass The content of boron oxide in the powder is X (B ₂ O ₃ ) (mol%), and the content of the alkali metal oxide 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 set to X (MO) (mol%), and the zinc oxide content in the low-softening point glass powder is set to X (ZnO) (mol%) When 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 following formula (2) is in the range of 1.5 to 5.5, and the following formula (3) The value of C 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).