WO2013176021A1 - Member comprising partition, paste for inorganic pattern formation, and pattern formation method - Google Patents

Abstract

The purpose of the present invention is: to provide a member for a plasma display panel and a member for a scintillator panel that comprise a partition having few residual organic components and exhibiting high strength and high reflectivity; and to provide a paste for inorganic pattern formation that is used to form such a partition. The present invention provides a member having a partition on a glass substrate, and the partition comprises a glass having a low softening point and a glass having a high softening point and comprising 65.5-69.0 mole% of SiO₂, 9.5-12.5 mole% of Al₂O₃, 8.0-12.0 mole% of B₂O₃, 0.5-3.5 mole% of MgO, and 7.5-10.5 mole% of CaO.

Description

Member having partition wall, inorganic pattern forming paste, and pattern forming method

The present invention relates to a member having a partition, an inorganic pattern forming paste, and an inorganic pattern forming method.

In recent years, it has become an important issue in the display industry to produce high-definition and low-power consumption displays with a high yield. Examples of the display include a plasma display, a liquid crystal display, and an organic EL display. Among these, the plasma display generates plasma discharge between the anode electrode and the cathode electrode facing each other in the discharge space provided between the front glass substrate and the rear glass substrate, and is enclosed in the discharge space. The display is performed by irradiating the phosphor provided in the discharge space with ultraviolet rays generated from the discharge gas to emit light.

The plasma display requires an insulating inorganic pattern, that is, a partition wall for partitioning the discharge space. As a method for forming these partition walls, a partition wall forming paste is repeatedly applied in a pattern by a screen printing plate, dried, then screen printing method for firing, masking with a resist on the dried partition material layer, Sand blasting method after shaving by sand blasting treatment, after baking the dried partition wall material, masking with a resist on the layer, etching method to etch, gold having pattern on coating film of partition wall forming paste A mold transfer method (imprint method) in which a mold is pressed to form a pattern, and a barrier rib material made of a photosensitive paste material is applied, dried, exposed and developed, and then baked. A known paste method (photolithographic method) is known. All of these inorganic pattern formation methods provide a paste coating film patterned using a partition forming paste containing a low softening point glass powder and an organic component, and the organic component is removed by baking to reduce the softness. This is a method of forming a partition which is an insulating inorganic pattern containing point glass. Among them, the photosensitive paste method is a method that can cope with an increase in area with high definition and a high cost merit.

In order to increase the definition of the plasma display, it is desired that the cross-sectional shape of the partition wall is narrow in both the bottom line width and the top line width. However, since the strength of the barrier ribs decreases as the width becomes narrower, the manufacturing process in which impact is applied to the barrier ribs such as the phosphor coating process between the barrier ribs and the sealing process of the front substrate and the rear substrate, and the panel after completion When an impact is applied, the partition wall collides with the opposing substrate, and the partition wall is easily damaged. This damage causes a panel non-lighting defect or an abnormal lighting defect such as color mixing, resulting in a decrease in yield. Therefore, it is an important issue to achieve both a narrow partition wall and high strength. In response to this problem, it has been reported that, by forming a layer with a large porosity only in the uppermost layer of the partition wall, the applied impact is absorbed by this high porosity layer, and large-scale damage is suppressed. (Patent Document 1). However, according to this method, since the porosity of the barrier ribs increases, there is a problem that the phosphor penetrates into the gaps of the barrier ribs when the phosphor is applied, and light emission is mixed to cause abnormal lighting.

On the other hand, the partition wall not only divides the light emitting area, but also affects the display characteristics of the display such as light emission luminance and color purity. In particular, in a plasma display, when the reflectance of the partition walls is low, the display light emitted from the phosphor layer applied to the side surfaces of the partition walls and the bottom surface between the partition walls is insufficiently reflected, resulting in low luminance. Therefore, there is a demand to increase the reflectance of the partition wall in order to improve the luminous efficiency.

Conventionally, a method of forming a partition wall having a high reflectance by a photosensitive paste method has been proposed (Patent Documents 2 and 3). In Patent Documents 2 and 3, a barrier rib having high reflectivity is obtained by forming a pattern with a photosensitive barrier rib forming paste in which inorganic fine particles (nanoparticles) having a high refractive index are uniformly dispersed, and then aggregating the nanoparticles during firing. Is forming. However, in this method, the nanoparticles dispersed in the paste are agglomerated again in the firing step, so it is difficult to control the particle diameter of the agglomerated particles, and the reflectance varies within the panel surface. Met. In addition, there is a problem that the cost of the nanoparticles as the raw material is high.

In the partition forming step, a partition is formed using a partition forming paste containing a low softening point glass and an organic component, and then fired to form the partition. At this time, the organic component is slightly added after firing. Remains. When this residual organic component is present in a large amount, there is a problem that the partition walls are colored and affect the display characteristics of the display such as the light emission efficiency and color purity of the panel. Furthermore, in the plasma display, 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 together to form a panel, which affects the front plate protective layer and increases the discharge voltage. There is a problem that the characteristics are deteriorated, and the impurity gas remains in the panel, so that the reliability of the panel cannot be increased and the yield is lowered.

Therefore, various methods for reducing the residual organic components after firing have been proposed in order to produce a display having excellent display characteristics such as luminous efficiency and color purity and high panel reliability (Patent Documents 4 to 6). Patent Document 4 is characterized by using a resin containing a hydroxyl group and a polymerizable unsaturated group as an organic component in the paste, for example, a polyol having excellent thermal decomposability at high temperatures. Patent Document 5 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 6 is characterized by using a low softening point glass having a glass transition point that is 10 ° C. higher than the temperature at which the weight loss rate of the organic component reaches 80% so that the decomposition product of the organic component does not remain in the glass. is there. However, these methods can reduce residual organic components due to poor thermal decomposability, but cannot suppress thermal decomposition products due to adsorption to glass, so the reduction of residual organic components in the partition is still insufficient. There was a problem.

Also, in the medical field, attention has been focused on members having partition walls. Conventionally, an X-ray image using a film has been widely used in a medical field. However, since X-ray images using film are analog image information, in recent years, digital radiation such as computed radiography (CR) and flat panel type radiation detectors (flat panel detector: FPD) has been used. Detection devices have been developed.

In a flat plate X-ray detector (FPD), a scintillator panel is used to convert radiation into visible light. The scintillator panel includes an X-ray phosphor such as cesium iodide (CsI), and the X-ray phosphor emits visible light in response to the irradiated X-rays, and the light emission is converted into an electrical signal by a TFT or CCD. Is converted into digital image information. However, FPD has a problem that the S / N ratio is low. This is because visible light is scattered by the phosphor itself when the X-ray phosphor emits light. In order to reduce the influence of this light scattering, a method of filling a phosphor in a cell partitioned by a partition has been proposed (Patent Documents 7 and 8).

However, as a method for forming such a partition wall, a conventionally used method is a method of etching a silicon wafer or a screen printing method using a glass paste which is a mixture of a pigment or ceramic powder and a low-melting glass powder. A method of forming a partition wall pattern by performing pattern printing in multiple layers using calcination and baking. In the method of etching a silicon wafer, the size of the scintillator panel that can be formed is limited by the size of the silicon wafer, and a large size such as a 500 mm square cannot be obtained. In order to make a large size, it is necessary to make a plurality of small sizes side by side. However, it is difficult to manufacture accurately, and it is difficult to manufacture a scintillator panel having a large area.

Also, with the multi-layer screen printing method using glass paste, high-precision processing is difficult due to changes in the dimensions of the screen printing plate. In addition, when performing multi-layer screen printing, a certain partition wall width is required to increase the strength of the partition pattern in order to prevent the collapse defect of the partition pattern. When the width of the barrier rib pattern is increased, the space between the barrier ribs is relatively narrowed, the volume in which the phosphor can be filled is reduced, and the filling amount is not uniform. For this reason, the scintillator panel obtained by this method has the drawbacks that the amount of X-ray phosphor is small, so that light emission becomes weak and light emission unevenness occurs. This is an obstacle to clear imaging in low-dose imaging.

In other words, in order to produce a scintillator panel that has high luminous efficiency and realizes clear image quality, a high-strength partition wall that can be processed with high accuracy over a large area and that does not easily break even if the partition wall width is narrowed. is necessary. Furthermore, in order to improve the extraction efficiency of visible light, it is required that the partition wall has a high reflectance.

JP 2006-012436 A JP 2001-229838 A JP 2001-27802 A JP 2001-305729 A JP 2008-50594 A JP-A-11-52561 Japanese Patent Laid-Open No. 5-60871 JP 2011-007552 A

Therefore, the present invention is to provide a member having a partition wall having high strength and high reflectance and having a small amount of residual organic components, and to provide an inorganic pattern forming paste for forming such a partition wall. And

In order to solve the above problems, the present invention has the following configuration. That is, the present invention is a member having a partition on a glass substrate. The partition includes a low softening point glass, SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.2. 5 mol%, B ₂ O ₃ : 8.0 to 12.0 mol%, MgO: 0.5 to 3.5 mol%, and CaO: 7.5 to 10.5 mol%, high And a softening point glass. Further, low softening point glass powder, SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.5 mol%, B ₂ O ₃ : 8.0 to 12.0 mol% %, MgO: 0.5 to 3.5 mol%, and CaO: 7.5 to 10.5 mol%, comprising a high softening point glass powder and an organic component, for forming an inorganic pattern Provide paste.

According to the present invention, it is possible to form an inorganic pattern having high strength and high reflectance and having a small amount of residual organic components.

The member of the present invention has a partition on a glass substrate, and the partition includes a low softening point glass, SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.5. High softening having a composition of mol%, B ₂ O ₃ : 8.0 to 12.0 mol%, MgO: 0.5 to 3.5 mol%, and CaO: 7.5 to 10.5 mol% Point glass.

High softening point glass refers to glass having a softening point of greater than 650 ° C. The low softening point glass means a glass having a softening point in the range of 450 to 650 ° C. It is preferable to contain each of the two types of glass having a softening point in the above-described range since the meltability in the firing process becomes appropriate. The softening point of glass can be measured by differential scanning calorimetry using glass powder.

As the high softening point glass, it is necessary to use a glass having the following composition. For example, the expression “65.5 to 69.0 mol%” means 65.5 mol% or more and 69.0 mol% or less.
SiO ₂ : 65.5 to 69.0 mol%
Al ₂ O ₃ : 9.5 to 12.5 mol%
B ₂ O ₃ : 8.0 to 12.0 mol%
MgO: 0.5 to 3.5 mol%
CaO: 7.5 to 10.5 mol%
SiO ₂ is a component that forms a glass skeleton. When the content is small, the reflectance of the partition walls is decreased, and the stability of the glass is decreased. Therefore, a content of 65.5 mol% or more is necessary. . On the other hand, when the content is increased, the breakage of the partition wall becomes remarkable, and the softening point of the glass becomes too high, resulting in an increase in production cost. Therefore, a content of 69.0 mol% or less is necessary. The content of SiO ₂ is more preferably 66.0 to 68.5 mol%.

Al ₂ O ₃ has the effect of stabilizing the glass by widening the vitrification range, and when the content is small, the reflectance of the partition walls is reduced, so a content of 9.5 mol% or more is necessary. . On the other hand, when the content is increased, the partition wall is significantly damaged, and thus the content rate is required to be 12.5 mol% or less. The content of Al ₂ O ₃ is more preferably 10.0 to 12.0 mol%.

B ₂ O ₃ is a component that forms a glass skeleton in the same manner as SiO _2, and is a component that enhances partition wall strength and suppresses breakage, so a content of 8.0 mol% or more is required. On the other hand, if the content increases, the glass becomes chemically unstable and the remaining organic components in the partition walls increase, so the content must be 12.0 mol% or less.

MgO is a component that reduces the remaining organic components of the partition walls, so a content of 0.5 mol% or more is necessary. On the other hand, when the content is increased, the partition wall is significantly damaged, and the reflectance of the partition wall is remarkably lowered. Therefore, the content rate is required to be 3.5 mol% or less.

CaO, like MgO, is a component that reduces the remaining organic components of the partition walls, so a content of 7.5 mol% or more is necessary. On the other hand, when the content is increased, the partition wall is significantly damaged, and the reflectance of the partition wall is lowered. Therefore, the content rate is required to be 10.5 mol% or less.

In addition to the above, the high softening point glass preferably contains 0.2 to 0.8 mol% of SrO. By containing 0.2 mol% or more of SrO, the remaining organic components are reduced. On the other hand, when SrO is contained in an amount of more than 0.8 mol%, the partition wall is significantly damaged.

Although the effect of reducing residual organic components by the inclusion of BaO is also observed, the content of BaO is preferably 0.1 mol% or less because damage to the partition walls becomes significant even when contained in a very small amount.

Further, the high softening point glass of the present invention preferably contains 0.1 to 1.5 mol% of Na ₂ O. By containing Na ₂ O in an amount of 0.1 mol% or more, the reflectance of the partition wall is significantly improved. On the other hand, when Na ₂ O is contained in an amount of more than 1.5 mol%, the partition wall is easily yellowed due to the influence of silver present in the electrode.

On the other hand, the Li 2 _O and K _{2 O,} the reflectance improvement effect of the partition walls not clear, since the strong influence of the yellowing, the content preferably 0.1 mol% or less.

The high softening point glass may contain ZnO, TiO ₂ or the like, but both of them lower the reflectance of the partition walls and make the partition damage remarkable, so the content is 0.1 mol% or less. It is preferable that

The glass component and its content can be specified and calculated from each raw material and its blending ratio at the time of glass powder production, but also specified and calculated from the analysis of glass powder, inorganic pattern forming paste or partition wall sample. Is possible. When the sample is glass powder, it can be quantitatively determined by performing atomic absorption analysis or inductively coupled plasma (hereinafter, “ICP”) emission spectral analysis. When the sample is a partition wall, it can be quantitatively determined by Auger electron spectroscopy. More specifically, the cross section of the partition wall is observed with a scanning electron microscope (hereinafter, “SEM”), and the low softening point glass and the high softening point glass are distinguished by the difference in light and shade of the SEM images. Elemental analysis. In the case where the sample is a partition wall, a means for selectively cutting out the high softening point glass or the low softening point glass from the partition wall and performing atomic absorption analysis or ICP emission spectroscopic analysis can be used supplementarily. When the sample is an inorganic pattern forming paste, the glass powder is isolated by operations such as filtration and washing of the inorganic pattern forming paste, and then the same analysis as the glass powder is performed, or the inorganic pattern forming paste is applied and After baking to form the partition, the same analysis as the partition can be performed.

As the low softening point glass, a low softening point glass having a known and commonly used composition can be used. Specifically, it is preferable to use a low softening point glass having the following composition.
SiO ₂ : 25 to 48 mol%
Al ₂ O ₃ : 4 to 15 mol%
Li ₂ O + Na ₂ O + K ₂ O: 4 to 17 mol%
B ₂ O ₃ : 27 to 40 mol%
MgO + CaO + SrO + BaO: 0 to 5.5 mol%
ZnO: 0 to 12 mol%
ZrO: 0 to 2 mol%
The SiO ₂ in the low softening point glass is preferably 25 to 48 mol%, more preferably 29 to 42 mol%, still more preferably 33 to 42 mol%. By making the content rate of silicon oxide 25 mol% or more, the thermal expansion coefficient can be kept small, and cracks can be made difficult to occur when baked on a glass substrate. Furthermore, the refractive index can be lowered. Moreover, by setting it as 48 mol% or less, the softening point of glass can be lowered | hung and the baking temperature to a glass substrate can be lowered | hung.

Al ₂ O ₃ is preferably 4 to 15 mol% and more preferably 8 to 15 mol% in order to improve the chemical stability of the glass.

Alkali metal oxides have an effect of not only facilitating control of the thermal expansion coefficient of glass but also lowering the softening point. Here, the alkali metal oxide refers to Li ₂ O, Na ₂ O, and K ₂ O, and including an alkali metal oxide refers to containing one or more of these. The total content of alkali metal oxides in the low softening point glass powder is preferably 4 to 17 mol%, more preferably 10 to 17 mol%. By setting it as 4 mol% or more, the softening point of glass can be reduced. Moreover, by setting it as 17 mol% or less, a thermal expansion coefficient can be suppressed small and a refractive index can be reduced, maintaining the chemical stability of glass. Further, since it can reduce the yellowing, the content of Na 2 _O accounted for the low softening point glass powder is preferably 3.5 mol% or less.

B ₂ O ₃ is preferably 27 to 41 mol% in order to suitably maintain the balance of glass composition and chemical stability. In order to improve the chemical stability of the glass, lower the softening point, lower the baking temperature on the glass substrate, and further lower the refractive index, it is more preferably 27-37 mol%, and 27-34 mol%. Further preferred.

In the present invention, the alkaline earth metal oxide refers to MgO, CaO, SrO, BaO. Alkaline earth metal oxides not only facilitate the control of the coefficient of thermal expansion, but also have the effect of lowering the softening point. The total value is preferably 5.5 mol% or less, more preferably 4 mol% or less, and even more preferably 2 mol% or less.

ZnO has the effect of lowering the softening point without greatly changing the thermal expansion coefficient of the glass. However, on the other hand, in order to deteriorate paste viscosity stability, the content of zinc oxide in the low softening point glass powder is preferably 12 mol% or less, more preferably 6 mol% or less, and further preferably 4 mol% or less. preferable.

As other components of the low softening point glass powder, ZrO or TiO ₂ having an effect of improving the chemical stability of the glass may be contained. Further, it may be contained Bi ₂ O ₃ or the like has the effect of reducing components other than the above, for example, the softening point.

The inorganic pattern forming paste is a pattern printing method such as a screen printing method, a sand blasting method, an etching method, a mold transfer method (imprinting method) or a photosensitive paste method (photolithography method), followed by baking. The mixture of an inorganic component and an organic component which can form an inorganic pattern by removing an organic component is said. The inorganic pattern forming paste of the present invention comprises a low softening point glass powder, SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.5 mol%, B ₂ O ₃ : A high softening point glass powder having a composition of 8.0 to 12.0 mol%, MgO: 0.5 to 3.5 mol%, and CaO: 7 to 10.5 mol%, and an organic component, It is characterized by including.

Examples of the organic component contained in the inorganic pattern forming paste of the present invention include a photosensitive organic component such as a photosensitive monomer, a photosensitive oligomer, or a photosensitive polymer. In this case, the inorganic pattern forming paste is a photosensitive paste.

A photosensitive paste is a pattern formed by irradiating an actinic ray to a coating film after being applied and dried to make the irradiated part insoluble in the developer, and then removing only the non-irradiated part with the developer. A paste that can be used. Here, the actinic ray means an electromagnetic wave having a wavelength range of 250 to 1100 nm, and more specifically, an ultraviolet ray such as an ultra-high pressure mercury lamp or a metal halide lamp, a visible ray such as a halogen lamp, a helium-cadmium laser, a helium-neon laser, Specific examples of the laser beam include an argon ion laser, a semiconductor laser, a YAG laser, and a carbon dioxide laser.

The photosensitive inorganic pattern forming paste of the present invention contains a low softening point glass powder as an inorganic component. The composition of the low softening point glass powder may be single, or a mixture of low softening point glass powders having a plurality of different compositions may be used. By baking a photosensitive inorganic pattern forming paste containing a low softening point glass powder at a temperature near or above the softening point of the low softening point glass powder to remove organic components such as photosensitive organic components An inorganic pattern containing a low softening point glass can be obtained.

In the photosensitive paste method, the refractive index of the low softening point glass powder is preferably 1.45 to 1.65. Here, the refractive index means a refractive index at a wavelength of 436 nm (g-ray of a mercury lamp) at 25 ° C. measured by a Becke line detection method. By using such a low softening point glass powder, the difference in refractive index between the inorganic component and the organic component is reduced, light scattering is suppressed, and high-precision inorganic pattern processing is facilitated. In the present invention, the refractive index of the low softening point glass is preferably 1.49 to 1.57, and preferably 1.51 to 1.55 in order to match the refractive index with the high softening point glass. More preferred.

The particle size of the low softening point glass powder is selected in consideration of the shape of the inorganic pattern to be produced, but 50% particles in the weight distribution curve measured by a particle size distribution measuring device (for example, MT3300; manufactured by Nikkiso). The diameter d ₅₀ (hereinafter referred to as “average particle diameter”) is preferably 0.1 to 4.0 μm, and the maximum particle diameter d _max (top size) is preferably 20 μm or less.

The photosensitive inorganic pattern forming paste of the present invention needs to contain a high softening point glass powder as a filler component as an inorganic component other than the low softening point glass powder. I do not care. Here, the filler component is added to improve the strength of the inorganic pattern and the firing shrinkage rate, and refers to inorganic fine particles that do not melt and flow even at the firing temperature. By adding a filler component, problems such as pattern collapse due to flow during pattern firing and peeling due to shrinkage can be suppressed, and the strength of the inorganic pattern can be improved. As the filler component, in consideration of dispersibility and filling properties in a photosensitive inorganic pattern forming paste, and suppression of light scattering during exposure, the average particle size (d ₅₀ ) is 1 to 4 μm, and the average refractive index is 1.4. Those with ˜1.7 are preferred.

When only the high softening point glass powder is used as the filler component, it is preferable to add the high softening point glass powder having a softening point of 650 to 1350 ° C. in a composition range of 50% by volume or less with respect to the total inorganic components. When the amount of the high softening point glass powder is more than 50% by volume, the density of the inorganic pattern to be formed tends to be lowered.

The total inorganic components are preferably contained in a solid content of the photosensitive inorganic pattern forming paste in a content of 35 to 70% by volume, and contained in a content of 40 to 65% by volume. It is more preferable. Here, the solid content means an organic component excluding a solvent and an inorganic component contained in the inorganic pattern forming paste. If the content of the inorganic component in the solid content is less than 35% by volume, pattern shrinkage due to firing increases and the shape tends to be poor. On the other hand, if it exceeds 70% by volume, the crosslinking reaction due to exposure becomes insufficient and pattern formation becomes difficult. In addition, the volume ratio of the low softening point glass and filler component of the inorganic pattern formed using the photosensitive inorganic pattern forming paste is the low softening point glass powder and filler component added to the photosensitive inorganic pattern forming paste. The volume ratio can be controlled.

The content (% by volume) of the inorganic component in the solid content can be controlled by the addition amount (% by mass) in consideration of the density of the inorganic component and the organic component when preparing the inorganic pattern forming paste. In addition, as a method for analyzing the content of the inorganic component, a method for obtaining by thermogravimetry (hereinafter referred to as “TGA”) and density measurement of the fired film of the inorganic component, or applying and drying a photosensitive inorganic pattern forming paste The paste dry film obtained in this way can be obtained by image analysis of a transmission electron microscope (hereinafter, “TEM”) observation image. When the density of the fired film of TGA and inorganic components is determined, for example, about 10 mg of a photosensitive inorganic pattern forming paste is used as a sample, and the weight change from room temperature to 600 ° C. is measured with TGA (for example, TGA-50; Shimadzu Corporation). Product). Usually, since the solvent in the inorganic pattern forming paste evaporates at 100 to 150 ° C., the weight after raising the temperature to 600 ° C. relative to the weight after evaporation of the solvent (corresponding to the weight of the inorganic component because the organic component is removed) ) To obtain the mass ratio of the inorganic component and the organic component. On the other hand, the content rate can be evaluated by evaluating the density of the inorganic component based on the film thickness, area and mass of the fired film. When the content ratio is determined by TEM observation, the cross section perpendicular to the film surface of the paste dry film is observed by TEM (for example, JEM-4000EX; manufactured by JEOL Ltd.), and the inorganic component and the organic are determined by the density of the image. The components may be distinguished and image analysis may be performed. The TEM evaluation area covers an area of about 20 μm × 100 μm and can be observed at a magnification of about 1000 to 3000 times.

The photosensitive inorganic pattern forming paste of the present invention comprises a photosensitive organic component such as a photosensitive monomer, a photosensitive oligomer or a photosensitive polymer, a non-photosensitive polymer component, an antioxidant, a photopolymerization initiator, a plasticizer, an increase agent. You may add additive components, such as a viscosity agent, a dispersing agent, an organic solvent, or a precipitation inhibitor, as needed.

As the photosensitive polymer, an alkali-soluble polymer is preferable. This is because the photosensitive polymer has alkali solubility, so that an alkaline aqueous solution can be used as a developing solution instead of an organic solvent having an environmental impact. The alkali-soluble polymer is preferably an acrylic copolymer containing an unsaturated acid such as an unsaturated carboxylic acid as a constituent monomer. Here, the acrylic copolymer refers to a copolymer containing at least an acrylic monomer as a copolymer component. Examples of the acrylic monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, Benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2- Hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropy Acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, acrylamide, aminoethyl acrylate Acrylic monomers such as phenyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate or thiophenol acrylate, benzyl mercaptan acrylate, or those obtained by substituting these acrylates with methacrylate. As the copolymer component other than the acrylic monomer, a compound having a carbon-carbon double bond can be used. Examples of such a compound include styrene, o-methylstyrene, m-methylstyrene, p- Examples thereof include styrenes such as methylstyrene, α-methylstyrene, chloromethylstyrene, and hydroxymethylstyrene, or 1-vinyl-2-pyrrolidone or vinyl acetate.

In order to impart alkali solubility to the acrylic copolymer, an unsaturated acid such as an unsaturated carboxylic acid may be added as a monomer. Examples of the unsaturated acid imparting alkali solubility include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, and acid anhydrides thereof. The acid value of the alkali-soluble polymer after adding these is preferably in the range of 50 to 150.

In the case of using an acrylic copolymer, an acrylic copolymer having a carbon-carbon double bond at the side chain or molecular end is used in order to increase the reaction rate of the curing reaction by exposure of the photosensitive inorganic pattern forming paste. It is preferable to combine. Examples of the group having a carbon-carbon double bond include a vinyl group, an allyl group, an acrylic group, and a methacryl group. An acrylic copolymer having such a functional group in the side chain or molecular end is composed of a glycidyl group or an isocyanate group, a carbon atom with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the acrylic copolymer. It can be synthesized by a reaction of a compound having a carbon double bond or 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 monomer is a compound containing a carbon-carbon double bond. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert- Butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, hepta Decafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate Relate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl acrylate Allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate Dipenta Lithritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, tetrapropylene glycol dimethacrylate, Acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, bisphenol A-propylene oxide adduct Diac Relay , Thiophenol acrylate or benzyl mercaptan acrylate, monomers in which 1 to 5 hydrogen atoms of the aromatic ring of these monomers are substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methylstyrene, m-methyl Styrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, vinylnaphthalene, vinylanthracene or vinylcarbazole Can be mentioned. In addition, a compound in which a part or all of the acrylate in the molecule of the compound containing a carbon-carbon double bond is substituted with methacrylate, γ-methacryloxypropyltrimethoxysilane, or 1-vinyl-2-pyrrolidone is also included. . In the polyfunctional monomer, an acrylic group, a methacryl group, a vinyl group, or an allyl group may be mixed.

The photosensitive inorganic pattern forming paste of the present invention preferably further contains a urethane compound. By containing the 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 | survive in a baking process. As a urethane compound, the compound shown by following General formula (1) is mentioned, for example.

Here, R ¹ and R ² are selected from the group consisting of a substituent containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an allyl group, an aralkyl group, and a hydroxyaralkyl group, Each may be the same or different. R ³ is an alkylene oxide group or alkylene oxide oligomer, and R ⁴ is an organic group containing a urethane bond. n is an integer of 1 to 10.

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

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

Examples of the urethane compound include UA-2235PE (molecular weight 18000, EO content 20%), UA-3238PE (molecular weight 19000, EO content 10%), UA-3348PE (molecular weight 22000, EO content 15%) or UA. -5348PE (molecular weight 39000, EO content 23%) (all manufactured by Shin-Nakamura Chemical Co., Ltd.) or a mixture thereof.

The content of the urethane compound in the organic components excluding the solvent is preferably 0.1 to 10% by mass. By setting the content to 0.1% by mass or more, the flexibility of the paste dry film can be improved, and the firing shrinkage stress when the paste dry film is fired can be reduced. On the other hand, when the content exceeds 10% by mass, the dispersibility of the organic component and the inorganic component is decreased, and the concentrations of the monomer and the photopolymerization initiator are relatively decreased, so that defects are easily generated.

The photosensitive inorganic pattern forming paste of the present invention may further contain a cellulose compound such as methylcellulose or ethylcellulose or a high molecular weight polyether as an organic component.

An antioxidant may be added to the photosensitive inorganic pattern forming paste of the present invention. Here, the antioxidant means one having at least one of a radical chain inhibiting action, a triplet elimination action, and a hydroperoxide decomposition action. When an antioxidant is added to the photosensitive inorganic pattern forming paste, the antioxidant captures radicals or returns the energy state of the excited photopolymerization initiator to the ground state, thereby causing extra light due to scattered light. The photoreaction is suppressed and the photoreaction occurs abruptly at an exposure amount that cannot be suppressed by the antioxidant, so that the contrast of dissolution and insolubility in the developer can be increased. Examples of the antioxidant include 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, α-naphthol Hydrazine hydrochloride, trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene, picric acid, key Dioxime, cyclohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, cuperone, 2,2′-thiobis (4-t-octylphenolate) -2-ethylhexylaminonickel (II), 4, 4'-thiobis- (3-methyl-6-t-butylphenol), 2,2'-methylenebis- (4-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl -5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] or 1,2,3-tri Examples thereof include hydroxybenzene. The addition ratio of the antioxidant in the photosensitive inorganic pattern forming paste is preferably 0.1 to 30% by mass, and more preferably 0.5 to 20% by mass. By making the addition amount of the antioxidant within this range, the photosensitivity of the paste for inorganic pattern formation is maintained, and the degree of polymerization is maintained and the pattern shape is maintained, while the contrast between the exposed part and the non-exposed part is maintained. Can be greatly increased.

As the photopolymerization initiator, a photo radical initiator that generates radicals upon irradiation with an active light source is preferable. Examples of the photo radical initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl- 4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, Thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl Ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene ) Cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 1-phenyl-1,2-butadion-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione -2- (O-ethoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, Michler's ketone, 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N- Light such as phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone or benzoin peroxide, eosin or methylene blue A combination of a reducing dye and a reducing agent such as ascorbic acid or triethanolamine can be mentioned. The photopolymerization initiator is preferably added in an amount of 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total amount of the photosensitive monomer and the photosensitive polymer. If the amount of the photopolymerization initiator is too small, the photosensitivity may be deteriorated. If the amount of the photopolymerization initiator is too large, the light absorption becomes too large to reach the deep part and the deep part is cured. Is insufficient.

It is also preferable to add an organic solvent in order to adjust the viscosity when applying the photosensitive inorganic pattern forming paste to the substrate according to the application method. Examples of the organic solvent include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, Examples include dichlorobenzene, bromobenzoic acid or chlorobenzoic acid.

The photosensitive inorganic pattern forming paste of the present invention comprises a low softening point glass powder, a filler component, a photosensitive organic component, a non-photosensitive polymer component, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a dispersant, and It is preferable that each component such as a solvent is prepared so as to have a predetermined composition, and then main kneading is performed using a kneading apparatus such as a three-roller to uniformly disperse it. It is also preferable to appropriately filter and degas the photosensitive inorganic pattern forming paste that has been subjected to the main kneading.

The basic structure of the AC type plasma display will be described below as an example.

The plasma display seals the front glass substrate and the rear glass substrate so that the phosphor layer formed on either the front glass substrate or the rear glass substrate or both faces the inner space, that is, the discharge space, This is a member in which a discharge gas such as Xe—Ne or Xe—Ne—He is sealed in the discharge space. In the front glass substrate, a transparent electrode (sustain electrode, scan electrode) for display discharge is formed on the substrate on the display surface side, but the gap between the sustain electrode and scan electrode is relatively small due to discharge. Narrower is preferable. Moreover, you may form a bus electrode in the back side of a transparent electrode in order to form a lower resistance electrode. However, the bus electrode is made of Ag, Cr / Cu / Cr, or the like, and is often opaque and obstructs the display of the cell. Therefore, the bus electrode is preferably provided on the outer edge of the display surface. In the case of an AC plasma display, a transparent dielectric layer and an MgO thin film as a protective film are often formed on the upper layer of the electrode. On the rear glass substrate, electrodes (address electrodes) for selecting the addresses of cells to be displayed are formed. The partition walls and phosphor layers for partitioning the cells may be formed on both the front glass substrate and the back glass substrate, but are often formed only on the back glass substrate.

The following explains how to make the back plate. As the glass substrate having a thickness of 1 to 5 mm, PP8 (manufactured by Nippon Electric Glass Co., Ltd.) and PD200 (manufactured by Asahi Glass Co., Ltd.), which are heat-resistant glass for soda glass or plasma display, can be used. A stripe-shaped conductive pattern for address electrodes is formed on a glass substrate with a metal such as silver, aluminum, chromium or nickel. As a method for forming a stripe-shaped conductive pattern, a metal paste mainly composed of a metal powder and an organic binder is printed by screen printing, and a photosensitive metal paste using a photosensitive organic component is applied as an organic binder. Thereafter, a photosensitive paste method can be used in which pattern exposure is performed using a photomask, unnecessary portions are dissolved and removed in a development process, and further, heated and baked at 350 to 600 ° C. to form an electrode pattern. Another example is an etching method in which chromium or aluminum is vapor-deposited on a glass substrate, a resist is applied, the resist is subjected to pattern exposure / development, and unnecessary portions are removed by etching.

Furthermore, it is preferable to provide a dielectric layer on the address electrode because the stability of the discharge can be improved and the falling or peeling of the partition formed on the upper layer of the dielectric layer can be suppressed. As a method for forming the dielectric layer, a dielectric paste mainly composed of an inorganic component such as a low softening point glass powder or a high softening point glass powder and an organic binder is screen-printed or entirely printed or applied by a slit die coater or the like. There are ways to do this.

Next, a method for forming partition walls by photolithography will be described. The partition pattern is preferably a stripe shape, a lattice shape, a waffle shape, or the like. First, a photosensitive partition wall forming paste is applied on a substrate on which a dielectric layer is formed. Examples of the coating method include a bar coater, a roll coater, a slit die coater, a blade coater, and screen printing. The coating thickness can be determined in consideration of the desired partition wall height and the shrinkage ratio due to firing of the partition wall forming paste, and can be adjusted by the number of coatings, the screen mesh or the viscosity of the partition wall forming paste.

Exposure is performed after drying the apply | coated photosensitive paste for barrier rib formation. In general, the exposure is performed through a photomask, as in normal photolithography. Moreover, you may use the method of drawing directly with a laser beam etc., without using a photomask. Examples of the exposure apparatus include a stepper exposure machine or a proximity exposure machine. Examples of the actinic rays used at this time include near infrared rays, visible rays, and ultraviolet rays, and ultraviolet rays are preferable. Examples of the ultraviolet light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, and a germicidal lamp, and an ultra-high pressure mercury lamp is preferable. Although the exposure conditions vary depending on the coating thickness of the photosensitive partition wall forming paste, the 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 .

Develop after exposure using the difference in solubility in the developer between the exposed and unexposed areas. Examples of the developing method include an immersion method, a spray method, and a brush method. Examples of the developer include an organic solvent in which an organic component in the photosensitive barrier rib forming paste can be dissolved, but a compound having an acidic group such as a carboxyl group is present in the photosensitive barrier rib forming paste. Development with an aqueous alkali solution is possible. Examples of the alkaline aqueous solution include an aqueous solution of sodium hydroxide, sodium carbonate, or potassium hydroxide, but an organic alkaline aqueous solution is preferable because an alkaline component can be easily removed during firing.

Examples of the organic alkali include general amine compounds such as tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine and diethanolamine.

If the concentration of the aqueous alkali solution is too low, it is difficult to remove the soluble part, while if it is too high, the partition walls may be peeled off or corroded, so 0.05 to 5% by mass is preferable, and 0.1 to 1% by mass is more preferable. The development temperature is preferably 20 to 50 ° C. in view of process control.

Next, baking is performed by holding in a baking furnace at a temperature of 520 to 620 ° C. for 10 to 60 minutes to form partition walls.

Next, a phosphor layer is formed using the phosphor paste. Examples of the method for forming the phosphor include a photolithography method using a photosensitive phosphor paste, a dispenser method, and a screen printing method. The thickness of the phosphor layer is preferably 10 to 30 μm, more preferably 15 to 25 μm. As the phosphor powder, which is one component of the phosphor paste, the following phosphors are preferable from the viewpoints of light emission intensity, chromaticity, color balance, life, and the like. For blue, an aluminate phosphor activated with divalent europium (for example, BaMgAl ₁₀ O ₁₇ : Eu) or CaMgSi ₂ O ₆ is preferable. In the case of green, Zn ₂ SiO ₄ : Mn, YBO ₃ : Tb, BaMg ₂ Al ₁₄ O ₂₄ : Eu, Mn, BaAl ₁₂ O ₁₉ : Mn or BaMgAl ₁₄ O ₂₃ : Mn are preferable from the viewpoint of panel luminance, and Zn ₂ SiO ₄ : Mn is more preferable. In red, similarly, (Y, Gd) BO ₃ : Eu, Y ₂ O ₃ : Eu or YPVO: Eu, YVO ₄ : Eu are preferable, and (Y, Gd) BO ₃ : Eu is more preferable. When the phosphor is formed through the firing process, the above-described dielectric layer and barrier ribs may be fired simultaneously.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to these. The average particle diameter _{(d 50)} of less of the inorganic powder and the maximum particle diameter _{(d max)} is a value measured using a MT3300 (manufactured by Nikkiso Co., Ltd.).

Example 1
A. Glass powder low softening point glass powder:
SiO _2: 40 _mol%, Al ₂ O 3: 10 mol%, _Li 2 O: 8 _{mol%, K} 2 O: 8 _{mol%, B 2} O 3: 30 mol%, MgO: 1 mol%, CaO: 1 A pulverized glass having a composition of mol%, ZnO: 1 mol%, ZrO ₂ : 1 mol% (softening point: 590 ° C., d ₅₀ : 2 μm, d _max : 10 μm)
High softening point glass powder: ground glass having the composition shown in Table 1 (softening point: all> 650 ° C., d ₅₀ : 2 μm, d _max : 10 μm)

B. Evaluation of residual organic component amount 0.75 g of a mixture of 20 g of high softening point glass powder and 40 g of ethyl cellulose solution (ethyl cellulose: 25 mass%, γ-BL: 75 mass%) is put in a 250 mL aluminum container and covered with an aluminum lid. Sealed and fired. The firing conditions were 10 ° C./min to 500 ° C. in air and 15 minutes at 500 ° C. Using a pyrolysis gas chromatograph mass spectrometer (GCMS-QP2010Plus; manufactured by Shimadzu Corporation), 15 mg of the calcined powder was heated at 550 ° C. in a He atmosphere for 5 minutes to detect and detect the components released by GC-MS. The total value of all the peak areas derived from the organic component among the obtained peaks was determined and used as the residual organic component amount. The evaluation results are shown in Table 2. When a large amount of residual organic components are contained in the powder after baking at 500 ° C., the residual organic components that are thermally decomposed and released upon subsequent heating at 550 ° C. increase, and the total value of peak areas also increases. In order to stabilize the characteristics of the plasma display panel, it is essential to use a high softening point glass with a small amount of residual organic component in this evaluation. If the amount of residual organic component is 3 × 10 ⁶ or more, the residual organic component Many ingredients are unsuitable. It is particularly preferable that the amount of residual organic components is 1.0 × 10 ⁶ or less.

C. Preparation of photosensitive partition wall forming paste A photosensitive partition wall forming paste 1 was prepared by the following procedure.
a. Organic vehicle An organic vehicle was prepared by weighing and mixing organic solids composed of the following raw materials and stirring to dissolve.
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 copolymer obtained by addition reaction of 0.4 equivalent of glycidyl methacrylate; weight average molecular weight 43000; acid value 100): 18 parts by weight photopolymerization initiator (2-benzyl-2) -Dimethylamino-1- (4-morpholinophenyl) -1-butanone; IC369; manufactured by BASF): 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 wt. UV absorber (Sudan IV; Tokyo Ohka Kogyo Co., Ltd .; absorption wavelength: 350 nm and 520 nm): 0.1 parts by weight solvent (.gamma.-butyrolactone): 42 parts by weight b. Photosensitive partition wall forming paste To 50 parts by weight of the obtained organic vehicle, 50 parts by weight of low softening point glass powder and 10 parts by weight of high softening point glass powder were added, and then kneaded by a three-roller kneader. A photosensitive partition wall forming paste was obtained. The produced photosensitive partition wall forming paste was defoamed by reducing the pressure to 1 kPa while stirring.

D. Fabrication of partition walls Using the photosensitive partition wall forming paste 1 fabricated in C, the partition walls 1 were fabricated in the following procedure. On a glass substrate PD-200 (Asahi Glass Co., Ltd .; 42 inch square), an address electrode pattern was formed 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, a photosensitive barrier rib forming paste for forming the lower layer of the barrier rib is formed on a back glass substrate on which the address electrode pattern and the dielectric layer are formed by a slit die coater to be a glass film having a thickness of 120 μm after firing. The coated film of the photosensitive partition wall forming paste 1 was formed by coating with a film thickness and drying at 100 ° C. for 1 hour. Subsequently, exposure was performed through an exposure mask. The exposure mask is a chromium mask designed so that a stripe-shaped barrier rib pattern can be formed in a plasma display with a pitch of 160 μm and an opening width of 25 μm. Exposure for each of the photosensitive barrier rib forming paste coated film from 100 mJ / cm ² by an ultra-high pressure mercury lamp with an output of 50 mW / cm ² to 500 mJ / cm ^2, were UV exposure to 5 mJ / cm ² intervals.

Next, after developing by applying a 0.3% by weight aqueous solution of monoethanolamine held at 35 ° C. for 300 seconds in a shower, the product was washed with water using a shower spray to remove the uncured space portion. . Thereafter, the partition wall 1 was formed by firing at 560 ° C. for 30 minutes.

E. Evaluation of barrier rib reflectivity Samples with different exposure doses prepared in D were cleaved to expose a cross section perpendicular to the longitudinal direction of the barrier rib 1, and the cross section was observed with a scanning electron microscope (S2400; manufactured by Hitachi, Ltd.). The partition wall width (bottom width) at the contact portion of the dielectric was measured. Since the bottom wall width of the partition wall becomes thicker as the exposure dose increases, a sample having the bottom width of the partition wall 1 after firing of 45 μm is selected from the prepared samples, and the sample is spectrocolorimeter (CM-2002; The reflectance at a wavelength of 530 nm and the b ^* value were evaluated. As described above, the higher the reflectance, the higher the light emission efficiency of the plasma display. Therefore, the reflectance is preferably high, and particularly preferably 48% or more. It is not suitable when the reflectance is 45% or less. The b ^* value is an index of yellowing, and the smaller the value, the more preferably 3. When the b ^* value is 5 or more, yellowing of the partition walls is remarkable, which is not preferable.

F. Separation resistance evaluation of barrier ribs Among the samples with different exposure doses prepared in D, a sample having a bottom width of 50 μm after baking was selected, and this sample was cut out to 5 cm × 13 cm, and the surface on which the barrier ribs of the substrate were not formed The four points of 1 cm square in the center of and the center one point were marked. Next, a “PD-200” glass substrate cut out to a size of 5 cm × 13 cm is placed on the side where the partition walls are formed and placed with the back plate side up, and a metal sphere weighing 114 g is placed 30 cm. It was dropped twice at 5 points marked from the height of. Thereafter, a 1 cm square portion at the center of the sample substrate was cut out, and a photograph of the partition wall missing portion was taken with a scanning electron microscope. The area of the cross section caused by the chip was measured by image analysis of the photograph taken, and the total number of the chip of the partition wall 1 and the number of large area chips having a cross section area of 2000 μm ² or more caused by the chip were measured. This evaluation is a model test for occurrence of chipping defects when the plasma display panel is impacted, and the number of large-area chipping is preferably small, particularly preferably 5 / cm ² or less. When the number of large area defects was more than 20 / cm ² , it was unsuitable. The evaluation results are shown in Table 2.

(Examples 2 to 12)
The same operation as in Example 1 was carried out except that a crushed glass having the composition shown in Table 1 was used as the high softening point glass powder to obtain partition wall forming pastes 2 to 12 and partition walls 2 to 12, respectively. . The same evaluation as Example 1 was performed about each high softening point glass powder and each obtained partition. The evaluation results are shown in Table 2.

(Comparative Examples 1 to 7)
The same operation as in Example 1 was performed except that a glass pulverized product having the composition shown in Table 1 was used as the high softening point glass powder to obtain partition wall forming pastes 13 to 19 and partition walls 13 to 19, respectively. . The same evaluation as Example 1 was performed about each high softening point glass powder and each obtained partition. The evaluation results are shown in Table 2.

The composition of the high softening point glass powder is SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.5 mol%, B ₂ O ₃ : 8.0 to 12.0 mol% In Examples 1 to 12 that satisfy the composition of MgO: 0.5 to 3.5 mol% and CaO: 7.5 to 10.5 mol%, the number of large area defects is small, the reflectance is high, And the good result that there are few residual organic components was shown. On the other hand, in Comparative Examples 1 to 7 in which the composition of the high softening point glass powder did not satisfy the above, any of the problems of large number of large area defects, low reflectance, and many residual organic components was observed.

(Examples 13 to 28)
For the combination of the high softening point glass powder of Example 1 and the low softening point glass powder having the composition shown in Table 3, the following evaluation was carried out in addition to the reflectance, b * and the number of large area defects. The evaluation results are shown in Table 4.

G. The partition wall of the substrate manufactured with the minimum partition wall bottom width D was observed, the partition wall bottom width where peeling did not occur was measured, and the minimum value was defined as the minimum partition wall bottom width. The case where the minimum partition wall bottom width was less than 40 μm was rated as “◎”, the case where it was 40 or more and less than 45 μm, and the case where it was 45 μm or more and less than 50 μm, Δ. Since the minimum barrier rib bottom width becomes thin when light scattering during exposure of the barrier rib paste is small, it is preferable that it is thin.

H. The substrate produced by the sinterability D was cleaved to expose the partition wall cross section, the partition wall cross section was observed with a scanning electron microscope, and the porosity was calculated by image analysis. The case where the sintering was sufficiently progressed and the void was less than 2% was designated as sinterability, and the case where the porosity was 2% or more and less than 5% was designated as sinterability. If the sintering is insufficient, the phosphor coating may be difficult.

I. Viscosity Stability Using a B-type viscometer with a digital calculation function (DV-II; manufactured by Brookfield, USA), the viscosity of the partition wall paste prepared in C at a temperature of 25 ° C. and a rotation speed of 3 rpm was measured. The partition wall paste viscosity was measured twice after the first day of production and after storage at 23 ° C. for 7 days, and the rate of increase in viscosity after 7 days of storage was calculated on the basis of the viscosity of the first day of production and used as an index of viscosity stability. A case where the rate of increase in viscosity is less than 3% is indicated as ◎, a case where it is 3% or more and less than 5% is given as ○, and a case where it is 5% or more and less than 8% is indicated as △. The smaller the change in viscosity, the better.

J. et al. Evaluation of chemical stability of glass The low softening point glass powder shown in Table 3 was remelted to form a block, and immersed in a 0.5% aqueous sodium carbonate solution at 75 ° C. for 10 hours. Asked. The case where the weight reduction rate was less than 0.7% was rated as ◎, the case where it was 0.7% or more and less than 0.9% was marked as ◯, and the case where it was 0.9% or more and less than 1.2% was marked as Δ. A smaller weight reduction rate indicates higher chemical stability of the glass, which is preferable.

Examples 13 to 18 all showed very good characteristics. Examples 19, 20, 24, 27, and 29, which have a relatively high amount of B ₂ O ₃ , exhibited relatively good characteristics although they were slightly inferior in chemical stability. Examples 22, 24, 28 and 29 with relatively high ZnO showed relatively good properties although their viscosity stability was slightly inferior. In Examples 21, 22, 23 and 28 in which the total amount of the alkaline earth metal was relatively large, the reflectance tended to be slightly lower, but all were good with a reflectance of 44% or more. In Examples 22 to 24 and 27 to 29 in which the refractive index is greater than 1.54 or less than 1.51, the minimum partition wall bottom width tended to be slightly thicker, but any of them can form a narrow partition wall of 50 μm or less. It was.

The present invention can be usefully used as a member for a plasma display panel or a member for a scintillator panel.

Claims (8)

1. A member having a partition on a glass substrate;
   The partition walls include low softening point glass, SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.5 mol%, B ₂ O ₃ : 8.0 to 12.0. And a high softening point glass having a composition of mol%, MgO: 0.5 to 3.5 mol%, and CaO: 7.5 to 10.5 mol%.
2. The member according to claim 1, wherein the high softening point glass further has a composition of SrO: 0.2 to 0.8 mol%.
3. The member according to claim 1 or 2, wherein the high softening point glass further has a composition of Na ₂ O: 0.1 to 1.5 mol%.
4. Low softening point glass powder,
   SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.5 mol%, B ₂ O ₃ : 8.0 to 12.0 mol%, MgO: 0.5 to 3 A high softening point glass powder having a composition of 0.5 mol% and CaO: 7.5 to 10.5 mol%;
   An inorganic pattern forming paste containing an organic component.
5. An inorganic pattern forming method, wherein the inorganic pattern forming paste according to claim 4 is applied on a glass substrate and baked to form an inorganic pattern.
6. A member having a partition wall produced by the inorganic pattern forming method according to claim 5.
7. A plasma display panel comprising the member according to any one of claims 1 to 3 or 6.
8. A scintillator panel having the member according to any one of claims 1 to 3 or 6.