TWI557086B - Member having partition wall, paste for forming inorganic pattern and method for forming pattern - Google Patents

Description

Member having partition walls, paste for forming inorganic pattern, and pattern forming method

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

In recent years, in the display industry, it has become an important issue to manufacture high-definition displays with low power consumption at high output. As the display, there are a plasma display, a liquid crystal display, an organic EL display, and the like. Among these, the plasma display is in a discharge space provided between the front glass substrate and the rear glass substrate, and a plasma discharge is generated between the opposing anode electrode and the cathode electrode, and the discharge space will be sealed from the discharge space. The ultraviolet light generated by the discharge gas inside is irradiated onto the phosphor provided in the discharge space, and is emitted to emit light.

A plasma display system requires an insulating inorganic pattern for separating the discharge spaces, that is, a partition wall. As a method of forming the partition walls, a screen printing method in which a partition wall forming paste is repeatedly applied into a pattern by a screen printing plate and dried, and then baked is known; in the dried partition wall a sandblasting method in which a layer of a material is shielded by a photoresist, and is fired by a sandblasting treatment; and after the dried partition wall material is fired, an etching method is performed by masking the layer on the layer with a photoresist; Pressing a mold having a pattern on the coating film of the partition forming paste and forming After the pattern, a pattern transfer method (imprint method) in which baking is performed, and a photosensitive paste method in which a partition material containing a photosensitive paste material is applied and dried, and subjected to exposure and development treatment, and then fired (photomicro Shadow method) and so on. In the inorganic pattern forming method, a patterned paste coating film is provided by using a paste for forming a partition wall containing a low softening point glass powder and an organic component, and the organic component is removed by firing to form a glass containing a low softening point. A method of partitioning walls of an insulating inorganic pattern. Among them, the photosensitive paste method is a method of high definition and capable of responding to a large area, and is a cost-effective method.

In order to achieve high definition of the plasma display, the cross-sectional shape of the partition wall requires a bottom line width and a top line width. However, as the width is refined, the strength of the partition wall is lowered, and therefore, the manufacturing step of applying the punch to the partition wall between the partitioning walls or the front substrate and the back substrate sealing step, or When the panel after the completion of the punching is applied, the partition wall collides with the opposing substrate, and the like, and the partition wall is likely to be damaged by a defect or the like. Since the panel is not bright or defective, or an abnormal lighting defect such as color mixing occurs, and the yield is lowered, the width of the partition wall and the increase in strength are both important issues. With respect to this problem, it has been reported that a layer having a large void ratio is formed only in the uppermost layer of the partition wall, and the applied punch is absorbed by the high void ratio layer, thereby suppressing large-scale damage (Patent Document 1). However, in this method, since the void ratio of the partition walls is increased, there is a problem that the phosphor is infiltrated into the gap of the partition wall when the phosphor is applied, and the color mixture of the light is emitted and the light is abnormally turned on.

On the other hand, the partition wall not only simply distinguishes the light-emitting region, but also affects the display characteristics of the display such as the light-emitting luminance and the color purity. In particular, in the plasma display, when the reflectance of the partition wall is low, the reflection of the light emitted from the phosphor layer applied to the bottom surface between the partition wall side surface or the partition wall is insufficient, and the brightness is lowered. Therefore, in order to improve luminous efficiency, it is necessary to increase the reflectance of the partition walls.

In the past, a method of forming a partition having a high reflectance by a photosensitive paste method has been proposed (Patent Documents 2 and 3). In Patent Literatures 2 and 3, a pattern of a photosensitive partition wall-forming paste in which high-refractive-index inorganic fine particles (nanoparticles) are uniformly dispersed is patterned, and a reflection is formed by agglomerating nanoparticles during firing. High partition wall. However, in this method, since the nanoparticles dispersed in the paste are reaggregated in the firing step, it is difficult to control the particle diameter of the aggregated particles, and the reflectance is uneven in the panel surface. Moreover, there is a problem that the cost of the nanoparticle as a raw material is high.

Further, in the step of forming the partition wall, the partition wall forming paste having the low softening point glass and the organic component is formed into a pattern, and then the partition wall is formed by firing. However, at this time, some micro organic components remain after the firing. When the amount of the residual organic component is large, there is a problem that the partition wall is colored and the display characteristics of the display such as the luminous efficiency and the color purity of the panel are affected. Further, in the plasma display, in the sealing step of laminating the front panel and the back panel, the organic component remaining on the partition wall is generated as a gas, which affects the front panel protective layer and causes a discharge voltage to rise. The problem of deterioration of characteristics or the problem that the yield of the panel cannot be improved and the yield is lowered because the impurity gas remains in the panel.

Therefore, in order to produce a display having excellent display characteristics such as luminous efficiency and color purity and high panel reliability, various methods for reducing residual organic components after firing have been proposed (Patent Documents 4 to 6). Patent Document 4 is characterized in that a resin containing a hydroxyl group and a polymerizable unsaturated group as an organic component in a paste, for example, a polyol having good thermal decomposition property at a high temperature is used. Patent Document 5 is characterized in that an acrylic copolymer having a polyalkylene oxide segment having a high oxygen atom content as an organic component is used in order to enhance the thermal decomposition property of the organic component. Patent Document 6 is characterized in that the organic component decomposed product does not remain in the glass, and a low-softening point glass having a glass transition point higher than a temperature at which the organic component has a reduction rate of 80% higher than 10 ° C is used. However, in such a method, it is possible to reduce the thermal decomposition property of the residual organic component, but it is not possible to suppress the adsorption of the thermal decomposition product to the glass. Therefore, the residual organic component of the partition wall is not lowered. Sufficient question.

Further, in the medical field, attention has been paid to members having partition walls. X-ray images using thin films have been widely used in medical fields in the past. However, since the X-ray image of the film is analog image information, in recent years, digital radiography such as a computed radiography (CR) or a flat panel detector (FPD) has been developed. Detection device.

In a flat panel X-ray detecting device (FPD), a scintillator panel can be used in order to convert radiation into visible light. The scintillator panel contains an X-ray phosphor such as cesium iodide (CsI), and the X-ray phosphor emits visible light according to the X-ray to be irradiated, and is converted into an electric signal by TFT or CCD. Convert X-ray information into numbers Bit image intelligence. However, FPD has a problem of low S/N ratio. This is due to the fact that the X-ray phosphor is illuminating, and the visible light or the like is scattered by the phosphor itself. In order to reduce the influence of the scattering of light, a method of filling a phosphor in an element partitioned by a partition wall has been proposed (Patent Documents 7 and 8).

However, as a method of forming the partition walls as described above, a conventionally usable method is a method of etching a tantalum wafer, or a glass paste which is a mixture of a pigment or a ceramic powder and a low-melting glass powder, using a screen. The printing method pattern is printed in a plurality of layers and then fired to form a partition pattern. In the method of etching a germanium wafer, the size of the scintillator panel that can be formed is limited according to the size of the germanium wafer, and a large size such as a rectangular shape of 500 mm cannot be obtained. In order to make a large size, it is necessary to manufacture a small size side by side, but it is difficult to produce it, and it is difficult to produce a large-sized scintillator panel.

Further, in the multi-layer screen printing method using a glass paste, it is difficult to process with high precision depending on the dimensional change of the screen printing plate or the like. Further, in the case of performing multi-layer screen printing, in order to prevent breakage of the partition pattern, a certain partition wall width is required in order to increase the strength of the partition pattern. When the width of the partition pattern is widened, the space between the partition walls is relatively narrow, and the volume of the fillable phosphor is reduced, and the filling amount is not uniform. Therefore, in the scintillator panel obtained by this method, since the amount of the X-ray phosphor is small, there is a disadvantage that the light emission is weak and the light emission is uneven. The above is a phenomenon in which a low-ray amount of photography is used to perform vivid photography.

In particular, in order to produce a scintillator panel having high luminous efficiency and achieving vivid image quality, it is necessary to process a large area with high precision, and to make the width of the partition wall thin and difficult to cause damage, and a high-strength partition wall. Furthermore, in order to improve the extraction efficiency of visible light, a high reflectance of the partition walls is required.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2006-012436

Patent Document 2 Japanese Patent Laid-Open Publication No. 2001-229838

Patent Document 3 Japanese Patent Laid-Open Publication No. 2001-27802

Patent Document 4 Japanese Patent Laid-Open Publication No. 2001-305729

Patent Document 5 Japanese Patent Laid-Open Publication No. 2008-50594

Patent Document 6 Japanese Patent Laid-Open No. Hei 11-52561

Patent Document 7 Japanese Patent Laid-Open No. Hei 5-60871

Patent Document 8 Japanese Patent Publication No. 2011-007552

Accordingly, an object of the present invention is to provide a member having a high strength and a high reflectance and having a partition wall having a small residual organic component, and a paste for forming an inorganic pattern for forming the partition wall as described above.

In order to solve the aforementioned problems, the present invention has the following constitution. That is, the present invention provides a member which is a member having a partition wall on a glass substrate, the partition wall comprising a low softening point glass and having SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.5 _{mole%, B 2 O 3: 8.0} ~ 12.0 mole%, MgO: 0.5 ~ 3.5 mole%, and CaO: 7.5 ~ 10.5 mole% of a high softening point glass. Further, a paste for forming an inorganic pattern comprising a low softening point glass powder; having SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.5 mol%, and B ₂ O ₃ : 8.0 to 12.0 a high softening point glass powder having a composition of MoM%, MgO: 0.5 to 3.5 mol%, and CaO: 7.5 to 10.5 mol%; and an organic component.

According to the present invention, an inorganic pattern having high strength, high reflectance, and little residual organic component can be formed.

The member of the present invention is characterized in that it has a partition wall on the glass substrate, the partition wall comprising a low softening point glass and having SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.5 mol %, B ₂ O ₃ : 8.0~12.0 mol%, MgO: 0.5~3.5 mol%, and CaO: 7.5~10.5 mol% of high softening point glass.

High softening point glass refers to glass having a softening point greater than 650 °C. Further, the low softening point glass refers to a glass having a softening point in the range of 450 to 650 °C. It is preferred that the two types of glass each having a softening point within the above range are appropriately prepared in the firing step. The softening point of the glass can be determined by differential scanning calorimetry using glass powder.

As the high softening point glass, it is necessary to use a glass having the composition shown below. Further, for example, the expression "65.5 to 69.0 mol%" means 65.5 mol% or more and 69.0 mol% or less.

SiO ₂ : 65.5~69.0 mol%

Al ₂ O ₃ : 9.5~12.5 mol%

B ₂ O ₃ : 8.0~12.0 mol%

MgO: 0.5~3.5 mol%

CaO: 7.5~10.5 mol%

SiO ₂ is a component that forms a glass skeleton. When the content is small, the reflectance of the partition walls is lowered, and the stability of the glass is lowered. Therefore, a content ratio of 65.5 mol% or more is required. On the other hand, when the content is increased, the damage of the partition walls becomes remarkable, and the softening point of the glass becomes too high and the manufacturing cost becomes high, so a content ratio of 69.0 mol% or less is required. The content of SiO ₂ is more preferably 66.0 to 68.5 mol%.

Al ₂ O ₃ has an effect of expanding the vitrification range and stabilizing the glass, and when the content is small, the reflectance of the partition walls is lowered, so a content ratio of 9.5 mol% or more is required. On the other hand, when the content is increased, the damage of the partition walls becomes remarkable, so the content ratio is required to be 12.5 mol% or less. The content of Al ₂ O ₃ is more preferably from 10.0 to 12.0 mol%.

Similarly to SiO _{2 ,} B ₂ O ₃ is a component that forms a glass skeleton, and is a component that increases the strength of the partition walls and suppresses damage. Therefore, a content ratio of 8.0 mol% or more is required. On the other hand, when the content is increased, the glass becomes chemically unstable, and the residual organic component of the partition wall increases. Therefore, the required content is 12.0 mol% or less.

Since MgO is a component which reduces the residual organic component of a partition, it is a content rate of 0.5 mol% or more. On the other hand, when the content is increased, the damage of the partition walls is remarkable, and the reflectance of the partition walls is remarkably lowered. Therefore, the required content ratio is 3.5 mol% or less.

Similarly to MgO, CaO is a component which reduces the residual organic component of the partition wall, and therefore requires a content ratio of 7.5 mol% or more. On the other hand, when the content is increased, the damage of the partition walls becomes remarkable, and the reflectance of the partition walls is lowered. Therefore, the content ratio is required to be 10.5 mol% or less.

In addition to the foregoing, the high softening point glass preferably contains 0.2 to 0.8 mol% of SrO. Residual organic components can be reduced by containing 0.2 mol% or more of SrO. On the other hand, when more than 0.8 mol% of SrO is contained, the damage of the partition walls becomes remarkable.

In addition, BaO has been confirmed to have an effect of reducing residual organic components by inclusion. However, since BaO is contained in a very small amount, the damage of the partition walls is also remarkable, and therefore the content is preferably 0.1 mol% or less.

Further, the high softening point glass of the present invention preferably contains 0.1 to 1.5 mol% of Na ₂ O. By containing 0.1 mol% or more of Na ₂ O, the reflectance of the partition walls can be remarkably improved. On the other hand, when more than 1.5 mol% of Na ₂ O is contained, the influence of silver present on the electrode causes the partition walls to be easily yellowed.

On the other hand, regarding Li ₂ O and K ₂ O, the effect of improving the reflectance of the partition walls is not clear, and the influence on the yellowing is strong, so the content ratio is preferably set to 0.1 mol% or less.

The high softening point glass may also contain ZnO, TiO ₂ or the like, but these all lower the reflectance of the partition walls, and the damage of the partition walls becomes remarkable, so the content ratio is preferably 0.1 mol% or less.

The constituents of the glass and the content thereof may be determined and calculated based on the respective raw materials and the blending ratio of the glass powder, but may be determined and calculated based on the glass powder, the inorganic pattern forming paste, or the sample of the partition wall. . When the sample is a glass powder, it can be quantitatively measured by performing atomic absorption analysis or inductively coupled plasma (hereinafter referred to as "ICP") luminescence spectroscopic analysis. When the sample is a partition wall, it can be quantitatively determined by using Auger electron spectroscopic analysis. More specifically, the scanning wall electron microscope (hereinafter referred to as "SEM") is used to observe the partition wall profile, and the low softening point glass and the high softening point glass are distinguished by the difference in the SEM image, and the beam is distinguished by the Auger electron beam. Individual elemental analysts. Further, when the sample is a partition wall, it is also possible to use a means for selectively removing high-softening point glass or low-softening point glass according to the partition wall, and performing atomic absorption analysis and ICP emission spectroscopic analysis. When the sample is a paste for inorganic pattern formation, the glass powder may be separated from the glass powder by an operation such as filtration or cleaning using the paste for forming an inorganic pattern, and the paste may be applied and baked according to the paste for forming an inorganic pattern. The partition walls were formed and the same analysis was performed with the partition walls.

As the low-softening point glass, a low-softening point glass of a conventionally known composition can be used. Specifically, it is preferred to use a low-softening point glass having the following composition.

SiO ₂ : 25~48 mol%

Al ₂ O ₃ : 4~15 mol%

Li ₂ O+Na ₂ O+K ₂ O: 4~17 mol%

B ₂ O ₃ : 27~40 mol%

MgO+CaO+SrO+BaO: 0~5.5 mol%

ZnO: 0~12 mol%

ZrO: 0~2 mol%

The SiO ₂ in the low-softening point glass is preferably from 25 to 48 mol%, more preferably from 29 to 42 mol%, and particularly preferably from 33 to 42 mol%. When the content of cerium oxide is 25 mol% or more, the thermal expansion coefficient can be suppressed to be small, and cracking is less likely to occur when the glass substrate is baked. Furthermore, the refractive index can be lowered. Further, by setting it to 48 mol% or less, the softening point of the glass can be lowered, and the baking temperature for the glass substrate can be lowered.

Al ₂ O ₃ is preferably from 4 to 15 mol%, more preferably from 8 to 15 mol%, because it can enhance the chemical stability of the glass.

The alkali metal oxide not only makes it easy to control the thermal expansion coefficient of the glass, but also has an effect of lowering the softening point. Here, the alkali metal oxide means Li ₂ O, Na ₂ O, and K ₂ O, and the alkali metal oxides contain one or more of these. The total content of the alkali metal oxides contained in the low-softening point glass powder is preferably from 4 to 17 mol%, more preferably from 10 to 17 mol%. By becoming 4 mol% or more, the softening point of the glass can be lowered. Further, by setting it to 17 mol% or less, the chemical stability of the glass can be maintained, and the thermal expansion coefficient can be suppressed to be small to lower the refractive index. Further, from the viewpoint of reducing yellowing, the content of Na ₂ O contained in the glass powder having a low softening point is preferably 3.5 mol% or less.

B ₂ O _{3 is} preferably 27 to 41 mol% in order to properly maintain the balance of the glass composition and chemical stability. In order to increase the chemical stability of the glass, to lower the softening point, and to lower the baking temperature for the glass substrate, or to lower the refractive index, it is more preferably 27 to 37 mol%, particularly preferably 27 to 34 mol%.

In the present invention, the alkaline earth metal oxide means MgO, CaO, SrO, or BaO. The alkaline earth metal oxide not only has an effect of controlling the thermal expansion coefficient of the glass but also has an effect of lowering the softening point. However, from the viewpoint of lowering the reflectance, the total content of the alkaline earth metal oxide is preferably 5.5. The ear is less than or equal to 4%, more preferably 4% by mole or less, and particularly preferably 2% by mole or less.

ZnO has an effect of lowering the softening point without significantly changing the thermal expansion coefficient of the glass. However, one of them may deteriorate the paste viscosity stability. Therefore, the content of zinc oxide contained in the glass powder having a low softening point is preferably 12 mol% or less, more preferably 6 mol% or less, and particularly preferably 4 Mole% or less.

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, the components other than the above may contain, for example, Bi ₂ O ₃ having an effect of lowering the softening point.

The paste for forming an inorganic pattern means that the pattern is formed by a method such as a screen printing method, a sand blast method, an etching method, a pattern transfer method (imprint method), or a photosensitive paste method (photolithography method). A mixture of an inorganic component and an organic component which are fired and removes an organic component to form an inorganic pattern. The paste for forming an inorganic pattern of the present invention is characterized by comprising a low-softening point glass powder; having SiO ₂ : 65.5 to 69.0 mol%, Al ₂ O ₃ : 9.5 to 12.5 mol%, and B ₂ O ₃ : 8.0 to 12.0 m Ears, MgO: 0.5 to 3.5 mol%, and CaO: 7 to 10.5 mol% of a composition of high softening point glass powder; and organic components.

The organic component contained in the paste for inorganic pattern formation of the present invention may, for example, be a photosensitive organic component such as a photosensitive monomer, a photosensitive oligomer or a photosensitive polymer. In this case, the paste for forming an inorganic pattern is a photosensitive paste.

The photosensitive paste refers to a paste which can be patterned by irradiating active light with a coating film after coating and drying to make the irradiated portion insoluble in the developing solution, and then removing only the non-irradiated portion by the developing solution. Here, the active light refers to an electromagnetic wave in a wavelength region of 250 to 1100 nm, and more specifically, an ultraviolet light such as an ultrahigh pressure mercury lamp or a metal halide lamp, a visible light line such as a halogen lamp, or a cadmium-cadmium laser. Laser light of a specific wavelength such as 氦-氖 laser, argon ion laser, semiconductor laser, YAG laser or 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 used singly or in combination with a low-softening point glass powder of a plurality of different compositions. By baking a photosensitive inorganic pattern forming paste containing a glass powder having a low softening point, it is fired at a temperature near the softening point or a softening point of the low softening point glass powder, and the organic component such as a photosensitive organic component is removed. 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 from 1.45 to 1.65. The refractive index herein refers to a refractive index measured by a Becquerel ray detection method at a wavelength of 436 nm (g-ray of a mercury lamp) at 25 °C. By using the low-softening point glass powder as described above, the difference in refractive index between the inorganic component and the organic component becomes small, and light scattering and high precision can be suppressed. The degree of inorganic pattern processing becomes easy. In the present invention, in order to integrate with the refractive index of the high softening point glass, the refractive index of the low softening point glass is preferably from 1.49 to 1.57, more preferably from 1.51 to 1.55.

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

The photosensitive inorganic pattern-forming paste of the present invention is required to contain a high-softening point glass powder which is a filler component as an inorganic component other than the low-softening point glass powder, but other filler components may be further added. The filler component herein refers to inorganic fine particles which are added so as not to melt at a firing temperature in order to improve the strength of the inorganic pattern or the rate of firing shrinkage. By adding the filler component, it is possible to suppress the problem of peeling or the like caused by the pattern collapse or shrinkage due to the flow at the time of firing of the pattern, and to enhance the strength of the inorganic pattern. The filler component is preferably an average particle diameter (d ₅₀ ) of 1 to 4 μm and an average refractive index of 1.4 in view of dispersibility or filling property in the photosensitive inorganic pattern forming paste and suppression of light scattering during exposure. ~1.7.

When only a high softening point glass powder is used as the filler component, a high softening point glass powder having a softening point of 650 to 1350 ° C is preferably added in a composition range of 50% by volume or less based on the total inorganic component. When the high softening point glass powder is more than 50% by volume, the denseness of the formed inorganic pattern is liable to lower.

The total inorganic component is preferably contained in a total content of 35 to 70% by volume in the solid content of the photosensitive inorganic pattern forming paste, and more preferably in a content ratio of 40 to 65% by volume. The solid component herein refers to an organic component excluding a solvent contained in the paste for forming an inorganic pattern, and an inorganic component. When the content of the inorganic component in the solid content is less than 35% by volume, the shrinkage of the pattern due to firing becomes large, and the shape tends to be poor. Further, when it is more than 70% by volume, the crosslinking causes the crosslinking reaction to become insufficient, and pattern formation becomes difficult. Further, the volume ratio of the low-softening point glass to the filler component of the inorganic pattern formed by using the photosensitive inorganic pattern-forming paste can be obtained by adding the low-softening point glass powder to the photosensitive inorganic pattern-forming paste. The volume ratio of the filler components is controlled.

The content ratio (% 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 in the production of the paste for inorganic pattern formation. In addition, as a method of analyzing the content rate of the inorganic component, a method of measuring the density of the fired film of the inorganic component by thermogravimetry (hereinafter referred to as "TGA") or a photosensitive inorganic pattern is used. A method of obtaining an image analysis of an image by a transmission electron microscope (hereinafter referred to as "TEM") of a paste-dried film obtained by coating and drying the paste. In the case of the measurement of the density of the fired film of the TGA and the inorganic component, for example, a sample of about 10 mg of the photosensitive inorganic pattern-forming paste is used as a sample, and a TGA (for example, TGA-50; manufactured by Shimadzu Corporation) evaluation room is used. The temperature changes from ~600 °C. Usually, since the solvent in the paste for inorganic pattern formation evaporates at 100 to 150 ° C, the temperature can be raised from the weight after evaporation with respect to the solvent to 600 ° C. The ratio of the weight (the weight of the inorganic component to the weight of the inorganic component is removed), and the mass 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, area, and mass of the fired film, the content ratio can be evaluated. In addition, when the content ratio is determined by TEM observation, the cross section perpendicular to the film surface of the paste-dried film is observed by TEM (for example, JEM-4000EX; manufactured by JEOL Ltd.), and the inorganic component and the organic component are distinguished by the shade of the image. The composition can be analyzed by image. As an evaluation area of the TEM, an area of about 20 μm × 100 μm is used, and it can be observed at about 1000 to 3000 times.

The photosensitive inorganic pattern forming paste of the present invention may optionally contain a photosensitive organic component such as a photosensitive monomer, a photosensitive oligomer or a photosensitive polymer, a non-photosensitive polymer component, an antioxidant, and light. An additive component such as a polymerization initiator, a plasticizer, a tackifier, a dispersant, an organic solvent or an anti-precipitant.

As the photosensitive polymer, an alkali-soluble polymer is preferred. Since the photosensitive polymer has alkali solubility, an alkaline aqueous solution can be used instead of an organic solvent having a burden on the environment as a developing solution. The alkali-soluble polymer is preferably an acrylic copolymer containing an unsaturated acid such as an unsaturated carboxylic acid as a constituent monomer. The acrylic copolymer as used herein means a copolymer containing at least an acrylic monomer in a copolymer component. The acrylic monomer herein may, for example, be methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, second butyl acrylate, isobutyl acrylate or acrylic acid. Butyl ester, n-amyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxy triethylene glycol acrylate, cyclohexyl acrylate, tricyclobutyl [5.2.1.0 ^2,6 ]癸-8-yl ester, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptafluorodecyl acrylate, 2-hydroxyethyl acrylate, Isodecyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxy ethylene glycol acrylate, methoxy two Ethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, octadecyl acrylate, trifluoroethyl acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, 1-naphthyl acrylate ,-2-naphthyl acrylate or thiophenol acrylate, benzyl thiol acrylate Etc. and the like of the acrylic monomer or an acrylate methacrylate were substituted. As the copolymerization component other than the acrylic monomer, a compound having a carbon-carbon double bond can be used. Examples of the compound as described above include styrene, o-methylstyrene, and m-methylstyrene. A styrene such as p-methylstyrene, α-methylstyrene, chloromethylstyrene or 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 which imparts alkali solubility include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, or fumaric acid or vinyl acetate or the like. The acid value of the alkali-soluble polymer after the addition is preferably in the range of 50 to 150.

When an acrylic copolymer is used, the reaction rate of the hardening reaction by exposure of the photosensitive inorganic pattern forming paste is increased, and the acrylic acid having a carbon-carbon double bond at the side chain or the molecular end is determined. Copolymers are preferred. Examples of the group having a carbon-carbon double bond include a vinyl group, an allyl group, an acryl group, or a methacryl group. The acrylic copolymer having a functional group as described above at a side chain or a molecular end may have a glycidyl group or an isocyanate group and carbon with respect to a mercapto group, an amine group, a hydroxyl group or a carboxyl group in the acrylic copolymer. Synthesis of a compound of a carbon double bond or a reaction of acrylonitrile, methacryloyl chloride or allyl chloride.

Examples of the compound having a glycidyl group and a carbon-carbon double bond include glycidyl methacrylate, glycidyl acrylate, allyl epoxidized propyl ether, and propylene propyl acrylate. , Crotonyl epoxypropyl ether, crotonyl crotonate or isopropyl crotonate. Examples of the compound having an isocyanate group and a carbon-carbon double bond include propylene sulfonate isocyanate, methacrylic acid methacrylate, acrylonitrile isocyanate or methacrylic acid isocyanate. Base ethyl ester.

The photosensitive monomer is a compound containing a carbon-carbon double bond, and examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, second butyl acrylate, and acrylic acid. Butyl ester, tert-butyl acrylate, n-amyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxy triethylene glycol acrylate, cyclohexyl acrylate, acrylic tricyclo [5.2 .1.0 ^2,6 ]癸-8-yl ester, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptafluorodecyl acrylate, acrylic acid - 2-Hydroxyethyl ester, isodecyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxy glycol acrylic acid Ester, methoxy diethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, octadecyl acrylate, trifluoroethyl acrylate, cyclohexyl methacrylate, 1,4-butyl Diol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate , diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy pentaacrylate, ditrimethylolpropane tetraacrylate, C Triol 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, bisphenol A- a diacrylate of an ethylene oxide adduct, a diacrylate of a bisphenol A-propylene oxide adduct, a thiophenol acrylate or a benzyl thiol acrylate or a hydrogen atom of an aromatic ring of the monomers 5 monomers substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α- Methyl styrene, α-methyl styrene chloride, brominated α- Butylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxy methyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole. Further, a part or all of the intramolecular acrylate of the compound containing a carbon-carbon double bond described above may be substituted with a methacrylate, γ-methylpropoxypropyltrimethoxy decane or 1- Vinyl-2-pyrrolidone. Further, an acrylic group, a methacryl group, a vinyl group or an allyl group may be mixed in the polyfunctional monomer.

The photosensitive inorganic pattern forming paste of the present invention preferably further contains a urethane compound. By containing urethane The compound can improve the softness of the dried film, reduce the stress during firing, and effectively suppress defects such as cracks or broken wires. Further, by containing a urethane compound, thermal decomposition property can be improved, and it is difficult to have an organic component remaining in the baking step. The urethane compound may, for example, be 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 allyl group, an aralkyl group, and a hydroxyaralkyl group. Individuals may be the same or different. R ³ is an oxyalkylene group or an alkylene oxide oligomer, and R ⁴ is an organic group containing a urethane bond. n is an integer from 1 to 10.

As the urethane compound as described above, a compound containing an ethylene oxide unit is preferred. Further, in the formula (1), R ⁴ is an oligomer containing an oxyethylene unit (hereinafter referred to as "EO") and an oxypropylene unit, and the EO content in the oligomer is in the range of 8 to 70% by mass. The compound is better. When the EO content is 70% by mass or less, the flexibility can be further improved and the firing stress can be reduced, so that defects can be effectively suppressed. Further, the thermal decomposition property is improved, and in the subsequent firing step, it is difficult to have an organic component remaining. Further, according to the EO content of 8% or more, the compatibility with other organic components can be improved.

Further, it is also preferred that the urethane compound has a carbon-carbon double bond. By reacting the carbon-carbon double bond of the urethane compound with the carbon-carbon double bond of the other crosslinking agent and containing it in the crosslinked body, the polymerization shrinkage can be further suppressed.

Examples of the urethane compound 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). The rate is 15%) or UA-5348PE (molecular weight 39000, EO content 23%) (all manufactured by Shin-Nakamura Chemical Co., Ltd.) or a mixture of these.

The solvent is excluded from the solvent, and the content of the urethane compound contained in the organic component is preferably from 0.1 to 10% by mass. When the content is 0.1% by mass or more, the flexibility of the dried paste film can be improved, and the firing shrinkage stress at the time of firing the dried film can be alleviated. On the other hand, when the content is more than 10% 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 lowered, so that defects are likely to occur.

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

An antioxidant may be added to the photosensitive inorganic pattern forming paste of the present invention. The antioxidant herein refers to one or more of a radical chain inhibiting action, a triplet elimination action, or a hydroperoxide decomposition action. When an antioxidant is added to the photosensitive inorganic pattern forming paste, the antioxidant traps the radical, and the energy state of the excited photopolymerization initiator returns to the basal state, thereby suppressing the unnecessary photoreaction caused by the scattered light, and By causing an intense photoreaction with an exposure amount that cannot be suppressed by an antioxidant, a contrast in which the developer is dissolved and insoluble can be improved. Examples of the antioxidant include p-benzoquinone, naphthoquinone, and p- 茬醌, p-formamidine, 2,6-dichloropurine, 2,5-diethoxycarbonyl-p-benzoquinone, 2,5-dihexyloxy-p-benzoquinone, hydroquinone, p - t-butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone, 2,5-di-third amylhydroquinone, di-tert-butyl-p- Cresol, hydroquinone monomethyl ether, α-naphthol, hydrazine hydrochloride, trimethylbenzylammonium chloride, trimethylbenzyl ammonium oxalate, phenyl-β-naphthylamine, p-benzylamine phenol , bis-β-naphthyl p-phenylenediamine, dinitrobenzene, trinitrobenzene, picric acid, anthraquinone, cyclohexanone oxime, 1,2,3-benzenetriol, tannic acid, triethyl Amine hydrochloride, xylylamine hydrochloride, copper iron, 2,2'-thiobis(4-thanooctylphenolate)-2-ethylhexylamino nickel (II), 4,4' -thiobis-(3-methyl-6-tert-butylphenol), 2,2'-methylenebis-(4-methyl-6-tert-butylphenol), triethylene glycol-double [3-(3-Terbutyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl) -4-hydroxyphenyl)propionate] or 1,2,3-trihydroxybenzene or the like. The addition ratio of the antioxidant in the photosensitive inorganic pattern forming paste is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 20% by mass. When the amount of the antioxidant added is within this range, the photosensitivity of the photosensitive inorganic pattern forming paste can be maintained, and the degree of polymerization can be maintained to maintain the pattern shape while increasing the contrast between the exposed portion and the non-exposed portion.

As the photopolymerization initiator, a photoradical initiator which generates a radical by irradiation with an active light source is preferred. Examples of the photoradical initiator include benzophenone, methyl o-benzyl benzoate, 4,4-bis(dimethylamino)benzophenone, and 4,4-double. (Diethylamino)benzophenone, 4,4-dichlorobenzophenone, 4-benzyl-4-methylbenzophenone, dibenzyl ketone, anthrone, 2,2-diethoxy Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyldichloroacetophenone, thiophene Tons of ketone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, diphenylethylenedione, benzylmethoxyethylacetal , benzoin, benzoin methyl ether, benzoin butyl ether, hydrazine, 2-tert-butyl fluorene, 2-pentyl hydrazine, β-chloropurine, onion ketone, benzofuranone, Dibenzocycloheptanone, phenylene onion ketone, 4-triazobenzylidene acetophenone, 2,6-bis(p-triazylbenzylidene)cyclohexanone, 2,6-double (p-triazylbenzylidene)-4-methylcyclohexanone, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)anthracene, 1-phenyl-1, 2-propanedione-2-(O-ethoxycarbonyl)anthracene, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)anthracene, 1-phenyl-3-ethoxypropane Triketo-2-(O-benzylindenyl) hydrazine, rice ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2 -benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, naphthalenesulfonium chloride, quinoline sulfonium chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylhydrazine or benzoin peroxide or towards Red or nail And other combinations of light reducing dye and of ascorbic acid or a reducing agent such as triethanolamine. 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. When the amount of the photopolymerization initiator is too small, the light sensitivity may be unsatisfactory. When the amount of the photopolymerization initiator is too large, the absorption of light becomes too large, and the light cannot reach the deep portion, and the hardening in the deep portion may become insufficient.

In order to adjust the viscosity when the photosensitive inorganic pattern forming paste is applied to the substrate in accordance with the coating method, it is preferred to add an organic solvent. Examples of the organic solvent include methyl sirolius, ethyl sirlox, butyl sirolimus, methyl ethyl ketone, and the like. Alkane, acetone, cyclohexanone, cyclopentanone, isobutanol, isopropanol, tetrahydrofuran, dimethyl hydrazine, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid Or chlorobenzoic acid.

The photosensitive inorganic pattern forming paste of the present invention preferably has 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, and a dispersion. After the respective components of the agent and the solvent are blended as a predetermined composition, they are kneaded by a kneading machine such as three rolls, and are uniformly dispersed. Moreover, it is also preferable to appropriately filter and defoam the photosensitive inorganic pattern forming paste which is finished by the main body kneading.

Hereinafter, an AC type plasma display will be taken as an example, and the basic structure and the like will be described.

A plasma display is a member that faces a phosphor layer formed by either or both of the front glass substrate or the back glass substrate facing the inner space, that is, facing the discharge space, and sealing the front glass substrate and the rear glass substrate. 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 (sustaining electrode, scanning electrode) for discharge for display is formed on the substrate on the display surface side, but it is preferable that the gap between the sustaining electrode and the scanning electrode is relatively narrow. Further, for the purpose of forming an electrode having a lower resistance, a bus bar electrode may be formed on the back side of the transparent electrode. However, the bus bar electrode is made of Ag, Cr/Cu/Cr or the like, and is often opaque and hinders the display of the element. Therefore, it is preferable to provide the outer edge portion provided on the display surface. In the case of an AC type plasma display, a MgO film is often formed on the upper layer of the electrode as a transparent dielectric layer and a protective film thereof. Happening. In the back glass substrate, an electrode (address electrode) for an element for address selection display is formed. The partition wall or the phosphor layer for the partition member may be formed on both the front glass substrate and the back glass substrate, but it is often formed only on the back glass substrate.

The method of manufacturing the back panel will be described below. 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 strip-shaped conductive pattern for address electrodes is formed on a glass substrate by a metal such as silver, aluminum, chromium or nickel. As a method of forming the strip-shaped conductive pattern, a method of pattern printing a metal paste containing a metal powder and an organic binder as a main component, and a photosensitive metal using a photosensitive organic component as an organic binder can be used. After the paste coating, pattern exposure is performed using a photomask, and an unnecessary portion is dissolved and removed by a developing step, and a photosensitive paste method in which an electrode pattern is formed by heating and firing at 350 to 600 ° C is usually performed. Further, an etching method may be employed. After depositing chromium or aluminum on a glass substrate, a photoresist is applied, and after the photoresist pattern is exposed and developed, unnecessary portions are removed by etching.

Further, since the stability of the discharge can be improved or the collapse or peeling of the partition formed on the upper layer of the dielectric layer can be suppressed, it is preferable to provide a dielectric layer on the address electrode. As a method of forming a dielectric layer, a dielectric material having a low-softening point glass powder or a high-softening point glass powder and an inorganic component and an organic binder as a main component is printed or coated by screen printing or a slit die coater. The method of paste, etc.

Next, a method of forming the partition wall by the photolithography method will be described. As a partition pattern, it is preferably strip, lattice or Honeycomb and so on. First, a photosensitive spacer for forming a partition wall is applied onto a substrate on which a dielectric layer is formed. As a coating method, a bar coater, a roll coater, a slit die coater, a knife coater, or screen printing can be mentioned, for example. The coating thickness can be determined by using the required height of the partition wall and the shrinkage ratio of the baking of the partition wall forming paste, and can be applied by the number of times of application, the mesh of the screen or the viscosity of the partition forming paste, and the like. Adjustment.

The applied photosensitive partition wall forming paste was dried and exposed. Exposure, as in the case of normal photolithography, is generally a method of exposure through a photomask. Further, a method of directly drawing with a laser beam or the like without using a photomask can be used. As the exposure device, for example, a stepper or a proximity exposure machine can be mentioned. Examples of the active light rays used at this time include near-infrared rays, visible rays, and ultraviolet rays, but ultraviolet rays are preferred. 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, or a germicidal lamp, but an ultrahigh pressure mercury lamp is preferred. The exposure conditions differ depending on the coating thickness of the photosensitive partition forming paste. However, an ultrahigh pressure mercury lamp having an output of 1 to 100 mW/cm ² is usually used for exposure for 0.01 to 30 minutes.

After the exposure, development is performed using a difference in solubility with respect to the developer of the exposed portion and the non-exposed portion. As a method of developing, for example, a dipping method, a spray method, or a brushing method can be mentioned. An organic solvent which can dissolve the organic component in the photosensitive partition-forming paste is used as the developer. However, when a photosensitive compound having a carboxyl group or the like is present in the photosensitive partition forming paste, the alkali can be used. The aqueous solution is developed. The aqueous alkaline solution may, for example, be an aqueous solution of sodium hydroxide, sodium carbonate or potassium hydroxide. However, in order to facilitate the removal of the alkaline component during firing, an aqueous solution of an organic alkali is preferred.

The organic base may, for example, be a general amine compound such as tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine or diethanolamine.

When the concentration of the alkaline aqueous solution is too low, it is difficult to remove the soluble portion. On the other hand, if the concentration is too high, the partition wall may be peeled off and corroded. Therefore, it is preferably 0.05 to 5% by mass, more preferably It is 0.1 to 1% by mass. Further, on the premise of step management, the development temperature is preferably 20 to 50 °C.

Next, it is kept in a baking furnace at a temperature of 520 to 620 ° C for 10 to 60 minutes and fired to form a partition wall.

Next, a phosphor layer is formed using a phosphor paste. As a method of forming the phosphor, for example, a photolithography method using a photosensitive phosphor paste, a dispenser method, or a screen printing method is used. The thickness of the phosphor layer is preferably from 10 to 30 μm, more preferably from 15 to 25 μm. From the viewpoint of luminous intensity, chromaticity, color balance, life, and the like, the phosphor powder which is one component of the phosphor paste is preferably the following phosphor. In the blue color, it is preferred to activate a divalent strontium aluminate phosphor (for example, BaMgAl ₁₀ O ₁₇ :Eu) or CaMgSi ₂ O ₆ . 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 or BaMgAl ₁₄ O ₂₃ : Mn is Preferably, Zn ₂ SiO ₄ : Mn is more preferred. In the red color, (Y, Gd) BO ₃ :Eu, Y ₂ O ₃ :Eu or YPVO:Eu, YVO ₄ :Eu is preferable, and (Y, Gd)BO ₃ :Eu is more preferable. When the phosphor is formed through the firing step, the dielectric layer and the partition walls described above may be simultaneously fired.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples. However, the present invention is not limited to these. In addition, the average particle diameter (d ₅₀ ) and the maximum particle diameter (d _max ) of the following inorganic powders are values measured by MT3300 (manufactured by Nikkiso Co., Ltd.).

(Example 1) A. Glass powder

Low softening point glass powder: having 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 Mo A pulverized material of glass having a composition of ear %, MgO: 1 mol %, CaO: 1 mol %, ZnO: 1 mol %, and ZrO ₂ : 1 mol % (softening point: 590 ° C, d ₅₀ : 2 μm, d _max : 10 μm)

High-softening point glass powder: a pulverized material of glass having the composition shown in Table 1 (softening point: both >650 ° C, d ₅₀ : 2 μm, d _max : 10 μm)

B. Evaluation of the amount of residual organic components

0.75 g of 20 g of a high-softening point glass powder and an ethyl cellulose solution (ethylcellulose: 25 mass%, γ-BL: 75 mass%) 40 g were placed in a 250 mL aluminum container, covered with an aluminum lid, and sealed. And firing. The firing conditions were raised in air at 10 ° C / min up to 500 ° C and held at 500 ° C for 15 minutes. 15 mg of the powder after calcination was subjected to GC-MS analysis using a pyrolysis gas chromatography mass spectrometer (GCMS-QP2010Plus; manufactured by Shimadzu Corporation), and the components released by heating at 550 ° C for 5 minutes in a He gas atmosphere. Further, the total value of the total peak areas from the organic components among the detected peaks was determined as the amount of residual organic components. The evaluation results are shown in Table 2. When the powder after calcination at 500 °C contains a large amount of residual organic components, the residual organic components released by thermal decomposition at 550 ° C after heating are also increased, and the total peak area is also increased. Will get bigger. In order to stabilize the characteristics of the plasma display panel, it is necessary to use a high-softening point glass having a small amount of residual organic components in the evaluation. When the amount of the residual organic component is 3 × 10 ⁶ or more, the amount of residual organic components is large, which is unsuitable. The amount of the residual organic component is particularly preferably 1.0 × 10 ⁶ or less.

C. Production of photosensitive spacer forming paste

The photosensitive partition forming paste 1 was produced in the following procedure.

a. organic color developing agent

An organic vehicle is prepared by weighing and mixing an organic solid component containing the following raw materials, and stirring and dissolving them.

Photosensitive monomer M-1 (trimethylolpropane triacrylate): 6 parts by weight

Photosensitive monomer M-2 (tetrapropylene glycol dimethacrylate): 6 parts by weight

Photosensitive polymer (additional reaction of 0.4 equivalent of glycidyl methacrylate to a carboxyl group containing a methacrylic acid/methyl methacrylate/styrene=40/40/30 copolymer) Weight average molecular weight 43000, acid value 100): 18 parts by weight

Photopolymerization initiator (2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-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-t-butyl-4-hydroxyphenyl)propionate]): 4 parts by weight

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

Solvent (γ-butyrolactone): 42 parts by weight

b. Photosensitive barrier forming paste

50 parts by weight of a low-softening point glass powder and 10 parts by weight of a high-softening point glass powder were added to 50 parts by weight of the obtained organic vehicle, and then kneaded by a kneader of three rolls to form a photosensitive partition wall. Use paste. The photosensitive spacer for forming a barrier layer was produced, and defoaming was performed by reducing the pressure to 1 kPa while stirring.

D. Production of partition walls

Using the photosensitive partition forming paste 1 produced by C, the partition 1 was produced in the following procedure. The address electrode pattern was formed by photolithography using a photosensitive silver paste on a glass substrate PD-200 (manufactured by Asahi Glass Co., Ltd., 42 吋 rectangle). 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, a photosensitive spacer forming paste for forming a lower layer of the partition wall is formed on the back glass substrate on which the address electrode pattern and the dielectric layer are formed, and is applied by a slot coater to be formed after firing. The film thickness of the glass film of the thickness of 120 micrometers was dried at 100 degreeC for 1 hour, and the coating film of the photosensitive partition formation paste 1 was formed. Next, exposure is performed through the exposure mask. The exposure mask is designed to be a chrome mask which can be formed by a stripe pattern of a strip shape of 160 μm in pitch, 25 μm in opening width, and a plasma display. Exposing the film to form a paste for the partition wall between the respective photosensitive, ultrahigh pressure mercury lamp output to 50mW / cm ² of from 100mJ / cm ² to 500mJ / cm ^2, each of 5mJ / cm ² exposed to ultraviolet rays.

Next, development was carried out by spraying a 0.3 mass% aqueous solution of monoethanolamine maintained at 35 ° C for 300 seconds, and then water-washing was performed using a shower spray to remove a space portion which was not subjected to photocuring. Thereafter, the partition wall 1 was formed by holding at 560 ° C for 30 minutes and firing.

E. Reflectance evaluation of the partition wall

The sample having a different exposure amount by D was cut, and the longitudinal direction and the vertical cross section of the partition 1 were exposed, and the cross section was observed by a scanning electron microscope (S2400, manufactured by Hitachi, Ltd.), and the partition wall and the dielectric body were measured. The partition wall of the contact portion is wide (bottom wide). Since the width of the bottom of the partition wall becomes thicker together with the increase in the amount of exposure, among the samples prepared, the sample having the bottom width of the partition wall 1 after firing is selected to be closest to 45 μm, and The sample was measured by the SCE mode of a spectrophotometer (CM-2002, manufactured by KONICA MINOLTA Co., Ltd.), and the reflectance at a wavelength of 530 nm and the b* value were evaluated. As described above, the higher the reflectance, the higher the luminous efficiency of the plasma display, so that the reflectance is higher, and particularly preferably 48% or more. When the reflectance is 45% or less, it is not appropriate. Further, the b* value is an indicator of yellowing, and the smaller the value, the better, and it is particularly preferable to be 3 or less. When the b* value is 5 or more, the yellowing of the partition wall is remarkable, which is less than ideal.

F. Evaluation of septal defect tolerance

A sample having a bottom width of 50 μm of the partition 1 after firing in the sample having different exposure amounts prepared by D was selected, and the sample was cut into 5 cm × 13 cm and 1 cm in the center of the surface of the substrate where the partition wall was not formed. The 4 points of the rectangle are marked with 1 point at the center. Next, the "PD-200" glass substrate cut into a size of 5 cm × 13 cm was placed on the surface side formed by the partition wall, and the back panel side was placed upward, and the metal ball having a weight of 114 g was dropped from a height of 30 cm. Each of the marked 5 points is 2 times. Thereafter, a 1 cm rectangular portion in the center of the sample substrate was cut out, and a photograph of the defective portion of the partition wall was taken by a scanning electron microscope. The image of the photograph taken was analyzed for the area of the cross section due to the defect, and the total number of defects of the partition 1 and the area of the cross section due to the defect were 2000 μm ² or more. This evaluation is a model test in which the defect of the plasma display panel is damaged, and the number of large-area defects is preferably small, and particularly preferably 5 pieces/cm ² or less. It is not appropriate when the number of large-area defects is more than 20 pieces/cm ² . The evaluation results are shown in Table 2.

(Examples 2 to 12)

As the high-softening point glass powder, the pulverized material of the glass having the composition shown in Table 1 was used, and the partition wall forming pastes 2 to 12 and the partition walls 2 to 12 were obtained in the same manner as in Example 1. The same evaluation as in Example 1 was carried out for each of the high-softening point glass powders and the respective partition walls obtained. The evaluation results are shown in Table 2.

(Comparative examples 1 to 7)

As the high-softening point glass powder, the pulverized material of the glass having the composition shown in Table 1 was used, and the partition wall forming pastes 13 to 19 and the partition walls 13 to 19 were obtained in the same manner as in Example 1. The same evaluation as in Example 1 was carried out for each of the high-softening point glass powders and the respective partition walls obtained. The evaluation results are shown in Table 2.

The composition of the high softening point glass powder satisfies 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%, and MgO: 0.5 to 3.5 m Examples 1 to 12 having a composition of % and CaO: 7.5 to 10.5 mol% showed good results in that the large-area defect was small, the reflectance was high, and the residual organic component was small. On the other hand, the composition of the high softening point glass powder did not satisfy the above Comparative Examples 1 to 7, and it was found that there were many problems such as a large area defect, a low reflectance, and a large residual organic component.

(Examples 13 to 28)

With respect to the combination of the high softening point glass powder of Example 1 and the low softening point glass powder of the composition shown in Table 3, the reflectance, the b*, and the large area defect number were added, and the following evaluation was performed. The evaluation results are shown in Table 4.

G. Minimum partition wall bottom width

The partition wall of the substrate produced by D was observed, and the bottom width of the partition wall where no peeling occurred was measured, and the minimum value was taken as the minimum partition wall bottom width. When the minimum partition wall bottom width is less than 40 μm, it is ◎, when it is 40 or more, it is ○ when it is less than 45 μm, and when it is 45 μm or more and less than 50 μm, it is Δ. Since the minimum partition wall width is thinner when the light scattering of the partition wall paste is small, the finer the better.

H. Sinterability

The substrate produced in D was cut and exposed to the partition wall cross section, and the partition wall cross section was observed by a scanning electron microscope, and the void ratio was calculated by image analysis. When the sintering is sufficiently performed, the porosity is less than 2%, and the sinterability is ◎. When the void ratio is 2% or more, the sinterability is ○, and when it is 5% or more, it is Δ. In the case where the sintering is insufficient, the coating of the phosphor may become difficult.

I. Viscosity stability

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

J. Evaluation of chemical stability of glass

The low softening point glass powder described in Table 3 was remelted to form a lump, and immersed in a 0.5% sodium carbonate aqueous solution at 75 ° C for 10 hours, and the weight reduction ratio before and after the immersion of the sample was determined. When the weight reduction rate is less than 0.7%, it is ◎, when 0.7% or more is less than 0.9%, it is ○, and when 0.9% or more is less than 1.2%, it is Δ. The smaller the weight reduction rate, the higher the chemical stability of the glass, which is preferable.

Examples 13 to 18 all showed extremely good characteristics. Examples 19, 20, 24, 27, and 29, which were relatively large in B ₂ O ₃ , showed relatively good properties although they were slightly inferior in chemical stability. Examples 22, 24, 28, and 29, in which ZnO is relatively large, exhibit poor properties, although the viscosity stability is somewhat poor. In Examples 21, 22, 23, and 28 in which the total amount of alkaline earth metals was relatively large, the reflectance was slightly lowered, but the reflectance was 44% or more and was good. In Examples 22 to 24 and 27 to 29 in which the refractive index is more than 1.54 or less than 1.51, the width of the bottom of the minimum partition wall tends to be slightly thicker, but a thin wide partition wall of 50 μm or less can be formed.

[Industrial availability]

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

Claims (8)

A member attached to a glass substrate having a partition wall comprising a low softening point glass and having SiO ₂ : 65.5-69.0 mol%, Al ₂ O ₃ : 9.5~12.5 mol%, B ₂ O ₃ : 8.0~12.0 mol%, MgO: 0.5~3.5 mol%, and CaO: 7.5~10.5 mol% of high softening point glass. The member of claim 1, wherein the high softening point glass system further has a composition of SrO: 0.2 to 0.8 mol%. The member of claim 1 or 2, wherein the high softening point glass system further has a composition of Na ₂ O: 0.1 to 1.5 mol%. An inorganic pattern forming paste comprising a low softening point glass powder; having 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% of the composition of the high softening point glass powder; and organic components. An inorganic pattern forming method of applying an inorganic pattern forming paste according to item 4 of the application of the patent application to a glass substrate, followed by firing to form an inorganic pattern. A member having a partition wall which is produced by an inorganic pattern forming method as in the fifth aspect of the patent application. A plasma display panel having a member according to any one of claims 1 to 3 or 6. A scintillator panel having a member according to any one of claims 1 to 3 or 6.