JP2006012436A - Display member and display using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-performance display in which warping of a barrier wall resulted from contraction stress in baking is reduced, and lighting failrue or abnormal lighting of a discharge cell by breakage of the barrier wall caused in application of vibration, impact or the like to a display panel is suppressed. <P>SOLUTION: The display member has a barrier wall consisting of a plurality of layers differed in porosity. The barrier wall is constituted so that the layer with the largest porosity is present only in the range of 75% upper layers of the barrier wall when the height of the barrier wall is taken as 100%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a display member and a display. In particular, the present invention relates to a display member and a display suitable for a back plate for a plasma display.

  In recent years, development of large flat panel displays such as DC-type and AC-type plasma displays, liquid crystal displays, and field emission displays has progressed, and some displays are already on the market and are forming a large market. A large flat panel display is formed with a structure having various functions such as pixel partitioning. For example, an AC type plasma display generates a plasma discharge between an anode and a cathode electrode facing each other in a discharge space provided between a front substrate and a rear substrate, and a Xe-Ne mixed gas sealed in the discharge space. The display is performed by irradiating a phosphor provided in the discharge space with ultraviolet rays having a very short wavelength such as 147 nm and 172 nm generated from a discharge gas such as the above. The structure is provided in order to suppress the spread of the discharge to a certain area and to perform display in a prescribed cell, and to ensure a uniform discharge space, and is called a partition (also referred to as a barrier or rib). ing. The shape of the partition generally includes a stripe shape or a lattice shape having a width of 20 to 120 μm and a height of 50 to 250 μm. The partition wall is generally formed by applying a paste made of a mixture of an organic material mainly composed of an organic binder and an inorganic material mainly composed of glass on a glass substrate, patterning the substrate by a sandblasting method, a photolithography method, or the like, followed by baking. There are many cases. At this time, warpage occurs due to shrinkage stress generated in the partition during firing, and a gap is formed between the rear substrate and the front substrate, and erroneous discharge (crosstalk) due to leakage of plasma discharge is likely to occur. It was. In addition, the warped partition wall may be damaged by contact with the front substrate, and debris may fall into the cell, resulting in generation of an unlit cell or an abnormally lit cell. In addition, abnormal projections generated on the front substrate may come into contact with the partition walls, which may cause damage to the partition walls during sealing or when an impact is applied, resulting in non-lighted cells or abnormally lit cells. As described above, it has been difficult to obtain a stable display due to a shape defect due to the warpage of the partition walls or damage to the partition walls due to insufficient impact resistance.

In order to solve these problems such as warpage of the partition walls and insufficient impact resistance, the porosity of the partition walls is improved by improving the porosity of the partition walls (see Patent Document 1), or by defining the roughness of the top of the partition walls. The stress concentration generated in the convex portion is reduced (see Patent Document 2), or the end of the partition wall is inclined (tapered) to relieve the contraction stress and reduce the warpage (see Patent Document 3). It has been proposed. However, the methods of Patent Documents 1 and 2 are not effective as countermeasures against the occurrence of unlit cells or abnormally lit cells caused by abnormal protrusions generated on the front substrate causing stress concentration on the partition walls and damaging the partition walls. . This is because, when stress concentration occurs, the partition walls often cannot withstand strong impacts caused by sealing or dropping of the panel. Further, in the method of Patent Document 3, even if the warpage of the end portion of the partition wall can be eliminated, the warpage other than the end portion of the partition wall cannot be eliminated.
Japanese Patent Laid-Open No. 10-134723 Japanese Patent Laid-Open No. 2003-234072 JP 11-1335025 A JP 2000-195430 A JP 2001-297706 A JP 2002-298743 A

  In view of the above, the present invention focuses on the problems of the above-described prior art and provides a high-performance display member and display. Specifically, it is an object of the present invention to provide a high-performance display in which the warpage of the barrier ribs is reduced and the discharge cell non-lighting and abnormal lighting are suppressed due to the damage of the barrier ribs.

  In order to solve the above problems, the present invention has the following configuration. That is, the present invention is a display member having a partition wall composed of a plurality of layers having different porosity, wherein the partition wall has a layer with the highest porosity of 75% when the partition wall height is 100%. It is a display member characterized by existing only in the range.

  Reduces the warpage of the barrier ribs caused by shrinkage stress during firing, and suppresses discharge cell non-lighting and abnormal lighting due to barrier rib damage that occurs when vibration, impact, etc. are applied to the display panel, realizing a high-performance display can do.

  The inventors diligently studied a high-performance display member in which the warpage of the barrier ribs was reduced and discharge cells were not turned off due to the damage of the barrier ribs caused by vibrations or shocks applied to the display panel, and abnormal lighting was suppressed. As a result, it has been found that this can be achieved by a partition wall having the structure described below. Hereinafter, an AC type plasma display will be described as an example of the display. However, the present invention is not limited to this and can be applied to other displays.

  That is, according to the present invention, the partition wall is composed of a plurality of layers having different porosity, and the layer having the highest porosity has a partition wall height of 100% (A in FIG. 1) and 75% of the upper layer of the partition wall (in FIG. 1). It is important that the display member is characterized by being included only in B).

  The warpage of the partition wall is caused by the difference in firing shrinkage between the lower part and the upper part of the partition wall. That is, since the lower part of the partition wall is in close contact with the dielectric layer and the shrinkage is limited, the shrinkage amount due to firing is small, but the shrinkage amount is large because the upper part of the partition wall does not limit the shrinkage. As a result, as shown in FIG. 2A, contraction stress that curves toward the upper part of the partition wall is generated, and the warp of the partition wall occurs. Firing shrinkage can be reduced by increasing the porosity after firing. Therefore, it is possible to reduce the firing stress and reduce the warpage by increasing the porosity of the entire partition wall, but it is possible to reduce the strength of the partition wall, increase the exhaust resistance due to adsorbed gas and moisture in the space, This is not preferable because there is a decrease in luminance caused by the generation of adsorbed gas and moisture.

  Therefore, when the layer having the largest porosity (high porosity layer) is introduced not only in the entire partition but only in the upper layer of the partition, the shrinkage is suppressed by adhesion with the dielectric layer in the lower layer of the partition, as shown in FIG. As shown in 2 (b), the high porosity layer with a small shrinkage amount can restrict free shrinkage and suppress the shrinkage, thereby suppressing the warp of the partition wall. On the other hand, since the high porosity layer is not a whole partition but only a part of the partition, the shrinkage of the partition can be reduced while suppressing the strength of the partition and the adverse effect of the adsorbed gas and moisture on the space.

  Here, the amount obtained by subtracting the length D having the lowest height from the length C having the highest height due to the warpage as shown in FIG. 2 can be quantitatively evaluated by defining the amount of warpage. The amount of warpage can be obtained by observing the cross section of the partition wall with an SEM (for example, S-2400 manufactured by Hitachi) and measuring the above C and D. It can also be obtained by measuring the profile of the partition wall shape using a laser microscope (for example, VK-9500 made by Keyence) and measuring the above C and D.

  Further, the introduction of the high porosity layer can suppress the breakage of the partition wall that occurs when vibration, impact, or the like is applied to the display panel. Although the partition wall strength can be improved by reducing the porosity of the partition wall as in Patent Document 1, the so-called brittleness increases conversely, so that when the impact applied to the partition wall exceeds the threshold value, as shown in FIG. May be greatly damaged. However, if there are many voids inside the partition wall as in the high porosity layer, the shape of the partition wall will change slightly as shown in FIG. 3B, but it will be greatly damaged even if a strong impact is applied. There is no. Therefore, when a high porosity layer is introduced as in the present invention, even if a strong impact or the like is applied to the partition wall, the high porosity layer absorbs the impact and is unlikely to cause major damage. For this reason, even if stress concentration occurs on the partition due to abnormal protrusions generated on the front substrate, the high porosity layer at the site where the stress concentration occurs is crushed, but a case where the partition itself is greatly damaged is less likely to occur.

  A partition wall having such a multilayer structure is disclosed in, for example, Japanese Patent Application Laid-Open No. 2000-195430 (Patent Document 4), which reduces unevenness of light emission intensity distribution in a cell, increases panel brightness, and causes variations in brightness between panels. For the purpose of reducing, it has been proposed as a multilayer barrier rib having different dielectric constants. In Japanese Patent Laid-Open No. 2001-297706 (Patent Document 5), a partition wall is formed for the purpose of maintaining a stable partition wall shape that does not lose its shape in the firing step and densifying the partition wall top portion in order to suppress unevenness of the partition wall top portion. It has been proposed as a multi-layer partition with a dense top layer. Japanese Patent Laid-Open No. 2002-298743 (Patent Document 6) proposes a multi-layer partition wall having different visible light reflectivities in order to improve luminous efficiency and contrast. However, in either case, a high porosity layer is not introduced and therefore the object of the present invention cannot be achieved.

  The high porosity layer must be contained in 75% of the upper layer of the partition wall, but is preferably within 50% of the upper layer of the partition wall. By entering within 50%, firing shrinkage of the partition upper layer can be effectively suppressed. More preferably, it is within 25%. By entering within 25%, the resistance to vibration and shock applied to the partition walls can be made effective.

  The thickness of the high porosity layer is preferably 1 to 25% or less, with the partition wall height being 100%. If it exceeds 25%, for example, the phosphor paste penetrates into the voids, and the handling of the coating is deteriorated, or the binder removal property of the penetrated paste organic component is deteriorated. If it is less than 1%, a desired effect cannot be obtained. More preferably, it is within 5 to 20%. This is because it is possible to further suppress the improvement in handling property of the phosphor paste application and the deterioration of the binder removal property of the paste component.

  The absolute thickness of the high porosity layer is preferably within 1 to 30 μm. When the thickness exceeds 30 μm, there is a decrease in partition strength, an increase in exhaust resistance due to adsorbed gas or moisture in the gap, and a decrease in luminance caused by generation of adsorbed gas or moisture from the gap during discharge. If it is 1 μm or less, the desired effect cannot be obtained. More preferably, it is within 5 to 20 μm. This is because the impact resistance of the partition walls can be improved and the influence of adsorbed gas and moisture can be reduced.

The porosity is preferably in the range of 10 to 90%. If it exceeds 90%, it will be difficult to maintain the shape of the partition as a structure. If it is less than 10%, it is difficult to obtain a desired effect. More preferably, it is 10 to 50%. This is because a strong impact can be absorbed and a strength that does not deform against a weak impact can be obtained. Here, the partition wall is composed of an inorganic component made of glass or filler and a space, and the ratio of the space that fills the entire partition wall is defined as the porosity. Porosity (P) is, P = 100 × when the measured density and _{d th} a true specific gravity of the barrier rib material and the _{d ex (d th -d ex)} / d th
It is convenient and preferable to measure the porosity by SEM observation. The cross section of the partition wall is observed with an SEM, and the porosity is calculated from the ratio of the void area to the total area of the void and the inorganic component.

  Further, a method for confirming the effect of suppressing the damage to the partition wall that occurs when vibration, impact, or the like is applied to the display panel will be described below. For example, a micro compression tester (MCTM-500) manufactured by Shimadzu Corporation can be used. From the load-displacement curve obtained by applying a diamond triangular pyramid indenter (ridge spacing 115 °) to the center of the partition line width and specifying the load speed and maximum load, the first bending point of the loading process is taken as the breaking point, Impact resistance can be tested.

  In addition, after the panel is manufactured, a glass plate is placed on the partition, and a sphere made of predetermined SUS or ceramic is dropped on the surface to check the number of unlit cells or abnormally lit cells, It is possible to test the impact resistance of the partition wall by confirming the damage state by observing with SEM.

  In addition, for example, after a panel is manufactured or a glass plate is placed on a partition wall, a trapezoidal wave or a half sine wave pulse is applied using an impact test apparatus (ASQ series, MDST series, etc.) manufactured by Yoshida Seiki Co., Ltd. It is possible to test the impact resistance of the partition walls by confirming the number of non-lighted cells or abnormally lit cells, or by directly observing the partition walls with an SEM and confirming the state of damage.

  Embodiments of the present invention are shown below. However, the present invention is not limited to this. FIG. 4 shows a first embodiment of the present invention. Striped barrier ribs are formed on a glass substrate on which address electrodes and dielectric layers are formed, and the barrier ribs are composed of a low porosity partition wall layer (lower layer) having a porosity of 10% or less and a high porosity of 10 to 90%. It consists of two layers, a porosity partition wall layer (uppermost layer).

  FIG. 5 shows a second embodiment of the present invention. The high porosity layer is the same as that of the first embodiment except that the high porosity layer is not in the uppermost layer of the partition wall but in the inside.

  FIG. 6 shows a third embodiment of the present invention. On the glass substrate on which the address electrode and the dielectric layer are formed, a grid-like partition is formed which includes a main partition parallel to the address electrode and an auxiliary partition perpendicular to the main partition, and a high porosity layer is the uppermost layer of the partition. By forming the barrier rib pattern in a lattice shape, the application area of the phosphor can be increased, and the light emission efficiency can be improved. As shown in FIG. 7, the partition walls may be waffle-shaped.

  FIG. 8 shows a fourth embodiment of the present invention. The third embodiment is the same as the third embodiment except that the high porosity layer is not in the uppermost layer of the partition but inside. As shown in FIG. 9, the partition walls may be waffle-shaped.

  FIG. 10 shows a fifth embodiment of the present invention. When a grid-like partition is formed on a glass substrate on which an address electrode and a dielectric layer are formed, a partition parallel to the address electrode is a main partition, and a partition perpendicular to the main wall is an auxiliary partition, the height of the main partition is It is higher than the height of the auxiliary partition. First, by making the barrier rib pattern into a lattice shape, the application area of the phosphor can be increased, and the light emission efficiency can be improved. Further, when the main partition is higher than the auxiliary partition, exhaust can be smoothly performed in the subsequent sealing step with the front plate. The height of the auxiliary partition is preferably 10 to 95% of the main partition. If it is less than 10%, the increase in the phosphor coating area is small, so that the luminous efficiency cannot be improved effectively for the increase in the process. If it exceeds 95%, the exhaust resistance increases. More preferably, it is 60 to 90%. This is because the luminous efficiency can be improved by increasing the coating area of the phosphor and the exhaust resistance can be kept low.

  FIG. 11 shows a sixth embodiment of the present invention. The high porosity layer is the same as that of the fifth embodiment except that the high porosity layer is not in the uppermost layer of the main partition wall but in the uppermost layer of the auxiliary partition wall and the main partition wall.

  FIG. 12 shows a seventh embodiment of the present invention. This is the same as in the sixth embodiment except that the high porosity layer is in the uppermost layer of the main partition, and in the uppermost layer of the auxiliary partition and inside the main partition. As shown in FIG. 13, the upper layer or more of the auxiliary partition may be a high porosity layer.

  When the high porosity layer is in the uppermost layer as in the first, third, fifth, and seventh embodiments, warpage can be reduced by suppressing firing shrinkage of the partition walls as described above. Moreover, even if stress concentration occurs due to abnormal protrusions on the front plate or convex portions on the top of the partition wall at the top of the partition wall, the high porosity layer absorbs the stress, so that the partition wall is not greatly damaged. Even if there is no high porosity layer in the uppermost layer of the partition as in the second, fourth, and sixth embodiments, the firing shrinkage of the partition can be suppressed, and the warpage can be reduced. Moreover, even if the high porosity layer is inside the partition wall, the partition wall is not greatly damaged because it absorbs stress concentration generated by abnormal projections on the front plate or convex portions on the top of the partition wall at the top of the partition wall. .

  Although the example of the partition including one kind of high porosity layer was shown so far, of course, the multilayer partition which has a different porosity layer may be sufficient.

  Next, the display member and display manufacturing procedure of the present invention will be described. Here, an AC type plasma display will be described as an example, but the manufacturing procedure is not necessarily limited to this structure.

  First, a method for manufacturing a back substrate will be described. As the glass substrate, “PD200” manufactured by Asahi Glass or “PP8” manufactured by Nippon Electric Glass, which is a heat-resistant glass for PDP, can be used in addition to soda glass. An address stripe electrode pattern is formed on a glass substrate with a metal such as silver, aluminum, chromium, or nickel. As a method of forming, after applying a metal paste mainly composed of these metal powder and organic binder by screen printing, or after applying a photosensitive metal paste using a photosensitive organic component as an organic binder, It is possible to use a photosensitive paste method in which pattern exposure is performed using a photomask, unnecessary portions are dissolved and removed in a development step, and further heated and baked at 400 to 600 ° C. to form an electrode pattern. Further, an etching method can be used in which after chromium or aluminum is vapor-deposited on a glass substrate, a resist is applied, and after the resist is subjected to pattern exposure and development, unnecessary portions are removed by etching. Furthermore, it is preferable to provide a dielectric layer on the address electrode. By providing the dielectric layer, it is possible to improve the stability of discharge and to prevent the partition wall formed on the upper layer of the dielectric layer from falling or peeling off. Further, as a forming method, there is a method in which a dielectric paste mainly composed of an inorganic powder such as glass or filler and an organic binder is printed or applied on the entire surface by screen printing, a slit die coater or the like.

  Subsequently, the step of forming the partition walls will be described. Examples of the method for forming the partition include a sand blast method, a mold transfer method, and a photolithography method. The material of the partition used in the present invention is not particularly limited, and a known material can be applied. The partition pattern is not particularly limited, but a lattice shape, a waffle shape or the like is preferable. As a manufacturing method, a sand blast method or a photolithography method is preferable from the viewpoint of processing accuracy and uniformity when a partition wall having a high aspect ratio is formed. For example, in the case of the photolithography method, a photosensitive glass paste can be used as the partition wall paste. In the following, the method for manufacturing the partition walls will be described with reference to FIG. 10 by taking the photosensitive glass paste method as an example.

  First, the photosensitive glass paste for the low porosity partition wall layer in FIG. 10 is applied. As a coating method, a coating method such as a bar coater, a roll coater, a slit die coater, a blade coater, or screen printing is used. The coating thickness can be determined in consideration of the desired partition wall height and the shrinkage rate due to baking of the paste. The coating thickness can be adjusted by the number of coatings, the screen mesh, and the paste viscosity. The coated photosensitive glass paste is dried and then exposed. The actinic ray used for the exposure is most preferably ultraviolet light, and as its light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp or the like is used. An exposure machine using parallel rays using an ultra-high pressure mercury lamp as a light source is common. In the case of FIG. 10, the exposure pattern may be a stripe pattern of auxiliary barrier ribs or a lattice pattern composed of main barrier ribs and auxiliary barrier ribs.

  Then, in order to form a part higher than the auxiliary partition of the main partition, the photosensitive glass paste for high porosity layers is apply | coated. As a coating method, the same method as the glass paste for the low porosity layer can be used. The coated photosensitive glass paste for the high porosity partition wall layer is dried and then exposed. The exposure method can use the same method as the glass paste for the low porosity layer. In the case of FIG. 10, the stripe pattern of the main partition is used as the exposure pattern.

  After the exposure, development is performed using the difference in solubility between the exposed portion and the unexposed portion in the developer to form a partition pattern. For the development, an immersion method, a spray method, a brush method, or the like is used. As the developer, a solution in which the organic components in the photosensitive glass paste, particularly the polymer can be dissolved, may be used. In the present invention, development with an aqueous alkaline solution is preferred.

  Baking for removing the resin component is performed from the partition pattern obtained by development. The firing atmosphere and temperature vary depending on the characteristics of the paste and the substrate, but are usually fired in air. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. The baking temperature is preferably a temperature at which the resin to be used sufficiently debinds. In the case where a cellulose resin is used as the resin, the temperature is, for example, 450 to 650 ° C. When an acrylic resin is used, the temperature is 430 to 650 ° C. If the firing temperature is too low, the resin component tends to remain, and if it is too high, the glass substrate may be distorted and cracked.

A phosphor is formed using a phosphor paste on a glass substrate on which address electrodes, dielectric layers, and barrier ribs are formed. It can be formed by a photolithography method, a dispenser method, a screen printing method or the like using a photosensitive phosphor paste. The thickness of the phosphor is not particularly limited, but is 0.01 to 0.03 mm, more preferably 0.015 to 0.025 mm. The phosphor powder is not particularly limited, but the following phosphors are preferable from the viewpoint of light emission intensity, chromaticity, color balance, lifetime, and the like. Blue is an aluminate phosphor (for example, BaMgAl ₁₀ O ₁₇ : Eu) or CaMgSi ₂ O ₆ activated with divalent europium. In 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, and BaMgAl ₁₄ O ₂₃ : Mn are preferable in terms of panel luminance. More preferably _Zn 2 _SiO 4: is Mn. In red, (Y, Gd) BO ₃ : Eu, Y ₂ O ₃ : Eu, YPVO: Eu, and YVO ₄ : Eu are also preferable. More preferred is (Y, Gd) BO ₃ : Eu.

  Next, a method for manufacturing the front substrate will be described. As the glass substrate, “PD200” manufactured by Asahi Glass or “PP8” manufactured by Nippon Electric Glass, which is a heat-resistant glass for PDP, can be used in addition to soda glass.

First, ITO is sputtered on a glass substrate, and a pattern is formed by a photoetching method. Subsequently, the black electrode paste for black electrodes is printed. The black electrode paste is composed mainly of an organic binder, a black pigment, a conductive powder, and a photosensitive component when used in a photolithography method. As the black pigment, a metal oxide is preferably used. Examples of metal oxides include titanium black, copper, iron, manganese oxides and their composite oxides, and cobalt oxides. Cobalt oxides are less susceptible to fading when mixed with glass and fired. Is excellent. Examples of the conductive powder include metal powder and metal oxide powder. As the metal powder, gold, silver, copper, nickel or the like that is usually used as an electrode material can be used without any particular limitation. Since this black electrode has a high resistivity, an electrode having a low resistivity is also produced to form a bus electrode. Therefore, a highly conductive electrode paste (for example, one containing Ag as a main component) is printed on the black electrode paste. Print on the side. As this conductive paste, the electrode paste used for the address electrode can also be suitably used. Then, a bus electrode pattern is prepared by batch exposure / development. In order to ensure the conductivity, a highly conductive electrode paste may be printed again before development, and may be collectively developed after re-exposure. After the bus electrode pattern is formed, baking is performed. Thereafter, it is preferable to form a black stripe or a black matrix in order to improve contrast. Next, a transparent dielectric is applied. The transparent dielectric paste is mainly composed of an organic binder, an organic solvent, and glass, but an additive such as a plasticizer may be appropriately added. The _{glass, PbO,} B 2 O _3, those containing SiO 2, CaO and the like are preferable. Moreover, a filler can also be added. As a coating method, methods such as screen printing, bar coater, roll coater, die coater, and blade coater can be used. The thickness is preferably 0.01 to 0.03 mm. Further, a protective film is formed. As the protective film, MgO, MgGd ₂ O ₄ , BaGd ₂ O ₄ , Sr _0.6 Ca _0.4 Gd ₂ O ₄ , Ba _0.6 Sr _0.4 Gd ₂ O ₄ , SiO ₂ , TiO ₂ , Al ₂ O ₃ and at least one kind from the above-mentioned group of low softening point glasses are preferably used, and MgO is particularly preferable. As a method for forming the protective film, a known technique such as EB vapor deposition or ion plating is suitable.

  Next, a method for manufacturing a plasma display panel will be described. After sealing the back substrate and the front substrate of the present invention, after evacuating while heating the space formed between the two substrates, a discharge gas composed of helium, neon, xenon, etc. is sealed. Seal. Xe5-15% -Ne bal. Mixed gas is preferable in terms of both discharge voltage and luminance. In order to increase the generation efficiency of ultraviolet rays, Xe may be further increased to about 30%.

  Finally, a PDP can be manufactured by mounting and aging the drive circuit.

  The photosensitive glass paste for a low porosity partition wall or a high porosity partition wall used in the present invention contains, for example, a photosensitive component selected from at least one of a reactive monomer, a reactive oligomer, and a reactive polymer. If necessary, binder, photopolymerization initiator, ultraviolet light absorber, sensitizer, sensitizer, polymerization inhibitor, plasticizer, thickener, antioxidant, dispersant, organic or inorganic precipitation inhibitor And an additive component such as a leveling agent, low melting point glass, and at least one kind of oxide or high melting point glass as a filler. Here, the reactivity in the reactive monomer, reactive oligomer and reactive polymer means that when the photosensitive paste is irradiated with actinic rays, the reactive monomer, reactive oligomer and reactive polymer are photocrosslinked, It means that the chemical structure changes through reactions such as polymerization, photodepolymerization, and photomodification.

  Moreover, the actinic light mentioned here refers to light in the wavelength region of 250 to 1100 nm causing such a chemical reaction, specifically, ultraviolet light such as an ultrahigh pressure mercury lamp and a metal halide lamp, visible light such as a halogen lamp, A laser beam having a specific wavelength such as a helium-cadmium laser, a helium-neon laser, an argon ion laser, a semiconductor laser, a YAG laser, and a carbon dioxide gas laser can be given.

  As the organic component used in the present invention, a compound having an ethylenically unsaturated group is preferably used. Examples of such a polymerizable monomer include a monomer having one or more photopolymerizable (meth) acrylate groups or allyl groups. Specific examples thereof include acrylic acid esters or methacrylic acid esters and carboxylic acids (eg, propionic acid acetate) of alcohols (eg, ethanol, propanol, hexanol, octanol, cyclohexanol, glycerin, trimethylolpropane, pentaerythritol, etc.). , Benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) and glycidyl acrylate, glycidyl methacrylate, allyl glycidyl, or tetraglycidyl methexylylene diamine, amide Derivatives (eg, acrylamide, methacrylamide, N-methylolacrylamide, methylenebisacrylamide, etc.), reaction products of epoxy compounds with acrylic acid or methacrylic acid, etc. Rukoto can. In the polyfunctional monomer, the unsaturated group may be present in a mixture of acrylic, methacrylic, vinyl, and allyl groups. These may be used alone or in combination.

  In the organic component, a polymer having an ethylenically unsaturated compound as the compound having an ethylenically unsaturated group may be used. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.

  The polymer used as the organic component in the present invention preferably has a carboxyl group. Polymers having carboxyl groups include, for example, monomers containing carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid or anhydrides thereof, and methacrylic acid esters, acrylic acid esters, It can be obtained by selecting monomers such as styrene, acrylonitrile, vinyl acetate, 2-hydroxyacrylate and copolymerizing using an initiator such as azobisisobutyronitrile.

  As the polymer having a carboxyl group, a copolymer having (meth) acrylic acid ester and (meth) acrylic acid as a copolymerization component is preferably used since the thermal decomposition temperature during firing is low. In particular, a styrene / methyl methacrylate / methacrylic acid copolymer is preferably used.

  The resin acid value of the copolymer having a carboxyl group is preferably 50 to 150 mgKOH / g. When the acid value exceeds 150, the allowable development width becomes narrow. On the other hand, if the acid value is less than 50, the solubility of the unexposed area in the developer is lowered. When the developer concentration is increased, the exposed portion is peeled off and it becomes difficult to obtain a high-definition pattern.

  As a method for introducing an ethylenically unsaturated bond into a side chain, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method in which a carboxylic acid such as chloride, allyl chloride or maleic acid is reacted.

  Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid, and glycidyl ether of isocrotonic acid. In particular, CH2 = CCH3COOCH2CHOHCH2- is preferably used.

  Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate. In addition, the ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is 0.05 to 1 molar equivalent with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to react.

  Preparation of an amine compound having an ethylenically unsaturated bond may be carried out by reacting glycidyl (meth) acrylate, (meth) acrylic acid chloride, (meth) acrylic anhydride, etc. having an ethylenically unsaturated bond with an amino compound. . A plurality of ethylenically unsaturated group-containing compounds may be mixed and used.

  When a binder component is required, polyvinyl alcohol, polyvinyl butyral, methacrylic acid ester polymer, acrylic acid ester polymer, acrylic acid ester-methacrylic acid ester copolymer, butyl methacrylate resin, or the like can be used as the polymer.

  The photopolymerization initiator used in the present invention is selected from those generating radical species. As photopolymerization initiators, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 1-phenyl-1,2-propanedione-2- (o-ethoxy) Carbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ' , 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-Benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propenaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4- Dimethylthio Xanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl- 1-propanaminium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2-bi Imidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-Hexafluorophosphate (1-), diphenyl sulfide derivative, bis η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 4,4-bis (dimethylamino) benzophenone, 4 , 4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy 2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β- Chloranthraki , Anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2, -Phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, N-phenylglycine, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide and eosin, methylene Light reducing dyes and ascorbic acid, such as Lou, a combination of a reducing agent such as triethanolamine.

  In the present invention, one or more of these can be used. A photoinitiator is added in 0.05-10 weight% with respect to the photosensitive organic component, More preferably, it is 0.1-10 weight%. If the amount of the polymerization initiator is too small, the photosensitivity will be poor, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed portion may be small.

  A sensitizer can be used together with a photopolymerization initiator to improve sensitivity and to expand the effective wavelength range for the reaction. Specific examples of the sensitizer include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis ( 4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone 4,4-bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4 -Dimethylaminophenylvinylene) Isonaphtho Sol, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), triethanolamine, methyl Diethanolamine, triisopropanolamine, N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate, diethylamino Isoamyl benzoate, (2-dimethylamino) ethyl benzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), 2-ethylhexyl 4-dimethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazo Le, such as 1-phenyl-5-ethoxycarbonyl-thiotetrazole the like.

  It is also preferable to use a sensitizing dye. For example, coumarin dyes, ketocoumarin dyes, xanthene dyes, thioxanthene dyes, cyanine dyes, merocyanine dyes, rhodocyanine dyes, styryl dyes, base styryl dyes, rhodocyanine dyes, oxonol dyes, etc. Can be mentioned.

  In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When adding a sensitizer to the photosensitive paste of this invention, the addition amount is 0.05-10 weight% normally with respect to the photosensitive organic component, More preferably, it is 0.1-10 weight%. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be reduced.

  In the present invention, it is also preferable to add an antioxidant. Antioxidants refer to those having radical chain inhibiting action, triplet elimination action, and hydroperoxide decomposition action. Since the photosensitive paste contains many inorganic fine particle components in a dispersed state, it is difficult to avoid light scattering inside the paste due to the exposure light, and it is thought that this is caused by pattern thickening and pattern filling (residual film formation). Likely to happen. It is desirable that the pattern walls are vertically cut and rectangular. Ideally, it is soluble in the developer below a certain exposure dose, and insoluble in the developer above it. That is, it is preferable that even if cured at a low exposure amount by light scattering, it is dissolved in the developer, the pattern shape is thickened and the filling between patterns is eliminated, and the range that can be resolved even when the exposure amount is increased is wide.

  When an antioxidant is added to the photosensitive paste, the antioxidant captures radicals and returns the energy state of the excited photopolymerization initiator and sensitizer to the ground state, thereby causing excess light due to scattered light. Since the reaction is suppressed and a photoreaction occurs abruptly at an exposure amount that cannot be suppressed by the antioxidant, it is possible to increase the contrast of dissolution and insolubility in the developer.

  Specifically, p-benzoquinone, naphthoquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, hydroquinone, p- t-butylcatechol, 2,5-dibutylhydroquinone, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butyl-p-cresol, hydroquinone monomethyl ether, α-naphthol, hydrazine hydrochloride Salt, trimethylbenzylammonium chloride, trimethylbenzylammonium oxalate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrobenzene, picric acid, quinonedioxime, Clohexanone oxime, pyrogallol, tannic acid, triethylamine hydrochloride, dimethylaniline hydrochloride, cuperone, (2,2′-thiobis (4-tert-octylphenolate) -2-ethylhexylamino nickel- (II), 4,4 '-Thiobis- (3-methyl-6-t-butylphenol), 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2'-thiobis- (4-methyl-6-t -Butylphenol), triethylene glycol-bis [3- (t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [(3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], 1,2,3-trihydroxybenzene, and the like. In the present invention, one or more of these can be used.

  The addition amount of the antioxidant is 0.1 to 30% by weight in the photosensitive paste, and more preferably 0.5 to 20%. If it is less than these ranges, the contrast of dissolution and insolubility in the developer is small, and if this range is exceeded, the sensitivity of the photosensitive paste decreases, requiring a large amount of exposure, and the degree of polymerization does not increase and the pattern shape Cannot be maintained.

  Moreover, by adding an ultraviolet absorber, scattered light inside the paste due to exposure light can be absorbed and scattered light can be weakened. Examples of the ultraviolet absorber include benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, benzotriazole compounds, indole compounds, inorganic fine-particle metal oxides, and the like. Among these, benzophenone compounds, cyanoacrylate compounds, benzotriazole compounds, and indole compounds are particularly effective. Specific examples thereof include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2 -Hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4 -(2-hydroxy-3-methyl (Chryloxy) propoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl BONASORB UA-3901 (produced by Orient Chemical Co., Ltd.), BONASORB U, which is an acrylate and indole-based absorbent A-3902 (manufactured by Orient Chemical Co., Ltd.) SOM-2-0008 (manufactured by Orient Chemical Co., Ltd.) and the like are exemplified, but not limited thereto. Furthermore, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type. In the present invention, one or more of these can be used.

  The amount of the UV absorber added is in the range of 0.001 to 10% by weight, more preferably 0.005 to 5% in the paste. Beyond these ranges, the transmission limit wavelength and the wavelength gradient width change, so that the ability to absorb scattered light is insufficient, the transmittance of exposure light is lowered, and the sensitivity of the photosensitive paste is lowered.

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

  An organic solvent is used to adjust the viscosity at the time of applying the photosensitive paste to the substrate according to the application method. As an organic solvent used at this time, 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, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and organic solvent mixtures containing one or more of these are used.

  In addition, the inorganic component in the present invention is inorganic fine particles of conductive powder such as glass, ceramics, Au, Ni, Ag, Pd, and Pt. Particularly useful is the case where glass powder is used.

  As a glass powder, it is preferable to contain 50 weight% or more of low melting glass with a glass transition point of 430-500 degreeC and a softening point of 470-580 degreeC in a paste. This is because pattern processing tends to be easily performed on a substrate used for a normal display.

  The average refractive index of the inorganic fine particles is preferably in the range of 1.5 to 1.65. By using glass fine particles formed by blending metal oxide so that the refractive index of the glass fine particles is 1.5 to 1.65, the refractive index of the glass powder and the photosensitive organic component is matched to suppress light scattering. By doing so, high-precision pattern processing tends to be possible. For example, a glass powder composed of silicon oxide: 22, aluminum oxide: 23, boron oxide: 33, lithium oxide: 9, magnesium oxide: 7, barium oxide: 4 and zinc oxide 2 (% by weight) has a glass transition point of 490. C., softening point: 528.degree. C. and refractive index at g-line wavelength (436 nm): 1.59, and can be preferably used as the inorganic fine particles of the present invention. More preferably, it is in the range of 1.53 to 1.62.

  The low-melting glass that can be preferably used as the inorganic fine particles used in the photosensitive paste of the present invention has, for example, the following composition (as oxide).

Lithium oxide, sodium oxide, potassium oxide
3-15% by weight
5-30% by weight of silicon oxide
Boron oxide 20-45% by weight
Barium oxide or strontium oxide
2 to 15% by weight
Aluminum oxide 10-25% by weight
Magnesium oxide or calcium oxide
2 to 15% by weight
As described above, at least one of alkali metal oxides of lithium oxide, sodium oxide or potassium oxide is used, and the total amount is preferably 3 to 15% by weight, more preferably 3 to 10% by weight.

  Alkali metal oxide not only facilitates control of the glass load softening point and thermal expansion coefficient, but also reduces the refractive index of the glass, thus reducing the refractive index difference from the photosensitive organic component. Becomes easier. By making the total amount of alkali metal oxides 3% by weight or more, the effect of lowering the melting point of the glass can be obtained, and by making it 15% by weight or less, the chemical stability of the glass is maintained and the thermal expansion coefficient. Can be kept small. As the alkali metal, lithium is preferably selected in consideration of lowering the refractive index of the glass and preventing ion migration.

  The blending amount of silicon oxide is preferably 5 to 30% by weight, more preferably 10 to 30% by weight. Silicon oxide is effective in improving the denseness, strength and stability of glass, and is effective in lowering the refractive index of glass. The thermal expansion coefficient can be controlled to prevent peeling due to mismatch with the glass substrate. By setting the content to 5% by weight or more, the thermal expansion coefficient is kept small, and no cracks occur when baked on a glass substrate. Further, the refractive index can be kept low. By setting it to 30% by weight or less, the glass transition point and the load softening point can be kept low, and the baking temperature on the glass substrate can be lowered.

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

  It is preferable that at least one of barium oxide and strontium oxide is used, and the total amount is 2 to 15% by weight, more preferably 2 to 10% by weight. These components are effective in adjusting the thermal expansion coefficient, and are preferable in terms of application of the baking temperature to the heat resistance of the substrate, electrical insulation, stability of the partition walls formed, and denseness. By setting the content to 2% by weight or more, devitrification due to crystallization can be prevented. Moreover, by setting it as 15 weight% or less, a thermal expansion coefficient can be restrained small and a refractive index can also be restrained small. Also, the chemical stability of the glass can be maintained.

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

  Furthermore, it is preferable that calcium oxide and magnesium oxide are blended for facilitating melting of the glass and controlling the thermal expansion coefficient. Calcium oxide and magnesium oxide are preferably blended in a total of 2 to 15% by weight. When the total amount is 2% by weight or more, devitrification of the glass due to crystallization can be prevented, and when the total amount is 15% by weight or less, the chemical stability of the glass can be maintained.

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

  As a method for producing the glass powder, for example, raw materials such as lithium oxide, silicon oxide, boron oxide, barium oxide and aluminum oxide are mixed so as to have a predetermined composition, melted at 900 to 1200 ° C., and then rapidly cooled. A glass frit is pulverized to a fine powder of 1 to 5 μm. High purity carbonates, oxides, hydroxides and the like can be used as raw materials. Depending on the type and composition of the glass powder, it is possible to use ultra-pure alkoxides of 99.99% or higher and organic metal raw materials, and to use powders that are homogenized by the sol-gel method. This is preferable because a high-strength insulating layer with few pores can be obtained.

The particle diameter of the glass powder used in the above is selected in consideration of the shape of the pattern to be produced. The powder has a 50% by weight particle diameter (average particle diameter) of 2 to 3.5 μm and a top size of 15 μm or less. It is preferable that Further, it is preferable that the 10% by weight particle diameter is 0.6 to 1.5 μm, the 90% by weight particle diameter is 4 to 8 μm, and the specific surface area is 1.5 to ^2.5 m ² / g. More preferably, the average particle size is 2.5 to 3.5 μm and the specific surface area is 1.7 to 2.4 m ² / g. Within this range, light can be sufficiently transmitted at the time of ultraviolet exposure, and a barrier rib pattern having a small line width difference between the upper and lower sides can be obtained. When the average particle size is 2.0 μm or less and the specific surface area exceeds 2.5 m ² / g, the powder becomes too fine and light is scattered during exposure to cure the unexposed portion, which is not preferable.

In order to maintain the pattern shape, it is preferable to use a filler as an inorganic component. As such a filler, refractory glass or oxide can be used. The filler also preferably has a refractive index in the range of 1.5 to 1.65 in order to match the average refractive index of the photosensitive organic component in the photosensitive paste and to suppress exposure light scattering. High melting point glass whose composition has been adjusted so that the average refractive index of the filler is within the above range, cordierite (2MgO · 2Al ₂ O ₃ · 5SiO ₂ ), Celsian (BaO · Al ₂ O ₃ · SiO ₂ ) Anorthite (CaO · Al ₂ O ₃ · 2SiO ₂ ), steatite (MgO—SiO ₂ ), spojumen (LiO ₂ · Al ₂ O ₃ · 4SiO ₂ ) and forsterite (2MgO · SiO ₂ ), silicon oxide, Aluminum oxide, titanium oxide, zirconium oxide, yttrium oxide, cerium oxide, magnesium oxide, zinc oxide, manganese oxide, copper oxide, iron oxide, holmium oxide, lead oxide, and tin oxide can be used. As high melting glass, what has a glass transition point of 500-1200 degreeC and a load softening point of 550-1200 degreeC is preferable. The composition of the high melting point glass is not limited to this, but for example, the following oxide conversion composition can be used.
Silicon oxide 15-50% by weight
Boron oxide 5-20% by weight
Barium oxide 2-10% by weight
Aluminum oxide 15-50% by weight.

    More specifically, for example, 38% by weight of silicon oxide, 10% by weight of boron oxide, 5% by weight of barium oxide, 36% by weight of aluminum oxide, and other components containing calcium oxide, zinc oxide, and magnesium oxide in small amounts. The average refractive index of the high melting point glass having a glass transition point of 625 ° C. and a load softening point of 750 ° C. is 1.59, which is equivalent to the average refractive index of the low melting point glass preferably used in the present invention.

  Moreover, it is also preferable to contain magnesium oxide as a filler in terms of contributing to discharge stability.

  The porosity can be adjusted by the mixing ratio of the low melting point glass and the filler. The porosity can be increased as the filler ratio is increased. In the low-porosity partition wall paste, although it depends on the material, the volume ratio of low melting point glass / filler = 5/95 to 25/75 is preferable. If the low melting point glass ratio is smaller than this, it is difficult to maintain the shape of the pattern, and if it is larger than this, the porosity becomes too high as a low porosity partition wall. On the other hand, the high porosity partition wall paste preferably has a low melting point glass / filler of 25/75 to 5/95 in volume ratio, although it depends on the material. If the low melting point glass ratio is smaller than this, the porosity is small and the shrinkage amount during firing becomes large, and if it is larger than this, the strength of the partition walls becomes too weak.

  After preparing these various components so as to have a predetermined composition, a photosensitive glass paste can be prepared by uniformly mixing and dispersing them with a three-roller or a kneader. The paste viscosity is appropriately adjusted depending on the addition ratio of glass powder, thickener, organic solvent, plasticizer, suspending agent and the like. The photosensitive paste is composed of 40 to 90% by weight of inorganic fine particles and 60 to 10% by weight of organic components, and is used for the purpose of forming a pattern substantially made of an inorganic substance by baking after pattern formation using photolithography. To do. In order to efficiently form an inorganic pattern with less photosensitive paste, it is preferable to use a photosensitive paste containing a larger amount of inorganic substance, but on the other hand, the transmittance of light used for pattern formation is reduced. When the content of the inorganic fine particles in the photosensitive paste is less than 40% by weight, it is industrially disadvantageous because many photosensitive pastes are required to form an inorganic pattern having a desired thickness. When the content of the inorganic fine particles in the photosensitive paste exceeds 90% by weight, the light transmittance is insufficient and a pattern shape is substantially impossible.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to this.

(Paste composition)
(1) Low porosity partition wall paste Low melting point glass (average particle size 2 μm) mainly composed of lead oxide, boron oxide, zinc oxide, silicon oxide, and barium oxide, and silicon oxide, boron oxide, and barium oxide as fillers , 52% glass powder in which the mixing ratio of high melting point glass (average particle size 2 μm) mainly composed of aluminum oxide is low melting point glass / filler = 20/80, methyl methacrylate / methacrylic acid copolymer (weight composition) Ratio 60/40, weight average molecular weight 32000) 12%, dipentaerythritol hexaacrylate 12%, benzophenone 1.94%, 1,6-hexanediol-bis [(3,5-di-t-butyl-4-hydroxy Phenyl) propionate] 0.05%, organic dye (Basic Blue 7) 0.01%, organic solvent (propylene glycol) Monomethyl ether acetate) 22% consisting of photosensitive paste.

(2) High porosity partition wall paste Low melting point glass (average particle size 2 μm) composed mainly of lead oxide, boron oxide, zinc oxide, silicon oxide and barium oxide and silicon oxide, boron oxide and barium oxide as fillers , 52% glass powder with a mixing ratio of high melting point glass (average particle size 2 μm) mainly composed of aluminum oxide material, low melting point glass / filler = 50/50, methyl methacrylate / methacrylic acid copolymer (weight composition) Ratio 60/40, weight average molecular weight 32000) 12%, dipentaerythritol hexaacrylate 12%, benzophenone 1.94%, 1,6-hexanediol-bis [(3,5-di-t-butyl-4-hydroxy Phenyl) propionate] 0.05%, organic dye (Basic Blue 7) 0.01%, organic solvent (propylene glycol) Monomethyl ether acetate) 22% consisting of photosensitive paste.

(Measurement of porosity)
The panel was cut into small pieces, the vertical cross section of the partition walls was observed with a scanning electron microscope (Hitachi, Ltd. S2400), and the porosity of the high porosity partition layer and the low porosity partition layer was calculated from the area ratio.

(Measurement of warpage)
The panel was cut into small pieces, and a vertical cross section of the partition was observed with a scanning electron microscope (Hitachi, Ltd. S2400), and the difference between the height of the part where the partition warped and the lowest part was taken as the amount of warpage.

(Impact test)
The ceramic ball having a weight of 80 g was gently dropped from the height of 20 cm onto the panel three times, and it was observed whether unlit cells or abnormally lit cells were generated.

Example 1
A sustain electrode having a pitch of 375 μm and a line width of 150 μm was formed on a glass substrate “PD200” manufactured by Asahi Glass Co., Ltd. using ITO. Further, a photosensitive silver paste was applied on the substrate, dried, exposed, developed and baked to form a sustain electrode having a line width of 50 μm and a thickness of 3 μm. Next, the transparent dielectric paste was applied by screen printing to a thickness of 50 μm so as to cover the sustain electrode of the display portion, and then baked at 570 ° C. for 15 minutes to form a front transparent dielectric. A magnesium oxide layer having a thickness of 0.5 μm was formed as a protective film by electron beam evaporation on the substrate on which the transparent dielectric was formed, thereby producing a 13-inch plasma display front plate.

Next, an address electrode was formed on the “PD200” using a photosensitive silver paste. A photosensitive silver paste was applied, dried, exposed, developed, and baked to form address electrodes having a line width of 50 μm, a thickness of 3 μm, and a pitch of 250 μm. Next, the dielectric layer paste was applied by screen printing to a thickness of 50 μm so as to cover the address electrodes of the display portion, and then baked at 570 ° C. for 15 minutes to form a dielectric layer. On the dielectric layer, a low porosity partition wall paste was applied by a slit die coater. Exposure was performed with an auxiliary partition pattern having a pitch of 1020 μm and a line width of 60 μm. Subsequently, a high porosity partition wall paste was applied by a slit die coater. Then, exposure was performed with a main partition wall pattern having a pitch of 360 μm and a line width of 60 μm so as to be orthogonal to the auxiliary partition wall pattern. After the development of the partition walls, baking was performed at 590 ° C. for 15 minutes to produce lattice-shaped partition walls in which the height of the main partition walls was 120 μm and the auxiliary partition walls were 20 μm lower than the main partition walls. That is, as shown in FIG. 10, the portion higher than the auxiliary partition wall was made to be a high porosity layer. Therefore, the layer with the largest porosity exists in the range within 75% from the upper layer of the partition wall.
Next, a phosphor was applied between adjacent barrier ribs. The phosphor was applied by a dispenser method in which a phosphor paste was discharged from the nozzle tip. The phosphor was baked at 500 ° C. for 10 minutes after being applied on the side wall of the partition wall so that the thickness was 25 μm after firing and on the dielectric so that the thickness was 25 μm after firing. A 13-inch plasma display back plate was produced as described above.

  Furthermore, the produced front plate and back plate were sealed using sealing glass, and Ne gas containing Xe 5% was sealed so as to have an internal gas pressure of 66500 Pa. A plasma display was fabricated by mounting a drive circuit.

The porosity of the low porosity layer and the high porosity layer of the partition walls was 6% and 55%, respectively. Further, the amount of warpage of the main partition wall in contact with the front substrate was 0 μm. Even in the impact test, no unlit cells or abnormally lit cells were generated.
(Comparative Example 1)
The same procedure as in Example 1 was performed except that the high-porosity partition wall paste was not used and all the low-porosity partition wall paste was used.

The porosity of the partition walls was 6%. Further, the warpage amount of the main partition wall was 4 μm. As a result of the impact test, one unlit cell and one abnormally lighted cell were generated.
(Example 2)
On the dielectric layer on which the address electrodes having a line width of 50 μm, a thickness of 3 μm, and a pitch of 3000 μm are formed, a low porosity partition wall paste is applied by a slit die coater, and after drying, a high porosity partition wall paste is applied to the slit die coater. The coating was carried out in the same manner as in Example 1 except that the exposure was performed with a stripe-shaped partition wall pattern having a pitch of 3000 μm and a line width of 1000 μm. That is, the upper layer 20 μm of the stripe-shaped partition wall having a height of 120 μm was a high porosity layer and the lower layer 100 μm was a low porosity layer. Therefore, the layer with the largest porosity exists in the range within 75% from the upper layer of the partition wall.

The porosity of the low porosity layer and the high porosity layer of the partition walls was 6% and 55%, respectively. The amount of warpage was 6 μm. Even in the impact test, no unlit cells or abnormally lit cells were generated.
(Comparative Example 2)
The same procedure as in Example 2 was performed except that the high-porosity partition wall paste was not used and all the low-porosity partition wall paste was used.

  The porosity of the partition walls was 6%. The amount of warpage was 40 μm. The impact test produced one unlit cell and two abnormally lit cells.

It is sectional drawing of a partition. (A) A schematic diagram of a partition without a high-porosity partition layer, and (b) a schematic diagram of a partition with a high-porosity partition layer in the uppermost layer. (A) Schematic diagram of how the partition walls are damaged by abnormal projections on the front substrate when there is no high porosity partition wall layer, and (b) partition walls due to abnormal projections on the front substrate when the top layer has a high porosity partition wall layer It is a schematic diagram of a mode that a shock is absorbed. It is a perspective view of the stripe-shaped partition which has a high porosity layer in the uppermost layer. It is a perspective view of the stripe-shaped partition which has a high porosity layer inside a partition. It is a perspective view of the lattice-like partition which has a high-porosity layer in the uppermost layer. It is a perspective view of a waffle-like partition having a high porosity layer as the uppermost layer. It is a perspective view of the grid-like partition which has a high-porosity layer inside a partition. It is a perspective view of a waffle-like partition wall having a high porosity layer inside the partition wall. FIG. 5 is a perspective view of a lattice-shaped partition wall having a high porosity layer as the uppermost layer of the main partition wall, and the main partition wall is higher than the auxiliary partition wall. FIG. 3 is a perspective view of a lattice-shaped partition wall having a high porosity layer in the main partition wall and the uppermost layer of the auxiliary partition wall, where the main partition wall is higher than the auxiliary partition wall. FIG. 4 is a perspective view of a lattice-shaped partition wall having a high porosity layer in the uppermost layer of the main partition wall, the inside of the main partition wall, and the uppermost layer of the auxiliary partition wall, and the main partition wall is higher than the auxiliary partition wall. FIG. 4 is a perspective view of a lattice-shaped partition wall having a high porosity layer in the uppermost layer of the main partition wall and the auxiliary partition wall, and the main partition wall is higher than the auxiliary partition wall.

Explanation of symbols

1: Partition 2: Dielectric layer 3: Address electrode 4: Partition pattern before firing 5: Low porosity layer 6: Partition pattern after firing 7: High porosity layer 8: Abnormal protrusion

Claims (6)

A display member having a partition wall composed of a plurality of layers having different porosity, wherein the partition wall is present only in the range of 75% of the upper layer of the partition wall when the height of the partition wall is 100%. A display member. The display member according to claim 1, wherein the layer having the largest porosity has a porosity greater than 10%. The display member according to claim 1 or 2, wherein the partition wall is a lattice-shaped pattern including a striped main partition wall and an auxiliary partition wall orthogonal to the main partition wall. The display member according to claim 3, wherein the height of the main partition is higher than the height of the auxiliary partition. A display using the display member according to claim 1. 6. A display according to claim 5, wherein the display is a plasma display.

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