JP4193878B2 - Method for manufacturing plasma display panel - Google Patents

Description

The present invention relates to a method for producing a flop plasma display panel. More specifically, in the plasma display panel, when forming a partition wall of a photosensitive paste method, the manufacturing method of the pulp plasma display panel to form a buffer layer provided between the glass substrate and the partition wall in order to prevent the peeling by firing About.

  A plasma display panel (PDP) can display at a higher speed than a liquid crystal panel and can be easily increased in size, and thus has penetrated into fields such as OA equipment and public information display devices. Progress in the field of high-definition television is also highly expected.

  Accompanying such expansion of applications, a fine color PDP having a large number of display cells has attracted attention. The PDP generates a plasma discharge between an anode and a cathode electrode opposed to each other in a discharge space provided between a front glass substrate and a back glass substrate, and emits ultraviolet rays generated from a gas sealed in the discharge space. The display is performed by touching the phosphor provided in the discharge space. In this case, partition walls (also referred to as barriers or ribs) are provided in order to suppress the spread of the discharge to a certain area and perform display in a prescribed cell, and to secure a uniform discharge space.

  The shape of the partition wall is approximately 30 to 80 μm in width and 100 to 200 μm in height. Usually, an insulating paste made of glass is printed and dried on a front glass substrate or a rear glass substrate by a screen printing method. The drying process is repeated 10 to 20 times to obtain a predetermined height, and then baked to form. However, in the normal screen printing method, especially when the panel size is increased, it is difficult to align the discharge electrode previously formed on the front transparent flat plate and the printing place of the insulating glass paste, and the positional accuracy is obtained. There is a difficult problem. In addition, the overlapping printing of the glass paste 10 to 20 times causes the waviness and disturbance of the side edges of the partition walls and the wall, and the accuracy of the height cannot be obtained, resulting in poor display quality. There are problems of poor workability and low yield. In particular, when the pattern width is 50 μm and the pitch is 100 μm or less, there is a problem that the partition bottom tends to bleed due to the thixotropy of the paste, making it difficult to form a sharp and residue-free partition.

  With the increase in area and resolution of PDPs, it is becoming more technically difficult and costly to produce high aspect ratio and high definition partition walls by such a screen printing method. .

  As a method for improving these problems, Patent Documents 1 to 4 propose a method in which the partition walls are formed by a photolithography technique using a photosensitive paste. However, in these methods, since the glass content of the photosensitive paste is small, a dense partition cannot be obtained after firing, and the sensitivity and resolution of the photosensitive paste are low. For this reason, it has been necessary to obtain a high aspect ratio partition wall by repeating the steps of screen printing, exposure and development. However, repeated printing / exposure / development has a problem in alignment and has a limit in cost reduction.

  Patent Document 2 discloses a method in which a photosensitive paste is coated on a transfer paper, and then a transfer film is transferred onto a glass substrate to form a partition. In Patent Documents 4 and 5, a dielectric is formed in a groove of a photoresist layer. Methods for filling the paste to form the partition walls have been proposed. Patent Document 6 proposes a method of forming partition walls using a photosensitive organic film. However, in these methods, since a transfer film, a photoresist, or an organic film is required, the number of processes is increased, so that there is a limit in reducing the cost. In addition, there is a problem in obtaining a partition wall having high definition and a high aspect ratio.

  Patent Documents 7 to 9 propose a method of forming a partition wall by sandblasting or liquid honing through a subtractive mask layer formed by a photolithography method, but the process is complicated because the subtractive mask layer needs to be formed. Thus, there is a problem that the peeling of the mask layer is troublesome. Further, there is a problem that it is difficult to process a line width of 50 μm or less and it is difficult to form a high-definition pattern.

Patent Document 10 proposes a method of forming a partition wall by a single exposure using a photosensitive paste method. However, this method has a problem that disconnection or peeling occurs when the partition pattern formed is fired to obtain the partition.
JP-A-1-296534 JP-A-2-165538 JP-A-5-342992 JP-A-6-295676 JP-A-3-57138 JP-A-4-109536 JP-A-6-314543 JP 7-282730 A JP 7-85792 A Japanese Patent Laid-Open No. 8-50811

  An object of the present invention is to provide a high-definition plasma display having a high yield by preventing separation of the partition during firing when forming the partition by a photosensitive paste method.

In order to achieve the above object, the present invention has the following configuration. That is, a method for manufacturing a plasma display panel in which partition walls are formed on a buffer layer provided on a glass substrate, comprising a glass powder and an organic component, and comprising at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer. A buffer layer forming paste of a plasma display panel containing a selected photosensitive component or a thermal polymerization component comprising a radical polymerizable monomer and a radical polymerization initiator is applied on a glass substrate and dried, and then the entire surface of the applied film is photocured or After forming a buffer layer having a crosslinked structure by thermal polymerization, applying a photosensitive paste composed of glass powder and a photosensitive organic component on the buffer layer, forming a partition pattern through exposure and development steps, Manufacture of a plasma display panel that forms the barrier ribs by firing the buffer layer and barrier rib pattern simultaneously It is the law.

  By using the buffer layer forming paste of the plasma display panel of the present invention, the partition walls are not peeled off during firing, so that a high-definition PDP can be manufactured with a high yield. Thereby, a high-definition plasma display can be provided.

  The barrier rib pattern formed by the photosensitive paste method is apt to cause strain stress due to non-uniformity of photocuring, and thus is easily peeled off during firing. When the separation of the partition wall occurs, color mixture occurs at the part where the partition wall is peeled off, and the peeled partition wall remains on the panel to crush pixels, resulting in a decrease in yield.

  In the present invention, the barrier rib pattern is formed on the buffer layer by the photosensitive paste method, and the barrier rib pattern and the buffer layer are fired at the same time, so that the adhesion of the barrier ribs is increased as compared with the case of forming on the glass substrate. It was found that peeling was suppressed and the yield was improved.

  The buffer layer used in the present invention is formed by applying a paste made of glass powder and an organic component on a glass substrate and then drying. After the barrier rib pattern and the buffer layer are fired at the same time after the barrier rib pattern is formed on the dried coated surface, the buffer layer and the barrier rib pattern are removed from the binder at the same time. Disconnection can be prevented. On the other hand, when a partition is formed on the buffer layer after firing only the buffer layer, it is difficult to prevent peeling or disconnection during firing because the adhesion between the partition and the buffer layer cannot be obtained. Further, when the barrier rib pattern and the buffer layer are fired simultaneously, there is an advantage that the number of steps is small. At the same time, since the organic component in the buffer layer has a crosslinked structure, it is not eroded by the developer during the formation of the partition pattern.

  In order to crosslink the organic component in the buffer layer, a method of imparting photosensitivity to the paste for the buffer layer, coating it on a glass substrate, drying it, performing exposure, and photocuring the buffer layer is simple. Preferably used. The buffer layer paste contains a photosensitive component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, and, if necessary, a photopolymerization initiator, an ultraviolet absorber, and a sensitization. Photosensitivity is imparted by adding additive components such as an agent, a sensitization aid, and a polymerization inhibitor.

  A crosslinked structure can also be obtained by thermal polymerization. In this case, there is a method in which a radical polymerizable monomer and a radical polymerization initiator are added to the buffer layer paste, the paste is applied, and then heated. Specific examples of the radical polymerizable monomer include ethylene, styrene, butadiene, vinyl chloride, vinyl acetate, acrylic acid, methyl acrylate, methyl vinyl ketone, acrylamide, acrylonitrile and the like. Examples of the radical initiator include benzoyl peroxide, lauroyl peroxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide-dimethylaniline, and the like.

  When a linear polymer is used as the organic component in the buffer layer, a non-soluble polymer must be selected in the developer compared to the case of having a crosslinked structure, and the buffer layer is cracked by erosion by the developer. Prone to occur.

  An organic binder, a plasticizer, a solvent, and a dispersant, a leveling agent, and the like can be added to the organic component used in the buffer layer paste. Specific examples of the organic binder include polyvinyl alcohol, cellulose polymer, silicon polymer, polyethylene, polyvinyl pyrrolidone, polystyrene, polyamide, high molecular weight polyether, polyvinyl butyral, methacrylic ester polymer, acrylic ester polymer, acrylic Acid ester-methacrylic acid ester copolymer, α-methylstyrene polymer, butyl methacrylate resin, and the like. It is necessary to select a binder that does not dissolve in the partition wall developer.

  When adjusting the viscosity of the buffer layer paste, it is preferable to use a binder component solvent. As the solvent, 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, dibromo Chlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and organic solvent mixtures containing one or more of these are used.

  Moreover, a plasticizer can also be included in a paste. Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.

  The amount of the glass powder used for the buffer layer paste is preferably 50 to 85% by weight based on the sum of the glass powder and the organic component. If it is less than 50% by weight, the buffer layer lacks the denseness and the surface flatness, so that the reflectance is lowered and luminance cannot be obtained. If it exceeds 85% by weight, cracks in the buffer layer due to firing shrinkage tend to occur.

  The buffer layer can also be formed by leaving a residue at the bottom of the partition wall in the partition pattern development process. This method is preferable because the number of steps can be reduced and the cost can be reduced. In this case, the buffer layer thickness can be controlled by the development time.

  The thickness of the buffer layer is preferably 3 to 20 μm, more preferably 6 to 15 μm for the formation of a uniform buffer layer. If the thickness exceeds 20 μm, it is difficult to remove the solvent during firing, and cracks are likely to occur. Also, since the stress applied to the glass substrate is large, problems such as warping of the substrate occur. If the thickness is less than 3 μm, it is difficult to maintain uniformity of thickness.

The buffer layer may be made of a glass having a thermal expansion coefficient (α) in the range of 50 to 400 ° C., and 50 to ₄₀₀ of 70 to ₈₅ × 10 ⁻⁷ / K, more preferably 72 to 80 × 10 ⁻⁷ / K. This is preferable because it matches the thermal expansion coefficient of the substrate glass and reduces the stress applied to the glass substrate during firing. If it exceeds 85 × 10 ⁻⁷ / K, a stress is applied to the surface on which the buffer layer is formed, and if it is less than 70 × 10 ⁻⁷ / K, the substrate is warped on the surface without the buffer layer. Stress is applied. For this reason, if heating and cooling of the substrate are repeated, the substrate may break. Further, when sealing with the front substrate, the two substrates may not be parallel and cannot be sealed due to warpage of the substrate.

  The glass contained in the buffer layer preferably has a glass transition point Tg of 430 to 500 ° C. and a softening point Ts of 470 to 580 ° C. When forming the buffer layer, if the glass transition point is higher than 500 ° C. and the thermal softening point is higher than 580 ° C., the glass substrate must be baked at a high temperature, and the glass substrate is distorted during baking. Further, a material having a glass transition point lower than 430 ° C. and a thermal softening point lower than 470 ° C. is not preferable because the buffer layer is distorted when the phosphor is applied and fired in the subsequent steps, and the film thickness accuracy cannot be maintained. .

  For the buffer layer, the use of glass fine particles containing 10 to 60% by weight of at least one of bismuth oxide, lead oxide and zinc oxide in glass makes it easy to control the thermal softening temperature and the thermal expansion coefficient.

  If the added amount of bismuth oxide, lead oxide, or zinc oxide exceeds 60% by weight, the heat-resistant temperature of the glass becomes too low and baking on the glass substrate becomes difficult.

  The thermal softening temperature and the thermal expansion coefficient can also be controlled by using glass fine particles containing lithium oxide, sodium oxide, and potassium oxide, but the content is preferably 5% by weight or less, more preferably 3% by weight. The stability of the paste can be improved by setting it to not more than%. Further, it is effective for preventing deformation and alteration of the substrate due to chemical reaction such as ion exchange with the substrate glass, and preventing reaction with the metal used for the electrode.

  In particular, the use of glass containing 10 to 60% by weight of bismuth oxide has advantages such as a long pot life of the paste.

As a glass composition containing bismuth oxide, 10 to 40 parts by weight of bismuth oxide in terms of oxides 3 to 50 parts by weight of silicon oxide 10 to 40 parts by weight of boron oxide 8 to 20 parts by weight of zinc oxide 10 to 30 parts by weight of zinc oxide It is preferable to contain 50% by weight or more of the composition.

  The photosensitive paste method of the present invention uses a photosensitive paste mainly composed of an inorganic component composed mainly of glass powder and an organic component having photosensitivity, burns a photomask pattern by exposure, and forms a partition pattern by development, Thereafter, the partition is obtained by firing. At this time, the exposure is preferably performed once or twice. The double exposure method is preferably used because it is photocured uniformly up to the bottom of the partition wall pattern, so that it is difficult to generate strain stress and prevents peeling and disconnection during firing. When the number of exposures exceeds 3, it is difficult to align, so that a fine partition wall shape cannot be obtained, and the number of steps increases, making it difficult to reduce costs.

  The glass material used for the partition wall of the present invention preferably has a refractive index of 1.50 to 1.65. Generally, glass used as an insulator has a refractive index of about 1.50 to 1.90, but when using the photosensitive paste method, the average refractive index of the organic component is larger than the average refractive index of the glass powder. If they are different, reflection / scattering at the interface between the glass powder and the photosensitive organic component increases, and a fine pattern cannot be obtained. Since the refractive index of a general organic component is 1.45 to 1.70, in order to match the refractive index of the glass powder and the organic component, the average refractive index of the glass powder is set to 1.50 to 1.65. It is preferable to do.

  When used as a partition for a plasma display or a plasma addressed liquid crystal display, a pattern is formed on a glass substrate having a low glass transition point and a low thermal softening point. Therefore, the partition material is a glass transition point of 430 to 500 ° C. and a thermal softening temperature of 470. It is preferable to use a glass material of ˜580 ° C.

  The amount of the glass powder used for the photosensitive paste method is preferably 65 to 85% by weight based on the sum of the glass powder and the organic component. If it is less than 65% by weight, the shrinkage rate at the time of firing is increased, which causes disconnection and peeling of the partition walls, which is not preferable. Also, pattern thickening and residual film during development are likely to occur. If it is larger than 85% by weight, the pattern forming property is deteriorated due to the small photosensitive component.

  As the composition of the partition wall material, silicon oxide is preferably blended in the glass in the range of 3 to 60% by weight, and if it is less than 3% by weight, the denseness, strength and stability of the glass layer are lowered, The coefficient of thermal expansion deviates from a desired value, and mismatching with the glass substrate is likely to occur. Moreover, by making it 60 weight% or less, there exists an advantage that a thermal softening point becomes low and baking to a glass substrate is attained.

  Boron oxide can improve electrical, mechanical, and thermal properties such as electrical insulation, strength, thermal expansion coefficient, and denseness of the insulating layer by blending in the glass in the range of 5 to 50% by weight. . If it exceeds 50% by weight, the stability of the glass decreases.

  Although it can also be obtained by using glass fine particles containing 3 to 20% by weight of at least one of lithium oxide, sodium oxide, and potassium oxide, oxides of alkali metals such as lithium, sodium, potassium, etc. 20% by weight or less, preferably 15% by weight or less, the stability of the paste can be improved.

As a glass composition containing lithium oxide, lithium oxide 2-15 parts by weight silicon oxide 15-50 parts by weight boron oxide 15-40 parts by weight barium oxide 2-15 parts by weight aluminum oxide 6-25 parts by weight in terms of oxide It is preferable to contain 50% by weight or more of the composition.

  In the above composition, sodium oxide or potassium oxide may be used instead of lithium oxide, but lithium oxide is preferable in terms of paste stability.

  By using a glass containing a total of 2 to 10% by weight of alkali metal oxides such as sodium oxide, lithium oxide and potassium oxide, the thermal softening temperature and thermal expansion coefficient can be easily controlled. Since the average refractive index can be lowered, it is easy to reduce the difference in refractive index from the organic substance. When it is less than 2%, it becomes difficult to control the heat softening temperature. If it is greater than 10%, the brightness is reduced by evaporation of the alkali metal oxide during discharge. Further, the addition amount of the alkali metal oxide is preferably less than 10% by weight, more preferably 8% by weight or less in order to improve the stability of the paste.

  In particular, among alkali metals, lithium oxide can be used to increase the stability of the paste, and when potassium oxide is used, the refractive index can be controlled even with a relatively small amount of addition. Therefore, addition of lithium oxide and potassium oxide is effective among alkali metal oxides.

  In addition, by adding aluminum oxide, barium oxide, calcium oxide, magnesium oxide, zinc oxide, zirconium oxide, etc., especially aluminum oxide, barium oxide, zinc oxide, etc., it is possible to improve hardness and workability. However, from the viewpoint of controlling the thermal softening point, the thermal expansion coefficient, and the refractive index, the content is preferably 40% by weight or less, more preferably 25% by weight or less.

  As a result, it has a heat softening temperature that can be baked on the glass substrate, can have an average refractive index of 1.50 to 1.65, and can easily reduce the difference in refractive index from the organic component.

  Glass containing bismuth oxide is preferable from the viewpoint of heat softening temperature and water resistance improvement, but glass containing 10% by weight or more of bismuth oxide often has a refractive index of 1.6 or more. For this reason, the thermal softening temperature, thermal expansion coefficient, water resistance, and refractive index can be easily controlled by using lead oxide together with an oxide of an alkali metal such as sodium oxide, lithium oxide or potassium oxide.

  In the measurement of the refractive index of the glass material in the present invention, it is accurate to confirm the effect by measuring at the wavelength of light exposed by the photosensitive paste method. In particular, it is preferable to measure with light having a wavelength in the range of 350 to 650 nm. Furthermore, refractive index measurement with i-line (365 nm) or g-line (436 nm) is preferable.

The porosity of the partition wall in the present invention is preferably 3% or less because of excellent adhesion to the substrate that prevents the partition wall from falling. The porosity (P) is defined as follows, where the theoretical density of the partition wall material is dth and the measured density of the partition wall is dex.
P = (dth−dex) / dth × 100
It is defined as The theoretical density is calculated from the component ratio of the partition walls and the specific gravity of each component. It is preferable to perform the measurement of the actually measured density using a normal Archimedes method. When the porosity is more than 3%, in addition to deterioration of the adhesion, the strength is insufficient, and discharge characteristics such as a reduction in luminance due to gas and moisture discharged from the pores during discharge are caused. Considering discharge characteristics such as the discharge life and luminance stability of the panel, 0.5% or less is more preferable.

Since the partition wall of the present invention is excellent in increasing the contrast, it may be colored black. By adding various metal oxides, the fired partition walls can be colored. For example, a black pattern can be formed by including 1 to 10% by weight of a black metal oxide in the photosensitive paste. By including at least one, preferably three or more of Cr, Fe, Co, Mn, and Cu oxides as the black metal oxide used at this time, blackening can be achieved.
In particular, a black pattern can be formed by containing 0.5 wt% or more of Fe and Mn oxides.

  In addition to black, a pattern of each color can be formed by using a paste to which an inorganic pigment that develops red, blue, green, or the like is added. These colored patterns can be suitably used for a color filter of a plasma display.

  Moreover, it is preferable that the specific gravity of the partition of this invention is 2-3. In order to make it 2 or less, the glass material must contain a large amount of alkali metal oxides such as sodium oxide and potassium oxide, which is not preferable because it evaporates during discharge and deteriorates discharge characteristics. . If it becomes 3.3 or more, the display becomes heavy when the screen is enlarged, or the substrate is distorted by its own weight, which is not preferable.

  The partition wall material of the present invention may contain 10 to 50% by weight of a filler having a glass softening point of 650 to 850 ° C. Thereby, in the photosensitive paste method, the shrinkage rate at the time of baking after pattern formation becomes small, and pattern formation becomes easy. As the filler, refractory glass or ceramics having a heat softening temperature of 600 ° C. or higher can be used.

  As the high melting point glass powder, a glass powder containing 15% by weight or more of silicon oxide and aluminum oxide is preferable, and the total content thereof is 50% by weight or more in the glass powder in order to provide necessary thermal characteristics. Is effective. As an example, it is preferable to use glass powder containing the following composition.

Silicon oxide: 15 to 50 parts by weight Boron oxide: 5 to 20 parts by weight Aluminum oxide: 15 to 50 parts by weight Barium oxide: 2 to 10 parts by weight The organic components of the photosensitive paste are photosensitive monomer, photosensitive oligomer, and photosensitive. It contains a photosensitive component selected from at least one of the polymers, and further includes a binder, a photopolymerization initiator, an ultraviolet absorber, a sensitizer, a sensitization aid, a polymerization inhibitor, a plasticizer, an enhancer, if necessary. Additive components such as a sticking agent, an organic solvent, an antioxidant, a dispersant, an organic or inorganic precipitation inhibitor are also added.

As the photosensitive component, there are a light-insolubilized type and a light-solubilized type,
(A) containing functional monomers, oligomers or polymers having one or more unsaturated groups in the molecule (B) containing photosensitive compounds such as aromatic diazo compounds, aromatic azide compounds, and organic halogen compounds (C) What is called a diazo resin, such as a condensate of a diazo amine and formaldehyde.

In addition, as a light-soluble type,
(D) Inorganic salt of diazo compound or complex with organic acid, containing quinone diazo (E) quinone diazo combined with appropriate polymer binder, for example, naphthoquinone-1,2-diazide of phenol, novolak resin 5-sulphonic acid ester and the like.

  As the photosensitive component used in the present invention, all of the above can be used. As the photosensitive paste, the photosensitive component that can be used simply by mixing with inorganic fine particles is preferably (A).

  The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl. Acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, Glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate Isobonyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, tri Fluoroethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipenta Erythritol hexaacryl , Dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylol Propane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, bisphenol A-propylene Of oxide adducts Acrylates such as diacrylate, thiophenol acrylate, benzyl mercaptan acrylate, etc., and monomers in which 1 to 5 hydrogen atoms of these aromatic rings are substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o -Methyl styrene, m-methyl styrene, chlorinated styrene, brominated styrene, α-methyl styrene, chlorinated α-methyl styrene, brominated α-methyl styrene, chloromethyl styrene, hydroxymethyl styrene, carboxymethyl styrene, vinyl Naphthalene, vinyl anthracene, vinyl carbazole, and those obtained by changing some or all of the acrylates in the molecule of the above compounds to methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, etc. It is. In the present invention, one or more of these can be used.

  In addition to these, the development property after exposure can be improved by adding an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

  The content of these monomers is preferably 5 to 30% by weight with respect to the sum of the glass powder and the photosensitive component. In other ranges, the pattern formability is deteriorated and the hardness after curing is not preferable.

  Examples of the binder include polyvinyl alcohol, polyvinyl butyral, methacrylic ester polymer, acrylic ester polymer, acrylic ester-methacrylic ester copolymer, α-methylstyrene polymer, and butyl methacrylate resin.

  Moreover, the oligomer and polymer obtained by superposing | polymerizing at least 1 type among the compounds which have the above-mentioned carbon-carbon double bond can be used. In the polymerization, it can be copolymerized with other photosensitive monomers so that the content of these photoreactive monomers is 10% by weight or more, more preferably 35% by weight or more.

  As a monomer to be copolymerized, the developability after exposure can be improved by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

  The acid value (AV) of the polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained is preferably 50 to 180, more preferably 70 to 140. When the acid value is less than 50, the allowable development width becomes narrow. Further, if the acid value exceeds 180, the solubility of the unexposed portion in the developing solution is lowered. Therefore, if the concentration of the developing solution is increased, the exposed portion is peeled off and it is difficult to obtain a high-definition pattern.

  By adding a photoreactive group to the side chain or molecular end of the polymer or oligomer described above, it can be used as a photosensitive polymer or photosensitive oligomer having photosensitivity. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.

  Such a side chain can be added to an oligomer or polymer by using an ethylenically unsaturated compound having a glycidyl group or an isocyanate group relative to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method of making an acid chloride or allyl chloride by addition reaction.

  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. 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 add.

  The amount of the polymer component consisting of the photosensitive polymer, photosensitive oligomer and binder in the photosensitive paste is excellent in terms of pattern formability and shrinkage after firing, so it is the sum of glass powder and photosensitive component. On the other hand, it is preferably 5 to 30% by weight. Outside this range, it is not preferable because pattern formation is impossible or the pattern becomes thick.

  Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4 -Benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p -T-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketanol, benzylmethoxyethyl acetal, benzoin, benzo Methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (P-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propane Dione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, Photoreducing dyes such as diphenyl disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, carbon tetrabrominated, tribromophenylsulfone, benzoin peroxide and eosin, methylene blue, and reducing agents such as ascorbic acid and triethanolamine The combination of these etc. is mention | raise | lifted. In the present invention, one or more of these can be used.

  A photoinitiator is added in 0.05-20 weight% with respect to the photosensitive component, More preferably, it is 0.1-15 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 area may be too small.

  It is also effective to add a UV absorber. High aspect ratio, high definition, and high resolution can be obtained by adding a compound having a high ultraviolet absorption effect. As the ultraviolet absorber, an organic dye, particularly an organic dye having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used. Specifically, azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, and the like can be used. . Even when an organic dye is added as a light-absorbing agent, it is preferable because it does not remain in the insulating film after baking and the deterioration of the insulating film characteristics due to the light-absorbing agent can be reduced. Of these, azo dyes and benzophenone dyes are preferable.

  The addition amount of the organic dye is preferably 0.05 to 1 part by weight with respect to the glass powder. If it is 0.05% by weight or less, the effect of adding the ultraviolet light absorber is reduced, and if it exceeds 1% by weight, the insulating film properties after firing are deteriorated, which is not preferable. More preferably, it is 0.1 to 0.18% by weight.

  An example of a method for adding an ultraviolet light absorber composed of an organic dye is to prepare a solution in which an organic dye is dissolved in an organic solvent in advance, and mix glass fine particles in the organic solvent in addition to kneading it at the time of preparing the paste. Thereafter, a method of drying is mentioned. By this method, so-called capsule-shaped fine particles in which the surface of each glass fine particle is coated with an organic film can be produced.

In the present invention, when a metal and an oxide such as Pb, Fe, Cd, Mn, Co, and Mg contained in the inorganic fine particles are contained in the paste, the paste gels in a short time by reacting with the photosensitive component. It may not be possible. In order to prevent such a reaction, it is preferable to add a stabilizer to prevent gelation. As a stabilizer to be used, a triazole compound is preferably used. As the triazole compound, a benzotriazole derivative is preferably used. Of these, benzotriazole is particularly effective. As an example of the surface treatment of glass fine particles with benzotriazole used in the present invention, a predetermined amount of benzotriazole with respect to inorganic fine particles was dissolved in an organic solvent such as methyl acetate, ethyl acetate, ethyl alcohol, and methyl alcohol. Thereafter, it is immersed in the solution for 1 to 24 hours so that these fine particles can be sufficiently immersed. After soaking, the particles are preferably air-dried at 20 to 30 ° C. to evaporate the solvent to produce fine particles treated with triazole.
The proportion of the stabilizer used (stabilizer / inorganic fine particles) is preferably 0.05 to 5% by weight.

A sensitizer is added in order to improve sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, 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-dimethylaminobenzal) acetone 1,3-carbonyl-bis (4-diethylamino) Benzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate And isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. 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 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 too small.

  A polymerization inhibitor is added to improve the thermal stability during storage. Specific examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples include methylphenol, chloranil, and pyrogallol. When adding a polymerization inhibitor, the addition amount is 0.001 to 1 weight% normally in the photosensitive paste.

  Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.

The antioxidant is added to prevent oxidation of the acrylic copolymer during storage. Specific examples of antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-4-ethylphenol, 2,2-methylene-bis- ( 4-methyl-6-tert-butylphenol), 2,2-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4-bis- (3-methyl-6-tert-butylphenol), 1 , 1,3-Tris- (2-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-tert-butylphenyl) butane, bis [3,3-bis -(4-Hydroxy-3-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like.
When adding an antioxidant, the addition amount is usually 0.001 to 1% by weight in the paste.

  An organic solvent may be added to the photosensitive paste of the present invention in order to adjust the viscosity of the solution. 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.

  The refractive index of the organic component is the refractive index of the organic component in the paste at the time when the photosensitive component is exposed by exposure. That is, when the paste is applied and the exposure is performed after the drying process, this is the refractive index of the organic component in the paste after the drying process. For example, after apply | coating a paste on a glass substrate, there exists the method of drying at 50-100 degreeC for 1 to 30 minutes, and measuring a refractive index.

  The measurement of the refractive index in the present invention is preferably performed by an ellipsometry method or a V block method which are generally performed, and it is accurate to confirm the effect that the measurement is performed at the wavelength of light to be exposed. In particular, it is preferable to measure with light having a wavelength in the range of 350 to 650 nm. Furthermore, refractive index measurement with i-line (365 nm) or g-line (436 nm) is preferable.

  Moreover, in order to measure the refractive index after an organic component superposes | polymerizes by light irradiation, it can measure by irradiating only the organic component with the same light as the case where light is irradiated with respect to the inside of a paste.

  As the sensitizer, one having absorption at the exposure wavelength is used. In this case, since the refractive index becomes extremely high near the absorption wavelength, the refractive index of the organic component can be improved by adding a large amount of a sensitizer. In this case, the sensitizer can be added in an amount of 3 to 10% by weight.

  The buffer layer paste and the photosensitive paste are usually prepared by mixing the above-mentioned various inorganic and organic components so as to have a predetermined composition, and then uniformly mixing and dispersing them with a three roller or kneader.

  The viscosity of the paste is appropriately adjusted depending on the addition ratio of inorganic fine particles, thickener, organic solvent, plasticizer, precipitation inhibitor, etc., but the range is 2000 to 200,000 cps (centipoise). For example, when the application to the glass substrate is performed by a spin coating method other than the screen printing method, 200 to 5000 cps is preferable. In order to obtain a film thickness of 10 to 20 μm by applying it once by the screen printing method, 4000 to 200,000 cps is preferable.

  Next, an example in which pattern processing is performed on the buffer layer using the buffer layer paste and the photosensitive paste will be described, but the present invention is not limited thereto.

  A buffer layer paste is applied to a thickness of 5 to 30 μm on the glass substrate. Here, when the paste is applied onto the substrate, surface treatment of the substrate can be performed in order to improve the adhesion between the substrate and the coating film. As the surface treatment liquid, silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tris- (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacryloxy) Propyl) trimethoxysilane, γ (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, or organic metals such as organic titanium, Organic aluminum, organic zirconium and the like. A silane coupling agent or an organic metal diluted with an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol to a concentration of 0.1 to 5% is used. . Next, this surface treatment liquid is uniformly applied onto the substrate with a spinner or the like, and then dried at 80 to 140 ° C. for 10 to 60 minutes, whereby the surface treatment can be performed.

  After applying the buffer layer paste, drying is performed to remove the solvent in the paste. Thereafter, when a light or heat polymerizable component is contained in the buffer layer paste, it is cured by light or thermal crosslinking to prevent erosion by the developer during the formation of the partition pattern.

  When forming the barrier rib pattern on the formed buffer layer, a method of patterning after directly applying or partially applying the photosensitive paste, and applying a patterned paste to the polymer film and buffering the patterned There is a method of transferring onto the layer. As a coating method, methods such as screen printing, bar coater, roll coater, die coater, and blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings and the viscosity of the paste.

  After coating, exposure is performed using an exposure apparatus. In general, the exposure is performed by mask exposure using a photomask, as in normal photolithography. As the mask to be used, either a negative type or a positive type is selected depending on the type of the photosensitive organic component. Alternatively, a method of directly drawing with a red or blue laser beam or the like without using a photomask may be used.

  As the exposure apparatus, a stepper exposure machine, a proximity exposure machine or the like can be used. Moreover, when performing exposure of a large area, a large area can be exposed with an exposure machine having a small exposure area by applying a photosensitive paste on a substrate such as a glass substrate and then performing exposure while transporting. it can.

Examples of the active light source used in this case include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferable. Mercury lamps, ultra-high pressure mercury lamps, halogen lamps, germicidal lamps, etc. can be used. Among these, an ultrahigh pressure mercury lamp is suitable. Although exposure conditions vary depending on the coating thickness, exposure is performed for 0.5 to 30 minutes using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² .

  The pattern shape can be improved by providing an oxygen shielding film on the surface of the coated photosensitive paste. As an example of the oxygen shielding film, a film such as polyvinyl alcohol (PVA) or cellulose, or a film such as polyester can be used.

  The PVA film is formed by uniformly applying an aqueous solution having a concentration of 0.5 to 5% by weight on a substrate by a method such as a spinner and then evaporating moisture by drying at 70 to 90 ° C. for 10 to 60 minutes. . In addition, it is preferable to add a small amount of alcohol to the aqueous solution because it improves the paintability with the insulating film and facilitates evaporation. A more preferable solution concentration of PVA is 1 to 3% by weight. Within this range, the sensitivity is further improved. The following reasons are presumed that the sensitivity is improved by application of PVA. That is, when the photosensitive component undergoes a photoreaction, if there is oxygen in the air, it is considered that the sensitivity of photocuring is disturbed, but if there is a PVA film, it is considered that the sensitivity can be improved during exposure because excess oxygen can be blocked. .

  When a transparent film such as polyester, polypropylene, or polyethylene is used, there is a method in which these films are pasted on the photosensitive paste after application.

  After exposure, development is performed using the difference in solubility between the photosensitive portion and the non-photosensitive portion in the developer. In this case, the immersion method, the shower method, the spray method, and the brush method are used.

  As the developer to be used, an organic solvent in which an organic component in the photosensitive paste can be dissolved can be used. Further, water may be added to the organic solvent as long as its dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an aqueous alkaline solution. A metal alkali aqueous solution such as sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution or the like can be used as the alkali aqueous solution. However, it is preferable to use an organic alkali aqueous solution because an alkaline component can be easily removed during firing.

  An amine compound can be used as the organic alkali. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine. The concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble part is not removed, and if the alkali concentration is too high, the pattern part may be peeled off and the non-soluble part may be corroded. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

  In the case of patterning on a glass substrate, baking is performed by holding at a temperature of 540 to 610 ° C. for 10 to 60 minutes.

  Moreover, you may introduce | transduce a 50-300 degreeC heating process for the purpose of drying and a preliminary reaction in each process of the above application | coating, exposure, image development, and baking.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to this. The concentration (%) in Examples and Comparative Examples is% by weight unless otherwise specified.
Example 1
<Preparation of organic components>
The following solvent and polymer were mixed to form a 40% solution, respectively, and heated to 60 ° C. while stirring to dissolve all the polymers homogeneously to obtain a polymer solution 1.
Polymer solution 1:
Solvent: gamma butyrolactone (γ-BL)
Polymer: 0.4 equivalents of glycidyl methacrylate (GMA) relative to the carboxyl groups of a copolymer consisting of 40% methacrylic acid (MAA), 30% methyl methacrylate (MMA) and 30% styrene (St) ) Is added to the photosensitive polymer having a weight average molecular weight of 43000 and an acid value of 95. The solution is then cooled to room temperature, and the components constituting the organic components shown below are added and dissolved in the proportions shown in Table 1 to obtain organic components A1 And A2 were obtained respectively. Thereafter, this solution was filtered using a 400 mesh filter to prepare an organic vehicle.
Organic dye: Sudan IV: Azo-based organic dye, chemical formula C ₂₄ H ₂₀ N ₄ O, molecular weight 380.45
Monomer: TMPTA: trimethylolpropane triacrylate initiator: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone sensitizer: 2,4-diethylthioxanthone sensitizer: p-dimethyl Aminobenzoic acid ethyl ester plasticizer: Dibutyl phthalate (DBP)
Thickener: SiO ₂ (concentration 15%) dissolved in 2- (2-butoxyethoxy) ethyl acetate
Solvent: γ-BL

  The glass powders (1) and (2) shown below are added to the obtained vehicles of the organic components A1 and A2 in the proportions shown in Table 2, and are kneaded with a kneader to produce a buffer layer paste and a barrier rib photosensitivity. A paste was produced. The glass powder used was finely powdered with an attractor in advance.

Glass powder (1): Composition Li ₂ O 9%, SiO ₂ 20%, B ₂ O ₃ 31%, BaO 4%, Al ₂ O ₃ 24%, ZnO 2%, MgO 6%, CaO 4%. Non-spherical powder having an average particle size of 2.6 μm, Tg (glass transition point) 480 ° C., Ts (softening point) 520 ° C., thermal expansion coefficient 79 × 10 ⁻⁷ / K, refractive index at g-line (436 nm) 58
Glass powder (2): Composition Bi ₂ O ₃ 27%, SiO ₂ 14%, B ₂ O ₃ 18%, BaO 14%, Al ₂ O ₃ 4%, ZnO 21%, Na ₂ O 2%, average particle diameter 3.4 μm non-spherical powder, Tg 486 ° C., Ts 531 ° C., coefficient of thermal expansion 74 × 10 ⁻⁷ / K, refractive index at g-line (436 nm) 1.75

  The obtained buffer layer paste B3 was applied onto a 125 mm square soda lime glass substrate by screen printing using a 325 mesh screen and dried, and a uniform film having a thickness of 14 μm was obtained after drying. The coating thickness was adjusted by the squeegee angle and speed.

The entire surface was exposed to ultraviolet light with an ultrahigh pressure mercury lamp having an output of 50 mW / cm ² from the upper surface, and photocured. The exposure amount was 1 J / cm ² .

  Next, the photosensitive paste B1 for barrier ribs was apply | coated and dried by the same method as the above on the coating film, and application | coating thickness was adjusted to 180 micrometers. Then, it hold | maintained at 80 degreeC for 1 hour, and dried.

Subsequently, UV exposure was performed with an ultrahigh pressure mercury lamp having an output of 50 mW / cm ² from the upper surface through a photomask. The exposure amount was 10 J / cm ² . A negative chrome mask having a pitch of 150 μm and a line width of 20 μm was used as the photomask.

  Next, a 0.3 wt% aqueous solution of monoethanolamine maintained at 35 ° C. was developed by showering for 85 seconds, and then washed with water using a shower spray to remove the uncured space portion. A striped barrier rib pattern was formed.

  Thus, the glass substrate in which the buffer layer and the partition were formed was baked for 30 minutes at 570 degreeC in the air, and the partition was produced.

The presence or absence of peeling after firing was evaluated. In the case where there was no separation of the partition walls, it was indicated as “◯”, and in the case where there was separation, the ratio of the number of the partition walls to the total number of the partition walls was expressed in%. The results are shown in Table 3.
Example 2
As the partition wall paste, the glass powder (3) shown below was used, and the partition wall paste B2 shown in Table 2 was prepared and used in the same manner as in Example 1 on the glass substrate as shown in Table 3. A partition wall was formed under the conditions. The presence or absence of peeling after firing was evaluated. The results are shown in Table 3.

Glass powder (3): Composition Li ₂ O 3%, K ₂ O 6%, SiO ₂ 21%, B ₂ O ₃ 33%, BaO 4%, Al ₂ O ₃ 20%, ZnO 13%, average particle size 2 1.6 μm non-spherical powder, Tg (glass transition point) 473 ° C., Ts (softening point) 520 ° C., coefficient of thermal expansion 79 × 10 ⁻⁷ / K, refractive index 1.60 at g-line (436 nm).
Example 3
After partition wall paste is applied and dried by 100 μm, exposure is performed through a photomask at an exposure amount of 5 J / cm ^2. Further, partition wall paste is further applied on the coated surface by 80 μm, dried, and mask exposure is performed at 4 J / cm ² . A partition wall was formed on the glass substrate under the conditions shown in Table 3 in the same manner as in Example 1 except that the partition pattern was formed. The presence or absence of peeling after firing was evaluated. The results are shown in Table 3.
Example 4
As the buffer layer paste, the glass powder (4) shown below was used, and the buffer layer paste B4 shown in Table 2 was prepared and used. A partition wall was formed under the conditions shown. The presence or absence of peeling after firing was evaluated.
The results are shown in Table 3.

Glass powder (4): composition Bi ₂ O ₃ 38%, SiO ₂ 7%, B ₂ O ₃ 19%, BaO 12%, Al ₂ O ₃ 3%, ZnO 21%, average particle diameter 3.4 μm Powder, Tg 476 ° C., Ts 525 ° C., coefficient of thermal expansion 77 × 10 ⁻⁷ / K, refractive index 1.75 at g-line (436 nm).
Example 5
A partition wall was formed on the glass substrate under the conditions shown in Table 3 in the same manner as in Example 1 except that the application thickness of the buffer layer paste was 10 μm. The presence or absence of peeling after firing was evaluated. The results are shown in Table 3.
Example 6
The following solvent and polymer were mixed to form a 40% solution, respectively, and heated to 60 ° C. with stirring to dissolve all the polymers homogeneously to obtain a polymer solution 2. Using this polymer solution, partition walls were formed on the glass substrate under the conditions shown in Table 3 in the same manner as in Example 1 except that the buffer layer paste B5 shown in Table 2 was prepared and used.
Polymer solution 2:
Solvent: Butyl carbitol acetate (BCA)
Polymer: ethylcellulose (non-photosensitive polymer), degree of substitution: 1.5, weight average molecular weight 50000
The presence or absence of peeling after firing was evaluated. The results are shown in Table 3.
Comparative Example 1
A partition wall was formed on the glass substrate under the conditions shown in Table 3 in the same manner as in Example 1 except that the buffer layer was not formed. The presence or absence of peeling after firing was evaluated. The results are shown in Table 3.
Comparative Example 2
After applying the buffer layer paste, drying and firing, the partition walls were formed on the glass substrate under the conditions shown in Table 3 in the same manner as in Example 1 except that the partition walls were formed on the fired buffer layer. Formed. The presence or absence of peeling after firing was evaluated. The results are shown in Table 3.

  Furthermore, a high-definition plasma display panel was obtained using a glass substrate on which a baked buffer layer and partition walls were formed.

Claims (6)

A method for manufacturing a plasma display panel in which partition walls are formed on a buffer layer provided on a glass substrate, comprising a glass powder and an organic component, and selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer. A buffer layer forming paste for a plasma display panel containing a photosensitive component or a thermal polymerization component consisting of a radical polymerizable monomer and a radical polymerization initiator is applied on a glass substrate and dried, and then the entire surface of the applied film is photocured or thermally polymerized. A buffer layer having a crosslinked structure is formed, a photosensitive paste composed of glass powder and a photosensitive organic component is applied on the buffer layer, and a partition wall pattern is formed through an exposure and development process, and then the buffer layer. And a method for manufacturing a plasma display panel, wherein the barrier rib pattern is simultaneously fired to form the barrier ribs. The thickness of the buffer layer is, the manufacturing method of the plasma display panel according to claim 1, characterized in that a 3 to 20 [mu] m. Buffer layer, manufacturing of plasma display panel according to claim 1 or 2, characterized in that the thermal expansion coefficient of _50~400 ℃ _(α) 50~400 is made of glass of 70~85 × ^{10 -7} / K Method. The method for producing a plasma display panel according to any one of claims 1 to 3 , wherein the buffer layer is made of glass having a glass transition point Tg of 430 to 500 ° C and a glass softening point Ts of 470 to 580 ° C. The method for manufacturing a plasma display panel according to any one of claims 1 to 4 , wherein the buffer layer is made of glass containing 10 to 60 wt% of bismuth oxide. Partition walls, a manufacturing method of a plasma display panel according to any one of claims 1 to 5, characterized in that it consists of glass having a refractive index from 1.50 to 1.65.