JP2010086718A - Method of manufacturing display member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a forming method for a dielectric layer and a barrier plate by a photosensitive paste method, excellent in productivity, and to achieve and provide a high definition and inexpensive display member. <P>SOLUTION: In this method of manufacturing the display member having an electrode and the dielectric layer covering the electrode on a glass substrate, and having the barrier plate disposed on the dielectric layer, the electrode or an electrode precursor is formed on the substrate, photosensitive paste comprising an inorganic component containing at least glass powder and a copper compound, and an organic component containing a photosensitive compound having an acidic group is applied so as to cover the electrode or the electrode precursor, it is dried, pattern-exposed, developed using an alkali aqueous solution, and baked. Thereby, the dielectric layer and the barrier plate are collectively formed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a high-definition and inexpensive display member.

  In recent years, the development of flat displays such as plasma displays (hereinafter referred to as PDP), field emission displays, fluorescent display tubes, liquid crystal display devices, electroluminescence displays, and light emitting diodes has been rapidly advanced. Among these, the PDP causes plasma discharge between the anode electrode and the cathode electrode facing each other in the discharge space provided between the front glass substrate and the rear glass substrate, and from the gas sealed in the discharge space. Display is performed by irradiating the generated ultraviolet rays to a phosphor provided in the discharge space. A gas discharge type display such as a PDP or a fluorescent display tube requires a dielectric layer for insulating the electrodes and the discharge space between the drive electrodes (scan / sustain electrodes, address electrodes) and maintaining the discharge. To do. Furthermore, an insulating partition for partitioning the discharge space on the dielectric layer is required.

  Conventionally, as a method of forming such a dielectric layer and barrier ribs, a dielectric layer having a predetermined thickness is formed using a dielectric paste by a die coating method, a screen printing method, etc., and then a sand blasting method using a barrier rib paste. There are known methods for forming partition walls by an etching method, a mold transfer (imprint) method, a photolithography method (photosensitive paste method), and the like. Among these, the photosensitive paste method is a method with particularly high cost merit (see Patent Documents 1 and 2).

In the conventional method, the dielectric layer and the barrier rib must be individually formed using different pastes, and there is a problem that the cost is high because there are many types of pastes and many processes. In order to solve this problem, a method of collectively forming a dielectric layer and a partition wall has been proposed (see Patent Documents 3 to 5). In Patent Documents 3 to 5, the dielectric layer and the barrier ribs are collectively formed by using a sandblasting method, an etching method, and a mold transfer method. However, the batch formation was difficult and could not be realized.
JP-A-9-31030 JP 2007-183595 A JP 2005-231127 A JP 2007-12622 A JP-A-11-283506

  Accordingly, the present invention focuses on the above-mentioned problems of the prior art and provides and provides a high-definition and inexpensive display member. Specifically, it is an object of the present invention to provide a method for forming a dielectric layer and partition walls that are excellent in productivity by a photosensitive paste method.

In order to solve the above problems, the present invention has the following configuration.
(1) A method of manufacturing a display member having an electrode on a glass substrate, a dielectric layer covering the electrode, and a partition disposed on the dielectric layer, wherein the electrode or the electrode precursor is formed on the substrate. And a coating film of a photosensitive paste containing an inorganic component containing glass powder and an organic component containing a photosensitive compound having an acidic group so as to cover the electrode or the electrode precursor. A method for producing a display member, characterized in that the dielectric layer and the partition walls are collectively formed by pattern exposure, development using an alkaline aqueous solution, and firing.
(2) The method for producing a display member according to (1), wherein the copper compound contained in the photosensitive paste is 0.001 to 3% by weight in the total inorganic components in terms of oxide.
(3) The method for producing a display member according to (1) or (2), wherein the photosensitive paste contains copper (II) particles having an average particle diameter of 0.01 to 10 μm.

  According to the present invention, the dielectric layer and the high-definition barrier rib can be formed at a low cost by forming the dielectric layer and the barrier rib at the same time using the photosensitive paste. Therefore, a high-definition and inexpensive display member can be realized and provided.

  As a glass substrate used in the method for producing a display member of the present invention, “PP8” (manufactured by Nippon Electric Glass Co., Ltd.) and “PD200” (manufactured by Asahi Glass Co., Ltd.), which are soda glass and heat-resistant glass, can be used. The size of the glass substrate is not particularly limited, and a glass substrate having a thickness of 1 to 5 mm can be used.

  In the method for producing a display member of the present invention, first, an electrode or an electrode precursor is formed on a substrate. Here, the electrode or the electrode precursor is formed by using a film forming technique such as a printing method, a slurry method, a vapor deposition method, a sputtering method, a slit die coating method, a spin coating method, or the like, for example, by a photolithography method. Is. For example, in a PDP front plate electrode, a narrow silver or chromium-copper-chromium electrode is formed on a wide transparent electrode made of a conductive metal oxide such as indium tin oxide (ITO), tin oxide, or zinc oxide. Scanning and sustaining electrodes with a laminated structure. For PDP backplate electrodes, address electrodes made of metal such as silver, aluminum, chromium, nickel, or organic components such as silver, aluminum, chromium, nickel, and binder resins An address electrode precursor containing

  The present invention is characterized in that a dielectric layer covering the electrodes and a partition wall formed on the dielectric layer are collectively formed. The dielectric layer here refers to, for example, a transparent dielectric layer generally formed on the scanning / sustaining electrode with a thickness of 10 to 40 μm on the PDP front plate, and on the address electrode on the PDP rear plate. Indicates a dielectric layer formed with a thickness of 5 to 20 μm. In addition, the partition wall here is, for example, a pattern formed on the transparent dielectric layer in the PDP front plate, generally having a height of 5 to 40 μm and a top width of 10 to 200 μm to prevent crosstalk. In general, the PDP back plate has a height of 50 to 200 μm, a top width of 20 to 100 μm, and an aspect ratio of 1 to 5 for partitioning the discharge space on the dielectric layer. Refers to the partition wall.

  In the present invention, it is essential to use a photosensitive paste in order to collectively form the dielectric layer and the partition walls.

  The photosensitive paste referred to in the present invention is developed by irradiating an actinic ray to a dried coating film, and the irradiated portion undergoes a reaction such as photocrosslinking, photopolymerization, photodepolymerization, photomodification, and the chemical structure changes. A paste that can be developed with a liquid. In particular, the present invention provides a negative photosensitive paste that can be patterned by making the irradiated part insoluble in the developer by irradiation with actinic light and then removing only the non-irradiated part with the developer. Good characteristics can be obtained. The actinic rays mentioned here refer to rays in the wavelength region of 250 to 1100 nm that cause such a chemical reaction.

  In this invention, after forming the coating film of the photosensitive paste so that the electrode or electrode precursor formed on the board | substrate may be covered, a dielectric material layer and a partition are collectively formed by pattern exposure, image development, and baking. The coating film of the photosensitive paste may be formed by applying the photosensitive paste by a bar coater, a roll coater, a slit die coater, a blade coater, screen printing, etc. and then drying it, or may be formed by pressure bonding by a transfer sheet method. May be.

Next, pattern exposure is performed on the coating film of the photosensitive paste. In general, the exposure is performed through a photomask, as in normal photolithography. Alternatively, a method of directly drawing with a 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. Examples of the active light source used at this time include near ultraviolet rays, ultraviolet rays, electron beams, X-rays, and laser beams. Among these, ultraviolet rays are most preferable, and as the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, or a germicidal lamp can be used. Among these, an ultrahigh pressure mercury lamp is suitable. Although the exposure conditions vary depending on the thickness of the dried coating film, exposure is usually performed for 0.01 to 30 minutes using an ultrahigh pressure mercury lamp with an output of 1 to 100 mW / cm ² .

  After the exposure, development is performed by utilizing the difference in solubility between the exposed portion and the unexposed portion in the developer. Usually, the immersion method, the spray method, the brush method, and the like are performed. As the developer, an organic solvent capable of dissolving the organic components in the photosensitive paste can be used. In the present invention, a photosensitive compound having an acidic group such as a carboxyl group is used in the photosensitive paste, and an alkaline aqueous solution is used. Develop using. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, potassium hydroxide aqueous solution or the like can be used. However, it is preferable to use an organic alkaline aqueous solution because an alkaline component can be easily removed during firing. As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine.

  The density | concentration of aqueous alkali solution is 0.05-5 mass% normally, More preferably, it is 0.1-1 mass%. If the alkali concentration is too low, it is difficult to remove the soluble part, and if the alkali concentration is too high, the pattern may be peeled off or corroded. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.

  Conventionally, the photosensitive paste used for the barrier rib formation is composed of at least an inorganic component containing glass powder and an organic component containing a photosensitive compound, and further, if necessary, a filler as an inorganic component and a non-photosensitive polymer as an organic component. From composition which added additive ingredient such as ingredient, antioxidant, ultraviolet absorber, organic dye, photoinitiator, sensitizer, sensitizer, plasticizer, thickener, dispersant, suspending agent It will be. Examples thereof include the photosensitive pastes described in Patent Documents 1 and 2 described above. The photosensitive paste in the present invention uses the same components as the photosensitive paste described in Patent Documents 1 and 2 for the photosensitive compound having an acidic group, which is an essential component, and the components other than the copper compound. it can.

  The photosensitive compound in the present invention is a compound selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer. The acidic group contained in the photosensitive compound is a functional group that enables alkali development by acidification of the acidic group due to reaction with an aqueous alkaline solution so that the photosensitive compound is solubilized in the aqueous alkaline solution. Specific examples include a carboxyl group, a phenolic hydroxyl group, and an acid anhydride.

  A photosensitive polymer having an acidic group will be described as an example of the photosensitive compound having an acidic group. As the photosensitive polymer having an acidic group, an acrylic copolymer can be preferably used. The acrylic copolymer is a copolymer containing at least an acrylic monomer as a copolymerization component. Specific examples of the acrylic monomer 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, di Cyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxy Acrylic monomers such as ethyl acrylate, stearyl acrylate, trifluoroethyl acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate, benzyl mercaptan acrylate, and these acrylates into methacrylates Listed are alternatives It is. As the copolymer component other than the acrylic monomer, a compound having a carbon-carbon double bond can be used, but preferably styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene. Styrenes such as chloromethyl styrene and hydroxymethyl styrene, 1-vinyl-2-pyrrolidone and the like.

  In order to give an acidic group to an acrylic copolymer, it is achieved by adding an unsaturated acid such as an unsaturated carboxylic acid as a monomer. Specific examples of the unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, or acid anhydrides thereof. The acid value of the polymer after adding these is preferably in the range of 50-150.

  In order to make an acrylic copolymer into a photosensitive polymer, a group having a carbon-carbon double bond may be added to the side chain or molecular end. Examples of the group having a carbon-carbon double bond include a vinyl group, an allyl group, an acrylic group, and a methacryl group. In order to add such a functional group to an acrylic copolymer, a glycidyl group or an isocyanate group and a carbon-carbon double bond with respect to the mercapto group, amino group, hydroxyl group, or carboxyl group in the acrylic copolymer. Or a compound having acrylic acid chloride, methacrylic acid chloride or allyl chloride. Examples of the compound having a glycidyl group and a carbon-carbon double bond include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonate, and glycidyl isocrotonate. Examples of the compound having an isocyanate group and a carbon-carbon double bond include acryloyl isocyanate, methacryloyl isocyanate, acryloylethyl isocyanate, and methacryloylethyl isocyanate.

  In the present invention, it is essential that the inorganic component of the photosensitive paste contains a copper compound. As a method for adding a copper compound to the photosensitive paste, glass powder or filler containing a copper compound as a constituent component may be added to the paste, or a copper compound may be added separately as an oxide, salt, or complex. good. Examples of copper compounds include copper oxide (I), copper oxide (II), copper chloride (I), copper chloride (II), copper sulfide, copper sulfate, copper acetate (I), copper acetate (II), nitric acid Copper (II), a copper acetylacetonate complex, a tetraammine copper complex, etc. are mentioned. From the viewpoint of ease of handling, it is preferable to add it as a glass powder or filler containing a copper compound as a constituent component or as copper (II) oxide.

  The photosensitive paste used in the present invention is prepared by mixing each component so as to have a predetermined composition, followed by main kneading using a kneading device such as a three-roller, and homogeneously dispersing. In addition, it is also preferable to appropriately filter and degas the photosensitive paste after the main kneading.

  FIG. 2 shows a conventional method for forming dielectric layers and barrier ribs using a conventional photosensitive paste containing no copper compound. First, a photosensitive paste coating film is provided on a substrate (FIG. 2a) (FIG. 2b) and exposed through a photomask (FIG. 2c). Thereafter, using the fact that the depth at which the unexposed portion dissolves during development is proportional to the development time, the dry coating thickness X, the dielectric layer dry film thickness Y, and the unexposed portion dissolution time T shown in FIG. The development time t for batch formation is obtained by the following formula (1) and developed (FIG. 2d). In this way, batch formation can be attempted by stopping the dissolution of the photosensitive paste in the middle, but if the development time becomes long, the electrode may be exposed (FIG. 2e), or due to variations in the development time, the dielectric layer Therefore, it is difficult to form the dielectric layer and the barrier ribs at the same time because there is a problem that the development margin is narrow.

t = T (XY) / X (1)
In the present invention, since the photosensitive paste contains a copper compound, dissolution of the unexposed portion stops at the time of development leaving a specific film thickness (residual film), so the film thickness of the dielectric layer due to variations in development time It was found that the variation can be suppressed and the narrow development margin, which is a problem of the prior art, can be solved. FIG. 3 shows a method of forming the dielectric layer and the barrier ribs collectively according to the present invention. A photosensitive paste coating film is provided on the substrate (FIG. 3a) (FIG. 3b) and exposed through a photomask (FIG. 3c). Thereafter, in the development process, the dissolution is stopped leaving a specific film thickness, so that the dielectric layer and the barrier ribs can be collectively formed (FIG. 3d). The reason why such a remarkable effect appears is not clear, but the following mechanism is conceivable.

  The dissolution of the unexposed portion proceeds from the upper part of the dry coating film in direct contact with the aqueous alkali solution during development. At the same time, the aqueous alkaline solution gradually penetrates into the film. The soaked alkaline aqueous solution reacts with the copper compound and the photosensitive compound having an acidic group, thereby generating a compound insoluble in the alkaline aqueous solution. Immediately after the start of development, there is little soaking of the alkaline aqueous solution, and the dissolution of the unexposed portion proceeds preferentially, but as the development time elapses, a compound insoluble in the alkaline aqueous solution is sufficiently generated at the bottom of the film. After a specific time, the unexposed portion is not developed at all.

  In this invention, it is preferable that the copper compound contained in the photosensitive paste is 0.001 to 3 weight% in all the inorganic components in conversion of an oxide. If it is less than 0.001% by weight, it is not preferable because a film remaining in an unexposed part hardly occurs during development and a desired effect cannot be obtained. When the amount is more than 3% by weight, the insolubilization reaction of the film during development proceeds quickly and the partition wall height is lowered, which is not preferable. More preferably, it is 0.001-0.5 weight%, More preferably, it is 0.001-0.05 weight%. The proportion of the copper compound in the inorganic component can be calculated from the blending amount of each component at the time of preparing the paste, but it can be obtained by baking the paste dry film or dry film obtained by applying and drying the photosensitive paste. It can also be determined by elemental analysis of the paste fired film. For example, the paste fired film can be quantitatively analyzed by inductively coupled plasma optical emission spectrometry (ICP-AES), fluorescent X-ray analysis, or the like to determine the ratio of the copper compound in the inorganic component.

In the present invention, the photosensitive paste preferably contains copper (II) oxide particles having an average particle diameter of 0.01 to 10 μm. The average particle diameter is a 50% particle diameter (d ₅₀ ) in the weight distribution curve, and can be evaluated using a laser diffraction / scattering particle size distribution measuring apparatus (for example, “MT3300” manufactured by Nikkiso). When the average particle size is less than 0.01 μm, it is difficult to uniformly disperse the copper oxide particles in the paste, and the surface smoothness of the partition walls and the dielectric layer is lowered by the aggregate, which is not preferable. When the average particle diameter is larger than 10 μm, the surface smoothness of the partition walls and the dielectric layer is lowered, which is not preferable. More preferably, it is 0.02-1 micrometer, More preferably, it is 0.02-0.1 micrometer. The surface smoothness may be evaluated, for example, by measuring the 10-point average height RzJIS when the cut-off value is 0.25 mm and the measurement length is 1.25 mm according to JIS B0601. RzJIS is preferably 10 μm or less. If it is larger than 10 μm, the front plate partition or the front plate dielectric and the back plate partition come into contact with each other during or after paneling, and the partition may be chipped and the pixels may be lost. More preferably, it is 3 μm or less.

  The glass powder in the present invention is preferably a low softening point glass powder, and a known glass insulating material can be applied. For example, glass such as lead borosilicate glass, bismuth borosilicate glass, and zinc borosilicate glass Can be used. In the present invention, the low softening point glass powder refers to a glass powder having a load softening temperature in the range of 400 to 600 ° C. This is because when the load softening temperature is within this range, there is no deformation of the pattern during sintering, and the meltability becomes appropriate. The load softening temperature of the glass powder can be measured, for example, by TMA (thermomechanical analysis).

  The proportion of the low softening point glass powder in the inorganic component is preferably 60% by volume to 100% by volume. When the content ratio is less than 60% by volume, sintering during firing becomes difficult, and the porosity of the pattern after firing increases, which is not preferable.

Particle size of the low-softening point glass powder is the shape of the pattern to be produced is selected in consideration, the 50% particle diameter (average particle diameter: d ₅₀₎ in weight distribution curve 0.1 to 3.0 m, The maximum particle size (top size: d _max ) is preferably 10 μm or less.

The low softening point glass powder that can be preferably used has, for example, the following composition in oxide notation.
Lithium oxide, sodium oxide or potassium oxide 3-15% by mass
Silicon oxide 5-30% by mass
Boron oxide 20-45 mass%
Zinc oxide 1-50% by mass
Aluminum oxide 0-25% by mass
Magnesium oxide or calcium oxide 0-15% by mass
Zirconium oxide 0-2% by mass
Barium oxide or strontium oxide 0-10% by mass
Copper oxide 0-5% by mass
In the present invention, it is preferable to add a filler as an inorganic component. The filler in the present invention is added to improve the strength of the partition wall, and refers to an inorganic powder that hardly melts and flows even at the firing temperature. Specifically, it refers to an inorganic powder that does not have a softening point, a melting point, or a decomposition temperature at 600 ° C. or less and exists as a solid at 600 ° C. As the filler, at least one selected from high softening point glass powder having a load softening temperature of 600 to 1200 ° C. and ceramic powder such as cordierite, alumina, silica, magnesia, and zirconia can be used. From the viewpoint of easy adjustment of the 50% particle diameter (average particle diameter: d ₅₀ ) and the average refractive index in the weight distribution curve, it is preferable to use a high softening point glass powder.

  In consideration of dispersibility and filling properties in the photosensitive paste, and suppression of light scattering during exposure, a filler having an average particle diameter of 0.1 to 3.0 μm can be preferably used. The proportion of the filler in the inorganic component is preferably 0 to 40% by volume. When the volume is more than 40% by volume, the denseness of the pattern to be formed tends to decrease, which is not preferable.

The high softening point glass powder that can be preferably used has, for example, the following composition in oxide notation.
Lithium oxide, sodium oxide or potassium oxide 0-5% by mass
Silicon oxide 15-50% by mass
Boron oxide 5-20% by mass
Zinc oxide 0-20% by mass
Aluminum oxide 10-50% by mass
Magnesium oxide or calcium oxide 1-15% by mass
Barium oxide or strontium oxide 0-10% by mass
Copper oxide 0-5% by mass
In the present invention, the dielectric layer and the barrier ribs are collectively formed by a process including exposure and development using a photosensitive paste, and then fired. Firing is performed in a firing furnace, and the firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in air, in an atmosphere of nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a roller conveyance type continuous firing furnace can be used. The baking temperature is preferably a temperature at which the resin to be used sufficiently debinds. Generally, baking is performed at 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.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to this. First, a method for manufacturing a substrate with an electrode pattern will be described.
(Method for producing substrate with electrode pattern)
A silver electrode pattern 2 was formed on a 42-inch soda lime glass plate 1 having a thickness of 1.8 mm using a photosensitive silver paste. The composition of the photosensitive silver paste was as follows.
Silver powder: SPN10J manufactured by Mitsui Mining & Smelting Co., Ltd., 73.0 parts by weight Glass powder: Bismuth borosilicate glass having a glass transition point of 460 ° C. and a softening point of 495 ° C., 2.5 parts by weight Photopolymer: Methacrylic acid / methyl methacrylate / What added 0.4 equivalent of glycidyl methacrylate with respect to the carboxyl group of the copolymer which consists of styrene = 40/40/30 (weight average molecular weight 43000, acid value 100).
Photosensitive monomer: trimethylolpropane triacrylate, 3.9 parts by weight photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (IC369 manufactured by Ciba Specialty Chemicals) .
Dispersant: Solsperse 20000, 0.5 parts by weight Organic solvent: γ-butyrolactone, 2.0 parts by weight A photosensitive silver paste is applied on a glass plate by a screen printing method (printing plate: 325 mesh / inch made of SUS). And dried at 120 ° C. for 10 minutes. After forming an electrode pattern of PDP rear panel address electrode dimensions (width 40 μm, pitch 160 μm) or PDP front panel bus electrode dimensions (width 55 μm, pitch 480 μm) by exposure and development, maximum temperature 590 ° C. (maximum temperature holding time) 18 minutes) to form an electrode on the glass substrate.
(Examples 1-7)
A dielectric layer and barrier ribs were collectively formed by the following procedure.
(A) Preparation of photosensitive paste The photosensitive paste was prepared as follows. Photosensitive monomers, photosensitive polymers, photopolymerization initiators, sensitizers, antioxidants and ultraviolet absorbers were weighed in the amounts shown in Table 1, and then γ-butyrolactone was added as a solvent to adjust the viscosity. Next, the inorganic component was adjusted at the ratio described in Table 2, and added so that the inorganic component in the solid content had the ratio described in Table 2, and then kneaded with a three-roller kneader to obtain a photosensitive paste. .

The raw materials used for the barrier rib photosensitive paste are as follows.
Photosensitive monomer M-1: trimethylolpropane triacrylate photosensitive monomer M-2: tetrapropylene glycol dimethacrylate photosensitive polymer: carboxyl group of copolymer consisting of methacrylic acid / methyl methacrylate / styrene = 40/40/30 To which 0.4 equivalent of glycidyl methacrylate was added and reacted (weight average molecular weight 43,000, acid value 100)
Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (IC369 manufactured by Ciba Specialty Chemicals).
Sensitizer: 2,4-diethylthioxanthone antioxidant: 1,6-hexanediol-bis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate])
Ultraviolet absorber: Sudan IV (Tokyo Ohka Kogyo Co., Ltd., absorption wavelength: 350 nm and 520 nm)
Low softening point glass powder G-1: 7% by mass of lithium oxide, 22% by mass of silicon oxide, 33% by mass of boron oxide, 3% by mass of zinc oxide, 19% by mass of aluminum oxide, 6% by mass of magnesium oxide, 5% by mass of barium oxide , Calcium oxide 5 mass% (glass transition temperature 491 ° C., d ₅₀ : 2 μm)
Low softening point glass powder G-2: 40% by mass of zinc oxide, 34% by mass of boron oxide, 11% by mass of silicon oxide, 12% by mass of potassium oxide, 2.5% by mass of sodium oxide, 0.5% by mass of copper oxide (glass (Transition temperature 563 ° C., d ₅₀ : 3 μm)
Filler: 1% by mass of potassium oxide, 38% by mass of silicon oxide, 9% by mass of boron oxide, 2% by mass of zinc oxide, 34% by mass of aluminum oxide, 5% by mass of magnesium oxide, 5% by mass of barium oxide, 4% by mass of calcium oxide, titanium oxide 2 wt% (glass transition temperature 670 _{℃, d} 50: 2μm)
(B) Batch formation of dielectric layer and barrier ribs A photosensitive paste was applied to the entire surface of the glass substrate on which the electrodes were formed with a slit die coater so as to have a dry coating film thickness described in Table 3, and 90 minutes at 100 ° C. It dried using the hot air dryer. Next, exposure was performed through an exposure mask. The exposure mask is a chrome mask designed to enable the formation of stripe-shaped barrier rib patterns in the plasma display shown in Table 3. The exposure was performed using an ultra-high pressure mercury lamp with an output of 50 mW / cm ² and ultraviolet exposure at an exposure amount shown in Table 3. Then, it developed with the shower of the monoethanolamine 0.2 mass% aqueous solution. In order to determine the development conditions, the time T1 until a defect such as peeling or meandering occurred on the partition wall was measured. Thereafter, development was performed by changing the development time by 20 points immediately after the start of development until T1, and the sample was held at a predetermined temperature to remove the binder, and then baked at 590 ° C. for 20 minutes to obtain an evaluation substrate. Development in which the evaluation of the evaluation substrate was carried out by observing the cross section with a scanning electron microscope (S-2400, manufactured by Hitachi, Ltd.) and the partition wall height and the dielectric layer thickness after firing were measured, and the dielectric layer thickness began to change. Time T2 was determined. At this time, a development margin capable of collectively forming the dielectric layer and the partition wall is indicated by T1-T2. The development margin defined here is synonymous with a development time range in which a desired partition wall height and dielectric layer thickness can be realized. The partition wall height and dielectric layer thickness described in Table 3 are values when development is performed in the range of time T2 to T1. The case where the development margin was 10 seconds or more was evaluated as ◯, and the case where the development margin was shorter than 10 seconds was evaluated as x. In addition, according to JIS B0601, the evaluation substrate was measured with Surfcom (manufactured by Tokyo Seimitsu Co., Ltd.) with a cut-off value of 0.25 mm, a measurement length of 1.25 mm, and the ten-point average height RzJIS at the top of the partition wall Asked.

  In Examples 1, 3, 4, 6, and 7, it was confirmed that the development margin was 20 seconds or longer and the development margin was wide. In addition, no cracks were observed on the surfaces of the dielectric layer and the partition wall, and a display member suitable for the PDP back plate having the partition wall height and dielectric layer thickness shown in Table 4 could be formed.

  In Example 2, it was confirmed that the development margin was 120 seconds and the development margin was wide. Further, no cracks were observed on the surfaces of the dielectric layer 3 and the partition walls 4, and a display member suitable for the PDP front plate having the partition wall height and the dielectric layer thickness shown in Table 4 could be formed.

In Example 5, it was confirmed that the development margin was 120 seconds and the development margin was wide. Further, no cracks were observed on the surfaces of the dielectric layer 3 and the partition walls 4, and a display member having the partition wall height and the dielectric layer thickness shown in Table 4 could be formed.
(Comparative Example 1)
Photosensitive pastes having the compositions shown in Tables 1 and 2 were prepared in the same manner as in Example 1. Using the produced photosensitive paste, a dry coating film was formed and exposed in the same manner as in Example 1. After the exposure, development is performed with a 0.2% by weight aqueous solution of monoethanolamine, and the unexposed partial dissolution time is measured. The development time that can form the same partition wall height and dielectric layer thickness as in Example 1 (1 ). Thereafter, a sample was produced by changing the developing time around 20 points at a calculated developing time of 20 points at intervals of 2 seconds, and baked in the same manner as in Example 1 to determine RzJIS, partition wall height, and dielectric layer thickness. The development time range in which a partition wall having a partition height of 100 μm and a dielectric layer having a dielectric layer thickness of 10 μm could be formed as a development margin.

  In Comparative Example 1, the development margin was 4 seconds, the development margin was very narrow, and it was difficult to collectively form the dielectric layer and the partition walls.

It is sectional drawing of the member for displays which concerns on this invention. It is process drawing which shows the batch formation method of the dielectric material layer and partition which used the conventional photosensitive paste. It is process drawing which shows the dielectric material layer and the bulk formation method of a partition of this invention.

Explanation of symbols

X: dry film thickness Y: dielectric layer dry film thickness T: unexposed part dissolution time t: development time 1: glass plate 2: electrode pattern 3: dielectric layer 4: partition wall 5: photosensitive paste

Claims (3)

A method for producing a display member having an electrode on a glass substrate, a dielectric layer covering the electrode, and a partition disposed on the dielectric layer, wherein the electrode or electrode precursor is formed on the substrate, and the electrode Alternatively, the electrode precursor is covered with an inorganic component containing glass powder and an organic component containing a photosensitive compound having an acidic group, and a coating film of a photosensitive paste containing a copper compound is provided on the inorganic component, and pattern exposure is performed. Then, the dielectric layer and the partition are collectively formed by developing and baking using an alkaline aqueous solution, and a method for producing a display member. The copper compound contained in the said photosensitive paste is 0.001 to 3weight% in all the inorganic components in conversion of an oxide, The manufacturing method of the member for a display of Claim 1 characterized by the above-mentioned. The method for producing a display member according to claim 1, wherein the photosensitive paste contains copper (II) oxide particles having an average particle diameter of 0.01 to 10 μm.

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