JP2005141059A - Inorganic material paste, plasma display member and plasma display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic material paste free of occurrence of defects in firing. <P>SOLUTION: The inorganic material paste comprises an inorganic component and an organic component, wherein two or more glass frits are included in the inorganic component and configured such that the softening point Ts(H) of a glass frit H having the highest softening point, the softening point Ts(L) of a glass frit L having the lowest softening point, the average particle diameter D50(L) of the glass frit L and the average particle diameter D50(H) of the glass frit H satisfy the formula: Ts(H)-Ts(L)≤100°C and D50(L)<D50(H). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an inorganic material paste, a plasma display member, and a plasma display.

  In recent years, circuit materials and displays have been reduced in size and definition, and there is a need for a pattern processing technique that can cope with them. In particular, in a plasma display, a method of processing a high-definition and narrow pattern without defects in the formation of barrier ribs is desired.

  Conventionally, as a method of patterning an inorganic material, a method of forming a pattern by a negative photosensitive paste method using a photosensitive paste has been proposed (for example, Patent Document 1, Patent Document 2, and Patent Document 3). See Patent Document 4).

  However, when an inorganic material pattern is formed, there is a problem that cracks and breaks occur in the pattern due to firing shrinkage stress in the firing step. In particular, the photosensitive paste has a relatively large amount of organic components as compared with the non-photosensitive paste. Therefore, a larger firing shrinkage force acts, and cracks and disconnections are likely to occur. In particular, when the definition is increased or the line width is reduced, peeling or disconnection is likely to occur.

In addition, the pattern formation method by the photosensitive paste method is excellent in terms of process simplicity and processing accuracy, but when there is foreign matter on the mask, foreign matter in the paste coating film and / or above the coating film at the time of exposure. There was also a problem that cracks and disconnections were likely to occur during firing.
JP-A-1-296534 (page 2) Japanese Patent Laid-Open No. 2-165538 (2nd page) Japanese Patent Laid-Open No. 5-342929 (2nd page) Japanese Patent Laid-Open No. 14-173597 (page 2)

  An object of the present invention is to provide a paste that is unlikely to be peeled off or disconnected when the definition is increased or the line width is reduced. It aims at suppressing the disconnection at the time of baking especially.

  In order to solve the above problems, the present invention has the following configuration. That is, the present invention is an inorganic material paste comprising an inorganic component and an organic component, wherein the inorganic component contains two or more types of glass frit, and the softening point and average particle diameter satisfy the following two formulas: It is an inorganic material paste.

Ts (H) -Ts (L) ≦ 100 ° C.
D50 (L) <D50 (H)
Here, Ts (H) is the softening point of the glass frit H having the highest softening point, Ts (L) is the softening point of the glass frit L having the lowest softening point, D50 (L) is the average particle diameter of the glass frit L, D50 (H) is the average particle size of the glass frit H.

  ADVANTAGE OF THE INVENTION According to this invention, the inorganic material paste without a defect in the pattern after baking can be provided.

  The inorganic material paste of the present invention is an inorganic material paste comprising an inorganic component and an organic component, and includes two or more types of glass frit in the inorganic component, and the softening point and average particle diameter satisfy the following two formulas: is required.

Ts (H) −Ts (L) ≦ 100 ° C. (1)
D50 (L) <D50 (H) (2)
Here, Ts (H) is the softening point of the glass frit H having the highest softening point, Ts (L) is the softening point of the glass frit L having the lowest softening point, D50 (L) is the average particle diameter of the glass frit L, D50 (H) is the average particle size of the glass frit H. Further, the glass frit means a glass frit sintered at a firing temperature and does not mean a filler (aggregate).

  The present invention will be described by taking a PDP as an example. However, the present invention is not limited to this, and is preferably applied to the formation of an insulating pattern such as a multilayer substrate, a conductive pattern, or a flow path such as a DNA chip.

  As a result of earnestly examining the occurrence location, generation temperature, shrinkage stress, etc. of the pattern defect during firing, the volume shrinkage change during firing with respect to temperature is satisfied by satisfying Equation (1) and Equation (2). It was found that the defect of the inorganic material pattern can be suppressed. Although the detailed mechanism is unknown, it is guessed as follows. When the above two formulas are satisfied, when a glass frit having a high softening point and a glass frit having a lower softening point are mixed, first, the glass frit having a low softening point starts to soften in the heating process in the firing process. Since it plays the role of a binder for binding a glass frit having a high softening point that has not yet started to soften, shrinkage behavior and volume change with respect to temperature become slow. On the other hand, when the glass softening point is one kind, since the softening of the glass proceeds rapidly at a certain temperature, a partially fragile portion (for example, a poorly dispersed portion, a foreign material portion, the vicinity of coarse glass frit particles, a concave portion of the pattern Etc.) will cause cracks and breaks.

  When only one of the formulas (1) and (2) is satisfied, bubbles are not included in the fired structure, and firing defects are not suppressed. Moreover, the thermal decomposition characteristic of an organic component may deteriorate.

  The main component of the inorganic component used in the present invention is not particularly limited and can be selected in consideration of the electrical characteristics, optical characteristics, mechanical characteristics, sinterability, etc. of the pattern. When used for a back plate dielectric pattern, a glass frit having a glass softening point in the range of 400 ° C. to 600 ° C. is preferable. The front-plate transparent dielectric pattern and the back-plate dielectric pattern may not be formed on the plasma display. However, the front-plate transparent dielectric pattern and the back-plate dielectric pattern may be partially uneven for the purpose of controlling discharge-electrical characteristics, or provided with protrusions, holes, and steps. is there.

The softening point of the glass frit can be measured with a differential thermal analyzer (DTA), a differential scanning calorimeter (DSC), or the like. In addition, thermomechanical expansion measurement (TMA) is performed using a rod (for example, diameter 6 mmφ, length 20 mm), and the point at which the change in length turns into contraction (deflection point) is obtained, and this can be defined as the softening point. . For the average particle size, a particle size distribution measuring device (for example, a device using a laser Doppler method or a laser diffraction / scattering method) can be used.
The particle size distribution of the glass frit used in the present invention is not particularly limited, but it is preferable that the glass frit H shows a two-peak distribution. This is because, when the distribution is double, the packing density of the glass frit can be increased, so that the probability that the glass frit comes into contact with each other increases and defects during firing tend to hardly occur. The maximum particle diameter is 15 μm or less, more preferably 10 μm, and even more preferably 7 μm or less.

  The particle size distribution of the glass frit L is also not particularly limited, but it is preferable that the particle size distribution is a single peak as much as possible. This is because a single mountain can be evenly distributed between the glass frit H. The maximum particle size is the same as that of the glass frit H.

In the present invention, the difference between D50 (H) and D50 (L) is preferably larger than 1.0 μm. When the difference in average particle diameter is larger than 1.0 μm, the probability that a glass frit having a low softening point is arranged in the gap between the glass frit having a high softening point is increased, so that the role as a binder is improved. Moreover, it is preferable that the average particle diameter of the glass frit L with a low softening point is 1.5 micrometers or less. It is because a baking defect can be suppressed by setting it as 1.5 micrometers or less. More preferably, it is 1.0 μm or less. Even more preferably, it is 0.8 μm or less. This is because even if they are blended at the same weight ratio, if the average particle size is small, the number density increases, so that the role as a binder is improved. When it is larger than 1.5 μm, the effect of suppressing the firing defects tends to be hardly exhibited, or fired bubbles are likely to be generated.
The method for pulverizing the glass frit is not particularly limited, but a wet pulverization method is preferable for reducing the average particle size.
The blending weight ratio of the glass frit L and the glass frit H is preferably in the range of 0.1: 99.9 to 50:50. More preferably, it is 0.1: 99.9-30: 70. Even more preferably, it is 0.1: 99.9 to 15:85. Even more preferably, it is 0.1: 99: 9 to 5:95. By setting it as this range, generation | occurrence | production of a firing defect can be suppressed. When it is out of this range, giant bubbles tend to be generated during firing.

  A filler (aggregate) may be contained for the purpose of improving shape retention and mechanical strength. The weight ratio of the filler and glass frit (total amount of glass frit softened during the firing process) is preferably 0.1: 99.9 to 40:60. More preferably, it is 4: 96-30: 70. Even more preferably, it is 15: 85-30: 70. The particle size distribution of the filler is not particularly limited, but is preferably similar to a glass frit having a high softening point from the viewpoint of dispersibility.

The composition of the glass frit used in the present invention is not particularly limited, and can be appropriately selected depending on the firing temperature and electrical / optical characteristics. For example, known PbO—B ₂ O ₃ system, PbO—ZnO—B ₂ O ₃ —SiO ₂ , PbO—ZnO—B ₂ O ₃ system, ZnO—BaO—B ₂ O ₃ system, Bi ₂ O ₃ system Glass, phosphate glass, and ZnO—B ₂ O ₃ glass are preferably used. A material having a thermal expansion coefficient close to that of the glass substrate to be used is preferable, and the difference in thermal expansion coefficient (for example, 30 ° C. to 400 ° C.) is 10 or less. More preferably, it is 5 or less. The filler is not particularly limited, and oxides such as alumina, silica, titania, cordierite, magnesia, and high softening point glass, and composite oxides thereof are suitable. Further, a white pigment or a black pigment may be added for the purpose of controlling the object color after firing.
Moreover, when using this invention by the photosensitive paste method, it is preferable that the difference in specific gravity of the glass frit L and the glass frit H is small. Specifically, the specific gravity difference is preferably 0.5 g / cm ³ or less. More preferably, it is 0.3 g / cm ³ . Even more preferably, it is 0.1 g / cm ³ or less. This is because within this range, the straightness of exposure light is improved and the pattern formability is improved.

  It does not specifically limit as an organic component used for this invention, It can select suitably by the pattern formation method. For example, when pattern formation is performed by sand blasting or screen printing, cellulose compounds such as methyl cellulose and ethyl cellulose, high molecular weight polyethers, acrylic resins, and the like can be used as the resin. Acrylic resins can be preferably used as a polymer because there are few firing residues after firing. For example, it is an acrylic resin made of a polymer or copolymer such as methyl acrylate, methyl methacrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, isobutyl acrylate, and isobutyl methacrylate.

  The ratio of the inorganic powder to the resin is 1 to 40 parts by weight, more preferably 2 to 30 parts by weight with respect to 100 parts by weight of the inorganic powder. When the amount of the binder is less than 1 part by weight, it is difficult to form a continuous film, cracks or the like are generated during drying, and dielectric breakdown tends to occur when a PDP is formed. On the other hand, when the amount is more than 40 parts by weight, voids are formed at the time of firing or firing residue increases, which also leads to PDP dielectric breakdown and quality degradation.

  The solvent is not particularly limited, and known solvents can be used. For example, alcohols, terpenes, ketones, ketone esters, ethers, esters, ether esters, amides, amide esters, lactams, Lactones and hydrocarbons can be used. For example, methanol, ethanol, isopropanol, benzyl alcohol, propylene glycol, terpineol, acetone, methyl ethyl ketone, cyclohexane, diethyl ketone, carbitol, methyl carbitol, butyl carbitol, propylene glycol monoethyl ether, ethyl acetate, butyl acetate, carbitol Examples include acetate, γ-butyrolactone, toluene, xylene, and tetramethylbenzene.

  When used in a photosensitive paste, a known material can be applied as the resin, but it is preferable to have a function of controlling the developability of the unexposed area. In particular, a polymer having a weight average molecular weight of 2000 to 60,000, more preferably 5000 to 40,000 having a carboxyl group in the molecular side chain is used. The acid value of the polymer is preferably from 50 to 160, particularly preferably from 70 to 140, from the standpoint of development tolerance and solubility in the unexposed area developer.

  When pattern processing is performed by light irradiation, the polymerization initiator is preferably a photopolymerization initiator. In some cases, a sensitizer may be added to assist the effect of the photopolymerization initiator.

  The photopolymerization initiator that can be used in the present invention is preferably used because it generates radical species. As photopolymerization initiators, 1-hydroxycyclohexyl-phenyl ketone, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoin and its derivatives, benzophenone and its derivatives, acetophenone and its derivatives, imidazole derivatives, Quinone derivatives, diphenyl sulfide derivatives, thioxanthone and derivatives thereof, dibenzyl ketone, fluorenone, anthrone and derivatives thereof, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4- Methylcyclohe Sanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N- Photoreducing dyes such as phenylthioacridone, 4,4-azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide and eosin, methylene blue and ascorbine The combination of reducing agents, such as an acid and a triethanolamine, etc. are mentioned.

In the photosensitive paste of this invention, these can be used 1 type, or 2 or more types. The photopolymerization initiator is preferably added in the range of 0.05 to 10% by weight, and more preferably 0.1 to 10% by weight with respect to the organic component. By setting the addition amount of the photopolymerization initiator within this range, good photosensitivity can be obtained while maintaining the remaining ratio of the exposed portion.
Any of the pastes used in the present invention preferably contains a crosslinking agent. By forming a three-dimensional network structure with radicals generated from the thermal polymerization initiator as a starting point, the cross-linking agent improves developer resistance during development, and cracks and breaks occur even if firing stress occurs during firing. Defects can be suppressed. As the crosslinking agent, a compound having an active carbon-carbon double bond is preferable, and monofunctional and polyfunctional compounds having a vinyl group, an allyl group, a (meth) acrylate group, and an acrylamide group as functional groups are applied. Particularly preferred is a polyfunctional (meth) acrylate compound containing 5 to 80% by weight in an organic component. Since various types of (meth) acrylate compounds have been developed, it is possible to select them in consideration of reactivity, refractive index, etc., and in some cases, to combine them. It is also preferable to use a method such as introducing a side chain having a carbon-carbon double bond into the polymer.

The photosensitive paste used in the present invention preferably further contains a urethane compound. By containing a urethane compound, the flexibility of the paste is improved, the stress during firing can be reduced, and defects such as cracks and disconnections can be effectively suppressed. Furthermore, the thermal decomposability is improved, and the firing residue is less likely to be generated in the firing process. Specific examples of urethane compounds preferably used in the present invention include UA-2235PE (molecular weight 18000, EO content 20%), UA-3238PE (molecular weight 19000, EO content 10%), UA-3348PE (molecular weight 22000, EO). Content rate 15%), UA-5348PE (molecular weight 39000, EO content rate 23%) (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like, but are not limited thereto. Moreover, you may use these compounds in mixture.
The content of the urethane compound is preferably 0.1 to 20% by weight in the paste. By making the content 0.1% by weight or more, an appropriate peeling suppression effect can be obtained. When it exceeds 20% by weight, the dispersibility of the organic component and the inorganic fine particles is lowered, and defects are easily generated.

  In order to adjust the paste characteristics, such as showing an appropriate viscosity when applying the paste, it is also preferable to further contain a polymer. Cellulose compounds such as methyl cellulose and ethyl cellulose, high molecular weight polyethers, and acrylic resins can be preferably used as polymers because there are few firing residues after firing. Moreover, as already mentioned above, it is very preferable to introduce a side chain having a carbon-carbon double bond into a polymer in order to form a three-dimensional network structure by polymerization.

  In addition to these, the inorganic material paste used in the present invention can contain various components such as a dispersant, a thickener, an anti-settling agent, an antioxidant, an ultraviolet absorber, and an organic dye. These can be prepared by mixing and dispersing homogeneously with a kneader such as a three-roller, roller mill, or bead mill after blending them to have a predetermined composition.

When forming and using the inorganic material paste used by this invention on a sheet | seat, it is preferable that a plasticizer is included. Known materials can be used as the plasticizer. For example, normal alkyl phthalates such as dimethyl phthalate, dibutyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalethyl glycolate, butyl phthalyl butyl glycolate Phthalic acid esters such as tri-2-ethylhexyl trimellitate, tri-n-alkyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, etc., trimellitic acid ester, dimethyl adipate, dibutyl Adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl azate, dimethyl sebacate, dibutyl sebacate, -Aliphatic dibasic acid esters such as 2-ethylhexyl sebacate, di-2-ethylhexyl malate, acetyl-tri- (2-ethylhexyl) citrate, acetyl-tri-n-butyl citrate, acetyl tributyl citrate Etc.
Known materials can be used for the cover film and base film of the transfer sheet. For example, polyethylene terephthalate, polyester, polystyrene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, nylon and the like can be used.
A method for applying the paste of the present invention on the film is not particularly limited, and a die coater, a blade coater, a comma coater, a reverse roll coater, a spray coater, or the like can be used. When preparing a laminated transfer sheet, a plurality of these coating methods may be used.

Hereinafter, the present invention will be described in accordance with a plasma display manufacturing procedure.
As a substrate for the back plate of the plasma display, a high strain point glass substrate such as soda glass, “PD-200” manufactured by Asahi Glass Co., Ltd. or “PP-8” manufactured by Nippon Electric Glass Co., Ltd. is usually used.

  On the glass substrate, an electrode is formed of a conductive metal. For the electrode pattern formation, a screen printing method, a photosensitive paste method, a press molding method, or the like is used, and the photosensitive paste method is particularly preferable because the pattern can be refined and the process can be simplified. Hereinafter, it demonstrates according to the procedure of the photosensitive paste method.

  A photosensitive paste for electrodes is applied on the entire surface or partially on the substrate. As a coating method, methods such as a screen printing method, a bar coater, a roll coater, a die coater, and a blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, screen mesh, paste viscosity, and coating amount. The coating thickness can be determined in consideration of the desired electrode height and the shrinkage ratio of the electrode paste due to firing, but usually the preferred electrode height after firing is in the range of 1 to 10 μm, considering firing shrinkage. The thickness of the applied electrode paste coating film is preferably in the range of 1 to 15 μm.

  After the photosensitive paste for electrodes is applied, it is dried and exposed. The actinic ray used for the exposure is most preferably ultraviolet light, and as its light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp or the like is used. An exposure machine using parallel rays using an ultra-high pressure mercury lamp as a light source is common.

  After the exposure, development is performed using the difference in solubility between the exposed portion and the unexposed portion in the developer. In this case, an immersion method, a spray method, a brush method, or the like is used. As the developer, a solution in which an organic component in the photosensitive electrode paste, particularly a polymer can be dissolved, may be used. The photosensitive or non-photosensitive polymer having a carboxyl group in the side chain preferably used in the present invention can be developed with an aqueous alkaline solution. The electrode patterning may be performed in consideration of shrinkage due to firing, but the electrode size after firing preferably has a pitch of 100 to 500 μm, a height of 1 to 10 μm, and a width of 15 to 200 μm.

  Next, a dielectric layer forming paste is applied on the substrate on which the address electrodes are formed, dried and fired to form a dielectric layer. The address electrode, dielectric layer, and barrier layer may be fired individually, but when firing in a batch to reduce the thermal history and reduce the stress applied to the substrate, a thermal polymerization initiator is added to the dielectric paste. It is effective to cure in the range of 120 to 200 ° C.

  Next, a partition wall pattern is formed using the inorganic material paste of the present invention. In the case of forming by the sandblast method, an inorganic material paste is applied by a screen printing method or a slit die coater and dried. Thereafter, a dry film resist is laminated, exposed through a photomask, and developed. After development, sand blasting is performed, and finally the dry film resist is peeled off and baked to form a partition pattern.

  For pattern formation of the photosensitive paste barrier rib, first, exposure is performed. The actinic ray used for the exposure is most preferably ultraviolet light, and as its light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp or the like is used. An exposure machine using parallel rays using an ultra-high pressure mercury lamp as a light source is common.

  After the exposure, development is performed using the difference in solubility between the exposed portion and the unexposed portion in the developer. In this case, an immersion method, a spray method, a brush method, or the like is used. As the developer, a solution in which an organic component in the photosensitive partition paste, particularly a polymer can be dissolved, may be used. In the present invention, development with an aqueous alkaline solution is preferred. The partition wall patterning may be performed in consideration of shrinkage due to firing. The size of the partition wall after firing is, for example, a pitch range of 100 to 500 μm, a height range of 60 to 200 μm, and a width range of 15 to 80 μm. It is preferable to be within. The partition pattern is mainly formed in a stripe shape, but is not particularly limited, and may have a lattice shape or a hexagonal shape.

  After the partition pattern is formed, baking is performed. In addition, the dielectric layer and the electrode pattern can be fired simultaneously with the firing. The firing atmosphere and temperature vary depending on the characteristics of the paste and the substrate, but are usually fired in air. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

  Since it is preferable that a calcination temperature is lower than the glass transition point of the glass substrate to be used, there exists an upper limit naturally. Normally, by setting the firing temperature to 600 ° C. or less and the firing time to 15 to 30 minutes, firing residue, partition sagging, and the like can be suppressed. The rate of temperature rise and the rate of temperature fall can be set within a range where the glass substrate is not cracked or warped.

A phosphor layer is formed by applying a phosphor paste that emits red, green, and blue light to the substrate on which the electrodes, the dielectric layer, and the barrier ribs thus formed are formed. As a forming method, a screen printing method, a dispenser method, a photosensitive paste method, or the like can be used.
In this way, the back plate of the plasma display can be created.

Next, a method for manufacturing the front plate will be described.
The glass substrate used for the front plate is the same as that described for the back plate.
A transparent electrode such as tin oxide or ITO is formed on a glass substrate by a lift-off method, a photo etching method, or the like.
Next, a bus electrode layer is patterned on the glass substrate on which the transparent electrode is formed by screen printing of silver, aluminum, copper, gold, nickel, or the like or photolithography using a photosensitive conductive paste.
A transparent dielectric layer paste is applied on a glass substrate on which a transparent electrode and a bus electrode are formed by a screen printing method, a slit die coater, or the like, dried and fired to form a dielectric layer.

The transparent dielectric material used in the present invention is not particularly limited, but a dielectric material such as lead glass or ZnO—B ₂ O ₃ glass containing PbO, B ₂ O ₃ or SiO ₂ is applied. No particular limitation is imposed on the glass composition, PbO: 30 to 80 wt%, B ₂ O _3: 1~30 wt%, SiO _2: 10~35 wt%, CaO: 0 wt%, ZnO: 0 % By weight. The softening point is not particularly limited, but is preferably in the range of 530 to 590 ° C or 430 to 470 ° C from the viewpoint of light transmittance. The glass transition point is also not particularly limited, but is preferably in the range of 440 to 480 ° C. or 390 to 420 ° C. in view of the firing stress.
The particle size distribution is an average particle size of 0.5 to 5 μm, more preferably 0.8 to 3.5 μm, from the viewpoint of dispersibility, surface roughness of the fired film, withstand voltage, and the like.

  Furthermore, for the purpose of improving the exhaust efficiency in the panel manufacturing process and concentrating the electric field on the discharge gap, protrusions such as stripes and dots (cylinders, triangular prisms, rectangular parallelepipeds, etc.) can also be manufactured. For example, in the case of a stripe shape, the width is 10 to 100 μm and the height is 5 to 50 μm. In the case of a cylindrical dot, the diameter is 20 to 100 μm and the height is 5 to 50 μm. Even in the case of forming such a protruding pattern, the inorganic material paste of the present invention can be used for the purpose of suppressing firing defects, and can be formed by a sand blast method or a photosensitive paste method.

Further, for the purpose of protecting the transparent dielectric layer and lowering the discharge voltage, a protective film may be formed so as to cover the transparent dielectric layer and the protrusions. In general, an oxide of an alkaline earth metal can be used for the protective film. In particular, MgO is preferably applied because it has excellent sputtering resistance and a high secondary electron emission coefficient. The MgO protective film is formed by electron beam vapor deposition, Mg target reactive sputtering, or ion plating.
In this way, the front plate can be manufactured.

Next, a method for manufacturing a plasma display will be described.
After sealing the back plate and front plate using the back plate and front plate of the plasma display member, discharge gas composed of helium, neon, xenon, etc. is formed in the space formed at the front and back substrate intervals. After sealing, a plasma display can be manufactured by attaching a drive circuit and performing aging.

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

(Measurement of glass softening point)
The glass softening point was measured using a thermomechanical characteristic evaluation apparatus (TMA / 6200 manufactured by Seiko Instruments Inc.) at a heating rate of 10 ° C./min until the glass was softened. The maximum point at which the glass softened and the change in the sample length turned negative was taken as the glass softening point. The sample had a diameter of 5 to 6 mmφ and a length of 20 mm. Prior to the measurement, annealing was performed for 10 hours at the same temperature as the glass transition point measured in advance to remove distortion.

(Measurement of average particle size)
Particle size distribution:
The average particle size (D50) of the glass frit was measured using a particle size distribution meter (HRA particle size analyzer “MODEL No. 9320-X100” manufactured by Microtrack Co., Ltd.) using a laser diffraction scattering method. Measurement conditions were as follows.
Sample amount: 100 mg
Dispersion conditions: Ultrasonic dispersion in purified water for 5 minutes. If dispersion is difficult, perform in 0.2% sodium hexametaphosphate aqueous solution.

(Defect evaluation method)
The partition wall (42-inch substrate) that had been fired was subjected to defect inspection using an image inspection apparatus. The size of the partition wall defect that can be detected is a complete disconnection of about 30 μm or more. If there is a defect of 30 μm or more, after applying the phosphor paste, other phosphors are mixed into the adjacent cells and mixed in color, making it unsuitable as a display. The number of defects is preferably 0, and is NG when there are 1 or more defects. 50 images were inspected and the total number of defects was evaluated.
Next, examples will be described. The concentration in the examples is% by weight unless otherwise specified. Moreover, the addition amount of binder resin in an Example table | surface shows the addition amount of only resin except a solvent.

The binder resin, polymerization initiator, crosslinking agent, glass frit and filler used as the paste component are as follows.
Binder resin A: Acrylic polymer (addition reaction of 0.4 equivalent of glycidyl methacrylate to the carboxyl group of styrene / methyl methacrylate / methacrylic acid copolymer. Weight average molecular weight 43,000, acid value 95). Used as a 40% γ-butyrolactone solution.
Binder resin B: ethyl cellulose (number average molecular weight 80000). Used as a 5% terpineol solution.
Crosslinking agent: trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., “TPA330”, trifunctional)
Urethane compound: UA-3348PE (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 22000)
Polymerization initiator A: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone glass frit A: 7% lithium oxide, 23% silicon oxide, 50% boron oxide, 2% barium oxide Aluminum oxide 13%, calcium oxide 1%, magnesium oxide 1%, zinc oxide 1%. Glass transition point 480 ° C., softening point 530 ° C., thermal expansion coefficient 75 × 10 ⁻⁷ / ° C., density 2.54 g / cm ³ , average refractive index 1.586.
Glass frit B: Alumina borosilicate glass, glass transition point 455 ° C., softening point 495 ° C., thermal expansion coefficient 85 × 10 ⁻⁷ / ° C., density 2.56 g / cm ³ .

Glass frit C: alumina borosilicate glass, glass transition point 428 ° C., softening point 458 ° C., thermal expansion coefficient 95 × 10 ⁻⁷ / ° C., density 2.55 g / cm ³ .

Glass frit D: PbO—B 2 O 3 —ZnO glass, glass transition point 472 ° C., softening point 522 ° C., thermal expansion coefficient 67 × 10 ⁻⁷ / ° C., density 4.5 g / cm ³
Glass frit E: PbO—B 2 O 3 —ZnO glass, glass transition point 398 ° C., softening point 430 ° C., thermal expansion coefficient 85 × 10 ⁻⁷ / ° C., density 4.22 g / cm ³ .

Glass frit F: bismuth oxide 38%, silicon oxide 6%, boron oxide 20%, zinc oxide 20%, aluminum oxide 4%. Glass transition point 475 ° C., softening point 515 ° C., coefficient of thermal expansion 75 × 10 ⁻⁷ / ° C., density 4.61 g / cm ³ .

In the electrode paste, 15 parts by weight of binder resin A, 1 part by weight of polymerization initiator A, 3 parts by weight of cross-linking agent A and 4 parts by weight of dipropylene glycol monomethyl ether were dissolved while heating to 50 ° C., followed by silver fine particles ( Average particle diameter 1.5 μm, specific surface area 0.80 m ² / g, 80 parts by weight), low melting point glass powder (glass transition point 460 ° C., softening point 495 ° C., 3 parts by weight) was added, and kneading machine was used. It was prepared by kneading.

  The dielectric paste was prepared by dissolving 20 parts by weight of a binder resin B, 5 parts by weight of a polymerization initiator B, 10 parts by weight of a crosslinking agent and dipropylene glycol monomethyl ether (20 parts by weight) while heating to 50 ° C. to obtain a glass frit (glass transition point). 475 ° C., softening point 515 ° C., 250 parts by weight) and filler (silicon oxide (“Aerosil 200” manufactured by Nippon Aerosil Co., Ltd.), 100 parts by weight) were added and kneaded with a three-roller kneader.

  The partition wall paste and the dielectric protrusion paste were prepared by adding 30 parts by weight of binder resin A, 2 parts by weight of a polymerization initiator, 4 parts by weight of a crosslinking agent, 3 parts by weight of a urethane compound and 5 parts by weight of dipropylene glycol monomethyl ether (5 parts by weight). Dissolve while heating, add a predetermined amount of the glass frit shown in Table 1, stir the filler (glass transition point 652 ° C., average particle size 2.4 μm) as necessary, and knead using a kneader. Made.

(Examples 1-5)
First, a back plate was produced. The electrode paste was applied on a glass substrate, dried and then exposed. Then, alkali development was performed and baking was performed at 590 ° C. to prepare an address electrode pattern. Next, the dielectric paste was applied using a screen printer and cured at 180 ° C. And the partition paste which added glass rit as shown in Table 1 was apply | coated with the slit die-coater so that it might become thickness 180 micrometers after drying, and it dried at 100 degreeC using the hot air dryer. After drying, it was exposed through a photomask and developed in a 0.5% ethanolamine aqueous solution. Further, the dielectric and the barrier ribs were simultaneously fired at 590 ° C. to prepare barrier rib patterns. The negative exposure mask used for the partition wall exposure had a width of 30 μm and a pitch of 300 μm. When the shape of the partition walls after firing was observed with a scanning electron microscope (SEM), all of the examples were good stripe patterns with a top width of 30 μm and a height of 120 μm. Similarly, 50 back plate substrates were produced.

次に画像検査装置を用いて隔壁欠陥を調べて、５０枚の隔壁欠陥総数を求めた。
欠陥の有無に関わらず、スクリーン印刷法でＲＧＢの蛍光体ペーストを塗布し、蛍光体層を形成した。隔壁欠陥が生じている部分を紫外線ランプで照射して調べたところ、混色が生じていた。隔壁欠陥が発生しなかった基板と予め作製しておいた前面板と張り合わせ、放電ガスを封入し、プラズマディスプレイを作製した。駆動回路を実装して表示させたところ、問題なかった。

Next, the partition wall defects were examined using an image inspection apparatus, and the total number of 50 partition wall defects was determined.
Regardless of the presence or absence of defects, an RGB phosphor paste was applied by screen printing to form a phosphor layer. When the portion where the partition wall defect occurred was examined by irradiating it with an ultraviolet lamp, color mixing occurred. A plasma display was manufactured by laminating a substrate on which no barrier rib defect occurred and a front plate prepared in advance, and enclosing a discharge gas. When the drive circuit was mounted and displayed, there was no problem.

(Examples 6 and 7)
First, the dielectric paste is 100 parts by weight of binder resin B, glass frit (glass transition point 475 ° C., softening point 515 ° C., 100 parts by weight), filler (silicon oxide (“Aerosil 200” manufactured by Nippon Aerosil Co., Ltd.)), 30 weights. Part) was added and kneaded with a three-roller kneader.

Next, 50 parts by weight of a binder resin and 100 parts by weight of glass frit (total amount, kind of which is as shown in Table 1) were mixed, and a partition paste was prepared with a three-roll kneader.
In the same manner as in Example 1, a dielectric paste was applied to a substrate on which address electrodes were formed by a screen printer, and baked at 590 ° C.
A partition paste was applied with a slit die coater, dried, laminated with a dry film resist, exposed using the same exposure mask as in Example 1, developed, and then sandblasted, stripped resist, and baked (590 ° C.). The partition walls had a good stripe pattern with a top width of 30 μm and a height of 120 μm. Similarly, 50 back plate substrates were produced.

Next, the partition wall defects were examined using an image inspection apparatus, and the total number of 50 partition wall defects was determined.
Regardless of the presence or absence of defects, an RGB phosphor paste was applied by screen printing to form a phosphor layer. When the part where the partition wall defect occurred was examined by irradiating it with an ultraviolet lamp, color mixing occurred. A plasma display was manufactured by laminating a substrate on which no barrier rib defect occurred and a front plate prepared in advance, and enclosing a discharge gas. When the drive circuit was mounted and displayed, there was no problem.

(Examples 8 to 10)
The front plate transparent dielectric paste was prepared by using a three-roll kneader in which 100 parts by weight of binder resin B and 120 parts by weight of glass frit (total amount and type were as shown in Table 1) were prepared in the same manner as in Example 1. A back plate was prepared.

  A bus electrode pattern was produced using a photosensitive electrode paste on a glass substrate on which an ITO pattern was produced by a photoetching method. The front plate dielectric paste was applied using a slit die coater, dried, and baked at 590 ° C. The thickness after firing was 30 μm. Dielectric projection paste was applied with a slit die coater, exposed and developed, and fired at the final 590 to produce stripe-like projections. The stripe shape was a good pattern with a width of 30 μm and a height of 20 μm. Similarly, 50 front plate substrates were produced.

Next, protrusion defects were examined using an image inspection apparatus, and the total number of defects of 50 sheets was obtained.
A front panel and a rear panel were bonded together, and a discharge gas was sealed in to produce a plasma display. When the drive circuit was mounted and displayed, abnormal discharge occurred in the part where the protrusion was defective. Other than that, there was no problem.

(Comparative Examples 1-3)
A back plate was prepared in the same manner as in Example 1 except that the partition wall paste was changed as shown in Table 1. When the shape of the partition walls after firing was observed with a scanning electron microscope (SEM), all of the examples were good stripe patterns with a top width of 30 μm and a height of 120 μm. Similarly, 50 back plate substrates were produced.

Next, the partition wall defects were examined using an image inspection apparatus, and the total number of 50 partition wall defects was determined.
Regardless of the presence or absence of defects, an RGB phosphor paste was applied by screen printing to form a phosphor layer. When the portion where the partition wall defect occurred was examined by irradiating it with an ultraviolet lamp, color mixing occurred. A plasma display was manufactured by laminating a substrate on which no barrier rib defect occurred and a front plate prepared in advance, and enclosing a discharge gas. When the drive circuit was mounted and displayed, there was no problem.

(Comparative Example 4)
A back plate was prepared in the same manner as in Example 6 except that the partition wall paste was changed as shown in Table 1. When the shape of the partition walls after firing was observed with a scanning electron microscope (SEM), all of the examples were good stripe patterns with a top width of 30 μm and a height of 120 μm. Similarly, 50 back plate substrates were produced.

Next, the partition wall defects were examined using an image inspection apparatus, and the total number of 50 partition wall defects was determined.
Regardless of the presence or absence of defects, an RGB phosphor paste was applied by screen printing to form a phosphor layer. When the portion where the partition wall defect occurred was examined by irradiating it with an ultraviolet lamp, color mixing occurred. A plasma display was manufactured by laminating a substrate on which no barrier rib defect occurred and a front plate prepared in advance, and enclosing a discharge gas. When the drive circuit was mounted and displayed, there was no problem.

(Comparative Example 5)
A front plate was prepared in the same manner as in Example 8 except that the dielectric protrusion paste was changed as shown in Table 1. The stripe shape was a good pattern with a width of 30 μm and a height of 20 μm. Similarly, 50 front plate substrates were produced.

Next, protrusion defects were examined using an image inspection apparatus, and the total number of defects of 50 sheets was obtained.
A front panel and a rear panel were bonded together, and a discharge gas was sealed in to produce a plasma display. When the drive circuit was mounted and displayed, abnormal discharge occurred in the part where the protrusion was defective. Other than that, there was no problem.

  Table 1 shows the total number of defects in Examples 1 to 10 and Comparative Examples 1 to 5. In any of the examples, the total number of defects is smaller than that of the comparative example, and the productivity is high. On the other hand, the comparative example has a large number of defects, and productivity is expected to decrease.

Claims (11)

An inorganic material paste containing an inorganic component and an organic component, wherein the inorganic component contains two or more types of glass frit, and the softening point and average particle size of the glass frit satisfy the following two formulas: Inorganic material paste.
Ts (H) -Ts (L) ≦ 100 ° C.
D50 (L) <D50 (H)
(Here, Ts (H) is the softening point of the glass frit H having the highest softening point, Ts (L) is the softening point of the glass frit L having the lowest softening point, and D50 (L) is the average particle diameter of the glass frit L. D50 (H) is the average particle size of the glass frit H.) The inorganic material paste according to claim 1, wherein a weight ratio of the glass frit L to the glass frit H is in a range of 0.1: 99.9 to 50:50. D50 (L) and D50 (H) satisfy | fill the following formula | equation, The inorganic material paste of Claim 1 characterized by the above-mentioned.
D50 (H) -D50 (L)> 1.0 μm The inorganic material paste according to claim 1, wherein the glass frit L has an average particle size of 1.5 μm or less. The inorganic material paste according to claim 1, comprising a filler that does not melt at a firing temperature. The inorganic material paste according to claim 2, wherein a weight ratio of the filler to the glass frit is 0.1: 99.9 to 40:60. The inorganic material paste according to claim 1, wherein a difference in specific gravity between the glass frit H and the glass frit L is 0.5 g / cm ³ or less. The inorganic material paste according to claim 1, which is used for forming a partition pattern of a plasma display. The inorganic material paste according to claim 1, wherein the organic component contains a photosensitive component. A plasma display member produced using the inorganic material paste according to claim 1. A plasma display produced by using the plasma display member according to claim 10.