JP2005343711A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition capable of suppressing generation of bubbles and pinholes and forming an inorganic molded body having high transparency and density by favorably thermally decomposing and removing a binder resin even at a relatively low firing temperature. provide.
Another object of the present invention is to provide a gas discharge display device that exhibits good image display performance by using the coating composition of the present invention.
SOLUTION: In addition to the inorganic material, ethyl cellulose and solvent used as the raw material of the inorganic molded body, an alkaline earth metal oxide, bis (dimethylphenylmethane) or bis (triphenylmethane) is mixed as a coating composition. Use the following.
[Selection] Figure 1

Description

  The present invention relates to a coating composition used for a dielectric layer, a sealing portion or the like in a gas discharge panel.

Conventionally, for example, in the manufacture of electrical components, glass sealing of a ceramic package covering a semiconductor element, glass sealing of a cathode ray tube (CRT), glass sealing of a gas discharge panel (PDP, etc.), or a dielectric layer or fluorescence For the purpose of forming a body layer or the like, a coating composition obtained by kneading an inorganic substance with a binder resin and a solvent is used.
Examples of the binder resin include cellulose derivatives such as nitrocellulose and ethylcellulose (see Patent Documents 1 and 2), poly-α-methylstyrene (see Patent Document 3), acrylic resins (see Patent Documents 4 and 5), and the like. However, ethyl cellulose is particularly suitable because of its dispersibility of inorganic substances and excellent coating properties.

As the inorganic substance, glass powder or a mixture of glass powder and ceramic powder can be used.
The coating composition is applied to a substrate or the like in a predetermined pattern and processed in a baking step to thermally decompose and remove organic components in the composition, thereby forming a molded body made of the inorganic substance. Yes.

Such a coating composition softens the inorganic substance at a low temperature (400 ° C. or less, preferably 350 ° C. or less) for the purpose of preventing the electric member from being thermally deteriorated by a high temperature related to baking. Is desired. For the same reason, it is desirable that the thermal decomposition and removal (referred to as “pre-firing”) of the binder resin in the components can be performed at a low temperature.
In addition, the said composition for application | coating may be called a paste composition, when it has high viscosity. The “paste” refers to a paste in which a predetermined component is dispersed in a liquid at a high concentration and exhibits a high viscosity as a whole.
JP 52-115815 A Japanese Patent Laid-Open No. 6-321619 Japanese Patent Laid-Open No. 2-124744 Japanese Patent Laid-Open No. 10-324541 JP-A-10-324869 JP 2003-54991 A

However, a conventional inorganic composition may not always be obtained with a conventional coating composition.
For example, in a certain coating composition, the thermal decomposition temperature of the binder resin may be equal to or higher than the softening point of the inorganic substance. In this case, in the firing process, melting of the inorganic substance starts from the stage where the thermal decomposition and removal of the binder resin is incomplete, and the binder resin is burned out in the state of being encapsulated in the inorganic substance, and bubbles and pinholes are formed inside the inorganic molded body. Cause the formation. In addition, the binder resin may remain in the softened inorganic substance without being completely decomposed, resulting in a carbide residue.

Such bubbles, pinholes, and carbide residues are a cause of defects in the inorganic molded body and cause the following problems.
For example, when an inorganic molded body having a cavity caused by bubbles or pinholes is used as a sealing material (for example, a material for a glass frit sealing portion), the outside air circulates in the cavity, so that sufficient airtightness cannot be maintained. If the inorganic formed body is used as the dielectric layer of the gas discharge panel, the transmitted light is scattered by the bubbles in the dielectric layer and the transparency is lowered, so that good image display performance cannot be obtained. Furthermore, since the density of the dielectric layer becomes sparse, there is a problem of dielectric breakdown and there is a risk that normal discharge cannot be performed.

  In order to solve such a problem, for example, in Patent Document 6, a substance that promotes the decomposition of a binder resin such as a peroxide, an azo compound, a heavy metal, or a heavy metal oxide is added to the coating composition, and an apparent binder resin is produced. A method for reducing the thermal decomposition temperature has been proposed. However, peroxides or azo compounds have a relatively high risk and are not suitable for manufacturing electrical members. In addition, when heavy metals or heavy metal oxides are used, there may be another problem that the inorganic molded body is colored by the residue of these heavy metals after firing or the transparency is lowered.

Thus, at present, there is still room for improvement in the coating composition.
The present invention has been made in view of the above-mentioned problems, and its purpose is to suppress the generation of bubbles and pinholes by satisfactorily thermally decomposing and removing the binder resin even at a relatively low firing temperature, and to achieve high transparency. It is providing the composition for application | coating which can form the inorganic molded object which has a density.

  Another object of the present invention is to provide a gas discharge display device that exhibits good image display performance by using the coating composition of the present invention.

In order to solve the above-mentioned problems, the present invention is an application composition for forming an inorganic molded body after being applied to a substrate and firing the same, and an inorganic substance that is a raw material of the inorganic molded body In addition to ethyl cellulose and a solvent, a coating composition in which at least one selected from the group consisting of an alkaline earth metal oxide and a compound represented by Chemical Formula 1 described later was mixed.

但し、化１中において、Ｒ１〜Ｒ４は、フェニル基またはＣ１〜Ｃ４のアルキル基を指す。
また、Ｒ５およびＲ６はＣ１〜Ｃ４のアルキル基を指す。

However, in Chemical Formula 1, R1 to R4 indicate a phenyl group or a C1 to C4 alkyl group.
R5 and R6 each represent a C1-C4 alkyl group.

Furthermore, n refers to any integer from 0 to 5.
The alkaline earth metal oxide is preferably made of a material having a purity of 80% or more.
The inorganic substance may be glass powder or a mixture of the glass powder and ceramic powder.

Here, the content rate of ethyl cellulose can also be set to the range of 0.05 weight percent or more and 0.5 weight percent or less of the whole coating composition.
When an alkaline earth metal oxide is included, the alkaline earth metal oxide can be at least one of magnesium oxide, calcium oxide, strontium oxide, and barium oxide.

Further, in the case where an alkaline earth metal oxide is contained, the content of the alkaline earth metal oxide is set to a range of 0.0025 weight percent or more and 0.25 weight percent or less of the entire coating composition. It can also be set.
On the other hand, when the compound represented by Chemical Formula 1 is included, the content of the compound is set to a range of 0.0025 weight percent or more and 0.25 weight percent or less of the entire coating composition. desirable.

  The present invention is also a method for producing a gas discharge device comprising a sealed container structure provided with a dielectric layer, wherein the dielectric layer is formed by using the coating composition of the present invention. The sealing process of the sealed container structure was performed.

According to the coating composition of the present invention having the above composition, in the firing step after coating on the substrate, the carbon radical caused by the compound represented by chemical formula 1, which is an additive, or an alkaline earth metal oxide is used. The thermal decomposition of ethyl cellulose contained as the binder resin is promoted.
For this reason, in a firing stage lower than the temperature related to the thermal decomposition of ethyl cellulose, that is, in a temperature state lower than the softening point of the inorganic substance (for example, a relatively low temperature firing condition such as a temporary firing condition of 350 ° C. or less). However, it is possible to thermally decompose and remove the ethyl cellulose.

Thereby, generation | occurrence | production of the bubble and pinhole derived from ethyl cellulose is suppressed, and the inorganic molded object which has high transparency and the outstanding density will be obtained.
The alkaline earth metal oxide added to the paste composition of the present invention refers to a commercially available material having a purity of 80% or more, and is an alkali originally contained in the glass powder added as an inorganic substance. It does not refer to the compositional part of the earth metal oxide. It has been found that the effect of the present invention cannot be obtained with an alkaline earth metal oxide resulting from such a glass composition.

1. Embodiment 1 (Regarding Paste Composition)
1-1. Configuration of paste composition Hereinafter, the paste composition which is the coating composition of Embodiment 1 will be described in detail.
The paste composition according to the first embodiment is selected from an inorganic substance as a raw material of an inorganic molded body, ethyl cellulose as a binder resin, a solvent, and an alkaline earth metal oxide or the structural formula 1 in addition to this. It is comprised by making it contain as an essential component and mixing this.

As a specific compound represented by Chemical Formula 1, bis (dimethylphenylmethane) (Ph (CH ₃ ) ₂ C—C (CH ₃ ) ₂ Ph represented by Chemical Formula 2 below is referred to as “BDM”. And bis (triphenylmethane) represented by chemical formula ₃ ((Ph) ₃ C—C (Ph) ₃ ) and the like.

これらの化合物は単独で用いてもよいし、２種類以上を混合して使用することもできる。化１で表される具体的な化合物をペースト組成物に入れる場合の含有率としては、ペースト組成物全体の０．００２５重量パーセントから０．２５重量パーセント（エチルセルロースに対して５重量パーセントから５０重量パーセント）の範囲にあることが好ましい。

These compounds may be used alone or in combination of two or more. When the specific compound represented by Chemical Formula 1 is added to the paste composition, the content is 0.0025 weight percent to 0.25 weight percent of the total paste composition (5 weight percent to 50 weight percent with respect to ethyl cellulose). Percent).

  As the alkaline earth metal oxide, at least one of magnesium oxide, calcium oxide, strontium oxide, and barium oxide can be used. The content of alkaline earth metal in the paste composition is in the range of 0.0025 to 0.25 weight percent (5 to 50 weight percent with respect to ethylcellulose) of the entire paste composition. preferable. Note that the alkaline earth metal oxide is preferably a material having a purity higher than that of a commercially available material, that is, a material having a purity of 80% or more, in order to obtain the effects of the present invention.

Note that either one of the compound represented by Chemical Formula 1 or the alkaline earth metal may be added, but both of them may be used.
The inorganic substance has a softening point in order to prevent thermal deterioration under a high-temperature firing process when applied to an electric member (ceramic package of a semiconductor element), a dielectric layer of a gas discharge device, or a glass sealing part. It is preferable to use a glass powder or a mixture of glass powder and ceramic powder of 400 ° C. or lower, preferably 350 ° C. or lower.

Examples of inorganic substances having a softening point of 400 ° C. or less include P ₂ O ₅ —SnO, P ₂ O ₅ —SnO—ZnO, Bi ₂ O ₅ , ZnO—B ₂ O ₃ —SiO ₂ , and PbO—. For glass powders such as B ₂ O ₃ —SiO ₂ system, PbO—B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ system, PbO—ZnO—B ₂ O ₃ —SiO ₂ system, or these glass powders, alumina powder, zirconia powder, silica powder, lead titanate, cordierite _{(2MgO-2Al 2 O 3 -5SiO} 3 system), mullite (Al ₂ O ₃ -SiO ₂ system) mixture comprising the addition of ceramic powders, such as It can be illustrated.

  As the solvent, those having good affinity with an inorganic substance and solubility of the binder resin, imparting an appropriate viscosity to the paste composition, and easily removing by drying are preferable. Specifically, n-butyl acetate, isoamyl acetate, butyl carbitol acetate, terpineol and the like can be used. These may be used alone or in combination of two or more. The content of the solvent in the paste composition can be appropriately adjusted in a range where the fluidity (viscosity) of the paste composition is suitable for the molding process or the coating process.

  Ethyl cellulose as the binder resin has excellent dispersibility of the inorganic substance and excellent coating properties of the paste composition. As the molecular weight of such ethyl cellulose, it is preferable that the weight average molecular weight is in the range of 5,000 to 500,000 considering the adhesion to the glass substrate. The ethyl cellulose content in the paste composition is preferably in the range of 0.05 weight percent to 0.5 weight percent of the total paste composition.

In addition to the above, various additives may be added to the paste composition as optional components. Examples of such additives include surfactants and storage stabilizers.
The paste composition according to Embodiment 1 comprises a ball mill, a mixer, and a homogenizer comprising the above essential components, that is, an inorganic substance, ethyl cellulose and a solvent, and at least one selected from alkaline earth metal oxides or Chemical Formula 1 above. It can obtain by kneading | mixing using kneading machines, such as.

1-2. Effect of Paste Composition According to the paste composition of the first embodiment having the above-described configuration, a substrate (substrate) such as glass is formed by a generally known forming method, that is, a dispenser method or a screen printing method. ) Applied directly to the surface. Thereafter, the applied paste composition is sequentially processed in a drying step and a baking step, whereby a layered or film-like inorganic molded body is finally formed.

Here, if the paste composition of the first embodiment is used, the number of bubbles and pinholes and the generation of cavities are suppressed as compared with conventional ones, and the inorganic formed body has high density and good transparency and airtightness. The excellent feature that can be realized is exhibited.
Specifically, since the paste composition contains an alkaline earth metal oxide and a compound of Chemical Formula 1 that have an action of promoting the decomposition of ethyl cellulose as a binder resin, the paste composition is relatively free in the firing step. In the low temperature stage (ranging from about 260 ° C. to about 280 ° C.), the thermal decomposition of ethyl cellulose is promoted, and the above effect is exhibited.

  Among these, the compound represented by the chemical formula 1 becomes a carbon radical generator under heating in the firing step. And since the said carbon radical works so that the molecular chain of ethyl cellulose which is a carbon compound may be cut | disconnected, there exists an effect which accelerates | stimulates the thermal decomposition of ethyl cellulose favorably by this. Here, FIG. 1 is a diagram showing the thermal decomposition rate of ethyl cellulose by a compound (here, BDM) represented by Chemical Formula 1 that generates a carbon radical (in the figure, the addition amount of BDM is described as a weight percent with respect to ethyl cellulose). ing). According to this figure, it is clarified that the effect of the carbon radical can be obtained when BDM is contained in ethyl cellulose at 10 weight percent or 20 weight percent. In addition, it can be seen that when 20% by weight of BDM is contained, the thermal decomposition rate at a lower temperature is higher.

Since the compound represented by Chemical Formula 1 is burned off in the firing step while performing such a radical action, it does not remain as a carbon residue in the finally obtained inorganic formed body.
The compound represented by Chemical Formula 1 is safer than the peroxide and azo compound used in the prior art (Patent Document 6) (flammable against spark arc discharge, etc. that may occur during the manufacture of electrical members). -Low explosive risk), suitable for manufacturing electrical components. Furthermore, since radical decomposition is not easily caused by light or the like, there is a merit that high stability can be stored for a long time even if it is included in the paste composition.

  On the other hand, according to the alkaline earth metal oxide, an effect of supplying abundant oxygen essential for combustion of ethyl cellulose in the firing step is exhibited. As a result, oxygen is bound to ethyl cellulose in the paste composition, and an environment in which chemical change is easily made to carbon dioxide gas is created, and the function of promptly accelerating the burning is performed. FIG. 2 is a diagram showing the thermal decomposition rate of ethyl cellulose when alkaline earth metal oxide (here, CaO) is added at 10 weight percent with respect to ethyl cellulose. If alkaline earth metal oxide is actually used, FIG. It can be confirmed that the thermal decomposition of ethyl cellulose is promoted. The alkaline earth metal oxide remains in the finally obtained inorganic molded body. However, according to the experiments by the inventors of the present application, the alkaline earth metal oxide does not have a property of promoting color development. It has been confirmed that the properties of the inorganic molded body are not impaired. For this reason, an uncolored and favorable inorganic molded object is obtained after a baking process.

When such an inorganic molded body is applied to a ceramic package of a semiconductor element, the transparency is not so much of a problem, but it has an advantage that it can be fired satisfactorily at a low temperature.
Further, even when the compound represented by the above chemical formula 1 and the alkaline earth metal oxide are used in combination, as shown in FIG. 3 (here, 5% by weight of BDM and CaO are included with respect to ethyl cellulose, respectively). ), Which is desirable because it can effectively promote the thermal decomposition of ethyl cellulose.

In addition, although each addition amount range of the said ethyl cellulose, the said compound, and the said alkaline-earth metal oxide may be outside the above-mentioned range, it is preferable to set based on said each range as much as possible. The basis for this is as follows.
First, when the content of ethyl cellulose is less than 0.05 weight percent of the entire paste composition, it may be difficult to bind and retain the inorganic substance sufficiently. On the other hand, if it exceeds 0.5 weight percent, the glass is not sufficiently sintered, and carbide residues, bubbles, and pinholes derived from the residual resin are more likely to occur during firing.

Moreover, when the content rate of the compound shown in the chemical formula 1 is less than 5 weight percent with respect to ethyl cellulose, the acceleration of thermal decomposition of ethyl cellulose is substantially weakened. On the other hand, when the ratio of the compound to the inorganic substance exceeds 50 weight percent, the binding force of ethyl cellulose is weakened.
On the other hand, when the content of the alkaline earth metal oxide is less than 0.5 weight percent with respect to ethyl cellulose, the acceleration of thermal decomposition of ethyl cellulose is substantially weakened. On the other hand, when it exceeds 50 weight percent with respect to ethylcellulose, the binding strength of ethylcellulose becomes weak.

2. Embodiment 2 (Gas Discharge Panel) Here, a gas discharge panel (PDP) which is a configuration example of a gas discharge display device using the paste composition of Embodiment 1 will be described.
2-1. Configuration of PDP FIG. 4 is a partial perspective view showing a main configuration of an AC surface discharge type plasma display panel 10 (hereinafter simply referred to as “PDP 10”) according to the second embodiment.

The PDP 10 is sized according to the 42-inch class VGA specification as an example, but the present invention may of course be applied to other sizes and specifications.
As shown in FIG. 4, the configuration of the PDP 10 is roughly divided into a front panel 20 and a back panel 26 that are disposed with their main surfaces facing each other.
A front panel glass 21 which is a substrate of the front panel 20 has a strip-shaped transparent electrode 220 (230) having a thickness of 0.1 μm and a width of 150 μm on one side, and a bus line 221 (231 having a thickness of 7 μm and a width of 95 μm). A plurality of display electrodes 22 (23) (X electrode 23, Y electrode 22) are arranged side by side in the x direction with the y direction as the longitudinal direction (23 and 230 are located at the back of the drawing). (Not shown). Each pair of display electrodes 22 and 23 is electrically connected to a panel drive circuit (not shown) near the end in the width direction (Y direction) of the front panel glass 21. At this time, the Y electrodes 22 are collectively connected to the panel drive circuit, and the X electrodes 23 are independently connected to the panel drive circuit. When power is supplied to the Y electrode 22 and the specific X electrode 23 from the panel drive circuit, surface discharge (sustain discharge) is performed in the gap (about 80 μm) between the display electrodes 22 and 23.

Further, the X electrode 23 also operates as a scan electrode, and makes an address discharge (address discharge) with the address electrode 28.
A surface of the front panel glass 21 on which the plurality of pairs of display electrodes 22 and 23 are disposed is coated with a dielectric layer 24 having a thickness of about 30 μm so as to cover the plurality of pairs of display electrodes 22 and 23. Further, a protective layer 25 having a thickness of about 1.0 μm is laminated on the dielectric layer 24.

  A plurality of address electrodes 28 having a thickness of 5 μm and a width of 60 μm are arranged in parallel on the one side of the back panel glass 27 serving as the substrate of the back panel 26 in the y direction with the x direction as the longitudinal direction. The adjacent pitch of the two address electrodes 28 is a constant interval (about 150 μm). The plurality of address electrodes 28 are independently connected to the panel drive circuit and individually supplied with power, and address discharge is performed between the specific address electrode 28 and the specific X electrode 23. It has become so.

The surface of the back panel glass 27 on which the plurality of address electrodes 28 are arranged side by side is coated with a dielectric film 29 having a thickness of 30 μm so as to cover the plurality of address electrodes 28. Further, on the dielectric film 29, a partition wall 30 having a height of about 150 μm and a width of about 40 μm is arranged with the x direction as the longitudinal direction in accordance with the pitch of the adjacent address electrodes 28.
Phosphor layers 31 to 33 corresponding to any one of red (R), green (G), and blue (B) are formed on the side surfaces of two adjacent partition walls 30 and the surface of the dielectric film 29 therebetween. ing. These RGB phosphor layers 31 to 33 are repeatedly arranged in the y direction.

The front panel 20 and the back panel 26 are opposed to each other so that the address electrodes 28 and the display electrodes 22 and 23 are orthogonal to each other, and are fritted glass sealing portions (not shown) that surround the outer peripheral edges of the panels 20 and 26. Glued. Thereby, the space between the panels 20 and 26 is sealed. Between the panels 20 and 26, a discharge gas composed of a rare gas component of an element selected from He, Xe, and Ne has a predetermined pressure (usually about 6.7 × 10 ^{4 to} 1.0 × 10 ⁵ Pa). It is enclosed with. A corresponding space between two adjacent barrier ribs 30 becomes a discharge space 34. A region where the pair of display electrodes 22, 23 and one address electrode 28 intersect with each other with the discharge space 34 therebetween corresponds to a cell for image display. As an example, the cell pitch in the x direction is set to about 1080 μm, and the cell pitch in the y direction is set to about 360 μm.

  When driving the PDP 10 having such a configuration, first, a pulse voltage is applied to the specific address electrode 28 and the specific X electrode 23 by the panel drive circuit to cause address discharge. After the address discharge, a pulse is applied between the pair of display electrodes 22 and 23 to cause sustain discharge, thereby generating short-wave ultraviolet light (a resonance line having a wavelength of about 147 nm as a central wavelength). By this ultraviolet irradiation, the phosphors contained in the phosphor layers 31 to 33 emit visible light, and an image is displayed.

  Here, the second embodiment is characterized in that the paste composition of the present invention is used as a material for the dielectric layer 24, the dielectric film 29, and the frit glass sealing portion. Accordingly, the dielectric layer 24, the dielectric film 29, and the frit glass sealing portion are configured to have higher density and airtightness by avoiding the generation of cavities due to bubbles and pinholes as compared with the conventional configuration. And has excellent transparency.

  For this reason, for example, the dielectric layer 24 provided on the front panel FP side that transmits visible light emission at the time of driving has excellent transparency, thereby avoiding problems such as visible light scattering and good image quality. Display performance is demonstrated. In addition, since the dielectric layer 24 and the dielectric film 29 are configured with high density, generation of dielectric breakdown due to discharge during driving is suppressed, and an accurate discharge is performed while preventing an address miss. Therefore, the image display performance is also improved from this point.

Furthermore, since high airtightness is exhibited in the frit glass sealing portion, the gas pressure of the panel can be kept good and can contribute to the maintenance of normal discharge.
In addition, the paste composition of the present invention may be used as a material for the partition wall 30.
2-2. Method for Manufacturing PDP Here, an example of the method for manufacturing the PDP 10 according to the second embodiment will be described.

2-2-1. Production of Front Panel FP Display electrodes are produced on the surface of a front panel glass made of soda-lime glass having a thickness of about 2.6 mm. Although an example in which the display electrode is formed by a printing method is shown here, it can be formed by a die coating method, a blade coating method, or the like.
First, an ITO (transparent electrode) material is applied on the front panel glass in a predetermined pattern. This is dried.

  On the other hand, using a photomask method, a photosensitive paste is prepared by mixing a photosensitive resin (photodegradable resin) with metal (Ag) powder and an organic vehicle. This is applied over the transparent electrode material and covered with a mask having a display electrode pattern to be formed. And it exposes from the said mask, and develops and bakes (baking temperature of about 590-600 degreeC). Thereby, a bus line is formed on the transparent electrode. According to this photomask method, the bus line can be thinned to a line width of about 30 μm as compared with the screen printing method in which the line width of 100 μm is conventionally limited. In addition, Pt, Au, Ag, Al, Ni, Cr, tin oxide, indium oxide, and the like can be used as the metal material for the bus line.

In addition to the above method, the electrode may be formed by performing an etching process after forming an electrode material by a vacuum deposition method, a sputtering method, or the like.
Next, the paste composition described in Embodiment 1 is applied on the formed display electrode by a screen printing method or the like. And after performing a drying process for a fixed period, a dielectric material layer is formed by performing a baking process at predetermined temperature. Thereby, a dielectric layer as a good inorganic formed body having high transparency is formed.

Next, a protective layer made of magnesium oxide is formed on the surface of the dielectric layer over a thickness of about 1 μm. As the formation method, a sputtering method or the like can be used.
This completes the front panel.
2-2-2. Fabrication of back panel On the surface of back panel glass made of soda-lime glass with a thickness of about 2.6 mm, a conductive material mainly composed of Ag is formed in stripes at regular intervals by screen printing. Application is performed to form an address electrode having a thickness of about 5 μm. Here, in order to make the PDP 1 to be manufactured, for example, the 40-inch class NTSC standard or VGA standard, the interval between two adjacent address electrodes is set to about 0.4 mm or less.

Subsequently, a lead-based glass paste is applied over the entire surface of the back panel glass on which the address electrodes are formed to a thickness of about 20 to 30 μm and baked to form a dielectric film.
Next, using the same lead-based glass material as the dielectric film, a partition wall having a height of about 60 to 100 μm is formed on the dielectric film between adjacent address electrodes. This partition can be formed, for example, by repeatedly screen-printing a paste containing the glass material and then firing it.

When the barrier ribs are formed, the wall surface of the barrier ribs and the surface of the dielectric film exposed between the barrier ribs include any of red (R) phosphor, green (G) phosphor, and blue (B) phosphor. A fluorescent ink is applied, and this is dried and fired to form phosphor layers.
The chemical composition of each color fluorescence of RGB is, for example, as follows.
Red phosphor; Y ₂ O ₃ ; Eu ³⁺
Green phosphor; Zn ₂ SO ₄ ; Mn
Blue phosphor; BaMgAl ₁₀ O ₁₇ ; Eu ²⁺
Each phosphor material having an average particle diameter of 2.0 μm can be used. This is put in a server at a rate of 50% by mass, and 1.0% by mass of ethyl cellulose and 49% by mass of a solvent (α-terpineol) are added and stirred and mixed in a sand mill to obtain 15 × 10 ⁻³ Pa · s. A phosphor ink is prepared. And this is sprayed and applied between adjacent partition walls with a nozzle having a diameter of 60 μm. At this time, the panel is moved in the longitudinal direction of the partition wall 20, and the phosphor ink is applied in a stripe shape. Thereafter, baking is performed at around 500 ° C. for 10 minutes to form a phosphor layer.

This completes the back panel.
Although the front panel glass and the back panel glass are made of soda lime glass, this is given as an example of the material, and other materials may be used.
2-2-3. Completion of PDP The produced front panel and back panel are opposed to each other, and the paste composition of the present invention is applied as sealing glass so as to surround the peripheral edges of both panels. And both panels are bonded together and dried for a certain period of time, followed by a firing step.

Thereafter, the inside of the discharge space is evacuated to a high vacuum (1.0 × 10 ⁻⁴ Pa), and Ne—Xe system or He—Ne—Xe system at a predetermined pressure (66.5 kPa to 101 kPa in this case). , A discharge gas such as He—Ne—Xe—Ar system is sealed.
Thus, the PDP 1 is completed.
In addition, when applying the paste composition of the present invention to a PDP, it is of course not necessary to apply to all of the dielectric film, dielectric layer, and glass frit sealing portion, and if used in a portion selected from these as appropriate. Good.

3. Examples and Performance Comparison Experiments Hereinafter, a performance comparison experiment in which a paste composition was produced as an example of the present invention and performed on the paste composition will be described. The composition of each example is described in Table 1 below.
<Example 1>
(1) Preparation of paste composition: 88.5 weight percent of glass powder having a composition containing 30 parts by weight of P ₂ O ₅ as an inorganic substance, 60 parts by weight of SnO, and 10 parts by weight of ZnO, and isoamyl acetate as a solvent A paste of the present invention was prepared by mixing and pulverizing a mixture of 11.4 weight percent, ethyl cellulose 0.1 weight percent, calcium oxide 0.01 weight percent (10 weight percent with respect to ethyl cellulose) in a ball mill for 30 minutes. A composition (Example 1) was prepared.

(2) Production of inorganic molded body: The paste composition prepared in (1) above was applied onto a glass substrate using a dispenser to form a uniform coating film on the substrate.
Next, the solvent was removed by drying by leaving the coating film at 25 ° C. for a whole day and night, followed by baking at 350 ° C. to produce an inorganic molded body on the glass substrate.
<Examples 2 to 4>
Example 1 except that magnesium oxide (Example 2), strontium oxide (Example 3), and barium oxide (Example 4) were contained in appropriate amounts instead of calcium oxide (Example 1 above). Thus, a paste composition was prepared, and each inorganic molded body was produced.

<Example 5>
According to the formulation shown in Table 1, a paste composition of the present invention was prepared in the same manner as in Example 1 except that bis (dimethylphenylmethane) was contained instead of calcium oxide, and then the obtained paste composition Except that the product was used, an inorganic molded body was produced in the same manner as in Example 1 by applying the paste composition, drying and removing the solvent, and firing.

<Example 6>
According to the formulation shown in Table 1, a paste composition of the present invention was prepared in the same manner as in Example 1 except that calcium oxide and bis (dimethylphenylmethane) were contained.
Next, an inorganic molded body was produced by applying the paste composition, drying and removing the solvent, and firing in the same manner as in Example 1 except that the obtained paste composition was used.

<Comparative Example 1>
A comparative paste composition was prepared in the same manner as in Example 1 except that the alkaline earth metal oxide and bis (dimethylphenylmethane) were not included.
Next, in the same manner as in Examples 1 to 6, the paste composition was applied, the solvent was removed by drying, and firing was performed to produce an inorganic molded body.

On the other hand, a measurement experiment was performed on the thermal degradability evaluation of ethyl cellulose corresponding to each of the examples and comparative examples. As the method, an alkaline earth metal oxide and bis (dimethylphenylmethane) are added in a weight ratio shown in Examples 1 to 6 to ethylcellulose contained in the paste composition, and this is mixed in a mortar. After the pulverization, the obtained mixed powder was subjected to thermogravimetric analysis. As the thermal decomposition temperature of ethyl cellulose measured at this time, an average value of the thermal decomposition start temperature and the thermal decomposition end temperature was calculated and shown in accordance with Examples 1 to 6 and Comparative Example.

<Experimental results and discussion>
The experimental results are shown in Table 1.

この表１から明らかなように、アルカリ土類金属酸化物、またはビス（ジメチルフェニルメタン）を含有させることで、エチルセルロースの熱分解温度が低下した。
これは、以下に示す作用によるものと考えられる。

As is apparent from Table 1, the thermal decomposition temperature of ethylcellulose was reduced by containing an alkaline earth metal oxide or bis (dimethylphenylmethane).
This is considered to be due to the following actions.

That is, in Examples 1 to 4, since the alkaline earth metal oxide supplies oxygen essential for the thermal decomposition of ethyl cellulose, the thermal decomposition is promoted. Further, in Example 5, the radical generated by radical decomposition of bis (dimethylphenylmethane) acts to cut the molecular chain of ethyl cellulose, and as a result, the thermal decomposition of ethyl cellulose is promoted.
Further, in Example 6, it can be confirmed that the thermal decomposition is further promoted by the action of the two additives of the alkaline earth metal oxide and bis (dimethylphenylmethane). For this reason, in order to acquire the favorable effect of this invention, it is estimated that it is effective to use these two additives together.

Moreover, about the evaluation of the inorganic molded object by each Example and a comparative example, when the inorganic molded object produced in Examples 1-6 was observed visually, all were colorless and transparent. Moreover, when the said inorganic molded object was observed using the microscope, the carbide | carbonized_material residue derived from binder resin, the bubble, and the pinhole were not seen.
On the other hand, when the inorganic molded body produced in Comparative Example 1 was similarly visually observed, it was brown and inferior in transparency. Moreover, when the said inorganic molded object was observed using the microscope, many carbide | carbonized_material residues derived from binder resin, a micro bubble, and a pinhole generate | occur | produced.

From this, it was found that if the paste compositions of Examples 1 to 6 were used, inorganic molded bodies having excellent transparency and airtightness could be obtained. Therefore, if the paste composition of the present invention is used for a PDP dielectric layer or a glass frit sealing part, it can be expected to realize excellent image display performance.
<Other matters>
In each of the above embodiments and examples, a configuration example of a paste composition having a high viscosity is shown as the coating composition of the present invention. You may apply to.

  The coating composition of the present invention is used for the manufacture of electrical members, for example, glass sealing of ceramic packages of semiconductor elements, glass sealing of cathode ray tubes (CRT), glass sealing of plasma display panels (PDP), and dielectric layers of PDPs. And is useful for forming a phosphor layer.

It is a figure showing the thermal decomposition rate of ethylcellulose at the time of putting bis (dimethylphenylmethane) (BDM) in a paste composition. It is a figure showing the thermal decomposition rate of ethyl cellulose at the time of putting alkaline-earth metal oxide (CaO) in a paste composition. It is a figure showing the thermal decomposition rate of ethylcellulose at the time of putting bis (dimethylphenylmethane) (BDM) and alkaline-earth metal oxide (CaO) in a paste composition. FIG. 5 is a partial perspective view showing a configuration of a PDP in a second embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 AC surface discharge type plasma display panel 20 Front panel 21 Front panel glass 22, 23 Display electrode 24 Dielectric layer 26 Back panel 28 Address electrode 31, 32, 33 Phosphor layer 38 Discharge space

Claims (8)

A coating composition for forming an inorganic molded body after firing on a substrate,
The composition for coating formed by mixing one or more selected from the group consisting of an alkaline earth metal oxide and a compound represented by the following chemical formula 1 in addition to the inorganic substance, ethyl cellulose, and the solvent that are the raw materials of the inorganic molded body. Stuff.

However, in Chemical Formula 1, R1 to R4 indicate a phenyl group or a C1 to C4 alkyl group.
R5 and R6 each represent a C1-C4 alkyl group.
Furthermore, n refers to any integer from 0 to 5.   2. The coating composition according to claim 1, wherein the alkaline earth metal oxide is made of a material having a purity of 80% or more.   The coating composition according to claim 1 or 2, wherein the inorganic substance is glass powder or a mixture of the glass powder and ceramic powder.   The coating composition according to any one of claims 1 to 3, wherein the ethyl cellulose content is set in a range of 0.05 to 0.5 weight percent of the entire coating composition. Stuff. When alkaline earth metal oxides are included,
The coating composition according to claim 1, wherein the alkaline earth metal oxide is at least one of magnesium oxide, calcium oxide, strontium oxide, and barium oxide. When alkaline earth metal oxides are included,
The content of the alkaline earth metal oxide is set in a range of 0.0025 weight percent or more and 0.25 weight percent or less of the entire coating composition. The coating composition according to 1. Wherein the compound represented by Formula 1 is included,
7. The coating composition according to claim 1, wherein the content of the compound is set in a range of 0.0025 weight percent or more and 0.25 weight percent or less of the entire coating composition. Composition. A method for producing a gas discharge device by sealing a sealed container structure provided with a dielectric layer,
A method for producing a gas discharge display device, comprising performing a dielectric layer forming step or a hermetically sealed container structure sealing step using the coating composition according to claim 1.

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