JP2000169764A - Glass paste composition, transfer film, and manufacture of plasma display panel using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass paste composition suitably employed for obtaining a film-forming material layer, which does not undergo any yellowing when formed as a dielectric layer by firing, a transfer film provided with a film- forming material layer, which does not undergo any yellowing when formed as a dielectric layer by firing, and a method for efficiently manufacturing PDP by use of the above-mentioned composition. SOLUTION: The glass paste composition comprises a glass powder and a binder resin, wherein a metal element and/or compound having a standard single electrode potential exceeding 0.8 V is contained. The transfer film includes a film-forming material layer formed by coating the glass paste composition on a support film. The manufacturing method comprises the step of forming a dielectric layer on a substrate by firing a film-forming material layer obtained from the glass paste composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a glass paste composition, a transfer film, and a method for manufacturing a plasma display panel.

[0002]

2. Description of the Related Art In recent years, a plasma display has attracted attention as a flat fluorescent display. FIG. 1 shows an AC type plasma display panel (hereinafter also referred to as “PDP”).
It is a schematic diagram which shows the cross-sectional shape of. In FIG. 1, reference numerals 1 and 2 denote glass substrates arranged opposite to each other, and reference numeral 3 denotes a partition. A cell is formed by the glass substrate 1, the glass substrate 2, and the partition 3. 4 is a transparent electrode fixed to the glass substrate 1, 5 is a bus electrode formed on the transparent electrode 4 for the purpose of lowering the resistance of the transparent electrode 4, 6 is an address electrode fixed to the glass substrate 2, 7 is The fluorescent substance held in the cell, 8 is a dielectric layer formed on the surface of the glass substrate 1 so as to cover the transparent electrode 4 and the bus electrode 5, and 9 is the surface of the glass substrate 2 so as to cover the address electrode 6. The formed dielectric layer, P, is a protective film made of, for example, magnesium oxide.

In FIG. 1 showing a cross-sectional shape of a PDP, silver is usually used as a constituent material of a bus electrode 5. Silver is
It has a low electric resistance and is suitable as an electrode material. As a method of forming the bus electrode 5 using silver as a constituent material,
A screen printing method including a step of applying a paste composition containing silver on the transparent electrode 4 by screen printing;
An exposure step of applying a photosensitive paste composition containing silver on the transparent electrode 4 and selectively irradiating the formed coating film with ultraviolet rays through a photomask, and forming the formed pattern latent image A photolithography method including a developing step for developing is known.

As a method for forming the dielectric layer 8, a paste-like glass powder-containing composition (glass paste composition) containing glass powder, a binder resin and a solvent is prepared, and this glass paste composition is screen-printed. A method is known in which a film-forming material layer is formed by applying the film-forming material to the surface of a glass substrate 1 by drying, and then the film-forming material layer is baked to remove organic substances and sinter the glass powder. ing.

Here, in order to make the dielectric layer 8 exhibit good transparency (high light transmittance), it is necessary to sufficiently defoam the film forming material layer in the firing step. Then, in order to sufficiently defoam the film forming material layer in the firing step,
Forming a film-forming material layer from a glass paste composition containing a glass powder having a low softening point, and increasing the fluidity of the film-forming material layer in the firing step by setting firing conditions at a high temperature for a long time. Is preferred.

[0006] The thickness of the film forming material layer formed on the glass substrate 1 is determined by taking into account the reduction in film thickness accompanying the removal of the organic substance in the firing step. It is necessary to be about 1.3 to 2.0 times the thickness,
For example, in order to make the thickness of the dielectric layer 8 20 to 50 μm, it is necessary to form a film forming material layer having a thickness of about 30 to 100 μm. On the other hand, when the glass paste composition is applied by a screen printing method, the thickness of a coating film formed by one application treatment is about 15 to 25 μm. Therefore, in order to make the film-forming material layer have a predetermined thickness, the glass paste composition needs to be repeatedly applied (multiple printing) a plurality of times (for example, 2 to 7 times) to the surface of the glass substrate. There is.

However, when the film forming material layer is formed by multiple printing using a screen printing method,
The dielectric layer formed by firing the film forming material layer does not have a uniform thickness (for example, the tolerance is within ± 5%). This is due to the multiple printing by the screen printing method,
This is because it is difficult to uniformly apply the glass paste composition to the surface of the glass substrate, and the larger the application area (panel size) and the greater the number of applications, the greater the degree of variation in the thickness of the dielectric layer. Will be large. Then, in the panel material (glass substrate having the dielectric layer) obtained through the coating process by the multiple printing, the dielectric characteristics vary in the plane due to the variation in the film thickness, and the dielectric characteristics vary. Causes display defects (luminance unevenness) in the PDP. Further, in the screen printing method, the mesh shape of the screen plate may be transferred to the surface of the film forming material layer, and the dielectric layer formed by firing such a film forming material layer has a smooth surface. Inferior to

As a means for solving the above-mentioned problems in the case where the film-forming material layer is formed by the screen printing method, the present inventors apply a glass paste composition on a supporting film, and dry the coating film. Forming a film forming material layer on the support film, transferring the film forming material layer formed on the support film to the surface of the glass substrate to which the electrodes are fixed, and baking the transferred film forming material layer to form the glass forming material layer. A method of manufacturing a PDP including a step of forming a dielectric layer on a surface of a substrate (hereinafter, also referred to as a “dry film method”) has been proposed (see JP-A-9-102273). According to such a manufacturing method, it is possible to form a dielectric layer having excellent film thickness uniformity and surface uniformity.

Further, the present inventors have proposed a support film, a film-forming material layer obtained from a glass paste composition, and a film-forming material layer, which can be suitably used for forming a dielectric layer of PDP. A composite film formed by laminating a cover film easily provided on the surface of a forming material layer has also been proposed (Japanese Patent Application No. 9-1016).
No. 53). The composite film (transfer film) having such a configuration is also advantageous in that it can be wound into a roll and stored.

[0010]

In the case where silver is used as a constituent material of a bus electrode, in the step of forming a dielectric layer covering the bus electrode, when a film forming material layer formed on a glass substrate is fired, Silver (A) which is a constituent material of the bus electrode
g) is oxidized to silver ions (Ag ⁺ ). The silver ions have high diffusivity (ion migration) and diffuse in the film forming material layer of the dielectric layer. The silver ions (Ag ⁺ ) diffused into the film-forming material layer are reduced by a combustion resin (a binder resin in a process of being removed) and a small amount of tin existing on the surface of the substrate to become silver (Ag), thereby forming a film. The silver (Ag) precipitates in the inside of the forming material layer or on the surface of the glass substrate (the boundary surface between the glass substrate and the film forming material layer), and the precipitated silver (Ag) aggregates and becomes colloidal. Then, the aggregated colloid becomes a yellow coloring point, and as a result, a phenomenon (hereinafter, referred to as “yellowing”) that the panel material (glass substrate having a dielectric layer) becomes yellowish occurs. Here, the degree of the yellowing phenomenon in the panel material, that is, the generation amount of the aggregated silver colloid in the dielectric layer increases as the fluidity (defoaming property) of the film forming material layer in the firing step increases.

The present invention has been made based on the above circumstances. A first object of the present invention is a glass paste composition containing a glass powder and a binder resin, and when used for forming a dielectric layer constituting a PDP, the glass paste composition comprises Provided is a glass paste composition that does not generate aggregated colloid of silver (Ag) in a dielectric layer formed by baking silver ions (Ag ⁺ ) even if silver ions (Ag ⁺ ) are diffused in the obtained film forming material layer. Is to do. A second object of the present invention is to provide a dielectric layer which covers a bus electrode made of silver when used for forming a dielectric layer constituting a PDP without yellowing and having a high light transmittance. An object of the present invention is to provide a glass paste composition capable of forming a glass sintered body.

A third object of the present invention is to provide a glass layer having excellent colorless and transparent properties as a dielectric layer covering a bus electrode made of silver when used for forming a dielectric layer constituting a PDP. An object of the present invention is to provide a transfer film capable of efficiently forming a body.

A fourth object of the present invention is to provide a method of manufacturing a PDP capable of efficiently forming a colorless and transparent glass sintered body as a dielectric layer for covering a bus electrode made of silver. Is to do.

[0014]

The glass paste composition of the present invention is characterized by containing a glass powder, a binder resin and a simple substance and / or a compound of a metal having a standard unipolar potential exceeding 0.8 V. .

[0015] The transfer film of the present invention is characterized in that a film-forming material layer obtained from the glass paste composition is formed on a support film.

The method of manufacturing a PDP according to the present invention is characterized by including a step of forming a dielectric layer on a substrate by firing a film-forming material layer obtained from the glass paste composition.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the glass paste composition of the present invention will be described in detail. The composition of the present invention contains, as essential components, at least one of a glass powder, a binder resin, a simple substance of a metal having a standard unipolar potential of more than 0.8 V, and a compound containing the metal.

<Glass powder> Constituting the composition of the present invention
The glass powder is not particularly limited,
Those having a softening point in the range of 400 to 600 ° C are preferred.
Good. When the softening point of the glass powder is less than 400 ° C
In the firing step of the film forming material layer by the composition,
And organic substances such as binder resin are not completely decomposed and removed
Since the glass powder melts at the stage,
Some of the organic material remains in the dielectric layer,
The layer is colored and its transparency (high transmittance) decreases
Tend. On the other hand, the softening point of the glass powder exceeds 600 ° C.
If necessary, it is necessary to bake at a temperature higher than 600 ° C
Therefore, distortion or the like is likely to occur in the glass substrate. Suitable
Specific examples of the glass powder include lead oxide and borate oxide.
Element, silicon oxide (PbO-B_TwoO_Three-SiO_TwoSystem)
Compound, zinc oxide, boron oxide, silicon oxide (ZnO
-B_TwoO_Three-SiO_TwoMixture), lead oxide, oxidation
Boron, silicon oxide, aluminum oxide (PbO-B_Two
O_Three-SiO_Two-Al_TwoO_ThreeMixture), oxidation
Lead, zinc oxide, boron oxide, silicon oxide (PbO-Zn
OB _TwoO_Three-SiO_TwoSystem).
Can be.

<Binder Resin> The binder resin constituting the composition of the present invention is preferably an acrylic resin. Since the acrylic resin is contained as the binder resin, the formed film forming material layer has an excellent (heating) property with respect to the substrate.
Adhesiveness is exhibited. Therefore, when a transfer film is produced by applying the composition of the present invention onto a support film, the resulting transfer film has excellent transferability (heat adhesion to a substrate) of the film-forming material layer. . As the acrylic resin constituting the composition of the present invention, glass powder having an appropriate tackiness can be bound, and is completely oxidized and removed by the baking treatment (400 ° C. to 600 ° C.) of the film forming material. (Co) polymers. Such acrylic resin includes a homopolymer of a (meth) acrylate compound represented by the following general formula (i), a copolymer of two or more (meth) acrylate compounds represented by the following general formula (i), And a copolymer of a (meth) acrylate compound represented by the following general formula (i) and a copolymerizable monomer.

[0020]

Embedded image

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group. ]

Specific examples of the (meth) acrylate compound represented by the general formula (i) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl ( (Meth) acrylate, isobutyl (meth)
Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) Acrylate, ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Alkyl (meth) acrylates such as isostearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Rokishipuropiru (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3
Hydroxyalkyl (meth) acrylates such as -hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; phenoxyethyl (meth)
Phenoxyalkyl (meth) acrylates such as acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2
-Alkoxyalkyl (meth) acrylates such as propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate and 2-methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxy Polyalkylenes such as polypropylene glycol (meth) acrylate Recol (meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl ( Examples thereof include cycloalkyl (meth) acrylates such as (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate; benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. Among them, in the above general formula (i), the group represented by R ¹ is preferably an alkyl group or an oxyalkylene group-containing group, and as a particularly preferred (meth) acrylate compound, butyl (meth) acrylate , Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate. The other copolymerizable monomer is not particularly limited as long as it is a compound copolymerizable with the above (meth) acrylate compound. For example, (meth) acrylic acid, vinyl benzoic acid, maleic acid, vinyl phthalic acid, etc. Unsaturated carboxylic acids; and vinyl group-containing radically polymerizable compounds such as vinylbenzyl methyl ether, vinyl glycidyl ether, styrene, α-methylstyrene, butadiene, and isoprene. In the acrylic resin constituting the composition of the present invention, the copolymer component derived from the (meth) acrylate compound represented by the general formula (i) is usually 70% by weight or more, preferably 90% by weight or more, more preferably 100% by weight. Here, specific examples of preferred acrylic resins include polymethyl methacrylate,
Examples thereof include polybutyl methacrylate and methyl methacrylate-butyl methacrylate copolymer. The molecular weight of the acrylic resin constituting the composition of the present invention is preferably from 4,000 to 300,000 as a weight average molecular weight in terms of polystyrene by GPC (hereinafter, also simply referred to as “weight average molecular weight”). Preferably it is set to 10,000 to 200,000. The content of the binder resin in the composition of the present invention is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the glass powder. If the ratio of the binder resin is too small,
Glass powder cannot be bound and held reliably, while
If this ratio is excessively large, a long time is required for the firing step, and the formed glass sintered body (dielectric layer) may not have sufficient strength and film thickness.

<Specific Inorganic Oxidant> The composition of the present invention contains a simple substance and / or compound of a metal having a standard unipolar potential exceeding 0.8 V (hereinafter, referred to as “specific inorganic oxidant”). It has features. In this specification, the "standard monopolar potential" is a standard monopolar potential based on hydrogen, that is, the standard electromotive force of a metal electrode when a standard hydrogen electrode is used as a standard electrode is represented by a hydrogen electrode scale. Refers to what is shown. Here, the silver of the standard single electrode potential (Ag ⁺ + e
^- = Ag) is 0.8 V, the standard unipolar potential is 0.8 V
Metals have a lower ionization tendency than silver and act as oxidizing agents for silver ions (Ag ⁺ ). Therefore,
According to the composition of the present invention containing the specific inorganic oxidizing agent containing such a metal, a reduction reaction of silver ions in the film forming material layer in the firing step of the film forming material layer formed thereby. (Ag ⁺ + e ⁻ → Ag) can be suppressed, and in the finally obtained dielectric layer, yellowing due to the aggregated colloid of silver does not occur.
Moreover, the function of the specific inorganic oxidizing agent (the function of suppressing the reduction reaction of silver ions) can be sufficiently exerted even under suitable firing temperature conditions described later.

Specific inorganic oxidizing agents constituting the composition of the present invention include simple substances such as cerium, manganese, gold and platinum, oxides, hydroxides and halides. Among these, cerium oxides, hydroxides, halides represented by cerium (IV) oxide and cerium (IV) fluoride, manganese oxides represented by manganese oxide (IV), hydroxides, Halides are preferred,
Particularly preferred are cerium oxides, hydroxides and halides represented by cerium (IV) oxide and the like.

The content ratio of the specific inorganic oxidizing agent in the composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 3 parts by weight based on 100 parts by weight of the glass powder. It is said. If the content ratio of the specific inorganic oxidizing agent is too small, yellowing of the dielectric layer (panel material) covering the bus electrode cannot be sufficiently prevented. On the other hand, when this content ratio is excessive, the panel material may be colored by the color of the specific inorganic oxidizing agent itself.

As a method of preparing a glass paste composition by containing a specific inorganic oxidizing agent, a method of kneading a glass powder, a binder resin, a specific inorganic oxidizing agent, and a solvent to form a paste, a component of the glass powder A specific inorganic oxidizing agent is introduced therein, and the obtained glass raw material is vitrified by an ordinary method, and then crushed to obtain a glass powder containing the specific inorganic oxidizing agent, and bound to the glass powder. A method of kneading a resin and a solvent to form a paste can be used.

<Solvent> The composition of the present invention usually contains a solvent. As the above-mentioned solvent, an affinity with glass powder, good solubility of a binder resin, can impart a suitable viscosity to the obtained composition, and can be easily evaporated and removed by drying. Is preferred. Specific examples of such a solvent include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, cyclohexanol and diacetone alcohol; Ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; acetic acid-n-
Alkyl esters of saturated aliphatic monocarboxylic acids such as butyl and amyl acetate; lactates such as ethyl lactate and n-butyl lactate; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and ethyl-3-ethoxypro Examples include ether-based esters such as pionate, and these can be used alone or in combination of two or more. From the viewpoint of maintaining the viscosity of the composition in a suitable range, the content of the solvent in the composition of the present invention is preferably 4 parts by weight based on 100 parts by weight of the glass powder.
It is preferably 0 parts by weight or less, more preferably 5 to 30 parts by weight.

In the composition of the present invention, in addition to the above essential components, various additives such as a dispersant, a tackifier, a surface tension regulator, a stabilizer and an antifoaming agent are contained as optional components. You may. As an example of a glass paste composition, a preferred example of a composition for forming a dielectric layer is as follows. As a glass powder, 50 to 80% by weight of lead oxide and 5 to 2% of boron oxide
100 parts by weight of a mixture of 0% by weight and 10 to 30% by weight of silicon oxide, 10 to 30 parts by weight of polybutyl methacrylate (acrylic resin), and 0.5 to 3 of a specific inorganic oxidizing agent
A composition containing, as essential components, 10 parts by weight of propylene glycol monomethyl ether (solvent) and 10 to 50 parts by weight of propylene glycol monomethyl ether (solvent) can be given.

The composition of the present invention is prepared by kneading the above-mentioned glass powder, binder resin, specific inorganic oxidizing agent, solvent and optional components using a kneader such as a roll kneader, a mixer or a homomixer. be able to. The composition of the present invention prepared as described above is a paste-like composition having fluidity suitable for application, and has a viscosity of usually 1,000 to 30,000 cp, preferably 3,0 cp. 000 to 10,000 cp.

The composition of the present invention can be particularly preferably used for producing a transfer film (transfer film of the present invention) described in detail below. Further, the composition of the present invention is obtained by directly applying the composition to the surface of a substrate by a conventionally known method for forming a film-forming material layer, that is, a screen printing method, and drying the coating film. It can also be suitably used for a method of forming a layer.

<Transfer Film> The transfer film of the present invention is a composite film suitably used in the step of forming a dielectric layer constituting a PDP, and the composition of the present invention is applied on a support film, It is provided with a film forming material layer formed by drying the film. That is, the transfer film of the present invention is formed by forming a film-forming material layer containing glass powder, a binder resin and a specific inorganic oxidizing agent on a support film.

(1) Structure of transfer film: FIG.
FIG. 1 is a schematic cross-sectional view showing a transfer film of the present invention wound in a roll shape, and FIG. 1 (b) is a cross-sectional view (partial detailed view of (X)) showing a layer configuration of the transfer film. . The transfer film shown in FIG. 2 is a composite film used for forming a dielectric layer constituting a PDP as an example of the transfer film of the present invention.
1, a film-forming material layer F2 formed releasably on the surface of the support film F1, and a cover film F3 easily provided on the surface of the film-forming material layer F2. The cover film F3 is formed of the film forming material layer F
Depending on the nature of 2, the transfer film may not be used for the purpose of reducing the weight of the wound roll.

Support film F1 constituting transfer film
Is preferably a resin film having heat resistance and solvent resistance and having flexibility. Since the support film F1 has flexibility, a paste-like composition (the composition of the present invention) can be applied using a roll coater, a blade coater, or the like, and thereby, a film having a uniform thickness can be formed. The material layer can be formed, and the formed film-forming material layer can be stored and supplied in a state wound in a roll. Examples of the resin forming the support film F1 include polyethylene terephthalate, polyester, polyethylene, polypropylene,
Examples thereof include fluorine-containing resins such as polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.
The thickness of the support film F1 is, for example, 20 to 100.
μm.

Film forming material layer F2 constituting transfer film
Is a glass sintered body (dielectric layer)
And contains glass powder, a binder resin and a specific inorganic oxidizing agent as essential components. The thickness of the film forming material layer F2 varies depending on the content ratio of the glass powder, the type and size of the panel, and is, for example, 5 to 200.
μm, and preferably 10 to 100 μm. If the thickness is less than 5 μm, the thickness of the finally formed dielectric layer becomes too small, and the desired dielectric characteristics may not be secured. Usually, if the thickness is 10 to 100 μm, the thickness of the dielectric layer required for a large panel can be sufficiently ensured.

Cover film F constituting transfer film
Reference numeral 3 denotes a film for protecting the surface of the film forming material layer F2 (the contact surface with the glass substrate). This cover film F3 is also preferably a resin film having flexibility. As the resin forming the cover film F3,
The resins exemplified as those forming the support film F1 can be mentioned. The thickness of the cover film F3 is, for example, 20 to 100 μm.

(2) Production method of transfer film: The transfer film of the present invention comprises a film-forming material layer (F2) formed on a support film (F1), and a cover film (F2) formed on the film-forming material layer (F2). It can be manufactured by providing (press bonding) F3).

As a method for forming the film-forming material layer, a composition of the present invention containing a glass powder, a binder resin, a specific inorganic oxidizing agent and a solvent is applied on a support film, and the coated film is dried to obtain the solvent. And a method for removing a part or all of the above.

As a method of applying the composition of the present invention on a support film, from the viewpoint of efficiently forming a coating film having a large film thickness (for example, 20 μm or more) and excellent film thickness uniformity, Coating method using a roll coater,
Preferred examples include a coating method using a blade coater such as a doctor blade, a coating method using a curtain coater, a coating method using a wire coater, and a coating method using a fountain coater. In particular, in a coating method using a fountain coater, since a predetermined amount of a coating solution is directly coated on a supporting film without recirculation, a coating film having excellent surface smoothness and uniform film thickness can be obtained. The surface of the support film to which the composition of the present invention is applied is preferably subjected to a release treatment. Thereby, after transferring the film-forming material layer, the support film can be easily peeled from the film-forming material layer. The coating film of the composition of the present invention formed on the supporting film is dried to remove a part or all of the solvent, and becomes a film forming material layer constituting the transfer film. The drying condition of the coating film of the composition of the present invention is, for example, about 40 to 150 ° C. for about 0.1 to 30 minutes. The residual ratio of the solvent after drying (the content ratio of the solvent in the film-forming material layer) is usually 10% by weight or less, and from the viewpoint of exhibiting the adhesion to the substrate and the appropriate shape-retaining property to the film-forming material layer, 1%. It is preferably about 5% by weight.

It is preferable that the surface of the cover film (usually thermocompression-bonded) provided on the film-forming material layer formed as described above is also subjected to a release treatment.
Thus, the cover film can be easily peeled from the film forming material layer before transferring the film forming material layer.

(3) Transfer of the film-forming material layer (method of using the transfer film): The film-forming material layer on the support film is collectively transferred to the surface of the substrate. According to the transfer film of the present invention, the film-forming material layer can be reliably formed on the glass substrate by such a simple operation, and therefore, in the process of forming the dielectric layer such as the dielectric layer constituting the PDP. The process can be improved (higher efficiency) and stable dielectric characteristics can be exhibited in the dielectric layer.

<Method of Manufacturing PDP (Formation of Dielectric Layer)>
In the production method of the present invention, a dielectric layer is formed on the surface of the substrate by transferring the film forming material layer constituting the transfer film of the present invention to the surface of the substrate, and firing the transferred film forming material layer. The step of performing

An example of the step of transferring the film forming material layer using the transfer film having the structure shown in FIG. 2 is as follows. The transfer film wound in a roll is cut into a size corresponding to the area of the substrate. The film-forming material layer (F) in the cut transfer film
After peeling the cover film (F3) from the surface of 2),
The transfer film is overlaid so that the surface of the film-forming material layer (F2) is in contact with the surface of the substrate. A heating roller is moved on the transfer film superimposed on the substrate to perform thermocompression bonding. The film-forming material layer (F) fixed to the substrate by thermocompression bonding
The support film (F1) is peeled off from 2). By the operation as described above, the film forming material layer (F2) on the support film (F1) is transferred onto the substrate. Here, as the transfer condition, for example, the surface temperature of the heating roller is 60
~ 120 ° C, roll pressure by heating roller is 1 ~ 5kg /
cm ² , the moving speed of the heating roller is 0.2 to 10.0 m /
Minutes. Such an operation (transfer step) can be performed by a laminator device. The substrate may be preheated, and the preheating temperature is, for example, 40 to 100 ° C.
It can be.

The film forming material layer (F2) transferred and formed on the surface of the substrate is baked to become an inorganic sintered body (dielectric layer).
Here, as a firing method, a method in which the substrate on which the film-forming material layer (F2) is transferred and formed is placed in a high-temperature atmosphere can be mentioned. Thereby, the organic substance (for example, binder resin, residual solvent,
Various additives) are decomposed and removed, and the glass powder is melted and sintered. Here, the firing temperature varies depending on the melting temperature of the substrate, the constituents in the film-forming material layer, and the like, but is, for example, 300 to 800 ° C, and more preferably 400 to 600 ° C.

[0044]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In the following, “parts” indicates “parts by weight”. Preparation of <Example 1> (1) Glass paste composition: as glass powder, lead oxide 70 wt%, boron oxide 10 _{wt%, PbO-B 2 O 3} -Si having a composition of silicon oxide 20 wt%
100 parts of an O ₂ -based mixture (softening point 500 ° C.), polybutyl methacrylate (weight average molecular weight: 5) as a binder resin
000), 20 parts of cerium (IV) oxide as a specific inorganic oxidizing agent, and 20 parts of propylene glycol monomethyl ether as a solvent by kneading using a dispersing machine to obtain a composition of the present invention having a viscosity of 4,000 cp. Was prepared.

(2) Production of transfer film: A support film (400 mm wide, 30 m long, 38 μm thick) made of polyethylene terephthalate (PET) which has been subjected to a release treatment from the composition of the present invention prepared in the above (1). ) Was applied using a blade coater.
The solvent was removed by drying at 5 ° C. for 5 minutes, whereby a 50 μm thick film forming material layer was formed on the support film. Next, a cover film (width 400 mm, length 30 m, thickness 25 μm) made of PET, which has been subjected to a release treatment in advance, is adhered on the film forming material layer to thereby form the present invention having the configuration shown in FIG. Was manufactured.

(3) Transfer of the film-forming material layer: After the cover film was peeled off from the transfer film obtained in the above (2), the surface of the glass substrate for a 20-inch panel (the bus electrode using silver as a constituent material was The transfer film (laminated body of the support film and the film-forming material layer) is overlapped so that the surface of the film-forming material layer abuts on the patterned substrate surface), and the transfer film is heated by a heating roll. Thermocompression bonded. Here, as the pressure bonding conditions, the surface temperature of the heating roll was 110 ° C., the roll pressure was 3 kg / cm, and the moving speed of the heating roll was 1 m / min. After the completion of the thermocompression bonding, the support film was peeled off from the film forming material layer fixed (heat-bonded) to the surface of the glass substrate, and the transfer of the film forming material layer was completed.

(4) Firing the film-forming material layer (forming a dielectric layer): The glass substrate on which the film-forming material layer was transferred and formed by the above (3) was placed in a firing furnace, and the temperature in the furnace was set to room temperature. To 590 ° C at a rate of 10 ° C / min.
By baking for 30 minutes in the temperature atmosphere, a dielectric layer made of a glass sintered body was formed on the surface of the glass substrate. In the panel material thus obtained (glass substrate having a dielectric layer), yellowing due to the aggregated colloid of silver was not observed. The light transmittance (measurement wavelength: 550 nm) of the formed dielectric layer was measured to be 85%, and this panel material was excellent in colorless transparency.

Example 2 One part of cerium (IV) oxide was added as a specific inorganic oxidizing agent to 100 parts of a mixture having a composition of 70% by weight of lead oxide, 10% by weight of boron oxide and 20% by weight of silicon oxide. Thus, a glass raw material was obtained. The obtained glass raw material was vitrified by a conventional method, and then pulverized to obtain a glass powder containing a specific inorganic oxidizing agent. 100 parts of the glass powder containing the specific inorganic oxidizing agent thus obtained, 20 parts of polybutyl methacrylate (weight average molecular weight: 50,000) as a binder resin,
Propylene glycol monomethyl ether 2 as solvent
By kneading 0 parts using a disperser, the viscosity is 4,
A composition of the invention was prepared at 000 cp. Then
A transfer film of the present invention was produced in the same manner as in Example 1 (2) except that the composition was used. Example 1 except that the transfer film thus obtained was used.
In the same manner as in (3), the film-forming material layer is transferred to the surface of the glass substrate for a 20-inch panel (the surface of the substrate on which the bus electrode made of silver is patterned).
By sintering in the same manner as in Example 1 (4) except that the glass substrate on which the film-forming material layer was transferred and formed in this manner, a dielectric made of a glass sintered body was formed on the surface of the glass substrate. A layer was formed. In the panel material thus obtained (glass substrate having a dielectric layer), yellowing due to the aggregated colloid of silver was not observed. Further, the light transmittance of the formed dielectric layer (measurement wavelength 550n)
m) was 85%, and the panel material was excellent in colorless transparency.

Comparative Example 1 A comparative composition having a viscosity of 4,000 cp was prepared in the same manner as in Example 1 (1) except that no specific inorganic oxidizing agent was used. A transfer film for comparison was produced in the same manner as in Example 1 (2) except that was used. Thereafter, Example 1 (3) was used except that the obtained transfer film for comparison was used.
In the same manner as described above, the film-forming material layer is transferred to the surface of the glass substrate for a 20-inch panel (the surface of the substrate on which the bus electrode made of silver is patterned). A dielectric layer made of a glass sintered body was formed on the surface of the glass substrate by performing a sintering treatment in the same manner as in Example 1 (4) except that a glass substrate onto which was formed by transfer was used. The panel material thus obtained (glass substrate having a dielectric layer) was found to have yellowing due to the aggregated colloid of silver, impairing the quality of the panel material.

[0050]

By applying the composition of the present invention to the formation of the dielectric layer constituting the PDP, even if silver ions (Ag ⁺ ) are diffused in the film forming material layer formed by the composition. No aggregated silver (Ag) colloid is generated in the dielectric layer formed by firing this. Therefore, according to the composition of the present invention, a glass sintered body having no yellowing and high light transmittance can be formed as a dielectric layer covering a bus electrode made of silver.

According to the transfer film of the present invention, when used for the formation of the dielectric layer constituting the PDP, the dielectric layer for covering the bus electrode made of silver has excellent colorless and transparent glass sintering properties. The body can be formed efficiently.

According to the production method of the present invention, a colorless and transparent glass sintered body can be efficiently formed as a dielectric layer for covering a bus electrode made of silver.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a cross-sectional shape of an AC type plasma display panel.

FIG. 2A is a schematic cross-sectional view illustrating a transfer film of the present invention, and FIG. 2B is a cross-sectional view illustrating a layer configuration of the transfer film.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Glass substrate 3 Partition 4 Transparent electrode 5 Bus electrode 6 Address electrode 7 Fluorescent substance 8 Dielectric layer 9 Dielectric layer P Protective layer F1 Support film F2 Film forming material layer F3 Cover film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) H01J 11/02 H01J 11/02 B (72) Inventor Shiro Takahashi 2-11-24 Tsukiji, Chuo-ku, Tokyo Within JSR Co., Ltd. (72) Kenji Okamoto 2-11-24 Tsukiji, Chuo-ku, Tokyo F-term within JSR Co., Ltd. (reference) 2H025 AA00 AB11 AB17 4J038 AA011 EA011 HA062 HA066 HA122 HA126 HA212 HA216 HA481 HA486 KA20 PC08 5C027 AA05 5C040 FA01 GD07 GD09 GF18 GF19 JA19 KA03 KA09 KA14 KB03 KB04 KB29 MA10

Claims (3)

[Claims] 1. A glass paste composition comprising a glass powder, a binder resin, and a simple substance and / or compound of a metal having a standard unipolar potential exceeding 0.8 V. 2. A transfer film, wherein a film-forming material layer obtained from the glass paste composition according to claim 1 is formed on a support film. 3. A method for manufacturing a plasma display panel, comprising a step of forming a dielectric layer on a substrate by firing a film forming material layer obtained from the glass paste composition according to claim 1. .