JPH11236246A - Pattern formation method - Google Patents

Abstract

(57) [Problem] To provide a pattern forming method for easily forming a base layer of a plasma display panel, a dielectric layer and an insulating layer of a front plate and a back plate with high layer thickness accuracy and a good surface condition. I do. SOLUTION: Using a transfer sheet provided with a transfer layer containing at least an inorganic component containing a glass frit and an organic component that can be removed by firing, the transfer layer is transferred onto a substrate, and the transfer layer is transferred to the transfer layer at 100 to 300 ° C. After the drying process is performed in the temperature range described above, the pattern is formed by baking to remove the organic components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming method capable of easily forming a dielectric layer, a base layer, an insulating layer and the like of a plasma display panel.

[0002]

2. Description of the Related Art In recent years, plasma display panels (P
DP), the formation of the dielectric layer, underlayer, insulating layer, etc.
While maintaining a high level of layer thickness accuracy and surface condition,
It is required that it can be implemented at low manufacturing cost.

Hitherto, formation of a dielectric layer or the like in a PDP has been performed by a printing method of forming a film by a printing method such as screen printing or offset printing using a paste having desired characteristics, and then drying and firing. Was.

[0004] However, the above-mentioned printing method is expected to simplify the process and reduce the manufacturing cost. However, the screen printing method has a limitation in printing accuracy due to the elongation of the mesh material constituting the screen printing plate. There is a problem that meshes are formed in the formed pattern or bleeding of the pattern occurs, and the surface condition of the pattern is poor. Further, in the offset printing method, as the number of printings increases, the pattern forming paste is not completely transferred to the substrate but remains on the blanket, and the layer thickness and the accuracy of the pattern are reduced. Therefore, it is necessary to replace the blanket at any time to prevent the blanket of the paste from remaining and maintain the accuracy of forming the dielectric layer. Therefore, there is a problem that the operation is extremely complicated.

[0005]

In order to solve such a problem, a transfer layer is provided on a base film by using a coating composition for forming a dielectric layer or the like so as to be peelable. There is a method in which a transfer layer is thermally transferred to an object to be transferred using a sheet and then baked to form a dielectric layer or the like.

However, since the transfer layer thermally transferred to the transfer object has a larger amount of organic binder components such as resin and plasticizer for imparting transferability than the film formed by the above-described printing method, dust is generated. It is easy to adhere, and once dust adheres, it is difficult to remove it by air blow or the like, which has hindered improvement in manufacturing yield. Furthermore, since the transfer layer thermally transferred to the transfer target has a large amount of organic binder components, there is a problem that abrupt removal of organic components occurs during the baking treatment, and cracks are easily generated on the baking surface. In particular, in the case of a shortened profile in which the temperature rise of the firing temperature is fast, cracking on the fired surface has been a major obstacle.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and provides a surface condition with a high layer thickness accuracy, such as a base layer of a plasma display panel, a dielectric layer and an insulating layer of a front plate and a back plate. It is an object of the present invention to provide a pattern forming method for easily forming a pattern.

[0008]

In order to achieve the above object, the present invention provides a substrate using a transfer sheet having a transfer layer containing at least an inorganic component containing a glass frit and an organic component removable by firing. Transferring the transfer layer on top,
The transfer layer was dried at a temperature in the range of 100 to 300 ° C., and then baked to remove organic components.

In the present invention as described above, the drying treatment after the transfer removes the organic components contained in the transfer layer to some extent, lowers the tackiness of the transfer layer, and enables rapid removal of the organic components in the firing treatment. Is prevented.

[0010]

Embodiments of the present invention will be described below with reference to the drawings.

The pattern forming method of the present invention will be described with reference to the example of forming a dielectric layer of a plasma display panel (PDP).

First, before explaining the formation of the dielectric layer, A
The C-type PDP will be described.

FIG. 1 is a schematic structural view showing an AC type PDP, in which a front plate and a rear plate are separated.
In FIG. 1, a PDP 1 has a front plate 11 and a rear plate 21 arranged in parallel and opposed to each other.
A barrier 26 is formed on the front side of 1 so as to be erected,
The front plate 11 and the rear plate 21 are held at regular intervals by the barrier 26. The front plate 11 includes a front glass substrate 12
On the back side of the front glass substrate 12, a composite electrode composed of a sustain electrode 13 which is a transparent electrode and a bus electrode 14 which is a metal electrode is formed in parallel with each other, and a dielectric layer 15 is formed so as to cover the composite electrode. The MgO layer 16 is further formed thereon. The back plate 21 has a back glass substrate 22. On the front side of the back glass substrate 22, an address electrode 24 is located between barriers 26 so as to be orthogonal to the composite electrode via a base layer 23. Are formed in parallel with each other, a dielectric layer 25 is formed so as to cover them, and a phosphor layer 27 is provided so as to cover the wall surface of the barrier 26 and the bottom surface of the cell. This AC type PD
In P, by applying a predetermined voltage from an AC power supply between the composite electrodes on the front glass substrate 12 to form an electric field,
Discharge is performed in each cell as a display element defined by the front glass substrate 12, the rear glass substrate 22, and the barrier 26. Then, the phosphor layer 27 is caused to emit light by the ultraviolet light generated by the discharge, and the light transmitted through the front glass substrate 12 is visually recognized by an observer.

Next, formation of the dielectric layer 25 on the back plate 21 of the above-described PDP by the pattern forming method of the present invention will be described.

FIG. 2 is a process chart for explaining the formation of a dielectric layer using the transfer sheet according to the present invention.

In FIG. 2, first, a back glass substrate 22 having an address electrode pattern 24 provided on an underlayer 23 is provided.
The transfer layer 33 side of the transfer sheet 31 is pressure-bonded to
(A)) Then, the transfer film 33 is transferred by peeling the base film 32 (FIG. 2B). In this transfer process,
When the transfer of the transfer layer 33 requires heating, the back glass substrate 22 may be heated, or may be heated by a pressure roll or the like.
The transfer layer 33 contains at least an inorganic component including a glass frit and an organic component that can be removed by firing.

Next, 10
Drying is performed at a temperature in the range of 0 to 300 ° C., preferably 150 to 250 ° C. to obtain the transfer layer 33 ′ (FIG. 2).
(C)). This drying process removes organic components contained in the transfer layer 33 to some extent, and reduces the transfer layer 3 having reduced tackiness.
3 ′, a hot air type or infrared type multi-stage oven, a batch type firing furnace, a continuous firing furnace,
It can be performed using a batch type drying furnace, a continuous drying furnace, or the like. If the temperature of the drying treatment is lower than 100 ° C., the removal of the organic components contained in the transfer layer 33 becomes insufficient even if the treatment time is lengthened. The effect is not obtained, energy is wasted, and glass frit is fused before the organic component is completely decomposed and volatilized and removed by baking in a later step, so that voids are easily generated, which is not preferable. The processing time can be appropriately set in consideration of the thickness of the transfer layer 33, the type and content of the inorganic and organic components used, within the range of the processing temperature described above. It is set within a range of about 5 to 60 minutes in consideration of efficiency.

By performing such a drying treatment, a transfer layer 33 'having reduced adhesiveness is obtained, and in the subsequent steps, dust is less likely to adhere to the transfer layer 33'.
Further, dust adhering to the transfer layer 33 'can be easily removed by air blow or the like, so that the production yield is high.

Next, baking is performed to remove organic components of the transfer layer 33 ', thereby forming the dielectric layer 25 (FIG. 2D). In this baking stage, the content of the organic component in the transfer layer 33 'is reduced in advance by the above-described drying treatment, so that abrupt removal of the organic component in the baking is prevented. Therefore, the obtained dielectric layer 25 has an excellent surface state free from defects such as cracks.

Next, the transfer sheet used in the pattern forming method of the present invention will be described.

FIG. 3 is a schematic sectional view showing an example of a transfer sheet that can be used in the present invention. 3, the transfer sheet 31 includes a base film 32 and a transfer layer 33. The transfer layer 33 is provided releasably from the base film 32 and contains at least an inorganic component including a glass frit and an organic component that can be removed by firing.

FIG. 4 is a schematic sectional view showing another example of a transfer sheet usable in the present invention. 4, the transfer sheet 41 includes a base film 42, a transfer layer 43 provided releasably on the base film 42, and a protective film 44 provided releasably on the transfer layer 43. . The transfer layer 43 contains at least an inorganic component including a glass frit and an organic component that can be removed by firing.

The transfer sheets 31 and 41 may be in the form of a sheet or a long sheet. In the case of the long sheet, the transfer sheets 31 and 41 may be in the form of a roll wound around a core. The core used is AB to prevent the generation of dust and paper dust.
A core formed of S resin, vinyl chloride resin, bakelite, or the like, a resin-impregnated paper tube, or the like is preferable.

Next, the structure of the transfer sheets 31, 41 will be described. Base film 32 constituting base film transfer sheet 31, 41,
Reference numeral 42 is a material that is stable with respect to the ink composition when the transfer layers 33 and 43 are formed, has flexibility, and does not cause significant deformation by tension or pressure.

As a material to be used, first, a resin film can be used. Specific examples of the resin film include a polyethylene film, an ethylene-vinyl acetate copolymer film, an ethylene-vinyl alcohol copolymer film, a polypropylene film, a polystyrene film, a polymethacrylate film, a polyvinyl chloride film, a polyvinyl alcohol film, and a polyvinyl film. Butyral film, nylon film, polyetherketone film, polyphenylene sulfide film, polysulfone film, polyethersulfone film, polytetrafluoroethylene-perfluoroalkylvinyl ether film, polyvinyl fluoride film, tetrafluoroethylene-ethylene film, tetrafluoroethylene -Hexafluoropropylene film, polychlorotrifluoroethylene Film, polyvinylidene fluoride film, polyethylene terephthalate film, 1,4-polycyclohexylene dimethylene terephthalate film, polyethylene naphthalate film, polyester film, cellulose triacetate film, polycarbonate film, polyurethane film, polyimide film, polyetherimide Films, films in which fillers are blended with these resin materials, and films using these resin materials
Axial stretching or biaxial stretching, a biaxially stretched film using these resin materials to increase the stretching ratio in the width direction from the flow direction, and using these resin materials to increase the stretching ratio in the flow direction from the width direction Biaxially stretched films, composites formed by laminating the same or different films of these films, and composites formed by co-extruding the same or different resins selected from the raw resin used for these films Films and the like can be mentioned. In addition, those obtained by treating the above resin film,
For example, silicon-treated polyethylene terephthalate, corona-treated polyethylene terephthalate, silicon-treated polypropylene, corona-treated polypropylene, or the like may be used.

Further, as the base films 32 and 42, a metal foil or a metal steel strip can be used. Specific examples of such a metal foil or metal steel strip include copper foil, copper steel strip, aluminum foil, aluminum steel strip, SUS430, SUS30.
1, SUS304, SUS420J2 and SUS63
And stainless steel strips such as No. 1 and beryllium steel strips. Further, the above-mentioned metal foil or metal steel strip bonded to the above-mentioned resin film may be used.

The thickness of the base films 32 and 42 is 4 to 400 μm, preferably 10 to 150 μm.
Can be set in the range. Transfer Layers The transfer layers 33 and 43 are formed by applying an ink composition containing at least an inorganic component including a glass frit and an organic component that can be removed by baking onto the base films 32 and 42 by direct gravure coating, gravure reverse coating, and reverse roll. It can be formed by coating and drying by a known coating method such as a coating method, a slide die coating method, a slit die coating method, a comma coating method, a slit reverse coating method and the like. (1) Inorganic component As the above glass frit, for example, the softening temperature is 3
50 to 650 ° C., and the coefficient of thermal expansion α ₃₀₀ is 60 × 10
^A glass frit having a temperature of ^{−7 to} 100 × 10 ⁻⁷ / ° C. can be used. Glass frit softening temperature 650 ℃
If the temperature exceeds the above, it is necessary to increase the firing temperature. For example, if the heat resistance of the pattern formation target is low, thermal deformation occurs in the firing step, which is not preferable. On the other hand, if the softening temperature of the glass frit is lower than 350 ° C., the glass frit is fused before the organic components are completely decomposed, volatilized and removed by baking, which is not preferable because voids are easily formed. Furthermore, the coefficient of thermal expansion α ₃₀₀ of the glass frit is 60 × 10
^{If it is} less than ^-7 / ° C or more than 100 × ^10-7 / ° C, the difference from the coefficient of thermal expansion of the pattern-formed body may become too large, causing distortion and the like, which is not preferable. The average particle size of such a glass frit is 0.1 to
A range of 10 μm is preferred. As such a glass frit, for example, a glass frit containing Bi ₂ O ₃ , ZnO or PbO as a main component can be used.

The transfer layers 33 and 43 are made of inorganic powder such as aluminum oxide, boron oxide, silica, titanium oxide,
Inorganic powders such as magnesium oxide, calcium oxide, strontium oxide, barium oxide, and calcium carbonate can be contained in a range of 30 parts by weight or less based on 100 parts by weight of the glass frit. Such an inorganic powder preferably has an average particle size in the range of 0.1 to 10 μm, and serves as an aggregate to prevent pattern casting during firing and to control the reflectance and the dielectric constant. Things.

Incidentally, in order to reduce the external light reflection of the formed pattern, the transfer layers 33 and 43 may contain a refractory black or white pigment as an inorganic powder.
Co-Cr-Fe, Co-
Mn-Fe, Co-Fe-Mn-Al, Co-Ni-C
r-Fe, Co-Ni-Mn-Cr-Fe, Co-Ni
-Al-Cr-Fe, Co-Mn-Al-Cr-Fe-
Si etc. can be mentioned. Examples of the fire-resistant white pigment include titanium oxide, aluminum oxide, silica, and calcium carbonate. (2) Organic Component As the organic component contained in the transfer layers 33 and 43 that can be removed by firing, a thermoplastic resin can be used.

The thermoplastic resin is contained as a binder for the above-mentioned inorganic component and for the purpose of improving transferability. Examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, and the like. n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl Acrylate, n-
Hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate ,
2-hydroxypropyl methacrylate, styrene, α
1 such as methylstyrene, N-vinyl-2-pyrrolidone, etc.
Examples thereof include polymers or copolymers composed of at least two or more species, and cellulose derivatives such as ethyl cellulose.

In particular, methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-
Butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, te
rt-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-
Preferred is a polymer or copolymer of at least one of hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and ethyl cellulose.

The thermoplastic resin has a molecular weight of 10,0.
The range of 00 to 500,000 is preferred.

Further, a photosensitive resin composition can be used as the organic component contained in the transfer layers 33 and 43 which can be removed by firing.

The photosensitive resin composition contains at least a polymer, a monomer and an initiator, and does not volatilize or decompose by firing and does not leave carbides in the fired film.

As the polymer, methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-
Butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, te
rt-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, styrene, α
-Methylstyrene, one or more of N-vinyl-2-pyrrolidone, acrylic acid, methacrylic acid, dimer of acrylic acid (for example, M-5600 manufactured by Toagosei Co., Ltd.), 2-methacryloyloxyethyl succinate 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl phthalate, 2-acryloyloxyethyl phthalate,
2-methacryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl hexahydrophthalate, itaconic acid, crotonic acid, maleic acid, fumaric acid,
Examples thereof include vinyl acetic acid, polymers or copolymers of one or more of these acid anhydrides, and carboxyl group-containing cellulose derivatives.

Further, there may be mentioned, for example, polymers obtained by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the above-mentioned copolymer, but the invention is not limited thereto.

The molecular weight of the above polymer is from 5,000 to
300,000, preferably 30,000 to 150,0
00 range. Further, other polymers such as a methacrylate polymer, a polyvinyl alcohol derivative, an N-methyl-2-pyrrolidone polymer, a cellulose derivative, and a styrene polymer can be mixed with the above-mentioned polymer.

As the reactive monomer constituting the photosensitive resin composition, a compound having at least one polymerizable carbon-carbon unsaturated bond can be used. Specifically, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Acrylate, isobonyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate,
Phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3
-Propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate,
Tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide-modified pentaerythritol triacrylate, ethylene oxide-modified pentaerythritol tetra Acrylate, propylene oxide-modified pentaerythritol triacrylate, propylene oxide-modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanetriol triacrylate , 2,2,4-trimethyl-1,3
-Pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate,
Pentaerythritol hexaacrylate, and the above acrylate changed to methacrylate, γ-
Methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, and the like. The reactive monomers described above can be used as one kind or a mixture of two or more kinds, or as a mixture with other compounds.

As photopolymerization initiators constituting the photosensitive resin composition, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone,
α-amino acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,2-diethoxyacetophonone, 2,2-dimethoxy-2-phenylacetophenone, -Hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-
Chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketal, benzylmethoxyethylacetal, benzoinmethylether, benzoinbutylether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloranthraquinone, anthrone, benzantrone , Dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6
-Bis (p-azidobenzylidene) cyclohexane,
2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxy Carbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl-
[4- (methylthio) phenyl] -2-morpholino-
1-propane, 2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl) -butanone-1, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphosphine,
Examples include a combination of a photoreducing dye such as camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide, eosin, and methylene blue with a reducing agent such as ascorbic acid and triethanolamine. One or more agents can be used.

The content of the thermoplastic resin or the photosensitive resin composition in the transfer layers 33 and 43 is 3 to 50 parts by weight, preferably 5 to 30 parts by weight based on 100 parts by weight of the above-mentioned inorganic component. Can be set in a range. When the content of the thermoplastic resin or the photosensitive resin composition is less than 3 parts by weight, the shape retaining properties of the transfer layers 33 and 43 are low, and in particular, there is a problem in storage stability and handling property in a roll state, and When the transfer sheets 31 and 41 are cut (slit) into a desired shape, inorganic components are generated as dust, which may hinder plasma display panel production. On the other hand, when the content of the thermoplastic resin or the photosensitive resin composition exceeds 50 parts by weight, the organic components cannot be completely removed by firing, and carbides remain in the film after firing, resulting in deterioration in quality. Not preferred.

Further, in the above-mentioned thermoplastic resin and photosensitive resin composition, sensitizers, polymerization terminators, chain transfer agents, leveling agents, dispersants, transferability-imparting agents, stabilizers, A foaming agent, a thickener, a suspending agent, a release agent and the like can be contained as required.

The transferability-imparting agent is added for the purpose of improving the transferability and the fluidity of the ink composition. For example, dimethylphthalate, dibutylphthalate, di-n
Normal alkyl phthalates such as octyl phthalate, phthalic acid esters such as di-2-ethylhexyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, and butyl phthalyl butyl glycolate; tri-2 -Ethylhexyl trimellitate, tri-
trimellitate such as n-alkyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, dimethyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di- 2
-Ethylhexyl acetate, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, di-2-ethylhexyl malate, acetyl-tri- (2-ethylhexyl) citrate, acetyl-tri-n-butyl citrate, Aliphatic dibasic acid esters such as acetyl tributyl citrate, polyethylene glycol benzoate, triethylene glycol di- (2
-Ethylhexoate), glycol derivatives such as polyglycol ether, glycerin derivatives such as glycerol triacetate and glycerol diacetyl monolaurate, polyesters composed of sebacic acid, adipic acid, azelaic acid, phthalic acid, etc., having a molecular weight of 300 to 3,000. Low molecular weight polyether, the same low molecular weight poly-α-styrene, the same low molecular weight polystyrene, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate,
Orthophosphates such as tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xyenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ricinoleates such as methyl acetyl ricinoleate, poly-1,3
-Polyester / epoxidized esters such as butanediol adipate and epoxidized soybean oil; and acetates such as glycerin triacetate and 2-ethylhexyl acetate.

The dispersant and the anti-settling agent are intended to improve the dispersibility and anti-settling property of the inorganic powder, and include, for example, phosphate ester type, silicone type, castor oil ester type and various types. Surfactants and the like, examples of the antifoaming agent include silicone-based, acrylic-based, various surfactants and the like, and examples of the release agent include silicone-based, fluorine oil-based, paraffin-based, and fatty acid-based , Fatty acid ester type, castor oil type, wax type, compound type and the like, and as the leveling agent, for example, fluorine type, silicone type, various surfactants and the like,
Each can be added in an appropriate amount.

Examples of the solvent used together with the thermoplastic resin or the photosensitive resin composition for forming the transfer layers 33 and 43 include, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol. , Α- or β
-Terpenes such as terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone and 4-heptanone; and aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene. , Cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene Glycol ethers such as ethylene glycol monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate,
Cellosolve acetate, ethyl cellosolve acetate,
Butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate,
Examples thereof include acetates such as 3-methoxybutyl acetate, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, ethyl 3-ethoxypropionate, methyl benzoate, N, N-dimethylacetamide, N, N-dimethylformamide and the like. As the protective film 44 constituting the protective film transfer sheet 41, a material that is flexible and does not significantly deform by tension or pressure can be used. Specifically, polyethylene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, polypropylene film, polystyrene film, polymethacrylic acid film, polyvinyl chloride film, polyvinyl alcohol film, polyvinyl butyral film, Nylon film, polyetheretherketone film, polysulfone film, polyethersulfone film, polytetrafluoroethylene-perfluoroalkylvinylether film, polyvinyl fluoride film, tetrafluoroethylene-ethylene film,
Tetrafluoroethylene-hexafluoropropylene film, polychlorotrifluoroethylene film, polyvinylidene fluoride film, polyethylene terephthalate film, polyethylene naphthalate film, polyester film, cellulose triacetate film, polycarbonate film, polyurethane film, polyimide film, polyether Imide films, films in which fillers are blended with these resin materials,
A film obtained by uniaxially or biaxially stretching a film using these resin materials, a biaxially stretched film in which the stretching ratio in the width direction is increased from the flow direction using these resin materials, and a width using these resin materials Biaxially stretched film with a higher draw ratio in the flow direction than in the direction, a film obtained by laminating films of the same or different types among these films, and
Composite films formed by co-extruding the same or different resins selected from the raw material resins used for these films can be used. Among these films, it is particularly preferable to use a biaxially stretched polyester film. Further, those obtained by treating the above resin film, for example, silicon-treated polyethylene terephthalate, corona-treated polyethylene terephthalate, melamine-treated polyethylene terephthalate, corona-treated polyethylene, corona-treated polypropylene, silicon-treated polypropylene, and the like may be used.

The thickness of the protective film 44 as described above is
It can be set in the range of 4 to 400 μm, preferably 6 to 150 μm.

In the above-described example of the pattern forming method of the present invention, a transfer sheet as shown in FIG. 3 is used, but when a transfer sheet provided with a protective film as shown in FIG. After the protective film is peeled and removed, a pattern such as a dielectric layer can be formed by the same operation as in FIG.

When the pattern layer to be formed is not a solid pattern but a pattern having a desired shape, patterning can be performed after the drying process. For example, when the organic component of the transfer layer has photosensitivity, the transferred and dried transfer layer is exposed through a predetermined photomask, developed, and then fired to form a pattern. Can be. If the organic component of the transfer layer has no photosensitivity, a mask is formed on the transferred and dried transfer layer, the transfer layer is etched by sandblasting or the like, and then baked to form a pattern. The formation can take place.

[0048]

Next, the present invention will be described in more detail with reference to examples.

First, an ink composition for forming a dielectric having the following composition was prepared.

Composition of ink composition Poly-n-butyl methacrylate / 2-hydroxyethyl methacrylate copolymer (8/2 (molar ratio)) 15 parts by weight (molecular weight = 300,000) Transfer of adipic ester Properties imparting agent: 10 parts by weight (Adeka Kaiser RS107 manufactured by Asahi Denka Kogyo Co., Ltd.) Glass frit: 65 parts by weight (main components: Bi ₂ O ₃ , ZnO, B ₂ O ₃ (alkali-free) Average particle size = 3 μm・ Titanium oxide powder: 7 parts by weight ・ Aluminum oxide powder: 5 parts by weight ・ Ethylene glycol monomethyl ether: 50 parts by weight Next, a polyethylene terephthalate film having a thickness of 25 μm as a base film (T-60 manufactured by Toray Industries, Inc.) Is prepared, and the ink composition is coated on the base film by a reverse coating method and dried ( 00 ℃,
(2 minutes) to form a transfer layer having a thickness of 25 μm. As a result, a transfer sheet for forming a dielectric having a layer configuration as shown in FIG. 3 was obtained.

Next, a laminator AL manufactured by Asahi Kasei Kogyo Co., Ltd.
At -700, the above transfer sheet was pressed onto a glass substrate heated to 100 ° C. with a hot roll at 40 ° C. Next, after cooling to room temperature, the base film was peeled off and the transfer layer was transferred to a glass substrate.

Next, the transfer layer was subjected to a drying treatment at the drying temperature and processing time settings shown in Table 1 below. After this drying treatment, the glass substrate was left in a non-clean room environment to forcibly attach dust, and then dust was removed by air blowing. The surface state of the transfer layer at this stage was observed.

Next, the glass substrate was fired at a maximum temperature of 570 ° C. to form a dielectric layer. The surface condition of the dielectric layer thus formed was observed, and the following criteria were evaluated together with the observation result of the surface condition of the transfer layer. The results are shown in Table 1 below.

Evaluation criteria ：: The transfer layer after the drying treatment has no tackiness, and the attached dust can be removed by air blow. No crack is observed in the dielectric layer obtained by firing.

Δ: Although the transfer layer after the drying treatment shows a slight decrease in tackiness, the attached dust may not be removed by air blowing. No crack is observed in the dielectric layer obtained by firing.

×: There is no decrease in the adhesiveness of the transfer layer due to the drying treatment, and it is difficult to remove the attached dust by air blowing. In addition, cracks are observed in the dielectric layer obtained by firing.

[0057]

[Table 1] As shown in Table 1, when the transfer layer was subjected to a drying treatment in a temperature range of 100 to 300 ° C. with an appropriate treatment time, it was possible to remove attached dust and to form the formed dielectric layer. It was confirmed that the surface condition was extremely good.

On the other hand, when the transfer layer is subjected to a drying treatment at 50 ° C., the drying treatment effect cannot be obtained even if the treatment time is lengthened, and it is difficult to remove the attached dust. The resulting dielectric layer had cracks and a poor surface condition.

[0059]

As described in detail above, according to the present invention, a transfer sheet provided with a transfer layer containing at least an inorganic component containing a glass frit and an organic component that can be removed by firing is transferred onto a substrate. Transfer the layer and apply 100 to
After performing a drying process in a temperature range of 300 ° C., the pattern is formed by baking to remove the organic components.
By the drying treatment after the transfer, the organic components contained in the transfer layer are removed to some extent, the tackiness of the transfer layer is reduced, and the adhesion of dust to the transfer layer during the manufacturing process is less likely to occur,
The attached dust can be easily removed by air blow or the like, and since the amount of organic components contained in the transfer layer before firing is reduced by the drying treatment, rapid removal of organic components during firing is prevented, for example, Even in a shortened profile in which the firing temperature is rapidly increased, there is no crack on the fired surface after firing, thereby forming a base layer of the plasma display panel, a dielectric layer of the front plate and the back plate, an insulating layer, and the like. It can be easily formed in a good surface condition with high thickness accuracy.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating an example of a plasma display panel.

FIG. 2 is a process diagram illustrating an example of forming a dielectric layer using a transfer sheet according to the pattern forming method of the present invention.

FIG. 3 is a schematic sectional view illustrating an example of a transfer sheet that can be used in the present invention.

FIG. 4 is a schematic sectional view showing another example of a transfer sheet that can be used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Plasma display panel 11 ... Front plate 21 ... Back plate 25 ... Dielectric layer 31, 41 ... Transfer sheet 32, 42 ... Base film 33, 43 ... Transfer layer 33 '... Transfer layer after drying process 44 ... Protective film

Claims (1)

[Claims] 1. A transfer sheet having a transfer layer containing at least an inorganic component containing a glass frit and an organic component removable by baking, the transfer layer is transferred onto a substrate, and the transfer layer is transferred to the transfer layer at 100 to 300 ° C. A drying process in the above temperature range, followed by baking to remove organic components.