JPH11111166A - Transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a reserving stability without generation of coaggulation brakage in a transfer layer by providing the transfer layer on a base film so as to be separable, the layer containing an inorganic component containing a glass frit and an organic component capable of being removed when baked, and making the content of residue solvent not more than a specified value. SOLUTION: An ink composition containing an inorganic component containing glass frit and an organic component capable of being removed when baked is applied as coating on a base film 2 composed of a resinous film such as a polyethylene film by the gravure-coating, slit die coating or the like, and then it is dried to form a transfer layer 3. As the organic component which can be baked and removed a thermosetting resin such as a polymer or copolymer composed of one kind or more of methylacryrate, methylmethacrylate, etc., is used. In the case where after the ink composition is applied as coating on the film 2 it is dried to form the transfer layer 3, the amount of residue solvent is set to be not more than 100 mg/m<2> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer sheet for forming an electrode pattern, a dielectric layer, a barrier and the like in a plasma display panel with high accuracy.

[0002]

2. Description of the Related Art In recent years, plasma display panels (P
DP) Fine pattern formation of electrodes, dielectrics, etc.
Alternatively, it is required that the formation of the barrier can be performed with higher accuracy and at low manufacturing cost.

Conventionally, a pattern formation in a PDP is performed by forming a predetermined pattern by a printing method such as screen printing or offset printing using a pattern forming paste having desired characteristics, and drying and baking to form a pattern. And so on.

[0004]

The above-mentioned printing method is expected to have a simple process and reduce the manufacturing cost. However, the screen printing method has a limitation in printing accuracy due to elongation of a mesh material constituting a screen printing plate. In addition, there is a problem that the formed pattern has meshes or bleeds of the pattern, and the edge accuracy of the pattern is low.
Further, in the offset printing method, as the number of printings advances, the pattern forming paste is not completely transferred to the substrate and remains on the blanket, so that the pattern accuracy is reduced.
Therefore, it is necessary to replace the blanket at any time in order to maintain the pattern accuracy, and there has been a problem that the operation is complicated.

On the other hand, as a thick film pattern having a high aspect ratio such as a PDP barrier, a barrier having a predetermined pattern has been conventionally formed by a screen printing method. In the screen printing method, since the limit of the film thickness that can be formed by one printing is several tens of μm, it is necessary to repeat printing and drying many times, generally ten times or more.
However, generally, the coating film formed by the screen printing method has a convex shape in which the peripheral portion is lowered, and when performing multiple overprinting as described above, dripping of the coating liquid in the pattern peripheral portion is accumulated. There has been a problem that the bottom has a wide cross-sectional shape.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is a transfer sheet capable of forming a high-definition pattern of electrodes, dielectrics, and the like, and a high-precision thick film pattern of barriers and the like. The purpose is to provide.

[0007]

In order to achieve the above object, the present invention comprises at least a base film and a transfer layer releasably provided on the base film, wherein the transfer layer is made of a glass frit. And an organic component that can be removed by baking, and the amount of residual solvent is 100 mg / m ² or less.

Further, the transfer sheet of the present invention has a structure in which a protective film is provided on the transfer layer so as to be peelable.

Further, the transfer sheet of the present invention is configured such that the organic component has photosensitivity.

Further, the transfer sheet of the present invention is configured such that the transfer layer contains a conductive powder as an inorganic component.

The present invention as described above has a residual solvent amount of 10
The transfer layer having a concentration of 0 mg / m ² or less does not cause cohesive failure, improves storage stability, and peels off from the base film during transfer, and peels off from the protective film when a protective film is provided. When the organic component has photosensitivity, patterning accuracy by exposure and development is improved.

[0012]

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

FIG. 1 is a schematic sectional view showing an embodiment of the transfer sheet of the present invention. In FIG. 1, a transfer sheet 1
Includes a base film 2 and a transfer layer 3. Transfer layer 3
Is provided so as to be peelable from the base film 2 and contains at least an inorganic component including a glass frit and an organic component that can be removed by baking, and has a residual solvent amount of 100 mg / m ² or less, preferably 50 mg / m ² or less. m ² or less.

FIG. 2 is a schematic sectional view showing another embodiment of the transfer sheet of the present invention. 2, the transfer sheet 11 includes a base film 12, a transfer layer 13 provided releasably on the base film 12, and a protective film 14 provided releasably on the transfer layer 13. . The transfer layer 13 contains at least an inorganic component including a glass frit and an organic component that can be removed by firing, and is set so that the amount of the residual solvent is 100 mg / m ² or less, preferably 50 mg / m ² or less.

In the present invention, if the amount of the residual solvent in the transfer layers 3 and 13 exceeds 100 mg / m ² , the transfer layers 3 and 13 are liable to cause cohesive failure. The transfer layers 3 and 13 undergo cohesive failure at the time of peeling, and the adhesion between the transfer layers 3 and 13 and the base films 2 and 12 and the protective film 14 becomes too high, so that the peelability is reduced. , And 11 are not preferred because the storage stability of them decreases. Further, as described later, when a photosensitive resin composition is used as the organic component that can be removed by baking, it is not preferable because the accuracy of patterning by exposure and development is reduced.

The transfer sheets 1 and 11 may be in the form of a sheet or a long sheet. In the case of the long sheet, the transfer sheets 1 and 11 may be in the form of a roll wound around a core. The core used is ABS to prevent the generation of dust and paper dust.
A core formed of resin, vinyl chloride resin, bakelite, or the like, a paper tube impregnated with resin, or the like is preferable.

Next, the structure of the transfer sheets 1 and 11 will be described. Base Film The base films 2 and 12 constituting the transfer sheets 1 and 11 of the present invention are stable with respect to the ink composition when forming the transfer layers 3 and 13, have flexibility, and
Use a material that does not significantly deform under tension or pressure.

As the 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, and the like can be used.

Further, metal foils or metal steel strips can be used as the base films 2 and 12. 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 2 and 12 as described above can be set in the range of 4 to 400 μm, preferably 10 to 150 μm. Transfer Layers The transfer layers 3 and 13 are provided with an ink composition containing at least an inorganic component including a glass frit and an organic component that can be removed by baking, on the base films 2 and 12, a direct gravure coating method, a gravure reverse coating method, and a 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. still,
After the transfer layer 13 is applied and formed on the protective film 14,
Alternatively, the base film 12 may be formed by pressing the base film 12 and pressing it. (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 these glass frit, for example, a glass frit containing Bi ₂ O ₃ or PbO as a main component can be used.

When a photosensitive resin composition as described below is used as the organic component that can be removed by baking, it is preferable to use a bismuth-based glass frit from the viewpoint of resistance to a polymer and the like.

The transfer layers 3 and 13 may be made of an inorganic powder such as aluminum oxide, boron oxide, silica, titanium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, or calcium carbonate. It can be contained in a range of 30 parts by weight or less based on parts by weight. Such an inorganic powder preferably has an average particle size in the range of 0.1 to 20 μm, and functions as an aggregate to prevent pattern casting during firing and to control the reflectance and the dielectric constant. Things.

The transfer sheets 1 and 11 provided with the transfer layers 3 and 13 containing at least the above glass frit as an inorganic component can be used for forming a dielectric layer of a plasma display panel.

When the transfer sheets 1 and 11 of the present invention are used for forming a barrier, the inorganic powder is used as an inorganic powder in order to reduce the reflection of external light from the formed barrier pattern and to improve the practical contrast. The black or white pigment described above can be contained in the transfer layers 3 and 13. Co-Cr-Fe, Co-Mn-
Fe, Co-Fe-Mn-Al, Co-Ni-Cr-F
e, Co-Ni-Mn-Cr-Fe, Co-Ni-Al
-Cr-Fe, Co-Mn-Al-Cr-Fe-Si and the like. Examples of the fire-resistant white pigment include titanium oxide, aluminum oxide, silica, and calcium carbonate.

When the transfer sheets 1 and 11 of the present invention are used for forming an electrode pattern, a conductive powder is contained in the transfer layers 3 and 13 as an inorganic powder.

As the conductive powder, Au powder, A powder
One or more of g powder, Cu powder, Ni powder, Al powder, Ag-Pd powder and the like can be used. The shape of the conductive powder may be various shapes such as a sphere, a plate, a lump, a cone, and a rod, but a spherical conductive powder having good dispersibility without cohesion is preferable. The average particle size is preferably in the range of 0.05 to 10 μm. Transfer layer 3, 13
Can be in the range of 2 to 20 parts by weight, preferably 2 to 10 parts by weight of the glass frit with respect to 100 parts by weight of the conductive powder. (2) Organic Component A thermoplastic resin can be used as the organic component contained in the transfer layers 3 and 13 which can be removed by firing.

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 10,000.
A range from 0 to 500,000 is preferred.

As the organic component contained in the transfer layers 3 and 13 which can be removed by firing, a photosensitive resin composition can be used.

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 carbide in the film after firing.

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, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, styrene, α-methylstyrene, N-vinyl-2-
One or more kinds of pyrrolidone and a dimer of acrylic acid, methacrylic acid, acrylic acid (for example, M
-5600), 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl phthalate, 2-acryloyloxyethyl phthalate, 2-methacryloyloxyethyl hexahydrophthalate, hexahydrophthalic acid Examples thereof include polymers or copolymers of one or more of 2-acryloyloxyethyl, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof, and cellulose derivatives having a carboxyl group.

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 it is not limited thereto.

The molecular weight of the above polymer is 5,000 to 3
00,000, preferably 30,000 to 150,000
A range of 0 is preferred. Further, other polymers such as a methacrylate polymer, an acrylate polymer, a cellulose derivative, an N-vinylpyrrolidone polymer, and polyvinyl alcohol may be mixed.

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. In the present invention, the above-mentioned reactive monomers can be used as one kind or a mixture of two or more kinds, or as a mixture with other compounds.

As the photopolymerization initiator 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. In the present invention, one or more of these photopolymerization initiators can be used.

The content of the thermoplastic resin or the photosensitive resin composition in the transfer layers 3 and 13 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 retention of the transfer layers 3 and 13 is low, and in particular, there is a problem in storage stability and handling in a roll state, and When the transfer sheets 1 and 11 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, the above-mentioned thermoplastic resin and photosensitive resin composition may contain, as additives, a sensitizer, a polymerization terminator, a chain transfer agent, a leveling agent, a dispersant, a transferability-imparting agent, a stabilizer, and an additive. 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. Examples thereof include dimethyl phthalate, dibutyl phthalate, and 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 above-mentioned 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 3 and 13 include, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol. , Α- or β-
Terpene such as terpineol, etc., 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, triethylene Glycol ethers such as 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. Also, two or more of these may be mixed. Protective film Protective film 14 constituting transfer sheet 11 of the present invention
Can be made of a material that is flexible and does not significantly deform under tension or pressure. 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, poly Chi terephthalate film, polyethylene naphthalate film, a polyester film, a cellulose triacetate film, polycarbonate film,
Polyurethane film, polyimide film, polyetherimide film, film in which filler is blended with these resin materials, uniaxially or biaxially stretched film using these resin materials, flow direction using these resin materials A biaxially stretched film with a higher stretching ratio in the width direction, a biaxially stretched film with a higher stretching ratio in the flow direction than the width direction using these resin materials, and a film of the same or different type among these films Examples thereof include a combined film and a composite film formed by co-extruding the same or different resins selected from the raw material resins used for these films. 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 can also be used.

The thickness of the protective film 14 as described above is
It can be set in the range of 4 to 400 μm, preferably 6 to 150 μm.

Next, an example of forming an electrode pattern of a plasma display panel (PDP) using the above-described transfer sheet of the present invention will be described.

Here, before describing electrode pattern formation and dielectric layer formation, an AC type PDP will be described.

FIG. 3 is a schematic structural view showing an AC type PDP, showing a state in which a front plate and a back plate are separated.
In FIG. 3, the PDP 51 has a front plate 61 and a rear plate 71 arranged in parallel and facing each other, and a barrier 76 is formed on the front side of the rear plate 71 so as to stand upright. The front plate 61 and the back plate 71 are held at regular intervals by the barrier 76. The front plate 61 has a front glass substrate 62, and composite electrodes composed of a sustain electrode 63, which is a transparent electrode, and a bus electrode 64, which is a metal electrode, are formed in parallel on the back side of the front glass substrate 62. And a dielectric layer 65 is formed over the
An O layer 66 is formed. The back plate 71 has a back glass substrate 72. On the front side of the back glass substrate 72, an address electrode 74 is located between barriers 76 so as to be orthogonal to the composite electrode via a base layer 73. Are formed in parallel with each other, a dielectric layer 75 is formed so as to cover them, and a phosphor layer 77 is provided so as to cover the wall surface of the barrier 76 and the bottom surface of the cell. In the AC type PDP, a predetermined voltage is applied from an AC power source between composite electrodes on the front glass substrate 62 to form an electric field, whereby the front glass substrate 62, the rear glass substrate 72, and the barrier 7 are formed.
Discharge is performed in each cell as a display element defined by the cells 6 and 6. Then, the phosphor layer 77 is caused to emit light by the ultraviolet light generated by the discharge, and the light transmitted through the front glass substrate 62 is visually recognized by the observer.

Next, the formation of the address electrodes 74 on the back plate 71 of the PDP will be described.

FIG. 4 is a process chart for explaining the pattern formation of the address electrodes 74 using the transfer sheet 1 of the present invention. In this case, the transfer layer 3 of the transfer sheet 1 contains a negative photosensitive resin composition as an organic component that can be removed by firing.

In FIG. 4, first, the transfer layer side of the transfer sheet 1 is pressed against the back glass substrate 72 provided with the base layer 73, and then the base film 2 is peeled off to transfer the transfer layer 3 (FIG. 4). (A)). If heating is necessary for the transfer of the transfer layer 3, the back glass substrate 72 may be heated, or may be heated by a pressure roll or the like.

Next, the transfer layer 3 is exposed through a photomask M (FIG. 4B). When a light-transmitting film is used as the base film 2, exposure may be performed before the base film 2 is peeled off.

Next, by developing the transfer layer 3,
The pattern 3 ′ made of a conductive photosensitive resin layer is
3 (FIG. 4 (C)), and then firing to remove the organic components of the pattern 3 ', thereby forming the address electrode pattern 74 (FIG. 4 (D)).

In the above example, the transfer sheet of the present invention as shown in FIG. 1 is used. However, when a transfer sheet provided with a protective film as shown in FIG. 2 is used,
After peeling and removing the protective film, a pattern can be formed by the same operation as in FIG. In the case where the dielectric layer 75 is formed entirely of solids, the organic components can be removed by firing immediately after the transfer layer is transferred.

[0052]

Next, the present invention will be described in more detail with reference to examples. Example 1 First, a conductive photosensitive resin composition having the following composition was prepared as an ink composition.

Composition of photosensitive resin composition: silver powder (spherical shape, average particle size: 1 μm): 96 parts by weight; glass frit: 4 parts by weight (main components: Bi ₂ O ₃ , SiO ₂ , B ₂ O ₃ (none) Alkali) softening point = 500 ° C., coefficient of thermal expansion α ₃₀₀ = 80 × 10 ⁻⁷ / ° C.) n-butyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer: 13 parts by weight (molecular weight = 70,000; Acid value = 140 mgKOH / g) Pentaerythritol triacrylate 11 parts by weight (M-305 manufactured by Toagosei Co., Ltd.) Photopolymerization initiator (Irgacure 369 manufactured by Ciba-Geigy Co., Ltd.) 1 part by weight 3-methoxybutyl acetate 20 parts by weight Next, a polyethylene terephthalate film (T-60 manufactured by Toray Industries, Inc.) having a thickness of 50 μm was prepared as a base film. Sufirumu on the above ink composition was applied by blade coating method in dry (100 ° C., 2 minutes) to form a transfer layer having a thickness of 17μm to. The residual solvent amount of the formed transfer layer was 30 mg / m ² .

Next, a polyethylene film (GF-3 (thickness: 90 μm) manufactured by Tamapoly Co., Ltd.) was laminated as a protective film on the transfer layer to form a transfer sheet (sample 1) as shown in FIG. .

The amount of residual solvent in the transfer layer was changed to 5 mg / m ² , 50 mg / m ² , 100 mg / m ² by changing the drying conditions.
^2, except that the ^{150mg / m 2, 300mg / m} 2 is
Transfer sheet (samples 2 to 6) in the same manner as sample 1 described above.
Was prepared.

Next, each of the above transfer sheets (samples 1 to 5)
6) was slit into a predetermined width, wound around an ABS resin core, and stored in a roll at 25 ° C. for 7 days.
Thereafter, the protective film was peeled off, and pressed on a glass substrate heated to 80 ° C. with a hot roll at 40 ° C. using an auto-cut laminator. Next, after cooling to room temperature, the base film was peeled off and the transfer layer was transferred to a glass substrate.

Next, an ultraviolet ray (light source: ultrahigh pressure mercury lamp) was irradiated (700 mJ) through a negative pattern mask (opening line width 70 μm) of the electrodes of the plasma display panel.
/ Cm ² ) to expose the transfer layer. Thereafter, development was performed using a 0.5% aqueous sodium carbonate solution to obtain a predetermined pattern. Next, the glass substrate was fired at 600 ° C. to form an electrode pattern.

The thickness and line width of the electrode pattern thus formed were measured and are shown in Table 1 below.

[0059]

[Table 1] As shown in Table 1, the transfer sheet of the present invention (Samples 1 to
It was confirmed that the electrode pattern formed by using 4) had a uniform thickness and a uniform line width, and was formed with high accuracy. It was also confirmed that the storage stability of the transfer sheet was high.

On the other hand, in the electrode pattern formed by using the transfer sheet (samples 5 to 6) having a high residual solvent amount, pattern flow, chipping, and disconnection during development frequently occurred. Also,
The storage stability of these transfer sheets is such that the transfer layer exudes from the side surface, cracks occur in the transfer layer, the protective film peels off, and the transfer layer cohesively breaks when the base film peels off during transfer. Was not enough.
Example 2 First, an ink composition for forming a dielectric having the following composition was prepared.

Composition of ink composition : Glass frit: 70 parts by weight (main component: Bi ₂ O ₃ , ZnO, B ₂ O ₃ (non-alkali) average particle size = 3 μm) TiO ₂ : 7 parts by weight Al ₂ O ₃ : 5 parts by weight (softening point of the above-mentioned inorganic component mixture = 570 ° C., Tg = 485 ° C. thermal expansion coefficient α ₃₀₀ = 80 × 10 ⁻⁷ / ° C.) n-butyl methacrylate / 2-hydroxyethyl methacrylate Polymer (8/2 (molar ratio)) 20 parts by weight (molecular weight = 300,000) Adipic ester-based transferability imparting agent 12 parts by weight (Adeka Kaiser RS107 manufactured by Asahi Denka Kogyo KK) Propylene Glycol monomethyl ether: 50 parts by weight Next, a polyethylene terephthalate film (T-60 manufactured by Toray Industries, Inc.) having a thickness of 25 μm was prepared as a base film. The above ink composition was coated on the film by a blade coating method and dried (100 ° C., 2 minutes) to form a transfer layer having a thickness of 25 μm. The residual solvent amount of the formed transfer layer was 20 mg / m ² .

Next, a silicon-treated polyethylene terephthalate film (SP-PET-O3-25-C manufactured by Tocelo Co., Ltd. (25 μm thick) was used as a protective film on the transfer layer.
m)) were laminated to form a transfer sheet (sample 1) as shown in FIG.

The amount of residual solvent in the transfer layer was changed to 40 mg / m ² , 80 mg / m ² , 150 mg / m ² by changing the drying conditions.
Except that a ² in the same manner as Sample 1 above, to produce a transfer sheet (Sample 2-4).

Next, each of the above transfer sheets (samples 1 to 5)
4) was slit to a predetermined width, wound around an ABS resin core to form a roll, and stored at 25 ° C. for 7 days. Thereafter, the protective film was peeled off, and pressed on a glass substrate (one on which an electrode pattern had already been formed) heated to 100 ° C. with a hot roll at 100 ° C. using an auto-cut laminator. Next, after cooling to room temperature, the base film was peeled off and the transfer layer was transferred to a glass substrate.

Next, the glass substrate was fired at 570 ° C. to form a dielectric layer.

The thickness and surface condition of the dielectric layer thus formed are shown in Table 2 below.

[0067]

[Table 2] As shown in Table 2, the transfer sheet of the present invention (Samples 1 to
It was confirmed that the dielectric layer formed by using 3) had a uniform thickness and good surface flatness. It was also confirmed that the storage stability of the transfer sheet was high.

On the other hand, the dielectric layer formed by using the transfer sheet (sample 4) having a high residual solvent amount had many pinholes, and the film thickness distribution was poor. In addition, the storage stability of the transfer sheet was insufficient because the transfer layer exuded from the side surface and cohesive failure of the transfer layer was observed when the base film was peeled off during transfer.

[0069]

As described in detail above, according to the present invention, an inorganic component containing glass frit is provided on a base film,
Contains at least an organic component that can be removed by firing, and
Since the transfer sheet having a residual solvent amount of 100 mg / m ² or less is provided so as to be peelable, the transfer layer hardly causes cohesive failure, has excellent storage stability, and peels off from the base film during transfer. Properties, and when provided with a protective film, good peelability with the protective film,
In addition, when the organic component has photosensitivity, the patterning accuracy by exposure and development is high.
It is possible to form a high-definition pattern such as a dielectric and a high-precision thick film pattern such as a barrier.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing one embodiment of a transfer sheet of the present invention.

FIG. 2 is a schematic sectional view showing another embodiment of the transfer sheet of the present invention.

FIG. 3 is a schematic configuration diagram illustrating an example of a plasma display panel.

FIG. 4 is a process chart for explaining an example of forming an electrode pattern using the transfer sheet of the present invention.

[Explanation of symbols]

 1,11 Transfer sheet 2,12 Base film 3,13 Transfer layer 14 Protective film M Photomask

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Konosuke Tanaka 1-1-1 Ichigaya Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. 1-1-1 Dai Nippon Printing Co., Ltd. (72) Inventor Toshihiko Takeda 1-1-1 Ichigaya Kagacho, Shinjuku-ku, Tokyo Dai-Nippon Printing Co., Ltd.

Claims (4)

[Claims] 1. A base film, comprising at least a transfer layer releasably provided on the base film, wherein the transfer layer contains at least an inorganic component containing a glass frit, and an organic component removable by firing, and 10 residual solvent
A transfer sheet characterized by being at most 0 mg / m ² . 2. The transfer sheet according to claim 1, further comprising a protective film removably provided on the transfer layer. 3. The transfer sheet according to claim 1, wherein the organic component has photosensitivity. 4. The transfer sheet according to claim 1, wherein the transfer layer contains a conductive powder as an inorganic component.